TW202112844A - Active-ray-sensitive or radiation-sensitive resin composition, active-ray-sensitive or radiation-sensitive film, pattern formation method, and electronic device manufacturing method - Google Patents

Abstract

The present invention provides: an active-ray-sensitive or radiation-sensitive resin composition having a solid material concentration of 10% by mass or more, the active-ray-sensitive or radiation-sensitive resin composition comprising a resin (A), a photo-acid generator (B-1), a photo-acid generator (B-2), and an acid diffusion controlling agent (D), wherein an acid generated from the photo-acid generator (B-1) has a pKa value of less than 0, an acid generated from the photo-acid generator (B-2) has a larger pKa value than that of the acid generated from the photo-acid generator (B-1), and the content of the photo-acid generator (B-2) is 0.001 to 0.10% by mass inclusive relative to the content of the photo-acid generator (B-1); an active-ray-sensitive or radiation-sensitive film formed from the active-ray-sensitive or radiation-sensitive resin composition; and a pattern formation method and an electronic device manufacturing method each using the active-ray-sensitive or radiation-sensitive resin composition.

Description

Sensitizing radiation or radiation sensitive resin composition, sensitizing radiation or radiation sensitive film, pattern forming method, and manufacturing method of electronic component

The present invention relates to a photosensitive ray-sensitive or radiation-sensitive resin composition, a photosensitive ray-sensitive or radiation-sensitive film, a pattern forming method, and a manufacturing method of electronic components. In more detail, the present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition, an actinic ray-sensitive or radiation-sensitive film, a pattern forming method using these, and a method of manufacturing an electronic component. The photosensitive ray-sensitive or radiation-sensitive resin composition reacts with actinic rays or radiation to change its properties, and can be used in the manufacturing process of electronic components such as semiconductors and integrated circuits (IC), as a solid The manufacturing process of photodiode, which is the main structural component of the imaging element, that is, the Complementary Metal Oxide Semiconductor (CMOS) image sensor, and the manufacturing and imprinting of circuit boards such as liquid crystals and thermal heads For the production of mold structures, other photofabrication steps, lithographic printing plates, and acid-curable compositions.

Since the resist for KrF excimer laser (248 nm), in order to compensate for the decrease in sensitivity caused by light absorption, a patterning method using chemical amplification has been used. For example, in the positive chemical amplification method, first, the photoacid generator contained in the exposure part is decomposed by light irradiation to generate acid. Then, in the post-exposure baking (PEB: Post Exposure Bake) process, etc., the alkali-insoluble group contained in the sensitizing radiation or radiation-sensitive resin composition is changed by the catalytic action of the generated acid. Into alkali-soluble base. After that, for example, an alkaline solution is used for development. Thereby, the exposure part is removed, and a desired pattern is obtained. In the method, as the alkaline developer, various alkaline developers have been proposed. For example, an aqueous alkaline developer of 2.38% by mass TMAH (tetramethylammonium hydroxide aqueous solution) is generally used as the alkaline developer.

For the miniaturization of semiconductor elements, the short wavelength of the exposure light source and the high numerical aperture (high NA (Numerical Aperture)) of the projection lens have been developed. Currently, an ArF excimer laser with a wavelength of 193 nm is being developed as the light source. Exposure machine. As a technique to further improve the resolution, a method of filling the space between the projection lens and the sample with a high refractive index liquid (hereinafter also referred to as "liquid immersion liquid") (that is, liquid immersion method) can be cited.

As the conventional sensitizing radiation-sensitive or radiation-sensitive resin composition, various types are known. For example, the one described in Patent Document 1 is known. Patent Document 1 describes a photoresist composition containing a polymer having a structural unit including an acid dissociable group dissociated by the action of an acid, a radiation-sensitive acid generator, and a solvent. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2015-57638

[The problem to be solved by the invention] The cross-sectional shape of the pattern obtained by exposing and developing the photosensitive ray-sensitive or radiation-sensitive film formed of the photosensitive ray-sensitive or radiation-sensitive resin composition is generally rectangular. However, particularly in the case of using a thick film (for example, a film thickness of 1 μm or more) sensitizing radiation-sensitive or radiation-sensitive film, there is a problem that the rectangularity of the cross-sectional shape of the pattern of the obtained thick film is reduced. For example, in the case of using a positive pattern forming method to form a line and space pattern with an aspect ratio of the line width of the space portion to the resist film thickness of 5 or more, the line width of the space portion of the obtained pattern becomes larger than that of the upper part of the pattern. Wide and narrow toward the lower part, it is required to improve the rectangularity at a higher level than the prior art.

The object of the present invention is to provide a photosensitive ray-sensitive or radiation-sensitive resin composition, a photosensitive ray-sensitive or radiation-sensitive film, and a photosensitive ray-sensitive or radiation-sensitive resin composition having excellent rectangularity in the cross-sectional shape of the pattern obtained in the pattern formation of a thick film, and The pattern formation method and the manufacturing method of the electronic component using the said sensitizing radiation-sensitive or radiation-sensitive resin composition.

[Means to solve the problem] The following aspects are included in the means for solving the above-mentioned problems.

[1] A sensitizing ray-sensitive or radiation-sensitive resin composition having a solid content concentration of 10% by mass or more, in the sensitizing ray-sensitive or radiation-sensitive resin composition, The resin composition contains a resin (A), a photoacid generator (B-1), a photoacid generator (B-2), and an acid diffusion control agent (D). The photoacid generator (B-1) ) The pKa of the acid generated is less than 0, and the pKa of the acid generated from the photoacid generator (B-2) is greater than the pKa of the acid generated from the photoacid generator (B-1), relative to the The content of the photo acid generator (B-1), and the content of the photo acid generator (B-2) is 0.001% by mass or more and 0.10% by mass or less. [2] The sensitizing radiation-sensitive or radiation-sensitive resin composition according to [1], wherein the pKa of the acid generated from the photoacid generator (B-1) is E ₁ , and the When the pKa of the acid generated by the photoacid generator (B-2) is E ₂ , E ₂ -E ₁ is 3 or more. [3] The sensitizing radiation-sensitive or radiation-sensitive resin composition according to [1] or [2], wherein the acid diffusion control agent ( The content of D) is 0.5% by mass or more and 10.0% by mass or less. [4] The sensitizing radiation-sensitive or radiation-sensitive resin composition according to any one of [1] to [3], wherein the resin (A) is decomposed by the action of an acid to increase its polarity. The base resin. [5] The actinic radiation-sensitive or radiation-sensitive resin composition according to any one of [1] to [4], wherein the resin (A) is a resin containing a repeating unit having a phenolic hydroxyl group. [6] The actinic radiation-sensitive or radiation-sensitive resin composition according to [5], wherein the resin (A) has a repeating unit derived from hydroxystyrene. [7] The sensitizing ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [6], wherein the resin (A) is composed of repeats represented by the following general formula (I) Unit resin.

[化1]

In the general formula (I), R ₄₁ , R ₄₂ and R ₄₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. Among them, R ₄₂ may be _{bonded to Ar 4} to form a ring. In this case, R ₄₂ represents a single bond or an alkylene group. X ₄ represents a single bond, -COO-, or -CONR ₆₄ -, and R ₆₄ represents a hydrogen atom or an alkyl group. L ₄ represents a single bond or a divalent linking group. Ar ₄ represents an (n+1)-valent aromatic hydrocarbon group, and when it _{bonds with R 42} to form a ring, it represents an (n+2)-valent aromatic hydrocarbon group. n represents an integer of 1-5. [8] The sensitizing radiation-sensitive or radiation-sensitive resin composition according to any one of [1] to [7], wherein the acid diffusion control agent (D) is a basic compound (DA), Basic compound (DB) whose basicity is reduced or disappeared by the irradiation of actinic rays or radiation, low-molecular compound (DD) that has a nitrogen atom and a group that is detached by the action of an acid, or has a nitrogen atom in the cation part The onium salt compound (DE). [9] The sensitizing radiation-sensitive or radiation-sensitive resin composition according to any one of [1] to [8], wherein the acid diffusion control agent (D) has the following formulas (D1) to (D5) A compound having a structure represented by any one of them.

[化2]

In formula (D1) and formula (D5), R ²⁰⁰ , R ²⁰¹ and R ²⁰² each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group. R ²⁰¹ and R ²⁰² may be bonded to each other to form a ring. R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ and R ²⁰⁶ each independently represent an alkyl group. [10] The sensitizing radiation-sensitive or radiation-sensitive resin composition according to any one of [1] to [9], wherein the photoacid generator (B-2) is the following formula d1-1 to A compound represented by any one of formula d1-3.

[化3]

In formula d1-1 to formula d1-3, R ⁵¹ represents an organic group. Z ^2c represents a hydrocarbon group. ^Here , the hydrocarbon group represented by Z 2c is one where a fluorine atom is not bonded to a carbon atom adjacent to a sulfur atom. R ⁵² represents an organic group, Y ³ represents a single bond or a divalent linking group, and Rf represents a substituent. R ⁵² and Rf may bond to form a ring. M ⁺ represents an ammonium cation, a cation or an iodonium cation. [11] The sensitizing radiation-sensitive or radiation-sensitive resin composition according to any one of [1] to [9], wherein the photoacid generator (B-2) is the following formula C-1 to A compound represented by any one of formula C-3.

[化4]

In formula C-1 to formula C-3, R ¹ , R ² , and R ³ each independently represent an organic group. L ¹ represents a divalent linking group or a single bond connecting a cationic site and an anionic site. -X ^- represents a group selected _{^{-COO -, -SO 3 -, -SO}} 2 -, and -N ^- anionic sites in -R ^4. R ⁴ represents a monovalent substituent having at least one of a carbonyl group, a sulfinyl group, and a sulfinyl group at the connection site to the adjacent nitrogen atom. R ¹ , R ² , R ³ , R ⁴ , and L ¹ may be bonded to each other to form a ring structure. In addition, in formula C-3, combining two of R ¹ to R ³ represents a divalent substituent, which may also be bonded to a nitrogen atom by a double bond. [12] A sensitizing ray-sensitive or radiation-sensitive film formed of the sensitizing ray-sensitive or radiation-sensitive resin composition as described in any one of [1] to [11], and having a film thickness of 1 μm the above. [13] A pattern forming method comprising: (i) using the sensitizing radiation-sensitive or radiation-sensitive resin composition as described in any one of [1] to [11] to form a film thickness of 1 μm or more on a substrate (Ii) the step of irradiating the sensitizing or radiation-sensitive film with actinic rays or radiation; and (iii) using a developer to irradiate the light The step of developing the sensitized or radiation-sensitive film of chemical rays or radiation. [14] A method of manufacturing an electronic component, including the pattern forming method as described in [13].

[Effects of the invention] According to the present invention, it is possible to provide an actinic ray-sensitive or radiation-sensitive resin composition, an actinic ray-sensitive or radiation-sensitive resin composition, and an actinic ray-sensitive or radiation-sensitive film having excellent rectangularity in the cross-sectional shape of the pattern obtained in the pattern formation of a thick film, and use The pattern formation method of the sensitizing radiation-sensitive or radiation-sensitive resin composition and the manufacturing method of the electronic component are described.

Hereinafter, the content of the present invention will be described in detail. The description of the structural elements described below may be based on a representative embodiment of the present invention, and the present invention is not limited to such an embodiment. Regarding the expression of the group (atomic group) in this specification, the expression that does not describe substituted and unsubstituted includes a group (atomic group) having a substituent together with a group (atomic group) that does not have a substituent. For example, the term "alkyl" includes not only an unsubstituted alkyl group (unsubstituted alkyl group) but also a substituted alkyl group (substituted alkyl group). In addition, the "organic group" in this specification refers to a group containing at least one carbon atom.

In addition, the type of the substituent, the position of the substituent, and the number of the substituent when it is referred to as "may have a substituent" in this specification are not particularly limited. The number of substituents can be, for example, one, two, three, or more. Examples of the substituent include a monovalent non-metal atomic group other than a hydrogen atom. For example, it can be selected from the following substituents T.

(Substituent T) Examples of the substituent T include halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom; alkoxy groups such as methoxy, ethoxy, and tert-butoxy; phenoxy and p-tolyloxy, etc. Aryloxy; alkoxycarbonyl groups such as methoxycarbonyl, butoxycarbonyl and phenoxycarbonyl; acetyloxy groups such as acetoxy, propoxy and benzyloxy; acetoxy, benzyl Aphthyl, isobutyryl, acrylic, methacrylic and methoxalyl groups; alkyl mercapto groups such as methyl mercapto and tertiary butyl mercapto; phenyl mercapto and p-tolyl mercapto Alkyl; Cycloalkyl; Aryl; Heteroaryl; Hydroxy; Carboxy; Carboxylic; Sulfo; Cyano; Alkylaminocarbonyl; Arylaminocarbonyl; Sulfonamide; Silyl group; amino group; monoalkylamino group; dialkylamino group; arylamino group, nitro group; methanoyl group; and combinations of these.

The "actinic rays" or "radiation rays" in this specification refer to, for example, the bright-ray spectrum of mercury lamps, extreme ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light: Extreme Ultraviolet), X-rays, and electrons. Beam (EB: Electron Beam) and so on. Unless otherwise specified, the "light" in this specification refers to actinic rays or radiation. The "exposure" in this manual, unless otherwise specified, includes not only exposure using the bright line spectrum of a mercury lamp, extreme ultraviolet, extreme ultraviolet, X-ray, and EUV light represented by excimer lasers, etc. Including exposure using particle beams such as electron beams and ion beams. In this specification, the term "to" is used to include the numerical values described before and after it as the lower limit and the upper limit.

In this specification, (meth)acrylate means acrylate and methacrylate, and (meth)acrylic means acrylic and methacrylic acid. In this specification, the weight average molecular weight (Mw), number average molecular weight (Mn), and degree of dispersion (also called molecular weight distribution) (Mw/Mn) of the resin components are defined as the use of gel permeation chromatography (Gel Permeation Chromatography). GPC measurement (solvent: tetrahydrofuran, flow rate (sample injection volume): 10 μL, column: manufactured by Tosoh (stock), HLC-8120GPC manufactured by Tosoh (stock)) TSK gel Multipore HXL-M, column temperature: 40°C, flow rate: 1.0 mL/min, detector: Refractive Index Detector (Refractive Index Detector).

Regarding the amount of each component in the composition in this specification, when there are multiple substances corresponding to each component in the composition, unless otherwise specified, it means the total amount of the corresponding multiple substances present in the composition. The term "step" in this specification includes not only independent steps, but even when it cannot be clearly distinguished from other steps, as long as the desired purpose of the step is achieved, it is also included in this term. The "total solid content" in this specification refers to the total mass of the components after removing the solvent from the total composition of the composition. In addition, the so-called "solid content" is a component after removing the solvent as described above, and for example, it may be a solid or a liquid at 25°C. In this manual, "mass%" and "weight%" have the same meaning, and "parts by mass" and "parts by weight" have the same meaning. In addition, in this specification, a combination of two or more preferable aspects is a more preferable aspect.

(Acceptable radiation or radiation-sensitive resin composition) The actinic radiation or radiation-sensitive resin composition of the present invention (hereinafter also referred to as "composition") is an actinic radiation or radiation-sensitive resin composition having a solid content of 10% by mass or more. The sensitizing radiation or radiation-sensitive resin composition contains resin (A), photoacid generator (B-1), photoacid generator (B-2), and acid diffusion control agent (D), The pKa of the photoacid generator (B-1) is less than 0, The pKa of the photo acid generator (B-2) is greater than the pKa of the photo acid generator (B-1), The content of the photo acid generator (B-2) relative to the content of the photo acid generator (B-1) is 0.001% by mass or more and 0.10% by mass or less.

The actinic radiation-sensitive or radiation-sensitive resin composition of the present invention is preferably a so-called resist composition, and may be a positive type resist composition or a negative type resist composition. In addition, it may be a resist composition for alkali development or a resist composition for organic solvent development. Typically, the composition of the present invention is preferably a chemically amplified resist composition.

The inventors of the present invention have found that the above-mentioned actinic radiation-sensitive or radiation-sensitive resin composition can obtain a thick film and a pattern excellent in the rectangularity of the cross-sectional shape. The reason is not clear, but it can be estimated as follows. The resist composition, which is a typical sensitizing radiation-sensitive or radiation-sensitive resin composition, contains a resin, a photoacid generator (B-1), an acid diffusion control agent, and a solvent. When a resist composition or the like is applied on a substrate to form a thick film resist film with a film thickness of 1 μm or more, in the thick film resist film, the solvent is less volatile than in the case of a thin film. In the area closer to the substrate (substrate interface side) and farther away from the substrate (air interface side), the resin or photoacid generator is easy to concentrate (exist in a large amount (that is, biased)) on the side closer to the substrate (substrate interface) Side) farther away from the substrate (air interface side)). On the other hand, the acid diffusion control agent is uniformly distributed over the entire thick film resist film. If the thick resist film in this state is exposed, a large amount of acid is generated in the area far from the substrate (air interface side), so the acid is easily diffused, and the rectangularity of the cross-sectional shape of the pattern is reduced. In contrast to this, it is considered that in the present invention, by adding a specific amount of a photoacid generator (B-2) that generates an acid weaker than the acid generated from the photoacid generator (B-1), the photoacid generator (B-2) Similar to the photoacid generator (B-1), it is also present in the region away from the substrate (air interface side), and the acid generated from the photoacid generator (B-1) can be moderately suppressed Diffusion, thereby improving the rectangularity of the cross-sectional shape of the pattern.

Hereinafter, the details of each component contained in the sensitizing radiation or radiation sensitive resin composition of the present invention will be described.

＜Resin (A)＞ The actinic radiation-sensitive or radiation-sensitive resin composition of the present invention contains resin (A). The resin (A) is preferably a resin having a group (acid-decomposable group) that is decomposed by the action of an acid to increase the polarity. The resin (A) is preferably a resin whose polarity increases due to the action of an acid and the solubility to the developer is changed.

The resin (A) is preferably a resin obtained by polymerizing at least an ethylenically unsaturated compound. The ethylenically unsaturated compound preferably has one to four ethylenically unsaturated bonds, more preferably one. Furthermore, the ethylenically unsaturated compound is preferably a monomer which is a monomer. In addition, the molecular weight of the ethylenically unsaturated compound is preferably 28 to 1,000, more preferably 50 to 800, and particularly preferably 100 to 600.

The resin (A) is more preferably a resin containing a structural unit having an acid-decomposable group. In this case, in the pattern forming method of the present invention described later, when an alkaline developer is used as the developer, a positive pattern can be preferably formed, and when an organic developer is used as the developer, , Can preferably form a negative pattern.

〔Structural units with acid-decomposable groups〕 The resin (A) preferably contains a structural unit having an acid-decomposable group (also referred to as "repeating unit").

As the resin (A), a known resin can be suitably used. For example, paragraph 0055 to paragraph 0191 of U.S. Patent Application Publication No. 2016/0274458 Specification, Paragraph 0035 to Paragraph 0085 of U.S. Patent Application Publication No. 2015/0004544 Specification, and U.S. Patent Application Publication No. 2016/ The well-known resin disclosed in paragraph 0045 to paragraph 0090 of Specification No. 0147150 is referred to as resin (A).

The acid-decomposable group preferably has a structure in which a polar group is decomposed by the action of an acid to be released (a leaving group) protected. Examples of polar groups include carboxyl groups, phenolic hydroxyl groups, sulfonic acid groups, sulfonamido groups, sulfonamido groups, (alkylsulfonyl groups) (alkylcarbonyl) methylene groups, (alkylsulfonyl groups). (Alkyl)(alkylcarbonyl)amido, bis(alkylcarbonyl)methylene, bis(alkylcarbonyl)amido, bis(alkylsulfonyl)methylene, bis(alkyl) Acidic groups such as sulfonyl)imino group, tris(alkylcarbonyl)methylene, and tris(alkylsulfonyl)methylene (groups dissociated in 2.38% by mass tetramethylammonium hydroxide aqueous solution) , And alcoholic hydroxyl groups.

In addition, the alcoholic hydroxyl group refers to a hydroxyl group other than the hydroxyl group (phenolic hydroxyl group) that is directly bonded to the aromatic ring and is bonded to a hydrocarbon group. As a hydroxyl group, an aliphatic group substituted with an electron withdrawing group such as a fluorine atom at the α-position Except for group alcohol groups (for example, hexafluoroisopropanol groups, etc.). The alcoholic hydroxyl group is preferably a hydroxyl group having a pKa (acid dissociation constant) of 12 or more and 20 or less.

As a preferable polar group, a carboxyl group, a phenolic hydroxyl group, and a sulfonic acid group are mentioned.

A preferable group as an acid-decomposable group is a group in which the hydrogen atom of these groups is substituted with a group that is released by the action of an acid (a leaving group). Examples of the group to be released by the action of an acid (a leaving group) include -C(R ³⁶ )(R ³⁷ )(R ³⁸ ), -C(R ³⁶ )(R ³⁷ )(OR ³⁹ ), and -C(R ⁰¹ )(R ⁰² )(OR ³⁹ ) and so on. In the formula, R ³⁶ to R ³⁹ each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. R ³⁶ and R ³⁷ may be bonded to each other to form a ring. R ⁰¹ and R ⁰² each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group.

The alkyl group of R ³⁶ to R ³⁹ , R ⁰¹ and R ⁰² is preferably an alkyl group having 1 to 8 carbon atoms, for example, methyl, ethyl, propyl, n-butyl, sec-butyl, hexyl, And octyl and so on. The cycloalkyl groups of R ³⁶ to R ³⁹ , R ⁰¹ and R ⁰² may be monocyclic or polycyclic. The monocyclic type is preferably a cycloalkyl group having 3 to 8 carbon atoms, and examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl. The polycyclic type is preferably a cycloalkyl group having 6 to 20 carbon atoms, for example, adamantyl group, norbornyl group, isobornyl group, camphenyl group, dicyclopentyl group, α-pinenyl group, tricyclic group Decyl, tetracyclododecyl, and androstanyl, etc. Furthermore, at least one carbon atom in the cycloalkyl group may be substituted with a hetero atom such as an oxygen atom. The aryl group of R ³⁶ to R ³⁹ , R ⁰¹ and R ⁰² is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group. The aralkyl group of R ³⁶ to R ³⁹ , R ⁰¹ and R ⁰² is preferably an aralkyl group having 7 to 12 carbons, and examples thereof include benzyl, phenethyl, and naphthylmethyl. The alkenyl groups of R ³⁶ to R ³⁹ , R ⁰¹ and R ⁰² are preferably alkenyl groups having 2 to 8 carbon atoms, and examples thereof include vinyl groups, allyl groups, butenyl groups, and cyclohexenyl groups. The ring formed by bonding R ³⁶ and R ^{37 to} each other is preferably a cycloalkyl group (monocyclic or polycyclic). The cycloalkyl group is preferably a monocyclic cycloalkyl group such as cyclopentyl and cyclohexyl, or a polycyclic ring such as norbornyl, tetracyclodecyl, tetracyclododecyl, and adamantyl. alkyl.

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.

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

[化5]

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 each independently represent an alkyl group or a cycloalkyl group, and Rx ^{Any two of 1} to Rx ³ may be bonded to form a ring structure, or may not form a ring structure.

As a divalent linking group of T, an alkylene group, an arylene group, -COO-Rt-, and -O-Rt- etc. are mentioned. In the formula, Rt represents an alkylene group, a cycloalkylene group or an arylene group, and T is preferably a single bond or -COO-Rt-. Rt is preferably a chain alkylene having 1 to 5 carbon atoms, more preferably -CH ₂ -, -(CH ₂ ) ₂ -, or -(CH ₂ ) ₃ -. T is more preferably 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. 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 preferably include methyl, ethyl, n-propyl, isopropyl, n-butyl, isopropyl Butyl, tertiary butyl, etc. The number of carbon atoms in the alkyl group is preferably 1-10, more preferably 1-5, and still more preferably 1-3. In ^{the alkyl group of Rx 1} , Rx ² and Rx ³ , a part of the inter-carbon bond may be a double bond. The cycloalkyl group of Rx ¹ , Rx ² and Rx ³ is preferably a monocyclic cycloalkyl group such as cyclopentyl and cyclohexyl, or norbornyl, tetracyclodecyl, tetracyclododecyl, adamantane Polycyclic cycloalkyl groups such as alkyl groups.

The ring structure formed by the two bonding of Rx ¹ , Rx ² and Rx ³ is preferably a monocyclic cycloalkane ring such as a cyclopentyl ring, a cyclohexyl ring, a cycloheptyl ring, and a cyclooctane ring, Or polycyclic cycloalkyl rings such as norbornane ring, tetracyclodecane ring, tetracyclododecane ring, and adamantane ring, more preferably cyclopentyl ring, cyclohexyl ring, or adamantane ring. As ^{a ring structure formed by two bonding of Rx 1} , Rx ² and Rx ³ , the structure shown below is also preferable.

[化6]

Specific examples of monomers corresponding to the structural unit represented by formula AI are listed below, but the present invention is not limited to these specific examples. Corresponds to the following specific examples of AI of formula Xa ¹ is a methyl group, optionally substituted Xa ¹ represents a hydrogen atom, a halogen atom other than fluorine atom, or a monovalent organic group.

[化7]

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

In addition, the resin (A) may have a structural unit described in paragraphs 0363 to 0364 of the specification of U.S. Patent Application Publication No. 2016/0070167, which includes a group that is decomposed by the action of an acid to generate an alcoholic hydroxyl group as a structural unit having acid decomposition. The structural unit of the sex base.

In addition, the resin (A) preferably contains a repeating unit having a structure (acid-decomposable group) protected by a leaving group in which a phenolic hydroxyl group is decomposed by the action of an acid as a repeating unit having an acid-decomposable group. In addition, in this specification, the phenolic hydroxyl group is a group in which the hydrogen atom of an aromatic hydrocarbon group is substituted with a hydroxyl group. The aromatic ring of the aromatic hydrocarbon group is a monocyclic or polycyclic aromatic ring, and examples thereof include a benzene ring and a naphthalene ring.

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

In formula (Y1) and formula (Y2), Rx ₁ to Rx ₃ each independently represent an alkyl group (linear or branched chain) or a cycloalkyl group (monocyclic or polycyclic). Among them, when all of Rx ₁ to Rx ₃ are alkyl groups (linear or branched), it is preferable that at least two of _{Rx 1} to Rx _{3 are methyl groups.} Among them, it is more preferred that Rx ₁ to Rx ₃ each independently represent a repeating unit of a linear or branched alkyl group, and it is more preferred that Rx ₁ to Rx ₃ each independently represent a repeating unit of a linear alkyl group. Two of Rx ₁ to Rx ₃ may be bonded to form a monocyclic ring or a polycyclic ring. The alkyl group of Rx ₁ to Rx ₃ is preferably an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tertiary butyl. The cycloalkyl group of Rx ₁ to Rx ₃ is preferably a monocyclic cycloalkyl group such as cyclopentyl and cyclohexyl, or norbornyl, tetracyclodecyl, tetracyclododecyl, and adamantyl Such as polycyclic cycloalkyl. As _{the cycloalkyl formed by bonding two of Rx 1} to Rx ₃ , monocyclic cycloalkyl such as cyclopentyl and cyclohexyl, or norbornyl, tetracyclodecyl, and tetracyclodecyl are preferred. Polycyclic cycloalkyl groups such as dialkyl and adamantyl. Among them, a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferred. Among _{the cycloalkyl groups formed by bonding two of Rx 1} to Rx ₃ , for example, one of the methylene groups constituting the ring may be substituted with a heteroatom such as an oxygen atom, or a group having a heteroatom such as a carbonyl group. The group represented by the formula (Y1) and the formula (Y2) is preferably a state in which, for example, Rx ₁ is a methyl group or an ethyl group, and Rx ₂ and Rx _{3 are} bonded to form the cycloalkyl group.

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 be bonded to each other to form a ring. As a monovalent organic group, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, etc. are mentioned. 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 can bond with each other to form a non-aromatic ring. Ar is more preferably an aryl group.

As a repeating unit having a structure (acid decomposable group) protected by a leaving group that is decomposed by the action of an acid, the phenolic hydroxyl group preferably has a hydrogen atom in the phenolic hydroxyl group from formula (Y1) to formula ( Y4) The repeating unit of the structure protected by the group represented.

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

[化8]

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. Among them, R ₆₂ may bond with Ar ₆ to form a ring. In this case, R ₆₂ represents a single bond or an alkylene group. X ₆ represents a single bond, -COO-, or -CONR ₆₄ -. R ₆₄ represents a hydrogen atom or an alkyl group. L ₆ represents a single bond or an alkylene group. Ar ₆ represents an (n+1)-valent aromatic hydrocarbon group, and when it _{bonds with R 62} to form a ring, it represents an (n+2)-valent aromatic hydrocarbon group. In the case of n≧2, Y ₂ each independently represents a hydrogen atom or a group released by the action of an acid. Among them, _{at least one of Y 2} represents a group that is detached by the action of an acid. The group that is detached by the action of acid as Y ₂ is preferably formula (Y1) to formula (Y4). n represents an integer of 1-4.

Each of the above groups may have a substituent. Examples of the substituent include an alkyl group (carbon number 1 to 4), a halogen atom, a hydroxyl group, an alkoxy group (carbon number 1 to 4), a carboxyl group, and an alkoxycarbonyl group. (C2-6), etc., preferably having a carbon number of 8 or less.

Hereinafter, specific examples of a repeating unit having a structure (acid-decomposable group) protected by a leaving group in which a phenolic hydroxyl group is decomposed by the action of an acid are given, but the present invention is not limited to these specific examples.

[化9]

[化10]

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

The content of the acid-decomposable group-containing structural unit contained in the resin (A) relative to all the structural units of the resin (A) (the total when there are multiple structural units having acid-decomposable groups) is preferably 5 mol% to 90 mol%, more preferably 10 mol% to 80 mol%, and still more preferably 15 mol% to 70 mol%. In addition, in the present invention, when the content of the "structural unit" is defined in molar ratio, the "structural unit" and the "monomer unit" have the same meaning. In addition, the "monomer unit" in the present invention can be modified after being polymerized by a polymer reaction or the like. The following is also the same.

[Having at least one structural unit selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure] 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.

As the lactone structure or sultone structure, any one may be used as long as it has a lactone structure or a sultone structure, preferably a 5-membered to 7-membered cyclic lactone structure or a 5-membered to 7-membered cyclic sultone Ester structure, more preferably other ring structure in the form of a bicyclic structure, spiro ring structure and 5-membered to 7-membered cyclic lactone structure, or other ring structure in the form of a bicyclic structure, spiro ring structure It is formed by condensing with 5-membered to 7-membered cyclic sultone structure. More preferably, it contains a lactone structure represented by any one of the following formulas LC1-1 to LC1-21, or a sultone structure represented by any one of the following formulas SL1-1 to SL1-3 The structural unit. In addition, the lactone structure or the sultone structure may be directly bonded to the main chain. As a preferable structure, it is LC1-1, LC1-4, LC1-5, LC1-8, LC1-16, LC1-21, SL1-1.

[化11]

The lactone moiety or the sultone moiety may have a substituent (Rb ² ) or may not have a substituent (Rb ² ). Preferred substituents (Rb ² ) include: alkyl groups having 1 to 8 carbons, cycloalkyl groups having 4 to 7 carbons, alkoxy groups having 1 to 8 carbons, and alkyl groups having 2 to 8 carbons. An oxycarbonyl group, a carboxyl group, a halogen atom other than a fluorine atom, a hydroxyl group, a cyano group, an acid-decomposable group, etc. More preferred are an alkyl group having 1 to 4 carbon atoms, a cyano group, and an acid-decomposable group. n2 represents an integer of 0-4. When n2 is 2 or more, a plurality of substituents (Rb ² ) may be the same or different. In addition, a plurality of substituents (Rb ² ) may be bonded to each other to form a ring.

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

[化12]

In the formula III, A represents an ester bond (a group represented by -COO-) or an amide bond (a group represented by -CONH-). n is the ^{number of repetitions of the structure represented by -R 0} -Z-, and represents an integer from 0 to 5, preferably 0 or 1, more preferably 0. When n is 0, -R ⁰ -Z- does not exist, and A and R ⁸ are bonded by a single bond. R ⁰ represents an alkylene group, a cycloalkylene group, or a combination thereof. When ^{there are a plurality of R 0} , 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 there are a plurality of Z, each independently represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond, or a urea bond. R ⁸ represents a monovalent organic group having a lactone structure or a sultone structure. R ⁷ represents a hydrogen atom, a halogen atom other than a fluorine atom, or a monovalent organic group (preferably a methyl group).

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

Specific examples of monomers corresponding to the structural unit represented by formula III and specific examples of monomers corresponding to the structural unit represented by formula A-1 described below are listed below, but the present invention is not limited to these specific examples . Specific examples corresponds to the following formula III R ⁷ and described below in the formula A 1-R _A ¹ is a methyl group, R ⁷ and R _A ¹ is optionally substituted other than a hydrogen atom, a fluorine atom halogen Atom, or monovalent organic group.

[化13]

In addition to the monomers described below, the monomers shown below can also be preferably used as the raw material of the resin (A).

[化14]

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

[化15]

In Formula A-1, R _A ¹ represents a hydrogen atom, a halogen atom other than a fluorine atom, or a monovalent organic group (preferably a methyl group), n represents an integer of 0 or more, and R _A ² represents a substituent. 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 a group formed with the group represented by -OC(=O)-O- in the formula A group of atoms in a monocyclic structure or a polycyclic structure.

The resin (A) preferably has the structural unit described in paragraphs 0370 to 0414 of the specification of US Patent Application Publication No. 2016/0070167 as having a structure selected from a lactone structure, a sultone structure, and a carbonate structure. At least one structural unit in the group.

The resin (A) may contain a structural unit (a) having at least two lactone structures (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, and may be a structure in which at least two lactone structures are connected by a single bond or a linking group. The lactone structure of the structural unit (a) is not particularly limited, and is preferably a 5-membered to 7-membered cyclic lactone structure, and preferably other ring structures to form a bicyclic structure, a spiro ring structure, and 5-membered ring structure. Ring ~ 7-membered ring lactone structure formed by condensing ring. As the lactone structure, for example, a lactone structure represented by any one of LC1-1 to LC1-21 can be preferably cited.

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

[化16]

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

Examples of the lactone structure possessed by the Rb partial structure include the aforementioned lactone structures. 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 connected 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 connected by a single bond or a linking group are each explained below.

-Structural unit (a1) having at least two lactone structure condensed rings- 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 more preferably is a structure in which two lactone structures are condensed. The structural unit (hereinafter, also referred to as "structural unit (a1)") having a structure in which at least two lactone structures have condensed rings may be, for example, a structural unit represented by the following formula L-2.

[化17]

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

The alkyl group of Re ₁ to Re ₈ preferably has a carbon number of 5 or less, and more preferably has a carbon number of 1, for example. Examples of the alkyl groups having 5 or less carbon atoms of Re ₁ to Re ₈ include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, n-pentyl, and isopentyl. Group, the second pentyl group, the third pentyl group, etc. Among them, Re ₁ to Re _{8 are} preferably hydrogen atoms.

Examples of the divalent linking group of Me ₁ include: alkylene, cycloalkylene, -O-, -CO-, -COO-, -OCO-, and combinations of two or more of these groups. base. The alkylene group of Me ₁ preferably has 1 to 10 carbon atoms, for example. In addition, it is more preferably a carbon number of 1 or 2. As the alkylene group having a carbon number of 1 or 2, for example, a methylene group or an ethylene group is preferable. The alkylene group of Me ₁ may be linear or branched. Examples include: methylene, ethane-1,1-diyl, ethane-1,2-diyl, propane-1, 1-diyl, propane-1,3-diyl, propane-2,2-diyl, pentane-1,5-diyl, hexane-1,6-diyl, etc. The cycloalkylene group of Me ₁ preferably has 5 to 10 carbon atoms, and more preferably has 5 or 6 carbon atoms, for example. Examples of the cycloalkylene group of Me ₁ include cyclopentyl, cyclohexyl, heptyl, cyclooctyl, and cyclodecylene. As the _{divalent linking group of Me 1} , the group formed by combining two or more groups is preferably, for example, a group formed by combining an alkylene group and -COO-, and a combination of -OCO- and an alkylene group Formed base. In addition, the group formed by combining two or more groups is more preferably a group formed by combining a methylene group and a -COO- group, and a group formed by combining a -COO- group and a methylene group.

Examples of the divalent linking group of Me ₂ and Me _{3 include alkylene and -O-.} The _{divalent linking group of Me 2} and Me ₃ is preferably methylene, ethylene, and -O-, and more preferably -O-.

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

Although the specific example of a structural unit (a1) is shown below, this invention is not limited to this. In the following formulae, R ₉ represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group, and * represents a bonding position with other structural units.

[化18]

[化19]

[化20]

-A structural unit (a2) having a structure in which at least two lactone structures are connected by a single bond or a linking group-A structure in which at least two lactone structures are connected by a single bond or a linking group is preferably two to four A structure in which each lactone structure is connected by a single bond or a linking group, and more preferably a structure in which two lactone structures are connected by a single bond or a linking group. Examples of the linking group include the same groups as those exemplified in the linking group _{of M 2} in formula L-3 described later. The structural unit (hereinafter, also referred to as "structural unit (a2)") having a structure in which two or more lactone structures are connected by a single bond or a linking group (hereinafter, also referred to as "structural unit (a2)") includes, for example, a structural unit represented by the following formula L-3.

[化21]

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

Examples of the linking group of M ₁ include an alkylene group, a cycloalkylene group, -O-, -CO-, -COO-, -OCO-, and a combination of two or more of these groups. The alkylene group of M ₁ preferably has 1 to 10 carbon atoms, for example. The alkylene group of M ₁ may be linear or branched, for example, methylene, ethane-1,1-diyl, ethane-1,2-diyl, propane-1, 1-diyl, propane-1,3-diyl, propane-2,2-diyl, pentane-1,5-diyl, hexane-1,6-diyl, etc. The cycloalkylene group of M ₁ preferably has 5 to 10 carbon atoms, for example. Examples of the cycloalkylene group of M ₁ include cyclopentyl, cyclohexyl, heptyl, cyclooctyl, and cyclodecylene. As _{the linking group of M 1} , the group formed by combining two or more groups is preferably a group formed by combining an alkylene group and -COO-, and a group formed by combining an alkylene group and -OCO-的基。 The base. In addition, the group formed by combining two or more groups is more preferably a group formed by combining a methylene group and a -COO- group, and a group formed by combining a -COO- group and a methylene group. Examples of the linking group for M ₂ include the same groups as those listed for _{the linking group for M 1.}

The lactone structure of Lc ₁ is, for example, a 5-membered to 7-membered cyclic lactone structure, and other ring structures are preferably formed in the form of a bicyclic structure, a spiro structure, and a 5-membered to 7-membered cyclic lactone structure Those who condensed the ring. The lactone structure is more preferably a lactone structure represented by any one of LC1-1 to LC1-21. As a further preferable lactone structure, LC1-1, LC1-4, LC1-5, LC1-6, LC1-13, LC1-14, and LC1-17 are mentioned. The lactone structure of Lc ₁ may include a substituent. Examples of the substituent that may be included in the lactone structure of Lc ₁ include the same substituents as the substituent ^{(Rb 2) of the lactone structure.} The lactone structure that Lc ₂ has, for example, the same structure as the lactone structure exemplified in the lactone structure that _{Lc 1 has.}

In the structural unit (a2), the structural unit represented by the formula L-3 is preferably a structural unit represented by the following formula L-4.

[化22]

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

The linking group of Mf _{1 has} the same meaning as the linking group _{of M 1} of the formula L-3. The linking group of Mf _{2 has} the same meaning as the linking group _{of M 2} of the formula L-3. Examples of the alkyl group of Rf ₁ include alkyl groups having 1 to 4 carbon atoms. The alkyl group having 1 to 4 carbons in Rf ₁ is preferably a methyl group or an ethyl group, and more preferably a methyl group. The alkyl group of Rf ₁ may have a substituent. Examples of the substituent that the alkyl group of Rf ₁ may have include alkoxy groups such as a hydroxyl group, a methoxy group, and an ethoxy group, and halogen atoms such as a cyano group and a fluorine atom. The alkyl group of Rf ₂ and Rf _{3 has} the same meaning as the alkyl group of Rf _1.

Mf ₁ and Rf ₁ may be bonded to each other to form a ring. Examples of the structure in which Mf ₁ and Rf ₁ are bonded to each other to form a ring include the lactone structure represented by LC1-13, LC1-14, or LC1-17 in the lactone structure. Mf ₂ and Rf ₂ or Rf ₃ may be bonded to each other to form a ring. Examples of the structure in which Mf ₂ and Rf ₂ are bonded to each other to form a ring include the lactone structure represented by LC1-7, LC1-8, or LC1-15 in the lactone structure. Examples of the structure in which Mf ₂ and Rf ₃ are bonded to each other to form a ring include the lactone structure represented by any one of LC1-3 to LC1-6 in the lactone structure. Although the specific example of a structural unit (a2) is shown below, this invention is not limited to this. * Indicates the bonding position with other structural units.

[化23]

The structural unit having at least two lactone structures generally has optical isomers, and any optical isomer may be used. In addition, one kind of optical isomer may be used alone, or a plurality of optical isomers may be mixed and used. In the case of mainly using one optical isomer, its optical purity (enantiomeric excess (ee)) is preferably 90% or more, more preferably 95% or more.

In the case where the resin (A) contains structural units having at least two lactone structures, relative to all the structural units in the resin (A), the content of the structural units having at least two lactone structures is preferably 10 moles. Ear%～60 mol%, more preferably 20 mol%～50 mol%, and still more preferably 30 mol%～50 mol%. Two or more structural units having at least two lactone structures may also be used in combination. When two or more repeating units having at least two lactone structures are contained, it is preferable that the total content of structural units having at least two lactone structures is the above-mentioned range.

The resin (A) may include one type of structural unit having at least one selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure alone, or two or more types may be used in combination.

In the case where the resin (A) includes a structural unit having at least one selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure, the resin (A) has at least one structural unit selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure. (A) The content of a structural unit having at least one selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure contained in (A) In the case of at least one structural unit in the group consisting of an ester structure and a carbonate structure, the total is preferably 5 mol% to 70 mol%, more preferably 10 mol% to 65 mol% %, more preferably 20 mol% to 60 mol%.

〔Structural units with polar groups〕 The resin (A) preferably contains a structural unit having a polar group. It does not specifically limit as a polar group, A hydroxyl group, a cyano group, a carboxyl group, etc. are mentioned. In addition, the repeating unit having a phenolic hydroxyl group will be described later. The structural unit having a polar group is preferably a structural unit having an alicyclic hydrocarbon structure substituted with a polar group. In addition, the structural unit having a polar group preferably does not have an acid-decomposable group. The alicyclic hydrocarbon structure in the alicyclic hydrocarbon structure substituted with a polar group is preferably an adamantyl group or a norbornyl group.

Specific examples of monomers corresponding to the structural unit having a polar group are listed below, but the present invention is not limited to these specific examples. In addition, the following specific examples are described as methacrylate compounds, but they may also be acrylate compounds.

[化24]

In addition, as a specific example of the structural unit having a polar group, the structural unit disclosed in paragraph 0415 to paragraph 0433 of the specification of U.S. Patent Application Publication No. 2016/0070167 can also be cited. Resin (A) may contain the structural unit which has a polar group individually by 1 type, and may use 2 or more types together. In the case where the resin (A) contains a structural unit having a polar group, relative to all the structural units in the resin (A), the content of the structural unit having a polar group is preferably 5 mol% to 40 mol%, and more It is preferably from 5 mol% to 30 mol%, and more preferably from 10 mol% to 25 mol%.

[Structural units that do not have any of acid-decomposable groups and polar groups] The resin (A) may further have a structural unit that does not have any of an acid-decomposable group and a polar group. The structural unit that does not have any of an acid-decomposable group and a polar group preferably has an alicyclic hydrocarbon structure. As a structural unit that does not have any of an acid-decomposable group and a polar group, for example, the structural unit described in paragraph 0236 to paragraph 0237 of the specification of U.S. Patent Application Publication No. 2016/0026083 can be cited. The preferable example of the monomer corresponding to the structural unit which does not have any of an acid-decomposable group and a polar group is shown below.

[化25]

In addition, as a specific example of a structural unit that does not have any of an acid-decomposable group and a polar group, the structural unit disclosed in paragraph 0433 of the specification of U.S. Patent Application Publication No. 2016/0070167 can also be cited. The resin (A) may contain one kind of structural unit that does not have any of an acid-decomposable group and a polar group alone, or may contain two or more kinds in combination. When the resin (A) contains a structural unit that does not have any of an acid-decomposable group and a polar group, relative to all the structural units in the resin (A), it does not have any of the acid-decomposable group or the polar group The content of the structural unit is preferably 5 mol%-40 mol%, more preferably 5 mol%-30 mol%, and still more preferably 5 mol%-25 mol%.

[Repeat unit (a3)] The resin (A) may 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 less when it is made into a homopolymer. In addition, 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 the glass transition temperature of homopolymers) Regarding the glass transition temperature of the homopolymer, the value is used when there is a catalog value or a literature value, and when there is no catalog value or a literature value, it is measured by the differential scanning calorimetry (DSC: Differential scanning calorimetry) method. . The weight average molecular weight (Mw) of the homopolymer used for the Tg measurement was set to 18000, and the degree of dispersion (Mw/Mn) was set to 1.7. As a DSC device, a thermal analysis DSC differential scanning calorimeter Q1000 manufactured by TA Instruments Japan Co., Ltd. was used, and the measurement was performed at a temperature increase rate of 10° C./min. In addition, the homopolymer used for Tg measurement may be synthesized by a known method using a corresponding monomer, for example, it can be synthesized by a general dropping polymerization method or the like. 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 the 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, it was further stirred at 80°C for 2 hours. After the reaction liquid was left to cool, it was re-precipitated and filtered with a large amount of methanol/water (mass ratio 9:1), and the obtained solid was dried to obtain a homopolymer (Mw: 18000, Mw/Mn: 1.7). The obtained homopolymer was subjected to DSC measurement. The DSC device and the heating rate are as described above.

Monomer a3 is not particularly limited as long as the glass transition temperature (Tg) when it is made into a homopolymer is 50°C or less, and it improves the resolution of the dot pattern and suppresses the roughness of the sidewall of the resist pattern that may occur during etching. From the viewpoint of temperature, the Tg when it is made into a homopolymer is preferably 30°C or less. The lower limit of Tg when the monomer a3 is made into a homopolymer is not particularly limited, but is preferably -80°C or higher, more preferably -70°C or higher, further preferably -60°C or higher, particularly preferably -50°C or higher . By setting the lower limit of the Tg when the monomer a3 is a homopolymer to the above range, the fluidity of the pattern during heating can be suppressed, and the verticality of the dot pattern can be further improved, which is preferable.

As the repeating unit (a3), it is preferable to have a repeating unit having a non-acid-decomposable alkyl group having a carbon number of 2 or more that can contain a hetero atom in the chain in terms of being able to more easily volatilize the residual solvent. The term "non-acid decomposability" in this specification refers to a property that does not cause a separation/decomposition reaction due to the acid generated by the photoacid generator. That is, the so-called "non-acid decomposable alkyl group", more specifically, include: an alkyl group that is not detached from the resin (A) by the action of an acid generated by a photoacid generator, or an alkyl group that is not decomposed by a photoacid An alkyl group that is decomposed by the action of the acid generated by the generator. The non-acid-decomposable alkyl group may be either linear or branched. Hereinafter, a repeating unit having a non-acid-decomposable alkyl group having a carbon number of 2 or more that can include a hetero atom in the chain will be described.

The non-acid-decomposable alkyl group with a carbon number of 2 or more that may contain a hetero atom in the chain is not particularly limited. Examples include an alkyl group with 2 to 20 carbon atoms and a chain with a heteroatom containing 2 carbon atoms. ~20 alkyl. Examples of alkyl groups having 2 to 20 carbon atoms containing heteroatoms in the chain include one or two or more -CH ₂ -via -O-, -S-, -CO-, -NR ₆ -, or the like These combine two or more to form a divalent organic-substituted alkyl group. The R ₆ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Examples of non-acid-decomposable alkyl groups that can contain heteroatoms in the chain and have a carbon number of 2 or more include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl groups. , Nonyl, decyl, lauryl, stearyl, isobutyl, sec-butyl, 1-ethylpentyl, and 2-ethylhexyl, and one or more of these -CH ₂ -A monovalent alkyl group substituted with -O- or -O-CO-.

The carbon number of the non-acid-decomposable alkyl group having a hetero atom and a carbon number of 2 or more is preferably 2 or more and 16 or less, more preferably 2 or more and 10 or less, and still more preferably 2 or more and 8 the following. 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, substituent T).

The repeating unit (a3) is preferably a repeating unit represented by the following general formula (1-2).

[化26]

In the 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 a carbon number of 2 or more that may contain a hetero atom in the chain.

The halogen atom represented by R ₁ is not particularly limited, and examples thereof include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The alkyl group represented by R ₁ is not particularly limited, and examples thereof include alkyl groups having 1 to 10 carbon atoms, and specific examples include methyl, ethyl, and tertiary butyl groups. 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, and examples thereof include cycloalkyl groups having 5 to 10 carbon atoms, and more specifically, cyclohexyl groups and the like. Among them, as R ₁ , a hydrogen atom or a methyl group is preferred.

The definition and preferable aspects of the non-acid-decomposable alkyl group having a carbon number of 2 or more and which may include a hetero atom in the chain represented by R _{2 are as described above.}

In addition, in terms of easier volatilization of the residual solvent, the repeating unit (a3) may be a non-acid-decomposable alkyl group that may include a heteroatom in the chain and has a carboxyl group or a hydroxyl group, or may include a heteroatom in the ring member. A repeating unit of non-acid-decomposable cycloalkyl having a carboxyl group or a hydroxyl group. Hereinafter, the repeating unit having a non-acid-decomposable alkyl group which can contain a hetero atom in the chain and has a carboxyl group or a hydroxyl group, or a non-acid-decomposable cycloalkyl group which can contain a hetero atom in the ring member and has a carboxyl group or a hydroxyl group is carried out. Description.

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

The non-acid-decomposable alkyl group that can contain a hetero atom in the chain is not particularly limited, and examples include an alkyl group having 2 to 20 carbon atoms and an alkyl group having 2 to 20 carbon atoms that contain a hetero atom in the chain. . Furthermore, at least one of the hydrogen atoms in the alkyl group is substituted with a carboxyl group or a hydroxyl group. Examples of alkyl groups having 2 to 20 carbon atoms containing heteroatoms in the chain include one or two or more -CH ₂ -via -O-, -S-, -CO-, -NR ₆ -, or the like These combine two or more to form a divalent organic-substituted alkyl group. The R ₆ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

As the carbon number of the non-acid-decomposable alkyl group which can contain a hetero atom in the chain, it is preferably 2-16, more preferably 2-10 in terms of more excellent crack resistance (less cracks are generated) , More preferably 2-8. Furthermore, the non-acid-decomposable alkyl group may have a substituent (for example, the substituent T). As a specific example of the repeating unit which has a non-acid-decomposable alkyl group which contains a hetero atom in a chain and has a carboxyl group, the repeating unit of the following structure is mentioned, for example.

[化27]

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

The non-acid-decomposable cycloalkyl group that may contain a heteroatom in the ring member is not particularly limited. For example, a cycloalkyl group having 5 to 20 carbon atoms (more specifically, a cyclohexyl group), and a ring member C5-20 cycloalkyl group containing heteroatoms. Furthermore, at least one of the hydrogen atoms in the cycloalkyl group is substituted with a carboxyl group or a hydroxyl group. Examples of the cycloalkyl group having 5 to 20 carbon atoms and containing a hetero atom in the ring member include one or two or more -CH ₂ -, -O-, -S-, -CO-, -NR ₆ -, Or a divalent organic-substituted cycloalkyl group formed by combining two or more of these. The R ₆ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Furthermore, the non-acid-decomposable cycloalkyl group may have a substituent (for example, the substituent T).

As a repeating unit having a non-acid-decomposable alkyl group that can contain a heteroatom in the chain and have a carboxyl group or a hydroxyl group, or a non-acid-decomposable cycloalkyl group that can contain a heteroatom in the ring member and have a carboxyl group or a hydroxyl group, it is essential In terms of more excellent effects of the invention, the repeating unit represented by the following general formula (1-3) is particularly preferred.

[化28]

In the general formula (1-3), R ₃ represents a hydrogen atom, a halogen atom, an alkyl group, or a cycloalkyl group. R ₄ represents a non-acid-decomposable alkyl group which may include a hetero atom in the chain and has a carboxyl group or a hydroxyl group, or a non-acid-decomposable cycloalkyl group which may include a hetero atom in a ring member and has a carboxyl group or a hydroxyl group.

In the general formula (1-3), R ₃ and R _{1 have} the same meaning, and preferred aspects are also the same.

The definition of a non-acid-decomposable alkyl group which may contain a heteroatom in the chain and has a carboxyl or hydroxyl group represented by R _{4, or a non-acid-decomposable cycloalkyl group which may contain a heteroatom in the ring member and has a carboxyl or hydroxyl group and} The preferred aspect is as described. Among them, R _{4 is} preferably a non-acid-decomposable cycloalkyl group which can include a hetero atom in the ring member and has a carboxyl group or a hydroxyl group. In addition, for example, repeating units of the following structures can also be cited as preferred repeating units.

[化29]

Examples of monomer a3 include ethyl acrylate (-22°C), n-propyl acrylate (-37°C), isopropyl acrylate (-5°C), n-butyl acrylate (-55°C), methyl N-Butyl acrylate (20°C), n-hexyl acrylate (-57°C), n-hexyl methacrylate (-5°C), n-octyl methacrylate (-20°C), 2-ethylhexyl acrylate (- 70℃), isononyl acrylate (-82℃), lauryl methacrylate (-65℃), 2-hydroxyethyl acrylate (-15℃), 2-hydroxypropyl methacrylate (26℃), 1-[2-(methacryloxy)ethyl] succinate (9°C), 2-ethylhexyl methacrylate (-10°C), second butyl acrylate (-26°C), Methoxy polyethylene glycol monomethacrylate (n=2) (-20°C), cetyl acrylate (35°C), etc. In addition, the Tg (°C) when it is made into a homopolymer is shown in parentheses.

In addition, methoxy polyethylene glycol monomethacrylate (n=2) is a compound of the following structure.

[化30]

Monomer a3 is preferably n-butyl acrylate, n-hexyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, 2-ethylhexyl acrylate, lauryl methacrylate, ten acrylate Hexaalkyl ester, 2-hydroxyethyl acrylate, and the compound represented by MA-5 below.

[化31]

The resin (A) may include only one type of repeating unit (a3), or two or more types. When the resin (A) has a repeating unit (a3), the content of the repeating unit (a3) relative to all repeating units of the resin (A) (the total when there are multiple repeating units (a3)) It is preferably 5 mol% or more, more preferably 10 mol% or more, and preferably 50 mol% or less, more preferably 40 mol% or less, and still more preferably 30 mol% or less. Among them, the content of the repeating unit (a3) in the resin (A) (the total when there are multiple repeating units (a3)) is preferably 5 mol% relative to all repeating units of the resin (A) ~50 mol%, more preferably 5 mol% to 40 mol%, and still more preferably 5 mol% to 30 mol%.

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

It does not specifically limit as a repeating unit which has a phenolic hydroxyl group, The repeating unit derived from hydroxystyrene, or the repeating unit derived from hydroxystyrene (meth)acrylate is mentioned. The repeating unit having a phenolic hydroxyl group is preferably a repeating unit represented by the following general formula (I). That is, the resin (A) is preferably a resin containing a repeating unit represented by the following general formula (I).

[化32]

In the general formula (I), R ₄₁ , R ₄₂ and R ₄₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. Among them, R ₄₂ may be _{bonded to Ar 4} to form a ring. In this case, R ₄₂ represents a single bond or an alkylene group. X ₄ represents a single bond, -COO-, or -CONR ₆₄ -, and R ₆₄ represents a hydrogen atom or an alkyl group. L ₄ represents a single bond or a divalent linking group. Ar ₄ represents an (n+1)-valent aromatic hydrocarbon group, and when it _{bonds with R 42} to form a ring, it represents an (n+2)-valent aromatic hydrocarbon group. n represents an integer of 1-5.

For the purpose of highly polarizing the repeating unit represented by the general formula (I), it is also preferable that n is an integer of 2 or more, or X ₄ is -COO- or -CONR ₆₄ -.

_{As the alkyl group represented by R 41} , R ₄₂ , and R ₄₃ in the general formula (I), preferred are optionally substituted methyl, ethyl, propyl, isopropyl, n-butyl, and second The alkyl group having 20 or less carbon atoms, such as butyl, hexyl, 2-ethylhexyl, octyl, and dodecyl, is more preferably an alkyl group having 8 or less carbon atoms, and still more preferably an alkyl group having 3 or less carbon atoms.

_{The cycloalkyl group represented by R 41} , R ₄₂ , and R ₄₃ in the general formula (I) may be a monocyclic ring or a polycyclic ring. Preferably, it is a monocyclic cycloalkyl group having 3 to 8 carbon atoms, such as cyclopropyl, cyclopentyl, and cyclohexyl which may have a substituent. _{Examples of the halogen atom represented by R 41} , R ₄₂ , and R ₄₃ in the general formula (I) include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like, and a fluorine atom is preferred. _{The alkyl group included in the alkoxycarbonyl group represented by R 41} , R ₄₂ , and R ₄₃ in the general formula (I) is preferably the same as the alkyl group in the above-mentioned R ₄₁ , R ₄₂ , and R ₄₃ By.

Examples of preferred substituents in each of the above groups include alkyl groups, cycloalkyl groups, aryl groups, amino groups, amide groups, ureido groups, urethane groups, hydroxyl groups, carboxyl groups, and halogen atoms. , Alkoxy group, thioether group, acyl group, acyloxy group, alkoxycarbonyl group, cyano group, nitro group, etc., the carbon number of the substituent is preferably 8 or less.

Ar ₄ represents an (n+1)-valent aromatic hydrocarbon group. When n is 1, the divalent aromatic hydrocarbon group may have a substituent. For example, phenylene, phenylene, naphthylene, and anthracenyl are preferably arylene groups having 6 to 18 carbon atoms, or include, for example, Heterocyclic aromatic hydrocarbon groups such as thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, and thiazole.

As a specific example of the (n+1) valence aromatic hydrocarbon group when n is an integer of 2 or more, it is preferable to remove (n-1) arbitrary hydrogens from the specific examples of the divalent aromatic hydrocarbon group. A base made of atoms. The (n+1)-valent aromatic hydrocarbon group may further have a substituent.

Examples of the substituents that the alkyl group, cycloalkyl group, alkoxycarbonyl group, and (n+1)-valent aromatic hydrocarbon group may have include: R ₄₁ , R ₄₂ , and in the general formula (I) Alkyl groups exemplified in R ₄₃ ; alkoxy groups such as methoxy, ethoxy, hydroxyethoxy, propoxy, hydroxypropoxy, and butoxy; aryl groups such as phenyl, and the like. _{The alkyl group of R 64} in -CONR _64- (R ₆₄ represents a hydrogen atom or an alkyl group) represented by X ₄ is preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, which may have a substituent, Alkyl groups with 20 or less carbon atoms, such as n-butyl, sec-butyl, hexyl, 2-ethylhexyl, octyl, and dodecyl, are more preferably alkyl groups with 8 or less carbon atoms. X _{4 is} preferably a single bond, -COO-, or -CONH-, and more preferably a single bond or -COO-.

The _{divalent linking group of L 4} is preferably an alkylene group, and the alkylene group is preferably an optionally substituted methylene, ethylene, propylene, butylene, hexylene, and octylene group. Alkylene groups having 1 to 8 carbon atoms. 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 biphenyl ring group. Among them, the repeating unit represented by the general formula (I) is preferably a repeating unit derived from hydroxystyrene. That is, Ar _{4 is} preferably a benzene ring group.

n represents an integer of 1 to 5, preferably represents an integer of 1 to 3, more preferably represents 1 or 2, and more preferably represents 1.

Although the specific example of the repeating unit which has a phenolic hydroxyl group is shown below, this invention is not limited to this. In the formula, a represents 1 or 2.

[化33]

The resin (A) may have one type of repeating unit (a4) alone, or two or more of them may be used in combination. When the resin (A) contains the repeating unit (a4), relative to all the repeating units in the resin (A), the content of the repeating unit (a4) in the resin (A) is preferably 40 mol% or more, more preferably It is 50 mol% or more, more preferably 60 mol% or more. In addition, with respect to all the repeating units in the resin (A), the content of the repeating unit (a4) is preferably 85 mol% or less, and more preferably 80 mol% or less.

Resin (A) has the above-mentioned structural units, and can be used to adjust dry etching resistance or standard developer suitability, substrate adhesion, resist profile, and general necessary characteristics as a resist. It has various structural units for the purpose of heat resistance and sensitivity. As such a structural unit, the structural unit corresponding to other monomers can be mentioned, but it is not limited to these.

Examples of other monomers include those selected from acrylic esters, methacrylic esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, and vinyl esters. The compound with an addition polymerizable unsaturated bond, etc. In addition to this, as long as it is an addition polymerizable unsaturated compound copolymerizable with a monomer corresponding to the various structural units described above, it may be copolymerized. In the resin (A), the molar ratio of each structural unit is appropriately set in order to adjust various properties.

When the sensitized radiation or radiation-sensitive resin composition of the present invention is used for fluorine-argon (ArF) laser exposure, from the viewpoint of the permeability of ArF light, the resin (A) is preferably substantially free of aroma. Family base. More specifically, among all the structural units of the resin (A), the structural unit having an aromatic group is preferably 5 mol% or less of the whole, more preferably 3 mol% or less, and ideally 0 mol%, That is, it is more preferable not to contain a structural unit having an aromatic group. In addition, the resin (A) preferably has a monocyclic or polycyclic alicyclic hydrocarbon structure.

It is also preferable that the resin (A) all include a (meth)acrylate-based structural unit in the structural unit. In this case, resins whose structural units are all methacrylate-based structural units, resins whose structural units are all acrylate-based structural units, and whose structural units are all composed of methacrylate-based structural units and acrylate-based structural units can be used. It is any resin of the resin to be formed, but it is preferable that the acrylic structural unit is 50 mol% or less with respect to all the structural units of resin (A).

When the sensitized radiation or radiation-sensitive resin composition of the present invention is used for exposure of krypton fluoride (KrF), electron beam (EB) or extreme ultraviolet (EUV) exposure, the resin (A) preferably contains Structural units with aromatic hydrocarbon groups. The resin (A) more preferably contains a structural unit having a phenolic hydroxyl group. As a structural unit which has a phenolic hydroxyl group, the said repeating unit (a4) is mentioned, for example. When the sensitized radiation-sensitive or radiation-sensitive resin composition of the present invention is used for KrF exposure, EB exposure, or EUV exposure, the resin (A) preferably has a hydrogen atom having a phenolic hydroxyl group by the action of an acid. The structure protected by the decomposing radical (departing radical). Relative to all the structural units in the resin (A), the content of the structural unit having an aromatic hydrocarbon group contained in the resin (A) is preferably 30 mol% to 100 mol%, more preferably 40 mol% to 100 mol% Mole%, more preferably 50 mole% to 100 mole%.

The weight average molecular weight of the resin (A) is preferably 1,000 to 200,000, more preferably 2,000 to 100,000, still more preferably 3,000 to 50,000, particularly preferably 3,000 to 30,000. The degree of dispersion (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 particularly preferably 1.1 to 2.0.

As a specific example of resin (A), resin A-1-resin A-7 used in an Example can be mentioned, but it is not limited to this.

The resin (A) may be used singly, or two or more of them may be used in combination. The content of the resin (A) is preferably 20% by mass or more, more preferably 40% by mass or more, and still more preferably 60% by mass or more with respect to the total solid content of the sensitized radiation or radiation-sensitive resin composition of the present invention , Particularly preferably above 80% by mass. The upper limit is not particularly limited, but is preferably 99.5% by mass or less, and more preferably 99% by mass or less.

〔Alkali-soluble resin with phenolic hydroxyl group〕 When the actinic radiation or radiation-sensitive resin composition of the present invention contains the crosslinking agent (G) described later, the actinic radiation or radiation-sensitive resin composition of the present invention preferably contains a phenolic hydroxyl group. The alkali-soluble resin (hereinafter, also referred to as "resin (C)"). The resin (C) preferably contains a structural unit having a phenolic hydroxyl group. In this case, typically, a negative pattern can be preferably formed. The crosslinking agent (G) may be in a form supported on the resin (C). In addition, among the resins (C), those corresponding to the resin whose polarity is increased by the action of acid are treated as the resin whose polarity is increased by the action of acid. In addition, in this case, the sensitized radiation-sensitive or radiation-sensitive resin composition of the present invention may include a resin whose polarity is increased by the action of an acid as the resin (C), and may also include at least Resins (C) other than resins with increased polarity and resins with increased polarity due to the action of acid. The resin (C) may contain the acid decomposable group. It does not specifically limit as a structural unit which has a phenolic hydroxyl group which resin (C) has, Preferably it is the said repeating unit (a4).

The resin (C) may be used singly, or two or more of them may be used in combination. When the photosensitive ray-sensitive or radiation-sensitive resin composition of the present invention contains resin (C), the content of resin (C) in the total solid content of the photosensitive ray-sensitive or radiation-sensitive resin composition of the present invention It is preferably 30% by mass or more, more preferably 40% by mass or more, and still more preferably 50% by mass or more. The upper limit is not particularly limited, but is preferably 99% by mass or less, more preferably 90% by mass or less, and still more preferably 85% by mass or less. As the resin (C), the resins disclosed in paragraphs 0142 to 0347 of the specification of U.S. Patent Application Publication No. 016/0282720 can be preferably used.

〔Hydrophobic resin〕 It is also preferable that the actinic radiation-sensitive or radiation-sensitive resin composition of the present invention contains a hydrophobic resin (also referred to as "hydrophobic resin (E)"). The sensitized radiation-sensitive or radiation-sensitive resin composition of the present invention preferably contains at least a hydrophobic resin (E) other than a resin whose polarity is increased by the action of an acid, and a hydrophobic resin (E) whose polarity is increased by the action of an acid. Resin. When the photosensitive ray-sensitive or radiation-sensitive resin composition of the present invention contains the hydrophobic resin (E), the static/dynamic contact angle of the surface of the photosensitive ray-sensitive or radiation-sensitive film can be controlled. Thereby, the development characteristics can be improved, outgassing can be suppressed, the followability of the liquid immersion liquid in the liquid immersion exposure can be improved, and the liquid immersion defect can be reduced. The hydrophobic resin (E) is preferably designed to be biased toward the surface of the resist film. However, unlike surfactants, it does not necessarily have a hydrophilic group in the molecule, and it does not help remove polar/non-polar substances. Mix evenly. In addition, in the present invention, a resin having a fluorine atom is treated as a hydrophobic resin and a fluorine-containing resin described later. Moreover, it is preferable that the resin containing the structural unit which has the said acid-decomposable group does not have a fluorine atom.

From the viewpoint of being biased in the surface layer of the film, the hydrophobic resin (E) preferably has a structure selected from the group consisting of "fluorine atom", "silicon atom", and "CH ₃ partial structure contained in the side chain part of the resin" At least one structural unit resin in the group consisting of. When the hydrophobic resin (E) contains fluorine atoms or silicon atoms, the fluorine atoms or silicon atoms in the hydrophobic resin (E) may be included in the main chain of the resin or may be included in the side chain.

The hydrophobic resin (E) preferably has at least one group selected from the group of (x) to (z) below. (X) Acid group (Y) A group that is decomposed by the action of an alkaline developer to increase its solubility in an alkaline developer (hereinafter, also referred to as a polarity conversion group) (Z) The base decomposed by the action of acid

Examples of the acid group (x) include: phenolic hydroxyl group, carboxylic acid group, fluorinated alcohol group, sulfonic acid group, sulfonamide group, sulfonamide group, (alkylsulfonyl group) (alkyl Carbonyl)methylene, (alkylsulfonyl)(alkylcarbonyl)imino, bis(alkylcarbonyl)methylene, bis(alkylcarbonyl)imino, bis(alkylsulfonyl) Group) methylene, bis(alkylsulfonyl)imino group, tri(alkylcarbonyl)methylene, tri(alkylsulfonyl)methylene, etc. As the acid group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), a sulfoximine group, or a bis(alkylcarbonyl)methylene group is preferable.

As the group (y) that is decomposed by the action of the alkaline developer to increase the solubility in the alkaline developer, for example, a lactone group, a carboxylate group (-COO-), an acid anhydride group (-C (O)OC(O)-), acid imino group (-NHCONH-), carboxylic acid thioester group (-COS-), carbonate group (-OC(O)O-), sulfate group (- OSO ₂ O-), sulfonate group (-SO ₂ O-), etc., preferably a lactone group or a carboxylate group (-COO-). The structural unit including these groups is a structural unit in which these groups are directly bonded to the main chain of the resin, and examples thereof include structural units formed of acrylate and methacrylate. These groups in the structural unit may be bonded to the main chain of the resin via the linking group. Alternatively, the structural unit may be introduced to the end of the resin using a polymerization initiator or chain transfer agent having these groups at the time of polymerization. As a structural unit which has a lactone group, what is the same as the structural unit which has a lactone structure demonstrated in the previous resin (A) section is mentioned, for example.

The content of the structural unit having the group (y) that is decomposed by the action of the alkaline developer to increase the solubility of the alkaline developer is based on all the structural units in the hydrophobic resin (E), and is preferably 1 Mole% to 100 mole%, more preferably 3 mole% to 98 mole%, and still more preferably 5 mole% to 95 mole%.

In the hydrophobic resin (E), the structural unit having a group (z) that is decomposed by the action of an acid may be the same as the structural unit having an acid-decomposable group listed in the resin (A). The structural unit having a group (z) that is decomposed by the action of an acid may have at least any one of a fluorine atom and a silicon atom. Relative to all the structural units in the resin (E), the content of the structural unit having the group (z) decomposed by the action of an acid is preferably 1 mol% to 80 mol%, more preferably 10 mol% ~80 mol%, more preferably 20 mol% to 60 mol%.

The hydrophobic resin (E) may further have a structural unit different from the above-mentioned structural unit.

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

On the other hand, particularly when the hydrophobic resin (E) contains a CH ₃ partial structure in the side chain portion, the hydrophobic resin (E) is also preferably in a form that does not substantially contain fluorine atoms and silicon atoms. In addition, the hydrophobic resin (E) preferably contains substantially only structural units that only contain atoms selected from carbon atoms, oxygen atoms, hydrogen atoms, nitrogen atoms, and sulfur atoms.

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

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

As the hydrophobic resin (E), well-known resins can be used alone, or a mixture of these can be appropriately selected and used. For example, the well-known resins disclosed in paragraphs 0451 to 0704 of the specification of U.S. Patent Application Publication No. 2015/0168830 and paragraphs 0340 to 0356 of the specification of U.S. Patent Application Publication No. 2016/0274458 can be preferably used as hydrophobic Resin (E). In addition, the structural unit disclosed in paragraph 0177 to paragraph 0258 of the specification of US Patent Application Publication No. 2016/0237190 is also preferable as a structural unit 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, it is preferably a resin containing an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, or an aryl group having a fluorine atom as a partial structure having a fluorine atom.

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

The alkyl group having a fluorine atom, the cycloalkyl group having a fluorine atom, and the aryl group having a fluorine atom are preferably groups represented by formula F2 to formula F4.

[化34]

In Formula F2 to Formula F4, R ⁵⁷ to R ⁶⁸ each independently represent a hydrogen atom, a fluorine atom, or an alkyl group (linear or branched chain). Among them, ^{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 each independently represent a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom. Preferably, all of R ⁵⁷ to R ⁶¹ and R ⁶⁵ to R ⁶⁷ are fluorine atoms. R ⁶² , R ⁶³ and R ^{68 are} preferably an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom (preferably a carbon number of 1 to 4), more preferably a carbon number of 1 to 4 perfluoroalkyl group. R ⁶² and R ⁶³ may be connected to each other to form a ring.

Among them, it is preferable that the fluorine-containing resin has alkali decomposability in terms of more excellent effects of the present invention. The so-called alkali decomposability of fluorine-containing resin means that 100 mg of fluorine-containing resin is added to a mixture of 2 mL of pH 10 buffer solution and 8 mL of THF, and the mixture is allowed to stand at 40°C. After 10 minutes, the content of fluorine-containing resin is 30 mol% or more of the total amount of decomposable groups undergoes hydrolysis. In addition, the decomposition rate can be calculated from the ratio of the raw material to the decomposition product obtained by NMR analysis.

From the viewpoints of focus depth tolerance, pattern linearity, improvement of development characteristics, suppression of outgassing, improvement of liquid immersion liquid followability in liquid immersion exposure, and reduction of liquid immersion defects, the fluorine-containing resin is preferably one of formula X Represents the structural unit. In addition, from the viewpoints of the tolerance of the focal depth, the linearity of the pattern, the improvement of the development characteristics, the suppression of outgassing, the improvement of the followability of the liquid immersion in the liquid immersion exposure, and the reduction of the liquid immersion defect, the sensitizing radiation of the present invention may be The radiation-sensitive resin composition preferably further includes a fluorine-containing resin having a structural unit represented by formula X.

[化35]

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 -, R ¹¹ and R ¹² each independently represent a substituent, and X represents oxygen Atom, or sulfur atom. L represents a (n+1) valent linking group, R ¹⁰ represents a group having a group that increases the solubility of the fluororesin in the alkaline aqueous solution by decomposing by the action of the alkaline aqueous solution, n represents a positive integer, When n is 2 or more, a plurality of R ¹⁰ may be the same as or different from each other.

Examples of the halogen atom of Z include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferred. Examples of the substituents of R ¹¹ and R ¹² include alkyl groups (preferably carbon number 1 to 4), cycloalkyl groups (preferably carbon number 6 to 10), and aryl groups (preferably carbon number 6～10). In addition, ^{the substituents of R 11} and R ¹² may further have substituents, and examples of such further substituents include alkyl groups (preferably with 1 to 4 carbon atoms), halogen atoms, hydroxyl groups, and alkoxy groups ( Preferably, it is a carbon number 1 to 4) and a carboxyl group. The linking group as L is preferably a divalent linking group or a trivalent linking group (in other words, n is preferably 1 or 2), and more preferably a divalent linking group (in other words, n is preferably 1). The linking group as L is preferably a linking group selected from the group consisting of an aliphatic group, an aromatic group, and a combination of these. For example, when n is 1, and the linking group as L is a divalent linking group, examples of the divalent aliphatic group include an alkylene group, an alkenylene group, an alkynylene group, or a polyalkyleneoxy group. Among them, an alkylene group or an alkenylene group is preferred, and an alkylene group is more preferred. The divalent aliphatic group can be a chain structure or a cyclic structure, but it is preferably a chain structure than a cyclic structure, and a linear structure is more preferable for a branched chain structure . The divalent aliphatic group may have a substituent. Examples of the substituent include halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine atom), hydroxyl group, carboxyl group, amino group, cyano group, aryl group, alkoxy group, Aryloxy, acyl, alkoxycarbonyl, aryloxycarbonyl, acyloxy, monoalkylamino, dialkylamino, arylamino, and diarylamino. As the divalent aromatic group, an aryl group can be mentioned. Among them, phenylene and naphthylene are preferred. The divalent aromatic group may have a substituent, and not only examples of the substituent in the divalent aliphatic group but also an alkyl group can be mentioned. In addition, L may be a divalent group obtained by removing two hydrogen atoms at any positions from the structure represented by the above-mentioned formulas LC1-1 to LC1-21 or formulas SL1-1 to SL-3. When n is 2 or more, as a specific example of the (n+1)-valent linking group, a group obtained by removing arbitrary (n-1) hydrogen atoms from the specific example of the divalent linking group can be cited. As a specific example of L, the following linking group can be mentioned, for example.

[化36]

In addition, these linking groups may further have a substituent as described above.

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

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

Examples of Y include: carboxylic acid ester group (-COO- or OCO-), acid anhydride group (-C(O)OC(O)-), acid imino group (-NHCONH-), carboxylic acid thioester group (-COS-), carbonate group (-OC(O)O-), sulfate group (-OSO ₂ O-), and sulfonate group (-SO ₂ O-), preferably carboxylate group .

As the electron withdrawing group, a partial structure represented by the following formula EW is preferred. The * in the formula EW represents a bonding bond directly bonding to the group Y in the formula W.

[化37]

In the formula EW, n ^ew is the number of repetitions of the linking group represented by -C(R ^ew1 )(R ^ew2 )-, and represents an integer of 0 or 1. When n ^ew is 0, it represents a single bond, which means that Y ^{ew1 is} directly bonded. Y ^ew1 includes halogen atoms, cyano groups, nitro groups, ^{halogenated (cyclo)alkyl groups represented by -C(R f1} )(R ^f2 )-R ^f3 described later, halogenated aryl groups, oxy groups, carbonyl groups, A sulfonyl group, a sulfinyl group, and a combination of these (wherein, when ^Yew1 is a halogen atom, a cyano group, or a nitro group, n ^ew is 1). R ^ew1 and R ^{ew 2} each independently represent any group, for example, a hydrogen atom, an alkyl group (preferably carbon number 1-8), cycloalkyl (preferably carbon number 3-10) or an aryl group (more Preferably, the carbon number is 6-10). At least two of R ^ew1 , R ^{ew 2} and Y ^ew1 may be connected to each other to form a ring. In addition, the "halogenated (cyclo)alkyl group" means an alkyl group and a cycloalkyl group in which at least a part is halogenated, and the "halogenated aryl group" means an aryl group in which at least a part is halogenated.

Y ^{ew1 is} preferably a halogen atom, a halogenated (cyclo)alkyl group represented by ^{-C(R f1} )(R ^f2 )-R ^{f3, or a halogenated aryl group.}

R ^f1 represents a halogen atom, a perhalogenated alkyl group, a perhalogenated cycloalkyl group, or a perhalogenated aryl group, preferably a fluorine atom, a perfluoroalkyl group or a perfluorocycloalkyl group, more preferably a fluorine atom or a trifluoromethyl group base. R ^f2 and R ^f3 each independently represent a hydrogen atom, a halogen atom, or an organic group, and R ^f2 and R ^f3 may be linked to form a ring. Examples of the organic group include an alkyl group, a cycloalkyl group, and an alkoxy group, and these may be substituted with a halogen atom (preferably a fluorine atom). R ^f2 and R ^{f3 are} preferably (halo)alkyl or (halo)cycloalkyl. More preferably, ^{R f2 represents the same group as R f1} , or is linked to R ^f3 to form a ring. Examples of the ring formed by linking R ^f2 and R ^f3 include a (halogenated) cycloalkyl ring.

The (halogenated) alkyl group in R ^f1 to R ^f3 may be linear or branched. The linear (halogenated) alkyl group preferably has 1 to 30 carbon atoms, more preferably It is 1～20.

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

[化38]

As the R ^f2 and R ^f3, R ^f2 and R ^f3, or formed by connecting ring (halo) cycloalkyl, preferably fluorine cycloalkyl _{-C (n) F (2n-} 2) H expressed by base. Here, the carbon number n is not particularly limited, but is preferably 5-13, more preferably 6.

^Examples of the (per)halogenated aryl group in Yew1 or R ^f1 include perfluoroaryl groups represented by _{-C (n)} F _(n-1). Here, the carbon number n is not particularly limited, but is preferably 5-13, more preferably 6.

As the ^{ring which at least two of Rew1} , ^Rew2 and Yew1 can be connected to each other, a cycloalkyl group or a heterocyclic group is preferable.

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

In the formula W, R ^{20 is} preferably an alkyl group substituted with one or more selected from the group consisting of a halogen atom, a cyano group, and a nitro group, and more preferably an alkyl group substituted with a halogen atom (haloalkyl) , More preferably a fluoroalkyl group. The number of carbon atoms of the alkyl group substituted by one or more selected from the group consisting of a halogen atom, a cyano group, and a nitro group is preferably 1-10, more preferably 1-5. More specifically, R ^{20 is} preferably an atomic group represented by -C(R' ¹ )(R' ^f1 )(R' ^f2 ) or -C(R' ¹ )(R' ² )(R' ^{f1 ).} R ^'1 and R' ² each independently represent a hydrogen atom, or a non-electron withdrawing group-substituted (preferably unsubstituted) alkyl group. ^R'f1 and ^R'f2 each independently represent a halogen atom, a cyano group, a nitro group, or a perfluoroalkyl group. As the R ^'1 and R' ² is alkyl may be linear chain may also be branched, preferably having 1 to 6 carbon atoms. As R ^'f1 and R' ^f2 is a perfluoroalkyl group may be linear chain may also be branched, preferably having 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 , -CF ₂ CF(CF ₃ ) ₂ , -C(CF ₃ ) ₃ , -C ₅ F ₁₁ , -C ₆ F ₁₃ , -C ₇ F ₁₅ , -C ₈ F ₁₇ , -CH ₂ CF ₃ , -CH ₂ C ₂ F ₅ , -CH ₂ C ₃ F ₇ , -CH (CF ₃ ) ₂ , -CH (CF ₃ ) C ₂ F ₅ , -CH ₂ CF (CF ₃ ) ₂ , and -CH ₂ CN. Among them, -CF ₃ , -C ₂ F ₅ , -C ₃ F ₇ , -C ₄ F ₉ , -CH ₂ CF ₃ , -CH ₂ C ₂ F ₅ , -CH ₂ C ₃ F ₇ , -CH (CF ₃ ) ₂ , or -CH ₂ CN, more preferably -CH ₂ CF ₃ , -CH ₂ C ₂ F ₅ , -CH ₂ C ₃ F ₇ , -CH(CF ₃ ) ₂ , or -CH ₂ CN , More preferably -CH ₂ C ₂ F ₅ , -CH(CF ₃ ) ₂ , or -CH ₂ CN, particularly preferably -CH ₂ C ₂ F ₅ , or -CH(CF ₃ ) ₂ .

The structural unit represented by the formula X is preferably a structural unit represented by the following formula X-1 or formula X-2, and more preferably a structural unit represented by the formula X-1.

[化39]

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.

The specific examples and preferred examples of the divalent linking group as L ² and L ³ are the same as those described in the formula X as the divalent linking group L. The electron withdrawing group as R ²⁰ is preferably a partial structure represented by the formula EW. Specific examples and preferred examples are also as described above, and more preferably a halogenated (cyclo)alkyl group.

In the formula X-1, L ² and R ^{20 are} not bonded to each other to form a ring, and in the formula X-2, L ³ and R ^{20 are} not bonded to each other to form a ring.

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

In addition, the structural unit represented by formula X is also preferably a structural unit represented by formula X-3.

[化40]

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, X ⁴ represents an oxygen atom or a sulfur atom, and m represents 0 or 1.

The specific examples and preferred examples of the divalent linking group as L ⁴ are the same as those described in the formula X as the divalent linking group. The electron withdrawing group as R ²⁰ is preferably a partial structure represented by the formula EW. Specific examples and preferred examples are also as described above, and more preferably a halogenated (cyclo)alkyl group.

Furthermore, in the formula X-3, L ⁴ and R ^{20 are} not bonded to each other to form a ring. X ^{4 is} preferably an oxygen atom.

In addition, the structural unit represented by formula X is also preferably a structural unit represented by formula Y-1 or a structural unit represented by formula Y-2.

[化41]

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 are each independently Represents 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 formula EW. Specific examples and preferred examples are also as described above, and more preferably a halogenated (cyclo)alkyl group.

Specific examples and preferred examples of the halogen atom as Z, ^{the group represented by R 11} OCH ₂ -, and the group represented by R ¹² OC(=O)CH ₂ -are the same as those described in the formula X.

Relative to all the structural units of the fluorine-containing resin, 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 further preferably 30 mol% Ear%～100mol%.

The preferable example of the structural unit which comprises hydrophobic resin (E) is shown below. As the hydrophobic resin (E), a resin in which these structural units are arbitrarily combined can be preferably used, but it is not limited to this.

[化42]

[化43]

The hydrophobic resin (E) may be used singly, or two or more of them may be used in combination. From the viewpoint of coexistence of liquid immersion liquid followability and development characteristics in liquid immersion exposure, it is preferable to mix and use two or more kinds of hydrophobic resins (E) having different surface energies.

When the actinic radiation or radiation-sensitive resin composition of the present invention contains the hydrophobic resin (E), the hydrophobic resin is relative to the total solid content of the actinic radiation or radiation-sensitive resin composition of the present invention. The content of (E) in the composition is preferably 0.01% by mass to 10% by mass, more preferably 0.05% by mass to 8% by mass.

[Photo Acid Generator] The composition of the present invention contains at least two photoacid generators among the photoacid generator (B-1) and the photoacid generator (B-2). The pKa of the acid generated from the photoacid generator (B-1) is less than zero. The pKa of the acid generated from the photoacid generator (B-2) is greater than the pKa of the acid generated from the photoacid generator (B-1). The content of the photoacid generator (B-2) is 0.001% by mass or more and 0.1% by mass or less with respect to the content of the photoacid generator (B-1).

In the composition of the present invention, by using a photoacid generator (B-2) that generates an acid that is relatively weak compared to the acid generated from the photoacid generator (B-1), if the photoacid generator (B-2) is activated by actinic rays Or the acid generated from the photoacid generator (B-1) collides with the unreacted photoacid generator (B-2) due to the irradiation of radiation, and the weak acid is released by the salt exchange, and the onium with the strong acid anion is produced. salt. In this process, the strong acid is exchanged for a weak acid with a lower catalytic ability. Therefore, apparently, the acid is deactivated and the acid diffusion can be controlled. Therefore, in the thick film resist film formed from the composition of the present invention, the resin (A) and the photoacid generator (B-1) are easily concentrated on the upper part of the film, and the photoacid generator (B-1) can be moderately suppressed. -1) The diffusion of the generated acid can improve the rectangularity of the cross-sectional shape of the pattern.

When the pKa of the acid generated from the photoacid generator (B-1) is E ₁ and the pKa of the acid generated from the photo acid generator (B-2) is E ₂ , E ₂ -E _{1 is} preferably 0.5 or more, more preferably 3 or more, and still more preferably 6 or more. E ₂ -E _{1 is} preferably 20 or less, more preferably 15 or less.

_{The pKa (E 1} ) of the acid generated from the photoacid generator (B-1) is less than 0, preferably -0.01 or less, more preferably -1 or less, and still more preferably -2 or less. E _{1 is} preferably -15 or more, more preferably -10 or more.

_{The pKa (E 2} ) of the acid generated from the photoacid generator (B-2) is preferably 0.5 or more, more preferably 1.0 or more. E _{2 is} preferably 7.0 or less, more preferably 6.0 or less.

The so-called pKa represents the acid dissociation constant pKa in an aqueous solution, and is defined, for example, by the Handbook of Chemistry (II) (Revised 4th edition, 1993, The Chemical Society of Japan, Maruzen Co., Ltd.). The lower the value of the acid dissociation constant pKa, the greater the 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, the following software package 1 can also be used to obtain the value of the database based on the Hammett's substituent constant and publicly known literature values by calculation. The values of pKa described in this manual all indicate values obtained by calculations using this software package.

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

Hereinafter, the photo acid generator (B-1) and the photo acid generator (B-2) will be described in detail.

＜Photoacid generator (B-1)＞ The composition of the present invention contains a photoacid generator (B-1). The photoacid generator (B-1) is a compound that generates acid by irradiation with actinic rays or radiation. As the photoacid generator (B-1), a compound that generates an organic acid by irradiation with actinic rays or radiation is preferred. Examples include: sulfonium salt compounds, iodonium salt compounds, diazonium salt compounds, phosphonium salt compounds, imine sulfonate compounds, oxime sulfonate compounds, diazonium compounds, disulfide compounds, and o-nitro groups Benzyl sulfonate compound.

As the photoacid generator (B-1), a known compound that generates an acid by irradiation with actinic rays or radiation can be used alone, or a mixture of these can be appropriately selected and used. For example, paragraphs 0125 to 0319 of U.S. Patent Application Publication No. 2016/0070167, paragraphs 0086 to 0094 of U.S. Patent Application Publication No. 2015/0004544, and U.S. Patent Application Publication No. 2016/ The well-known compound disclosed in paragraph 0323 to paragraph 0402 of Specification No. 0237190 is used as a photoacid generator (B-1).

[Compounds represented by formula ZI, formula ZII or formula ZIII] As a preferable aspect of the photoacid generator (B-1), for example, a compound represented by the following formula ZI, formula ZII, or formula ZIII can be cited.

[化44]

In the formula ZI, R ²⁰¹ , R ²⁰² and R ²⁰³ each independently represent an organic group. The number of carbon atoms in the organic group of ^{R 201} , R ²⁰² and R ^{203 is preferably 1-30, more preferably 1-20.} In addition, two of R ²⁰¹ to R ²⁰³ may be bonded 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 bonding two of R ²⁰¹ to R ²⁰³ include alkylene (for example, butylene, pentylene) and -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -. Z ^- represents an anion.

[The cation in the compound represented by the formula ZI] As a preferable aspect of the cation in the formula ZI, the compound (ZI-1), the compound (ZI-2), the compound (ZI-3) and the compound ( The corresponding base in ZI-4). Furthermore, the photoacid generator (B-1) may be a compound having a plurality of structures represented by formula ZI. For example, at least one R ZI another compound of formula may be represented by R is a compound represented by the formula ZI ²⁰¹ ~ R ²⁰³ in ²⁰¹ ~ R ²⁰³ via at least a single bond or a linking group formed by bonding The structure of the compound.

-Compound ZI-1- First, the compound (ZI-1) will be described. Compound (ZI-1) is ^{an aryl alumium compound in which at least one of R 201} to R ²⁰³ of the formula ZI is an aryl group, that is, a compound having an aryl alumium as a cation. In the aryl amber 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 or cycloalkyl groups. As the aryl alumite compound, for example, a triaryl alumite compound, a diaryl alkyl alumite compound, an aryl dialkyl alumite compound, a diaryl cycloalkyl alumite compound, and an aryl dicycloalkyl alumite compound are mentioned.

The aryl group of the aryl alumium compound is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The aryl group may be an aryl group containing a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom, or the like. Examples of the heterocyclic structure include pyrrole residues, furan residues, thiophene residues, indole residues, benzofuran residues, and benzothiophene residues. When the aryl alumium 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 aryl cyanide compound is preferably 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, for example Examples include methyl, ethyl, propyl, n-butyl, second butyl, tertiary butyl, cyclopropyl, cyclobutyl, and cyclohexyl.

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

-Compound ZI-2- Next, the 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 without an aromatic ring. The aromatic ring referred to here 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, and more preferably has 1 to 20 carbon atoms. R ²⁰¹ to R ²⁰³ are each independently preferably an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group, more preferably a linear or branched 2-oxoalkyl group, a 2-oxocycloalkyl group, or The alkoxycarbonylmethyl group is more preferably a linear or branched 2-oxoalkyl group.

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

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

[化45]

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, and a cycloalkyl group. A carbonyloxy 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, 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 be bonded respectively to form a ring structure, and the ring structure may be respectively It independently contains an oxygen atom, a sulfur atom, a keto group, an ester bond, or an amide bond. Examples of the ring structure include an aromatic or non-aromatic hydrocarbon ring, an aromatic or non-aromatic heterocyclic ring, and a polycyclic condensed ring formed by combining two or more of these rings. Examples of the ring structure include a 3-membered ring to a 10-membered ring, preferably a 4-membered ring to an 8-membered ring, and more preferably a 5-membered ring or a 6-membered ring.

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

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

[化46]

In formula ZI-4, l represents an integer from 0 to 2, r represents an integer from 0 to 8, and R ¹³ represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, or A group having a cycloalkyl group, these groups may have a substituent, and R ¹⁴ 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 ring An alkylsulfonyl group or a group having a cycloalkyl group, these groups may have a substituent, R ¹⁵ each independently represents an alkyl group, a cycloalkyl group or a naphthyl group, these groups may have a substituent, two R ¹⁵ Can be bonded to each other to form a ring. When two R ¹⁵ are bonded to each other to form a ring, a hetero atom such as an oxygen atom or a nitrogen atom may be included in the ring skeleton. In one aspect, it is preferable that two R ¹⁵ are alkylene groups, and they are bonded to each other to form a ring structure. Z ^- represents an anion.

In the formula ZI-4, ^{the alkyl group of R 13} , R ¹⁴ and R ¹⁵ is linear or branched, preferably having 1 to 10 carbon atoms, more preferably methyl, ethyl, n-butyl, or Tertiary butyl and so on.

[Cation in the compound represented by the formula ZII and the compound represented by the formula ZIII] Next, the formula ZII and the formula ZIII will be described. In formula ZII and formula ZIII, R ²⁰⁴ to R ²⁰⁷ each independently represent an aryl group, an alkyl group, or a cycloalkyl group. The aryl group of R ²⁰⁴ to R ²⁰⁷ is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The aryl group of R ²⁰⁴ to R ²⁰⁷ may be an aryl group containing a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom, or the like. Examples of the skeleton of the aryl group having a heterocyclic structure include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene. As ^{the alkyl group and cycloalkyl group of R 204} to R ²⁰⁷ , preferably, a straight chain alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (e.g., methyl, ethyl, propyl , Butyl, and pentyl), C3-10 cycloalkyl (such as cyclopentyl, cyclohexyl, and norbornyl).

The aryl group, alkyl group, and cycloalkyl group of R ²⁰⁴ to R ^{207 may each independently have a substituent.} Examples of the substituents that the aryl group, alkyl group, and cycloalkyl group of R ²⁰⁴ to R ²⁰⁷ may have include alkyl groups (for example, carbon numbers 1 to 15), cycloalkyl groups (for example, carbon numbers 3 to 15), Aryl group (for example, carbon number 6-15), alkoxy group (for example, carbon number 1-15), halogen atom, hydroxyl group, phenylthio group, etc. Z ^- represents an anion.

Anionic compounds of formula [~ ZI] represented by Formula ZII ZI of formula Z ^-, ZII the formula Z ^-, of the formula ZI-3 Zc ^-, and ZI-4 of the formula Z ^-, preferably It is an anion represented by the following formula An-1.

[化47]

In the formula An-1, pf represents an integer from 0 to 10, qf represents an integer from 0 to 10, rf represents an integer from 1 to 3, and Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. When rf is an integer of 2 or more, a plurality of -C(Xf) ₂ -may be the same or different, and R ^4f and R ^5f each independently represent a hydrogen atom, a fluorine atom, an alkyl group, or at least one fluorine atom For the substituted alkyl group, when pf is an integer of 2 or more, a plurality of -CR ^4f R ^5f -may be the same or different, respectively, 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, respectively, and W represents an organic group.

Xf represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. The number of carbon atoms in the alkyl group is preferably 1-10, more preferably 1-4. In addition, the alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group. Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms. Xf is more preferably a fluorine atom or CF ₃ . In particular, two Xf are preferably fluorine atoms.

R ^4f and R ^5f each independently represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom. When there are a plurality of R ^4f and R ^5f , each may be the same or different. The alkyl group as R ^4f and R ^5f may have a substituent, and preferably has 1 to 4 carbon atoms. R ^4f and R ^{5f are} preferably hydrogen atoms. The 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 the formula An-1.

L ^f represents a divalent linking group, and when there are a plurality of L ^{fs, they} may be the same or different. Examples of the divalent linking group include: -COO-(-C(=O)-O-), -OCO-, -CONH-, -NHCO-, -CO-, -O-, -S-,- SO-, -SO ₂ -, alkylene group (preferably carbon number 1 to 6), cycloalkylene group (preferably carbon number 3 to 15), alkenylene group (preferably carbon number 2 to 6) And a divalent linking group formed by combining a plurality of these. Among these, preferred are -COO-, -OCO-, -CONH-, -NHCO- _{, -CO-, -O-, -SO 2} -, -COO-alkylene-, -OCO-alkylene -, -CONH-alkylene- or -NHCO-alkylene-, more preferably -COO-, -OCO-, -CONH-, -SO ₂ -, -COO-alkylene- or -OCO-alkylene alkyl-.

W represents an organic group (for example, an alkyl group, a cycloalkyl group, an aryl group, a heterocyclic group, etc.), and preferably represents an organic group containing a cyclic structure. Among these, a cyclic organic group is preferred. Examples of the cyclic organic group include an alicyclic group, an aryl group, and a heterocyclic group. The alicyclic group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include monocyclic cycloalkyl groups such as cyclopentyl, cyclohexyl, and cyclooctyl. Examples of the polycyclic alicyclic group include polycyclic cycloalkyl groups such as norbornyl group, tricyclodecyl group, tetracyclodecyl group, tetracyclododecyl group, and adamantyl group. Among them, alicyclic groups having a bulky structure with 7 or more carbon atoms, such as norbornyl group, tricyclodecyl group, tetracyclodecyl group, tetracyclododecyl group, and adamantyl group, are preferred.

The aryl group may be monocyclic or polycyclic. As this aryl group, a phenyl group, a naphthyl group, a phenanthryl group, and an anthracenyl group are mentioned, for example. The heterocyclic group may be monocyclic or polycyclic. The polycyclic type can further inhibit the diffusion of acid. In addition, the heterocyclic group may be aromatic or not. Examples of the heterocyclic ring having aromaticity include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Examples of the heterocyclic ring having no aromaticity include a tetrahydropyran ring, a lactone ring, a sultone ring, and a decahydroisoquinoline ring. Examples of the lactone ring and the sultone ring include the lactone structure and the sultone structure exemplified in the resin. 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 the substituent include an alkyl group (which may be either linear or branched, and preferably has 1 to 12 carbon atoms), cycloalkyl (which may be any one of monocyclic, polycyclic, and spirocyclic rings, Preferably it is carbon number 3-20), aryl group (preferably carbon number 6-14), hydroxyl group, alkoxy group, ester group, amide group, urethane group, urea group, thioether group, Sulfonamide group, sulfonate group, etc. Furthermore, the carbon (carbon that contributes to ring formation) constituting the cyclic organic group may be a carbonyl carbon.

As the anion represented by the formula An-1, 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 ) _{q f} -W, SO ₃ ^-- CF ₂ -CH(CF ₃ )-OCO-(L ^f )q'-W is preferable. Here, L ^f , qf and W are the same as the formula An-1. q'represents an integer of 0-10.

In one aspect, the ZI formula Z ^-, ZII the formula Z ^-, of the formula ZI-3 Zc ^-, and ZI-4 of the formula Z ^-, also preferably represented by the following formula 4的 anions.

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In Formula 4, X ^B1 and X ^B2 each independently represent a hydrogen atom or a monovalent organic group that does not have a 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. It is preferable ^{that at least one of X B3} and X ^B4 is a fluorine atom or a monovalent organic group having a fluorine atom, and it is more preferable that both X ^B3 and X ^B4 are a fluorine atom or a monovalent organic group having a fluorine atom. More ^{preferably, both X B3} and X B4 are alkyl groups substituted with fluorine. L ^f , qf and W are the same as the formula An-1.

ZI of formula Z ^-, ZII the formula Z ^-, of the formula ZI-3 Zc ^-, and ZI-4 of the formula Z ^-, preferably an anion represented by the following formula 5.

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In Formula 5, Xa each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom, and Xb each independently represents a hydrogen atom or an organic group having no fluorine atom. The definitions and preferred aspects of rf, pf, qf, R ^4f , R ^5f , L ^f and W are the same as the formula An-1.

ZI of formula Z ^-, ZII the formula Z ^-, of the formula ZI-3 Zc ^-, and ZI-4 of the formula Z ^- may be a benzenesulfonate anion, preferably a branched alkyl or by cycloalkyl Benzenesulfonate anion with substituted group.

Aromatic sulfonate anion, preferably also represented by the following formula SA1 ^- Z in formula ZI ^-, Z in formula ZII ^-, the formula ZI-3 Zc ^-, and in formula Z ZI-4 .

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In the formula SA1, Ar represents an aryl group, and may further have a sulfonate anion and a substituent other than ^{-(DR B ).} Examples of the substituent that may be further include a fluorine atom, a hydroxyl group, and the like.

n represents an integer of 0 or more. n is preferably 1 to 4, more preferably 2 to 3, 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, an oxalylene group, an oxalyl group, a sulfonate group, an ester group, and a group containing a combination of two or more of these.

R ^B represents a hydrocarbon group.

D is preferably a single bond, R ^B is an aliphatic hydrocarbon structure. R ^{B is more} preferably isopropyl or cyclohexyl.

The following shows preferred examples of the alium cation in the formula ZI and the iodonium cation in the formula ZII.

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

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The cation and anion can be combined arbitrarily and used as a photoacid generator (B-1).

The photoacid generator (B-1) is an ionic compound containing a cation and an anion, and the anion may include any of the formula An-1, the following formula An-2, and the following formula An-3. Of ions.

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In Formula An-2 and Formula An-3, Rfa each independently represents a monovalent organic group having a fluorine atom, and a plurality of Rfa may be bonded to 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 the alkyl group is preferably 1-10, more preferably 1-4. In addition, the alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group. In addition, it is preferable that a plurality of Rfa are bonded to each other to form a ring.

The photoacid generator (B-1) may be in the form of a low-molecular compound, or may be incorporated in a part of the polymer. In addition, the form of the low-molecular compound and the form incorporated into a part of the polymer may be used in combination. The photoacid generator (B-1) is preferably in the form of a low-molecular compound. When the photoacid generator (B-1) is in the form of a low-molecular compound, the molecular weight is preferably 3,000 or less, more preferably 2,000 or less, and still more preferably 1,000 or less. When the photoacid generator (B-1) is incorporated into a part of the polymer, it may be incorporated into a part of the resin (A), or it may be incorporated differently from the resin (A) In the resin.

The photoacid generator (B-1) may be used singly, or two or more of them may be used in combination.

The content of the photoacid generator (B-1) in the composition of the present invention (the total when there are multiple types) is based on the total solid content of the composition of the present invention, and is preferably 0.1% by mass to 35 % By mass, more preferably 0.5% by mass to 25% by mass, still more preferably 0.5% by mass to 20% by mass, particularly preferably 1.0% by mass to 20% by mass.

＜Photoacid generator (B-2)＞ The composition of the present invention contains a photoacid generator (B-2). The photoacid generator (B-2) is a compound that generates acid by irradiation with actinic rays or radiation. As the photoacid generator (B-2), a compound that generates an organic acid by irradiation with actinic rays or radiation is preferred. Examples include: sulfonium salt compounds, iodonium salt compounds, diazonium salt compounds, phosphonium salt compounds, imine sulfonate compounds, oxime sulfonate compounds, diazonium compounds, disulfide compounds, and o-nitro groups Benzyl sulfonate compound.

The photoacid generator (B-2) is preferably a compound containing a salt structure of a cation and an anion, and more preferably a compound represented by any one of the following formulas d1-1 to d1-3.

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In formula d1-1 to formula d1-3, R ⁵¹ represents an organic group. Z ^2c represents a hydrocarbon group. However, ^{the hydrocarbon group represented by Z 2c} is assumed to have no fluorine atom bonded to the carbon atom adjacent to the sulfur atom. R ⁵² represents an organic group, Y ³ represents a single bond or a divalent linking group, and Rf represents a substituent. R ⁵² and Rf may bond to form a ring. M ⁺ represents an ammonium cation, a cation or an iodonium cation.

In formula d1-1, R ⁵¹ represents an organic group. The organic group is not particularly limited, and examples thereof include an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, a cycloalkoxycarbonyl group, and an aryloxycarbonyl group.

Examples of the alkyl group include an alkyl group having 1 to 20 carbon atoms, which may be linear or branched, preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 5 carbon atoms. Examples of the alkenyl group include alkenyl groups having 2 to 5 carbon atoms, which may be linear or branched, and are preferably alkenyl groups having 2 to 3 carbon atoms. The cycloalkyl group includes, for example, a cycloalkyl group having 3 to 20 carbon atoms, and a cycloalkyl group having 3 to 10 carbon atoms is preferred. The cycloalkyl group may have a heteroatom between the carbon-carbon bond. As a hetero atom, an oxygen atom, a sulfur atom, and a nitrogen atom are mentioned, for example. Examples of the aryl group include an aryl group having 6 to 14 carbon atoms, and an aryl group having 6 to 10 carbon atoms is preferred. The heterocyclic group may be monocyclic or polycyclic. The polycyclic type can further inhibit the diffusion of acid. In addition, the heterocyclic group may be aromatic or not. Examples of the heterocyclic ring having aromaticity include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Examples of the heterocyclic ring having no aromaticity include a tetrahydropyran ring, a lactone ring, a sultone ring, and a decahydroisoquinoline ring. Examples of the lactone ring and the sultone ring include the lactone structure and the sultone structure exemplified in the resin. The heterocyclic ring in the heterocyclic group is particularly preferably a furan ring, a thiophene ring, a pyridine ring, or a decahydroisoquinoline ring. As an acyl group, a C1-C20 acyl group is mentioned, for example. Examples of the alkoxycarbonyl group include those in which the alkyl group is substituted with an oxycarbonyl group. Examples of the cycloalkoxycarbonyl group include groups in which the cycloalkyl group is substituted with an oxycarbonyl group. Examples of the aryloxycarbonyl group include groups in which the aryl group is substituted with an oxycarbonyl group.

The alkyl group, alkyl group, alkenyl group, cycloalkyl group, aryl group, heterocyclic group, acyl group, alkoxycarbonyl group, cycloalkoxycarbonyl group, and aryloxycarbonyl group may further have a substituent. As a substituent, the said substituent T is mentioned, for example.

In the formula d1-2, Z ^2c represents a hydrocarbon group. The hydrocarbon group represented by Z ^{2c may have a substituent.} As a substituent, the said substituent T is mentioned, for example. The hydrocarbon group represented by Z ^2c may have a hetero atom between the carbon-carbon bond. As a hetero atom, an oxygen atom, a nitrogen atom, a sulfur atom, etc. are mentioned, for example. The hydrocarbon group represented by Z ^2c is not particularly limited, but is preferably a group represented by the following formula An-2, for example.

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In the formula An-2, pf represents an integer from 0 to 10, qf represents an integer from 0 to 10, tf represents an integer from 0 to 3, R ⁴⁰ and R ⁵⁰ each independently represent a hydrogen atom or an organic group, and tf is 2 or more In the case of an integer of, a plurality of -CR ⁴⁰ R ⁵⁰ -may be the same or different, and R ^4f and R ^5f each independently represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom, When pf is an integer of 2 or more, a plurality of -CR ^4f R ^5f -may be the same or different, respectively, L ^f represents a divalent linking group, and when qf is an integer of 2 or more, a plurality of L ^f may be They may be the same or different, and W represents an organic group. * Indicates the position of the bond. However, the group represented by the formula An-2 is set to a carbon atom that is bonded to the sulfur atom in the formula d1-2, and a fluorine atom is not bonded.

R ⁴⁰ and R ⁵⁰ each independently represent a hydrogen atom or an organic group, and preferably represent a hydrogen atom. As the organic group, the same organic group as the above- ^{mentioned R 51 can be mentioned.}

In the formula ^{An-2, pf, qf, R 4f,} R 5f, L f, and W are of the formula in 1 ^{An-pf, qf, R 4f, R} 5f, L f, and W the same.

In formula d1-3, R ⁵² represents an organic group. As the organic group, the same organic group as the above- ^{mentioned R 51 can be mentioned.}

In formula d1-3, Y ³ represents a single bond or a divalent linking group. As the divalent linking group, for example, an alkylene group, a cycloalkylene group, an arylene group, -O-, -CO-, -COO-, -OCO-, -SO ₂ -, and two of these A combination of more than one group. The alkylene group preferably has 1 to 10 carbon atoms, for example. In addition, it is more preferably a carbon number of 1 or 2. As the alkylene group having a carbon number of 1 or 2, for example, a methylene group or an ethylene group is preferable. The alkylene group may be linear or branched, for example: methylene, ethane-1,1-diyl, ethane-1,2-diyl, propane-1,1 -Diyl, propane-1,3-diyl, propane-2,2-diyl, pentane-1,5-diyl, hexane-1,6-diyl, etc. The cycloalkylene group preferably has 5 to 10 carbon atoms, and more preferably has 5 or 6 carbon atoms. Examples of the cycloalkylene group include cyclopentyl group, cyclohexylene group, cycloheptyl group, cyclooctyl group, cyclodecylene group and the like. The arylene group preferably has 6 to 10 carbon atoms, for example. Examples of the arylene group include phenylene group, naphthylene group, and the like.

In formula d1-3, Rf represents a substituent. As the substituent, an organic group is preferred. As the organic group, the same organic group as the above- ^{mentioned R 51 can be mentioned.} Rf preferably represents a hydrocarbon group containing a fluorine atom, more preferably represents a fluoroalkyl group, and still more preferably represents a fluoroalkyl group having 1 to 5 carbon atoms.

In formula d1-1 to formula d1-3, M ⁺ represents an ammonium cation, a cation or an iodonium cation. A preferable aspect when M ⁺ represents a cation is the same as the cation in the formula ZI described as a preferable aspect of the photoacid generator (B-1). A preferable aspect when M ⁺ represents an iodonium cation is the same as the iodonium cation in the formula ZII described as a preferable aspect of the photoacid generator (B-1). A preferable aspect when M ⁺ represents an ammonium cation includes a quaternary ammonium cation, preferably an ammonium cation in which four alkyl groups having 1 to 10 carbon atoms are substituted.

The photoacid generator (B-2) may be a compound having a cation site and an anion site in the same molecule, and the cation site and anion site are linked by a covalent bond. As a photoacid generator (B-2) of this aspect, the compound represented by any one of following formula C-1-formula C-3 is preferable.

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In formula C-1 to formula C-3, R ¹ , R ² , and R ³ each independently represent an organic group. L ¹ represents a divalent linking group or a single bond connecting a cation site and an anion site. -X ^- represents a group selected _{^{-COO -, -SO 3 -, -SO}} 2 -, and -N ^- anionic sites in -R ^4. R ⁴ represents a monovalent substituent having at least one of a carbonyl group, a sulfinyl group, and a sulfinyl group at the connection site to the adjacent nitrogen atom. R ¹ , R ² , R ³ , R ⁴ , and L ¹ may be bonded to each other to form a ring structure. In addition, in formula C-3, ^{two of R 1} to R ³ are combined to represent one divalent substituent, which can be bonded to a nitrogen atom by a double bond.

In formula C-1 to formula C-3, R ¹ , R ² , and R ³ each independently represent an organic group. Examples of the organic groups in R ¹ to R ³ include alkyl groups, cycloalkyl groups, aryl groups, alkoxycarbonyl groups, cycloalkoxycarbonyl groups, aryloxycarbonyl groups, alkylaminocarbonyl groups, and cycloalkylamines. Carbonyl, and arylaminocarbonyl, etc. Preferably, it is an alkyl group, a cycloalkyl group, or an aryl group.

^{Examples of L 1} as the divalent linking group include linear or branched alkylene, cycloalkylene, arylene, carbonyl, ether bond, ester bond, amide bond, urethane bond, urea A bond, and a base formed by combining two or more of these. L ^{1 is} preferably an alkylene group, an arylene group, an ether bond, an ester bond, or a combination of two or more of these.

The photoacid generator (B-2) may be in the form of a low-molecular compound, or may be incorporated in a part of the polymer. In addition, the form of the low-molecular compound and the form incorporated into a part of the polymer may be used in combination. The photoacid generator (B-2) is preferably in the form of a low-molecular compound. When the photoacid generator (B-2) is in the form of a low-molecular compound, the molecular weight is preferably 3,000 or less, more preferably 2,000 or less, and still more preferably 1,000 or less. When the photoacid generator (B-2) is incorporated into a part of the polymer, it may be incorporated into a part of the resin (A), or it may be incorporated differently from the resin (A) In the resin.

The photoacid generator (B-2) may be used alone or in combination of two or more.

The content of the photoacid generator (B-2) relative to the content of the photoacid generator (B-1) is 0.001 mass% or more and 0.10 mass% or less, preferably 0.005 mass% or more and 0.10 mass% or less, more Preferably it is 0.01 mass% or more and 0.10 mass% or less, More preferably, it is 0.05 mass% or more and 0.10 mass% or less.

The specific examples of the photoacid generator (B-2) are shown below, but the present invention is not limited to these.

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＜Acid diffusion control agent (D)＞ The actinic radiation-sensitive or radiation-sensitive resin composition of the present invention contains an acid diffusion control agent (D). The acid diffusion control agent (D) functions as a quencher that captures acid generated from a photoacid generator during exposure, and suppresses the acid decomposability in the unexposed portion caused by excess acid generation The reaction of the resin. For example, a basic compound (DA), a basic compound (DB) whose basicity decreases or disappears by irradiation with actinic rays or radiation, and a low-molecular molecule having a nitrogen atom and a group detached by the action of an acid can be used. A compound (DD) or an onium salt compound (DE) having a nitrogen atom in the cation part is used as the acid diffusion control agent (D). Among them, the actinic radiation-sensitive or radiation-sensitive resin composition of the present invention preferably contains a nitrogen-containing compound as the acid diffusion control agent (D), and more preferably contains a nitrogen-containing basic compound. In the sensitizing radiation-sensitive or radiation-sensitive resin composition of the present invention, a known acid diffusion control agent can be suitably used. For example, paragraphs 0627 to 0664 of U.S. Patent Application Publication No. 2016/0070167, paragraphs 0095 to 0187 of U.S. Patent Application Publication No. 2015/0004544, and U.S. Patent Application Publication No. 2016 The well-known compounds disclosed in paragraphs 0403 to 0423 of the specification /0237190 and paragraphs 0259 to 0328 of the specification of U.S. Patent Application Publication No. 2016/0274458 are used as the acid diffusion control agent (D).

〔Basic Compound (DA)〕 As the basic compound (DA), preferably, a compound having a structure represented by any one of the following formulas (D1) to (D5) is mentioned.

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In formula (D1) and formula (D5), R ²⁰⁰ , R ²⁰¹ and R ²⁰² each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group. R ²⁰¹ and R ²⁰² may be bonded to each other to form a ring. R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ and R ²⁰⁶ each independently represent an alkyl group.

When R ²⁰⁰ , R ^201, and R ²⁰² represent an alkyl group, for example, an alkyl group having 1 to 20 carbon atoms may be mentioned, and it may be linear or branched. As for the alkyl group, the alkyl group having a substituent is preferably an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, or a cyanoalkyl group having 1 to 20 carbon atoms. The specific examples and preferred ranges of the alkyl group represented by R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ and R ²⁰⁶ are the same as the alkyl group when ^{R 200} , R ²⁰¹ and R ^{202 represent an alkyl group.} R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ and R ²⁰⁶ may be the same or different. The alkyl group in formula (D1) and formula (D5) is more preferably unsubstituted.

When R ²⁰⁰ , R ²⁰¹ and R ²⁰² represent a cycloalkyl group, for example, a cycloalkyl group having 3 to 20 carbon atoms can be cited.

When R ²⁰⁰ , R ²⁰¹ and R ²⁰² represent an aryl group, for example, an aryl group having 6 to 20 carbon atoms can be cited.

As the basic compound (DA), guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, piperidine, etc. are preferred, and imidazole is more preferred. Structure, diazabicyclic structure, onium hydroxide structure, onium carboxylate structure, trialkylamine structure, aniline structure or pyridine structure compound, alkylamine derivative with hydroxyl group and/or ether bond, or hydroxyl group And/or aniline derivatives of ether linkages, etc.

[Basic compound (DB) whose alkalinity decreases or disappears by irradiation with actinic rays or radiation] The basic compound (DB) (hereinafter, also referred to as "compound (DB)") whose basicity decreases or disappears by irradiation with actinic rays or radiation is a compound that has a proton-accepting functional group and is Irradiation of actinic rays or radiation decomposes and the proton acceptor property decreases, disappears, or the proton acceptor property changes to acidity.

The so-called proton-accepting functional group is a functional group having a group or electrons that can interact with protons electrostatically. For example, it refers to a functional group having a macrocyclic structure such as a cyclic polyether, or a functional group that does not contribute to π conjugation. The non-covalent electron pair is the functional group of the nitrogen atom. The nitrogen atom having a non-covalent electron pair that does not contribute to π conjugation is, for example, a nitrogen atom having a partial structure represented by the following formula.

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Examples of preferable partial structures of the proton-accepting functional group include a crown ether structure, an aza crown ether structure, a primary to tertiary amine structure, a pyridine structure, an imidazole structure, and a pyrazine structure.

The compound (DB) is decomposed by irradiation with actinic rays or radiation to produce a compound in which the proton acceptor property decreases or disappears, or the proton acceptor property changes to acidity. Here, the decrease or disappearance of proton acceptor, or the change from proton acceptor to acidity, is the change in proton acceptor caused by the addition of protons to the proton acceptor functional group. Specifically, it is It means that when a compound having a proton-accepting functional group (DB) and a proton generate a proton adduct, the equilibrium constant in the chemical equilibrium decreases. The proton acceptability can be confirmed by performing a pH measurement.

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

The so-called acid dissociation constant pKa represents the acid dissociation constant pKa in an aqueous solution, and is defined, for example, by the Handbook of Chemistry (II) (Revised 4th edition, 1993, The Chemical Society of Japan, Maruzen Co., Ltd.). The lower the value of the acid dissociation constant pKa, the greater the 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, the following software package 1 can also be used to obtain the value of the database based on the Hammett's substituent constant and publicly known literature values by calculation. The values of pKa described in this manual all indicate values obtained by calculations using this software package.

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

[Low-molecular compound (DD) having a nitrogen atom and a group detached by the action of an acid] The low-molecular compound (DD) having a nitrogen atom and a group that is released by the action of an acid (hereinafter, also referred to as "compound (DD)") preferably has a nitrogen atom that is released by the action of an acid -Based amine derivatives. The group to be released by the action of an acid is preferably an acetal group, a carbonate group, a urethane group, a tertiary ester group, a tertiary hydroxyl group, or a semiamine acetal ether group, and more preferably a urethane group Ester group, or semiamine acetal ether group. The molecular weight of the compound (DD) is preferably 100-1000, more preferably 100-700, and still more preferably 100-500. The compound (DD) may have a urethane group containing a protective group on the nitrogen atom. The protecting group constituting the urethane group can be represented by the following formula d-1.

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In formula d-1, R ^b each independently represents a hydrogen atom, an alkyl group (preferably carbon number 1-10), cycloalkyl group (preferably carbon number 3-30), aryl group (preferably carbon number 3-30), aralkyl (preferably carbon number 1-10), or alkoxyalkyl (preferably carbon number 1-10). R ^b may be connected to each other to form a ring. The alkyl group, cycloalkyl group, aryl group, and aralkyl group represented by R ^b can be independently passed through functional groups such as hydroxyl, cyano, amino, pyrrolidinyl, piperidinyl, morpholinyl, and pendant oxy groups. Alkoxy or halogen atom substitution. The same applies to the alkoxyalkyl group represented by ^{R b.}

As R ^b , a linear or branched alkyl group, a cycloalkyl group, or an aryl group is preferable, and a linear or branched alkyl group or a cycloalkyl group is more preferable. Examples of the ring formed by connecting two R ^{b to} each other include alicyclic hydrocarbons, aromatic hydrocarbons, heterocyclic hydrocarbons, and derivatives thereof. As a specific structure of the group represented by formula d-1, the structure disclosed in paragraph 0466 of the specification of U.S. Patent Application Publication No. 2012/0135348 can be cited, but it is not limited to this.

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

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In Formula 6, l represents an integer from 0 to 2, and m represents an integer from 1 to 3, and satisfies l+m=3. R ^a represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group. When 1 is 2, two ^Ras may be the same or different, and two ^Ras may be connected to each other and form a heterocyclic ring together with the nitrogen atom in the formula. Heteroatoms other than the nitrogen atom in the formula may be included in the heterocyclic ring. R ^b in the formula 1 d-R ^b in the same sense, the preferred embodiments 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 a group that is the same as the alkyl group, cycloalkyl group, aryl group, and aryl group ^{as R b.} And the aralkyl group may be substituted, and the groups are the same.

Specific examples of the above R ^a is alkyl, cycloalkyl, aryl, and aralkyl groups (the group may be substituted with those of the group) include the specific examples of R ^b and on the same base . As the specific structure of the particularly preferred compound (DD) in the present invention, the compound disclosed in paragraph 0475 of the specification of U.S. Patent Application Publication No. 2012/0135348 can be cited, but it is not limited to this.

The onium salt compound (DE) having a nitrogen atom in the cation part (hereinafter also referred to as "compound (DE)") is preferably a compound having a basic part including a nitrogen atom in the cation part. The basic part is preferably an amine group, and more preferably an aliphatic amine group. More preferably, all atoms adjacent to the nitrogen atom in the basic site are hydrogen atoms or carbon atoms. In addition, from the viewpoint of improving basicity, it is preferable that the electron-withdrawing functional group (carbonyl group, sulfonyl group, cyano group, halogen atom, etc.) is not directly bonded to the nitrogen atom. As a preferable specific structure of the compound (DE), the compound disclosed in paragraph 0203 of the specification of U.S. Patent Application Publication No. 2015/0309408 can be cited, but it is not limited to this.

The following shows preferred examples of other acid diffusion control agents.

[化67]

[化68]

[化69]

In the sensitizing radiation-sensitive or radiation-sensitive resin composition of the present invention, the acid diffusion control agent (D) may be used alone or in combination of two or more kinds. The content of the acid diffusion control agent (D) in the composition of the present invention (the total when there are multiple types) is based on the total solid content of the composition of the present invention, and is preferably 0.01% by mass to 10% by mass , More preferably 0.01% by mass to 5% by mass.

Relative to the content of the photoacid generator (B-1), the content of the acid diffusion control agent (D) is preferably 0.5% by mass or more and 10.0% by mass or less, more preferably 1.0% by mass or more and 7.0% by mass or less, and further Preferably, it is 1.5% by mass or more and 5.0% by mass or less.

＜Solvent＞ The sensitizing radiation-sensitive or radiation-sensitive resin composition of the present invention preferably contains a solvent (also referred to as "solvent (F)"), and more preferably contains an organic solvent. In the sensitizing radiation-sensitive or radiation-sensitive resin composition of the present invention, a known resist solvent can be suitably used. For example, paragraphs 0665 to 0670 of U.S. Patent Application Publication No. 2016/0070167, paragraphs 0210 to 0235 of U.S. Patent Application Publication No. 2015/0004544, and U.S. Patent Application Publication No. 2016/ A well-known solvent disclosed in paragraph 0424 to paragraph 0426 of specification 0237190, and paragraph 0357 to paragraph 0366 of specification U.S. Patent Application Publication No. 2016/0274458. Examples of solvents that can be used when preparing the composition include: alkanediol monoalkyl ether carboxylate, alkanediol monoalkyl ether, alkyl lactate, alkyl alkoxypropionate, cyclic internal Esters (preferably carbon number 4-10), monoketone compounds that may have a ring (preferably carbon number 4-10), alkylene carbonate, alkyl alkoxy acetate, and alkyl pyruvate And other organic solvents.

As the organic solvent, a mixed solvent obtained by mixing a solvent containing a hydroxyl group and a solvent not containing a hydroxyl group in the structure can also be used. As a solvent containing a hydroxyl group and a solvent not containing a hydroxyl group, the exemplified compounds can be appropriately selected. As the solvent containing a hydroxyl group, an alkanediol monoalkyl ether, an alkyl lactate, etc. are preferred, and propylene glycol is more preferred. Monomethyl ether (PGME (propylene glycol monomethyl ether): 1-methoxy-2-propanol), propylene glycol monoethyl ether (PGEE), methyl 2-hydroxyisobutyrate, or ethyl lactate. In addition, as a solvent that does not contain a hydroxyl group, an alkanediol monoalkyl ether acetate, an alkyl alkoxy propionate, a ring-containing monoketone compound, a cyclic lactone, or an alkyl acetate is preferred. Etc. Among these, more preferred are propylene glycol monomethyl ether acetate (PGMEA (propylene glycol monomethyl ether acetate): 1-methoxy-2-acetoxypropane), ethyl ethoxy propionate, 2-heptanone, γ-butyrolactone, cyclohexanone, cyclopentanone or butyl acetate, more preferably propylene glycol monomethyl ether acetate, γ-butyrolactone, ethyl ethoxy propionate, cyclic Hexanone, cyclopentanone or 2-heptanone. As a solvent that does not contain a hydroxyl group, propylene carbonate is also preferred. Among these, from the viewpoint of the uniformity of the formed layer, the solvent particularly preferably contains γ-butyrolactone. The mixing ratio (mass ratio) of the solvent containing a hydroxyl group and the solvent not containing a hydroxyl group is 1/99 to 99/1, preferably 10/90 to 90/10, more preferably 20/80 to 60/40. In terms of coating uniformity, a mixed solvent containing 50% by mass or more of a solvent not containing a hydroxyl group is preferable. The solvent preferably contains propylene glycol monomethyl ether acetate, may be a single solvent of propylene glycol monomethyl ether acetate, or may be a mixed solvent of two or more containing propylene glycol monomethyl ether acetate.

The solid content concentration of the sensitized radiation or radiation-sensitive resin composition of the present invention is 10% by mass or more, preferably 10% by mass to 50% by mass, more preferably 15% by mass to 45% by mass, and still more preferably 20% by mass. Mass%～40% by mass. The so-called solid content concentration is the mass percentage of the mass of other components other than the solvent with respect to the total mass of the composition of the present invention.

＜Crosslinking agent＞ The actinic radiation-sensitive or radiation-sensitive resin composition of the present invention may contain a compound that crosslinks the resin by the action of an acid (hereinafter, also referred to as a crosslinking agent (G)). As a crosslinking agent (G), a well-known compound can be used suitably. For example, the well-known compounds disclosed in paragraphs 0379 to 0431 of the specification of U.S. Patent Application Publication No. 2016/0147154 can be preferably used as paragraphs 0064 to paragraph 0141 of the specification of U.S. Patent Application Publication No. 2016/0282720. Crosslinking agent (G). The crosslinking agent (G) is a compound having a crosslinkable group that can crosslink the resin. Examples of the crosslinkable group include: hydroxymethyl, alkoxymethyl, oxymethyl, and alkoxy Methyl ether group, ethylene oxide ring, and oxetane ring, etc. The crosslinkable group is preferably a hydroxymethyl group, an alkoxymethyl group, an oxirane ring or an oxetane ring. The crosslinking agent (G) is preferably a compound (including resins) having two or more crosslinkable groups. The crosslinking agent (G) is more preferably a phenol derivative having a hydroxymethyl group or an alkoxymethyl group, a urea-based compound (a compound having a urea structure), or a melamine-based compound (a compound having a melamine structure). A crosslinking agent may be used individually by 1 type, and may use 2 or more types together. With respect to the total solid content of the composition, the content of the crosslinking agent (G) is preferably 1% by mass to 50% by mass, more preferably 3% by mass to 40% by mass, and still more preferably 5% by mass to 30% by mass.

＜Surface active agent＞ The sensitizing radiation-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, it is preferably a fluorine-based and silicone-based surfactant (specifically, a fluorine-based surfactant, a silicone-based surfactant, or those having both fluorine atoms and silicon atoms). Surfactant) at least one of them.

The sensitizing radiation-sensitive or radiation-sensitive resin composition of the present invention contains a surfactant, and when an exposure light source with a wavelength of 250 nm or less, especially a wavelength of 220 nm or less, is used, adhesion can be obtained with good sensitivity and resolution And the resist pattern with few development defects. Examples of the fluorine-based or silicone-based surfactant include the surfactants described in paragraph 0276 of the specification of U.S. Patent Application Publication No. 2008/0248425. In addition, other surfactants other than the fluorine-based or silicone-based surfactants described in paragraph 0280 of the specification of U.S. Patent Application Publication No. 2008/0248425 may be used.

These surfactants may be used alone or in combination of two or more. When the sensitized radiation-sensitive or radiation-sensitive resin composition of the present invention contains a surfactant, the content of the surfactant relative to the total solid content of the composition is preferably 0.0001% by mass to 2% by mass, and more preferably It is 0.0005 mass% to 1 mass%. On the other hand, when the content of the surfactant is set to 0.0001% by mass or more with respect to the total solid content of the composition, the surface deflection existence of the hydrophobic resin improves. Thereby, the surface of the sensitized radiation-sensitive or radiation-sensitive film can be made more hydrophobic, and the water followability during liquid immersion exposure can be improved.

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

The sensitizing radiation-sensitive or radiation-sensitive resin composition of the present invention preferably dissolves the components in a predetermined organic solvent, preferably the mixed solvent, and filters it, for example, coating on a predetermined organic solvent. On the support (substrate). The pore size (pore size) of the filter used for filter filtration is preferably 0.2 μm or less, more preferably 0.05 μm or less, and still more preferably 0.03 μm or less. In addition, when the solid content of the sensitized radiation or radiation-sensitive resin composition is high (for example, 25% by mass or more), the pore size of the filter used for filter filtration is preferably 3 μm or less, and more It is preferably 0.5 μm or less, and more preferably 0.3 μm or less. The filter is preferably a filter made of polytetrafluoroethylene, polyethylene, or nylon. In filter filtration, for example, as disclosed in Japanese Patent Laid-Open No. 2002-62667, cyclic filtration can be performed, and multiple filters can also be connected in series or parallel to perform filtration. In addition, the composition may be filtered multiple times. Furthermore, the composition may be degassed before and after filtration by the filter.

The thickness of the resist film containing the sensitized radiation-sensitive or radiation-sensitive resin composition of the present invention is not particularly limited, but is preferably 1 μm or more, more preferably 2 μm or more and 50 μm or less, and still more preferably 2 μm or more and 20 μm or less. The solid content concentration in the composition is set to an appropriate range to have an appropriate viscosity, and the coating properties or film-forming properties are improved, whereby such a film thickness can be formed.

＜Use＞ The actinic ray-sensitive or radiation-sensitive resin composition of the present invention is an actinic ray-sensitive or radiation-sensitive resin composition whose properties are changed by reaction with light irradiation. In more detail, the photosensitive radiation-sensitive or radiation-sensitive resin composition of the present invention relates to a semiconductor manufacturing process such as an integrated circuit (IC), the manufacturing of a circuit board such as a liquid crystal or a thermal head, etc. A photosensitive ray-sensitive or radiation-sensitive resin composition used in the production of a mold structure for imprinting, other photosensitive etching processing steps, or the production of a lithographic printing plate or an acid-curable composition. The resist pattern formed by the sensitized radiation-sensitive or radiation-sensitive resin composition of the present invention can be used in an etching step, an ion implantation step, a bump electrode formation step, a rewiring formation step, and a microelectromechanical system (Micro Electro Mechanical System). Systems, MEMS) etc.

(Sensitized radiation or radiation sensitive film) The actinic radiation or radiation-sensitive film (preferably a resist film) of the present invention is a film formed from the actinic radiation or radiation-sensitive resin composition of the present invention. The actinic radiation or radiation-sensitive film of the present invention is a cured product of the actinic radiation or radiation-sensitive resin composition of the present invention. The cured product in the present invention may be any one having at least a part of the solvent removed from the sensitizing radiation or radiation-sensitive resin composition of the present invention. Specifically, the actinic radiation or radiation-sensitive film of the present invention can be obtained, for example, by coating the actinic radiation or radiation-sensitive resin composition of the present invention on a support such as a substrate and then drying. The drying refers to removing at least a part of the solvent contained in the sensitizing 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, and examples thereof include drying by heating (for example, 70° C. to 130° C., 30 seconds to 300 seconds). It does not specifically limit as a heating method, A well-known heating mechanism can be used, For example, a heater, an oven, a hotplate, an infrared lamp, an infrared laser, etc. are mentioned.

The components contained in the sensitizing radiation or radiation-sensitive film of the present invention are the same as the components included in the sensitizing radiation or radiation-sensitive resin composition of the present invention after removing the solvent, and preferred aspects are also the same. The content of each component contained in the sensitizing radiation or radiation-sensitive film of the present invention corresponds to the "total content" in the description of the content of each component other than the solvent of the sensitizing radiation or radiation-sensitive resin composition of the present invention. The description of "solid content" is replaced with "total mass of sensitizing radiation or radiation sensitive film".

The thickness of the sensitizing radiation-sensitive or radiation-sensitive film of the present invention is preferably 1 μm or more, more preferably 2 μm or more and 50 μm or less, and still more preferably 2 μm or more and 20 μm or less.

(Pattern formation method) The pattern forming method of the present invention is a pattern forming method having the following steps, namely (I) The step of using the photosensitive ray-sensitive or radiation-sensitive resin composition of the present invention to form a photosensitive ray-sensitive or radiation-sensitive film with a film thickness of 1 μm or more on a substrate; (Ii) The step of irradiating actinic rays or radiation to the sensitized ray-sensitive or radiation-sensitive film; and (Iii) A step of using a developing solution to develop an actinic ray-sensitive or radiation-sensitive film irradiated with actinic rays or radiation.

<Step (i) Film forming step> The pattern forming method of the present invention includes step (i) (film forming step). As a method of forming the sensitizing radiation or radiation sensitive film in the film forming step, for example, the drying described in the item of the sensitizing radiation or radiation sensitive film can be used to form the sensitizing radiation or radiation sensitive film. Sexual film method.

[Substrate (support)] The substrate is not particularly limited. In addition to semiconductor manufacturing steps such as ICs, or circuit substrate manufacturing steps such as liquid crystals or thermal heads, it can be used in other photolithography steps such as photolithographic processing. Language substrate used. Specific examples of the support include inorganic substrates such as _{silicon, SiO 2, and SiN.}

<Step (ii) Exposure Step> Step (ii) (exposure step) is a step of exposing the sensitized radiation or radiation-sensitive film with light. The exposure method may be liquid immersion exposure. The pattern forming method of the present invention may include multiple exposure steps. The type of light (actinic rays or radiation) used in the exposure can be selected in consideration of the characteristics of the photoacid generator and the shape of the pattern to be obtained. Examples include infrared light, visible light, ultraviolet light, far ultraviolet light, Extreme ultraviolet light (EUV), X-ray, electron beam, etc. are preferably extreme ultraviolet light. For example, it is preferably an actinic ray with a wavelength of 250 nm or less, more preferably 220 nm or less, and still more preferably 1 nm to 200 nm. Specifically, the light used is KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ₂ excimer laser (157 nm), X-ray, EUV (13 nm) , Or electron beam, etc., preferably KrF excimer laser, EUV or electron beam. In the case of a KrF excimer laser, the exposure amount is preferably 5 mJ/cm ² to 200 mJ/cm ² , and more preferably 10 mJ/cm ² to 150 mJ/cm ² . In the case of an electron beam, ^{exposure is performed so that it becomes about 0.1 μC/cm 2} to 20 μC/cm ² , preferably about 3 μC/cm ² to 10 μC/cm ² , and in the case of extreme ultraviolet light, The exposure is performed so that it becomes about 0.1 mJ/cm ² to 20 mJ/cm ² , preferably about 3 mJ/cm ² to 15 mJ/cm ^2.

<Step (iii) Development step> The developer used in step (iii) (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 alkaline aqueous solution.

〔Alkaline developer〕 As the alkaline developer, a quaternary ammonium salt represented by tetramethylammonium hydroxide can be preferably used. In addition to this, inorganic bases, primary to tertiary amines, alkanolamines, and cyclic amines can also be used. Alkaline aqueous solutions such as amines. Furthermore, the alkaline developer may contain an appropriate amount of at least one of alcohols and surfactants. The alkali concentration of the alkaline 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 using an alkaline developer is preferably 10 seconds to 300 seconds. The alkali concentration, pH, and development time of the alkaline developer can be appropriately adjusted according to the formed pattern.

〔Organic developer〕 The organic developer is preferably 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.

-Ketone solvent- Examples of ketone solvents include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methylpentyl ketone), 4-heptanone, 1- Hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetonylacetone, Ionone, diacetone alcohol, acetyl carbinol, acetophenone, methyl naphthyl ketone, isophorone, and propylene carbonate, etc.

-Ester solvent- Examples of ester solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol Monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-Methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, butyl butyrate, 2 -Methyl hydroxyisobutyrate, isoamyl acetate, isobutyl isobutyrate, and butyl propionate, etc.

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

A plurality of the solvents may be mixed, or may be mixed with solvents or water other than the above. The water content of the entire developer is preferably less than 50% by mass, more preferably less than 20% by mass, still more preferably less than 10% by mass, and particularly preferably contains substantially no water. Relative to the total amount of the developer, 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 still more preferably 90% by mass Above and 100% by mass or less, particularly preferably 95% by mass or more and 100% by mass or less.

-Surfactant- The organic developer may contain a known surfactant in an appropriate amount as necessary. The content of the surfactant relative to the total mass of the developer is preferably 0.001% by mass to 5% by mass, more preferably 0.005% by mass to 2% by mass, and still more preferably 0.01% by mass to 0.5% by mass.

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

〔Development method〕 As a development method, for example, a method of immersing a substrate in a tank filled with a developer solution for a fixed period of time (dipping method); a method of using surface tension to deposit the developer solution on the surface of the substrate and standing still for a fixed period of time (puddle method) ); the method of spraying developer on the surface of the substrate (spray method); or the method of continuously spraying the developer on the substrate rotating at a fixed speed while scanning the developer spray nozzle at a fixed speed (dynamic distribution method), etc.

It is also possible to combine the step of developing using an alkaline aqueous solution (alkaline development step) and the step of developing using a developer containing an organic solvent (organic solvent development step). This allows pattern formation not only to dissolve the intermediate exposure intensity area, and therefore it is possible to form a finer pattern.

<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 forming method of the present invention may include multiple pre-heating steps. The pattern forming method of the present invention preferably includes a post-exposure heating (PEB: Post Exposure Bake) step after the exposure step and before the development step. The pattern forming method of the present invention may include a heating step after multiple exposures. The heating temperature is preferably 70°C to 130°C, more preferably 80°C to 120°C in any of the pre-heating step and the post-exposure heating step. The heating time in any of the pre-heating step and the post-exposure heating step is preferably 30 seconds to 300 seconds, more preferably 30 seconds to 180 seconds, and still more preferably 30 seconds to 90 seconds. Heating can be performed by the mechanism included in the exposure device and the developing device, or by using a heating plate or the like.

<Steps of forming resist underlayer film> 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 forming step. The step of forming a resist underlayer film is to form a resist underlayer film (for example, spin on glass (Spin On Glass, SOG), spin on carbon (Spin On Carbon, SOC), etc.) between the resist film and the support. Anti-reflective film, etc.) steps. As the resist underlayer film, a known organic or inorganic material can be suitably used.

＜Protection film formation procedure＞ The pattern forming method of the present invention may further include a step of forming a protective film (protective film forming step) before the development step. The protective film forming step is a step of forming a protective film (top coat layer) on the upper layer of the resist film. As the protective film, a known material can be suitably used. For example, U.S. Patent Application Publication No. 2007/0178407 Specification, U.S. Patent Application Publication No. 2008/0085466 Specification, U.S. Patent Application Publication No. 2007/0275326 Specification, U.S. Patent Application Publication No. 2016/ The protective film forming composition disclosed in specification 0299432, specification of U.S. Patent Application Publication No. 2013/0244438, and International Publication No. 2016/157988. The composition for forming a protective film is preferably one containing the acid diffusion control agent. You may form a protective film on the upper layer of the resist film containing the said hydrophobic resin.

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

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

[In the case of a development step using an organic developer] The rinsing liquid used in the rinsing step after the development step using a developer containing an organic solvent is not particularly limited as long as it does not dissolve the resist pattern, and a solution containing a general organic solvent can be used. As the eluent, it is preferable to use an eluent 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. Lotion. Specific examples of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents include the same ones as those described in the developer containing an organic solvent. As the rinsing liquid used in the rinsing step at this time, a rinsing liquid containing a monohydric alcohol is more preferable.

Examples of monohydric alcohols used in the rinsing step include linear, branched, or cyclic monohydric alcohols. Specific examples include: 1-butanol, 2-butanol, 3-methyl-1-butanol, tertiary butanol, 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 methyl isobutyl methanol. 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 methyl Isobutyl methanol and so on.

Each component may mix multiple types, and may mix and use with organic solvents other than the said. The water content in the rinsing liquid is preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 3% by mass or less. By setting the moisture content to 10% by mass or less, good development characteristics can be obtained.

The eluent may contain an appropriate amount of surfactant. In the rinsing step, a rinsing liquid containing an organic solvent is used to clean the substrate that has been developed with an organic developer. The method of cleaning treatment is not particularly limited. For example, it can be applied: a method of continuously spraying rinsing liquid on a substrate rotating at a fixed speed (spin coating method), and a method of immersing the substrate in a tank filled with rinsing liquid for a fixed period of time (Dipping method), or a method of spraying rinsing liquid on the surface of the substrate (spray method), etc. Among them, it is preferable to perform a cleaning process by a spin coating method. After cleaning, the substrate is rotated at a rotation speed of 2,000 rpm to 4,000 rpm (revolutions per minute) to remove the eluent from the substrate. In addition, it is also preferable to include a heating step (Post Bake) after the rinsing step. Through the heating step, the developer and rinsing liquid remaining between and inside the patterns are removed. In the heating step after the rinsing step, the heating temperature is preferably 40°C to 160°C, more preferably 70°C to 95°C. The heating time is preferably 10 seconds to 3 minutes, more preferably 30 seconds to 90 seconds.

＜Improvement of surface roughness＞ For the pattern formed by the pattern forming method of the present invention, a method of improving the surface roughness of the pattern can be applied. As a method of improving the surface roughness of the pattern, for example, a method of processing a resist pattern by a plasma containing hydrogen-containing gas disclosed in the specification of U.S. Patent Application Publication No. 2015/0104957 can be cited. In addition to this, Japanese Patent Laid-Open No. 2004-235468, U.S. Patent Application Publication No. 2010/0020297, "Proc. of SPIE (The International Society for Optical Engineering)) "(Vol. 8328 83280N-1) "EUV Resist Curing Technique for LWR Reduction and Etch Selectivity Enhancement" is a well-known method described in "EUV Resist Curing Technique for LWR Reduction and Etch Selectivity Enhancement." In addition, the resist pattern formed by the method can be used, for example, as a core material for the spacer process disclosed in Japanese Patent Laid-Open No. 3-270227 and U.S. Patent Application Publication No. 2013/0209941 ( Core).

(Method of manufacturing electronic components) The manufacturing method of the electronic component of this invention includes the pattern formation method of this invention. The electronic components manufactured by the method of manufacturing electronic components of the present invention can be preferably mounted on electrical and electronic equipment (for example, home appliances, office automation (OA) related equipment, media related equipment, optical equipment, and communication equipment, etc.) )in. [Example]

Examples are listed below to more specifically describe the embodiments of the present invention. The materials, usage amount, ratio, processing content, and processing order shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the embodiment of the present invention. Therefore, the scope of the embodiments of the present invention is not limited to the specific examples shown below. In addition, unless otherwise specified, "parts" and "%" are quality standards.

<Resin (A)> The structure of the resin (A-1 to A-7) used is shown below. Furthermore, the weight average molecular weight (Mw), number average molecular weight (Mn), and degree of dispersion (Mw/Mn) of the resin are measured by GPC (carrier: tetrahydrofuran (THF)) as described above. Styrene conversion amount). In addition, the composition ratio of the resin (the content ratio of each repeating unit to all repeating units, unit: mole % ^{) was measured by 13} C-nuclear magnetic resonance (NMR). Pd represents the molecular weight distribution (Mw/Mn).

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

Refer to PCT/JP2018/018239 (International Publication No. 2018/212079) for the value of the glass transition temperature (Tg) when the monomer corresponding to each repeating unit of the resin in this specification and the examples is made into a homopolymer. The record.

＜Photoacid generator (B-1)＞ The structure of the photoacid generator (B-1) used is shown below. Bu represents n-butyl.

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＜Photoacid generator (B-2)＞ The structure of the photoacid generator (B-2) used is shown below.

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

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The following shows the surfactants used. W-1: PF6320 (manufactured by OMNOVA (stock)) W-2: Megafac F176 (manufactured by DIC (stock); fluorine series) W-3: Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.; silicon-based)

The following shows the solvents used. SL-1: Propylene glycol monomethyl ether (1-methoxy-2-propanol) SL-2: Propylene glycol monomethyl ether acetate (1-methoxy-2-acetoxypropane) SL-3: 2-Heptanone SL-4: Ethyl Lactate SL-5: γ-butyrolactone SL-6: Propyl Carbonate

<Preparation of sensitized radiation or radiation-sensitive resin composition> Each component shown in Table 1 was mixed so that it might become a solid content concentration (mass %) described in Table 1, and a solution was obtained. Then, the obtained solution was filtered with a polyethylene filter having a pore size of 3 μm, thereby preparing a sensitizing radiation-sensitive or radiation-sensitive resin composition (resist composition). In the resist composition, the so-called solid content in this embodiment refers to all components other than the solvent. The obtained resist composition was used in Examples and Comparative Examples. In Table 1, the content (mass %) of each component other than the solvent means the content ratio with respect to the entire resist composition including the solvent. In addition, the content ratio (mass %) of the solvents used with respect to all solvents is described in Table 1. In Table 1, "the amount of (B-2) relative to the amount of (B-1)" represents the content (mass%) of the photoacid generator (B-2) relative to the photoacid generator (B-1) content. The photoacid generator (B-2) is dissolved in the solvent used in a predetermined amount and diluted to adjust the concentration. In Table 1, the "pKa" in the column of the photoacid generator (B-1) is the pKa of the acid generated from the photoacid generator (B-1), and the "pKa" in the column of the photoacid generator (B-2) "Is the pKa of the acid generated from the photoacid generator (B-2), and the "pKa" in the acid diffusion control agent column is the pKa of the conjugate acid of the acid diffusion control agent.

[Table 1] Resist composition Resin Photo acid generator (B-1) Photo acid generator (B-2) Acid diffusion control agent Surfactant Solvent Solid content concentration (mass%) The amount of (B-2) relative to the amount of (B-1) (mass%) species Content (mass%) species pKa Content (mass%) species pKa Content (×10 ^-2 mass%) species pKa Content (mass%) species Content (mass%) Solvent 1 The ratio of solvent 1 (mass%) Solvent 2 The ratio of solvent 2 (mass%) R-1 A-4 27.63 T-3 -6.54 0.342 P-7 3.01 0.000342 D-1 7.77 0.0084 W-2 0.02 SL-1 80 SL-2 20 28 0.001 R-2 A-1 32.56 T-5 -3.26 0.403 P-1 1.35 0.004030 D-4 10.48 0.01 W-1 0.04 SL-1 40 SL-4 60 33 0.01 R-3 A-2 35.52 T-4 -2.70 0.439 P-9 4.30 0.013170 D-3 11.24 0.011 W-2 0.02 SL-2 30 SL-5 70 36 0.03 R-4 A-4 27.63 T-1 -3.57 0.342 P-2 1.83 0.003078 D-2 11.24 0.0084 W-1 0.03 SL-1 50 SL-2 50 28 0.009 R-5 A-4 27.63 T-3 -3.27 0.342 P-5 1.07 0.034200 D-1 7.77 0.0084 W-2 0.02 SL-1 80 SL-2 20 28 0.10 R-6 A-7 33.55 T-6 -3.36 0.415 P-2 1.83 0.020750 D-5 9.99 0.01 W-2 0.02 SL-1 50 SL-2 50 34 0.05 R-7 A-4 27.63 T-3 -3.27 0.342 P-8 4.79 0.000342 D-1 7.77 0.0084 W-2 0.02 SL-1 80 SL-4 20 28 0.001 R-8 A-5 37.49 T-1 -3.57 0.464 P-7 3.01 0.003712 D-2 11.24 0.011 W-1 0.04 SL-1 50 SL-2 50 38 0.008 R-9 A-3 26.64 T-1 -3.57 0.329 P-7 3.01 0.016450 D-2 11.24 0.0081 W-1 0.03 SL-1 50 SL-2 50 27 0.05 R-10 A-3 26.64 T-5 -3.26 0.329 P-6 1.97 0.003290 D-2 8.51 0.0081 W-1 0.02 SL-2 100 - - 27 0.01 R-11 A-6 33.55 T-7 -3.36 0.415 P-5 1.07 0.020750 D-5 9.99 0.01 W-2 0.02 SL-1 50 SL-2 50 34 0.05 R-12 A-1 32.56 T-2 -0.03 0.403 P-5 1.07 0.036270 D-4 10.48 0.01 W-2 0.04 SL-3 70 SL-5 30 33 0.09 R-13 A-3 26.64 T-2 -0.03 0.329 P-4 0.53 0.001316 D-4 10.48 0.0081 W-1 0.03 SL-1 50 SL-2 50 27 0.004 R-14 A-2 35.52 T-5 -3.26 0.439 P-4 0.53 0.004390 D-3 11.24 0.011 W-3 0.03 SL-3 40 SL-6 60 36 0.01 R-15 A-4 27.63 T-3 -3.27 0.342 P-3 1.48 0.034200 D-2 7.77 0.0084 W-2 0.02 SL-1 80 SL-2 20 28 0.10 R-16 A-4 27.63 T-1 -3.57 0.342 - - 0 D-2 7.77 0.0084 W-2 0.02 SL-1 80 SL-2 20 28 - R-17 A-4 27.63 T-3 -3.27 0.342 P-5 1.07 0.04 D-1 7.77 0.0084 W-2 0.02 SL-2 100 - - 28 0.11 R-18 A-4 27.63 P-5 1.07 0.342 P-8 4.79 0.02 D-3 11.24 0.0084 W-1 0.02 SL-2 50 SL-5 50 28 0.05 R-19 A-3 8.88 T-1 -3.57 0.110 P-7 3.01 0.005500 D-2 11.24 0.0027 W-1 0.03 SL-1 50 SL-2 50 9 0.05

The content of the photoacid generator (B-2) is measured as follows. A 10% by mass acetonitrile solution of the resist composition was prepared, and filtered with a polytetrafluoroethylene (PTFE) filter (DISMIC-25JP, manufactured by ADVANTEC) with a pore size of 0.20 μm. Gas chromatography (GC) of WAX series column (DB-HeavyWAX (#123-7162), manufactured by Agilent Technologies) FID detector (Agilent-6890A, manufactured by Agilent Technologies) The analysis was performed using a device (Agilent-6890A, manufactured by Agilent Technologies) method. The content of (B-2) was quantified by using the absolute calibration curve method of each compound.

<Pattern formation method (1): KrF exposure, alkaline aqueous solution development> Using the spin coater "ACT-8" manufactured by Tokyo Electronics, on an 8-inch Si substrate (Advanced Materials Technology) that has been treated with hexamethyldisilazane (hereinafter, also referred to as "substrate" )) No anti-reflective layer is provided on the substrate, and the prepared resist composition is added dropwise while the substrate is in a static state. After the dripping is completed, the substrate is rotated, and the rotation speed is maintained at 500 rpm for 3 seconds, then at 100 rpm for 2 seconds, then at 500 rpm for 3 seconds, and again at 100 rpm for 2 seconds, and then increase to The film thickness is set at a rotation speed (1200 rpm) and maintained for 60 seconds. After that, heating and drying were performed on a hot plate at 130°C for 60 seconds to form a positive resist film with a film thickness of 3 μm. For this resist film, a mask having a line and space pattern with a line width of 250 nm and a line width of 750 nm in the space part of the pattern formed after reduced projection exposure and development was used, and KrF excimer mine was used. Scanner (manufactured by ASML, PAS5500/850C, wavelength 248 nm), pattern exposure was performed under the exposure conditions of NA=0.68 and σ=0.60. After irradiation, bake at 130°C for 60 seconds, use 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution as an alkaline developer and immerse for 60 seconds, rinse with pure water for 30 seconds and dry , So as to form a line and space pattern with a line width of 250 nm in the space part and a line width of 750 nm in the line part. According to the above procedure, a patterned wafer for evaluation having a substrate and a pattern formed on the surface of the substrate was obtained.

<Performance evaluation> [Pattern rectangularity] Observe the cross-sectional shape of the line and space pattern with a line width of 250 nm/line width of 750 nm/film thickness of 3 μm in the space part, using a length measuring scanning electron microscope (SEM, _{S-9380II of Hitachi, Ltd.), measured the line width (H T} ) of the space from the upper surface of the resist pattern toward the 0.3 μm part of the substrate in the film thickness direction, and the distance from the resist pattern. _{The line width (H M} ) of the space where the upper surface faces the substrate 1.5 μm in the film thickness direction, and the line width (H M) of the space where the upper surface of the resist pattern faces the substrate 2.7 μm in the film thickness direction _B ), calculate the average value, and show it in Table 3 below. Further, in Table 3, for the evaluation of A or B who also describes the difference between the target critical dimension H _T (Critical Dimension, CD) (250 nm) in the. Value of the difference H _T and the target CD is smaller the better. In addition, the obtained values were used for evaluation based on the criteria described in Table 2 below, and are shown in Table 3 below.

[Table 2] 0 nm≦H _T -H _B ＜100 nm 0 nm≦H _T -H _M ＜50 nm 0 nm≦H _M -H _B ＜50 nm A Satisfy Satisfy Satisfy B Satisfy Not satisfied Satisfy B Satisfy Satisfy Not satisfied C Not satisfied Satisfied or dissatisfied C Satisfy Not satisfied Not satisfied 0 nm≦H _T -H _B ＜100 nm 0 nm≦H _T -H _M ＜100 nm C Satisfy Not satisfied

[table 3] Resist composition H _T (nm) H _M (nm) H _B (nm) Rectangularity of pattern H _T and the difference between the target CD (250 nm) (nm) of Example 1 R-1 281 212 186 B 31 Example 2 R-2 275 227 180 A 25 Example 3 R-3 268 233 195 A 18 Example 4 R-4 286 242 190 B 36 Example 5 R-5 262 226 193 A 12 Example 6 R-6 268 228 188 A 18 Example 7 R-7 288 233 195 B 38 Example 8 R-8 320 260 224 B 70 Example 9 R-9 258 234 210 A 8 Example 10 R-10 274 217 187 B twenty four Example 11 R-11 269 229 185 A 19 Example 12 R-12 270 224 181 A 20 Example 13 R-13 312 252 223 B 62 Example 14 R-14 275 226 185 A 25 Example 15 R-15 262 225 188 A 12 Comparative example 1 R-16 346 227 182 C - Comparative example 2 R-17 112 235 195 C - Comparative example 3 R-18 170 120 10 C - Comparative example 4 R-19 The target film thickness could not be formed, and evaluation could not be performed.

Comparative Example 3 in Comparative Example 1, the difference between the offset value and the target CD H _T is large, the value can not be calculated.

According to the results of Table 3, the pattern cross-sectional shape of the thick film obtained from the composition of the present invention has excellent rectangularity. [Industrial availability]

According to the present invention, it is possible to provide an actinic ray-sensitive or radiation-sensitive resin composition, an actinic ray-sensitive or radiation-sensitive resin composition, and an actinic ray-sensitive or radiation-sensitive film having excellent rectangularity in the cross-sectional shape of the pattern obtained in the pattern formation of a thick film, and use The pattern formation method of the sensitizing radiation-sensitive or radiation-sensitive resin composition and the manufacturing method of the electronic component are described.

Although the present invention has been described in detail with reference to specific embodiments, it is clear to those having ordinary knowledge in the technical field to which the present invention pertains that various changes or modifications can be added without departing from the spirit and scope of the present invention. This application is based on a Japanese patent application (Japanese Patent Application No. 2019-158895) filed on August 30, 2019, and the content is incorporated into this application as a reference.

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Claims (14)

A sensitizing ray-sensitive or radiation-sensitive resin composition, the solid content of which is 10% by mass or more, in the sensitizing ray-sensitive or radiation-sensitive resin composition, The sensitizing radiation or radiation-sensitive resin composition contains resin (A), photoacid generator (B-1), photoacid generator (B-2), and acid diffusion control agent (D), The pKa of the acid generated from the photoacid generator (B-1) is less than 0, The pKa of the acid generated from the photo acid generator (B-2) is greater than the pKa of the acid generated from the photo acid generator (B-1), The content of the photo acid generator (B-2) relative to the content of the photo acid generator (B-1) is 0.001% by mass or more and 0.10% by mass or less. _{The sensitizing radiation-sensitive or radiation-sensitive resin composition according to claim 1} , wherein the pKa of the acid generated from the photoacid generator (B-1) is E 1, and the photoacid generator (B-1) is When the pKa of the acid generated by the generator (B-2) is E ₂ , E ₂ -E ₁ is 3 or more. The sensitized radiation-sensitive or radiation-sensitive resin composition according to claim 1 or claim 2, wherein the acid diffusion control agent (D) is less than or equal to the content of the photoacid generator (B-1) The content is 0.5% by mass or more and 10.0% by mass or less. The actinic radiation-sensitive or radiation-sensitive resin composition according to claim 1 or 2, wherein the resin (A) is a resin having a group that is decomposed by the action of an acid to increase the polarity. The actinic radiation-sensitive or radiation-sensitive resin composition according to claim 1 or 2, wherein the resin (A) is a resin containing a repeating unit having a phenolic hydroxyl group. The photosensitive radiation-sensitive or radiation-sensitive resin composition according to claim 5, wherein the resin (A) has a repeating unit derived from hydroxystyrene. The sensitized radiation-sensitive or radiation-sensitive resin composition according to claim 1 or claim 2, wherein the resin (A) is a resin containing a repeating unit represented by the following general formula (I),

In the general formula (I), 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; wherein, R ₄₂ may be bonded _{to Ar 4} To form a ring, R _{42 in this case} represents a single bond or an alkylene; X ₄ represents a single bond, -COO-, or -CONR ₆₄ -, R ₆₄ represents a hydrogen atom or an alkyl group; L ₄ represents a single bond or Divalent linking group; Ar ₄ represents an (n+1) valent aromatic hydrocarbon group, and when it _{bonds with R 42} to form a ring, it represents an (n+2) valent aromatic hydrocarbon group; n represents 1 to 5 Integer. The sensitizing radiation-sensitive or radiation-sensitive resin composition according to claim 1 or claim 2, wherein the acid diffusion control agent (D) is a basic compound (DA), which is irradiated by actinic rays or radiation On the other hand, basic compounds (DB) that have reduced or disappeared basicity, low-molecular compounds (DD) that have a nitrogen atom and a group detached by the action of an acid, or onium salt compounds (DE) that have a nitrogen atom in the cation part . The sensitizing radiation-sensitive or radiation-sensitive resin composition according to claim 1 or claim 2, wherein the acid diffusion control agent (D) has any one of the following formulas (D1) to (D5) The compound of the structure represented,

In formula (D1) and formula (D5), R ²⁰⁰ , R ²⁰¹ and R ²⁰² each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group; R ²⁰¹ and R ²⁰² may be bonded to each other to form a ring; R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ and R ²⁰⁶ each independently represent an alkyl group. The sensitizing radiation-sensitive or radiation-sensitive resin composition according to claim 1 or claim 2, wherein the photoacid generator (B-2) is any one of the following formula d1-1 to formula d1-3 The compound represented by

In formulas d1-1 to d1-3, R ⁵¹ represents an organic group; Z ^2c represents a hydrocarbon group; wherein, ^{the hydrocarbon group represented by Z 2c} is one where a carbon atom adjacent to a sulfur atom is not bonded with a fluorine atom; R ⁵² represents an organic group Group, Y ³ represents a single bond or a divalent linking group, Rf represents a substituent; R ⁵² and Rf can bond to form a ring; M ⁺ represents an ammonium cation, a cation or an iodo cation. The sensitizing radiation-sensitive or radiation-sensitive resin composition according to claim 1 or claim 2, wherein the photoacid generator (B-2) is any one of the following formula C-1 to formula C-3 The compound represented by

In formulas C-1 to C-3, R ¹ , R ² , and R ³ each independently represent an organic group; L ¹ represents a divalent linking group or a single bond that connects the cation site and the anion site; -X ^- represents an option from _{^{-COO -, -SO 3 -, -SO}} 2 -, and -N ^- anionic sites in -R ^4; R ⁴ represents the coupling portion with the adjacent nitrogen atom having a carbonyl group, a sulfo acyl, sulfinyl and At least one monovalent substituent in the group; R ¹ , R ² , R ³ , R ⁴ , and L ¹ may be bonded to each other to form a ring structure; in addition, in formula C-3, R ¹ to R ³ The combination of the two represents a divalent substituent, which can also be bonded to the nitrogen atom by a double bond. A sensitizing radiation or radiation-sensitive film, which is formed of the sensitizing radiation or radiation-sensitive resin composition according to any one of Claims 1 to 11, and has a film thickness of 1 μm or more. A pattern forming method has: (I) Using the sensitizing ray-sensitive or radiation-sensitive resin composition according to any one of Claims 1 to 11 to form a sensitizing ray-sensitive or radiation-sensitive film with a film thickness of 1 μm or more on a substrate A step of; (Ii) The step of irradiating the actinic ray or radiation-sensitive film with actinic rays or radiation; and (Iii) A step of developing the sensitizing ray-sensitive or radiation-sensitive film irradiated with actinic rays or radiation using a developing solution. A method for manufacturing an electronic component includes the pattern forming method as described in claim 13.