TWI780290B - Photosensitive radiation-sensitive or radiation-sensitive resin composition, manufacturing method of resin for photosensitive radiation-sensitive or radiation-sensitive resin composition, photosensitive radiation-sensitive or radiation-sensitive film, pattern forming method, and manufacturing method of electronic device - Google Patents

Abstract

The present invention provides a product that is excellent in resolving power and roughness characteristics and suppresses scum An actinic radiation-sensitive or radiation-sensitive resin composition with excellent CDU generation and excellent stability over time, containing the following (A) to (C), the content of the compound whose conjugate acid pKa is 4.0 or more relative to the total The solid content is 1 ppm or less on a mass basis. (A) A resin having a repeating unit represented by the general formula (1), which is decomposed by the action of an acid and has an increased solubility in an alkaline developer; (B) by irradiation with actinic rays or radiation A compound that generates an acid; (C) a fluorine-containing compound having a group that is decomposed by the action of an alkaline developer and whose solubility in an alkaline developer is increased.

Description

Actinic radiation-sensitive or radiation-sensitive resin composition, photosensitive Manufacturing method of resin for radiation-sensitive or radiation-sensitive resin composition, actinic radiation-sensitive or radiation-sensitive film, pattern forming method, and manufacturing method of electronic device

The present invention relates to an actinic radiation-sensitive or radiation-sensitive resin composition, a method for producing a resin for the actinic radiation-sensitive or radiation-sensitive resin composition, an actinic radiation-sensitive or radiation-sensitive film, a pattern forming method, and an electronic device The manufacturing method. More specifically, the present invention relates to a manufacturing process that can be preferably used in large scale integrated circuits (Large Scale Integration, LSI) and high-capacity microwafer manufacturing processes, mold manufacturing processes for nanoimprinting, and high Actinic radiation-sensitive or radiation-sensitive resin composition, actinic radiation-sensitive or radiation-sensitive resin composition for superlithography process and other photofabrication processes applicable to the manufacturing process of density information recording media Manufacturing method using resin, actinic radiation-sensitive or radiation-sensitive film, pattern forming method and manufacturing method of electronic device.

In the past, in the manufacturing process of semiconductor devices such as integrated circuits (Integrated Circuit, IC) and large-scale integrated circuits, microfabrication was performed by lithography using photoresist compositions. In recent years, with the high integration of integrated circuits, it is required to form ultra-fine patterns in the sub-micron region or the quarter-micron region. Subsequently, it was found that there is a tendency for the exposure wavelength to be shortened from g-rays to i-rays, and then to excimer laser light. Currently, ArF excimer lasers with a wavelength of 193nm are being developed. An exposure machine that emits light as a light source. Also, as a technique for further improving resolution, a so-called liquid immersion method in which a liquid with a high refractive index (hereinafter also referred to as "immersion liquid") is filled between a projection lens and a sample is being developed.

Also, currently, lithography using electron beam (EB), X-rays, extreme ultraviolet (EUV) and the like in addition to excimer laser light is being developed. Accordingly, chemically amplified resist compositions that are sensitive to various radiations effectively and have excellent sensitivity and resolution are being developed.

For example, Patent Document 1 describes an actinic radiation-sensitive or radiation-sensitive resin composition, which contains: a resin that is decomposed by the action of an acid and has an increased solubility in an alkaline developer; A compound that generates an acid when exposed to or radiation; and a fluorine-containing compound having a group that is decomposed by the action of an alkaline developer and has an increased solubility in an alkaline developer (also called "alkali decomposable fluorine-containing Compound"), thereby providing an actinic radiation-sensitive or radiation-sensitive resin composition excellent in sensitivity, resolution, roughness characteristics, pattern shape, and ability to suppress development defects.

[Prior Art Literature] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open No. 2014-167589

However, in recent years, there is a demand for a photosensitive device with excellent CDU (Critical Dimension Uniformity: Critical Dimension Uniformity) that further improves the resolution and roughness characteristics by further miniaturizing the formed pattern, and suppresses the generation of scum. chemical radiation or radiation sensitive resin composition. Also, it is required that a Actinic radiation-sensitive or radiation-sensitive resin composition capable of exhibiting excellent resolving power over a long period of time (excellent stability over time).

The object of the present invention is to provide an actinic radiation-sensitive or radiation-sensitive resin composition that is excellent in resolving power and roughness characteristics, suppresses the generation of scum, has excellent CDU, and is excellent in stability over time. Another object of the present invention is to provide a method for producing a resin for an actinic ray-sensitive or radiation-sensitive resin composition, and an actinic ray-sensitive or radiation-sensitive resin composition using the above-mentioned actinic ray-sensitive or radiation-sensitive resin composition. A radiation film, a method for forming a pattern, and a method for manufacturing an electronic device.

According to the research of the present inventors, when there is a compound with a conjugate acid pKa of 4.0 or more in an actinic radiation-sensitive or radiation-sensitive resin composition containing an alkali-decomposable fluorine-containing compound, if the content exceeds a certain range , the expected performance cannot be achieved. This is presumably because the alkali-decomposable fluorine-containing compound is decomposed by the action of the compound whose conjugate acid has a pKa of 4.0 or more.

Furthermore, the inventors of the present invention conducted further studies and found that the above-mentioned problems can be solved by reducing the content of the compound having a conjugate acid pKa of 4.0 or more to a certain amount or less. This is considered to be because, by setting the content of the compound whose pKa of the conjugate acid is 4.0 or more to a certain amount or less, even after a long period of time after the preparation of the actinic radiation-sensitive or radiation-sensitive resin composition, it is not easy to Decomposition of the alkali-decomposable fluorine-containing compound is caused, and the effect can be fully exerted.

That is, the present inventors found that the above-mentioned problems can be achieved by the following structure.

[1] An actinic radiation-sensitive or radiation-sensitive resin composition comprising the following (A) to (C), wherein the pKa of the conjugate acid in the actinic radiation-sensitive or radiation-sensitive resin composition is at least 4.0 The content of the compound is 1 ppm or less on a mass basis with respect to the total solid content of the above-mentioned actinic radiation-sensitive or radiation-sensitive resin composition.

(A) A resin having a repeating unit represented by the general formula (1), which is decomposed by the action of an acid and has an increased solubility in an alkaline developer; (B) by irradiation with actinic rays or radiation Acid-generating compounds; (C) fluorine-containing compounds having a group that is decomposed by the action of an alkaline developer and whose solubility in an alkaline developer is increased,

In the general formula (1), R ₁ represents a hydrogen atom or a monovalent organic group. X ₁ represents a divalent linking group. Y ₁ and Z ₁ each independently represent a monovalent organic group. Y ₁ and Z ₁ may be connected to form a ring.

[2] The actinic radiation-sensitive or radiation-sensitive resin composition according to [1], wherein the fluorine-containing compound (C) has a fluoroalkyl group.

[3] The actinic radiation-sensitive or radiation-sensitive resin composition as described in [1] or [2], wherein the fluorine-containing compound (C) has a repeating unit represented by the general formula (2).

In the general formula (2), R ₂₁ represents a hydrogen atom or a monovalent organic group. X ₂ represents a divalent linking group. R ₂₂ and R ₂₃ each independently represent a fluoroalkyl group. R ₂₄ represents a hydrogen atom, a fluorine atom, or a monovalent organic group.

[4] The actinic radiation-sensitive or radiation-sensitive resin composition as described in [3], wherein X ₂ in the above general formula (2) has a lactone structure.

[5] The actinic radiation-sensitive or radiation-sensitive resin composition according to any one of [1] to [4], wherein the molecular weight of the fluorine-containing compound (C) is 1,000 to 100,000.

[6] The actinic radiation-sensitive or radiation-sensitive resin composition according to any one of [1] to [5], wherein relative to the total solid content of the above-mentioned actinic radiation-sensitive or radiation-sensitive resin composition, Content of the said fluorine-containing compound (C) is 0.1-10 mass %.

[7] The actinic radiation-sensitive or radiation-sensitive resin composition according to any one of [1] to [6], wherein relative to the total solid content of the above-mentioned actinic radiation-sensitive or radiation-sensitive resin composition, Content of the said fluorine-containing compound (C) is 0.1-5 mass %.

[8] The actinic radiation-sensitive or radiation-sensitive resin composition as described in any one of [1] to [7], wherein the above-mentioned resin (A) further has a compound represented by the following general formula (H-1): the repeating unit.

[Chem 3]

In the general formula (H-1), R ₃₁ , R ₃₂ and R ₃₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. R ₃₃ may bond with Ar ₃ to form a ring, and R ₃₃ in this case represents an alkylene group.

X ₃ represents a single bond or a divalent linking group.

Ar ₃ represents an aromatic ring group with a valence of (n3+1), and when it is bonded to _R33 to form a ring, it represents an aromatic ring group with a valence of (n3+2).

n3 represents an integer from 1 to 4.

[9] The actinic radiation-sensitive or radiation-sensitive resin composition as described in any one of [1] to [8], wherein Y in the above general formula ( ₁ ) is an alicyclic ring having 3 to 10 carbon atoms base.

[10] The actinic radiation-sensitive or radiation-sensitive resin composition according to any one of [1] to [9], which contains an acid diffusion controller whose conjugate acid pKa is less than 4.0.

[11] The actinic radiation-sensitive or radiation-sensitive resin composition according to any one of [1] to [10], which is a chemically amplified positive resist composition.

[12] A method for producing a resin for an actinic radiation-sensitive or radiation-sensitive resin composition, comprising the step of washing the following (A) with an acidic aqueous solution.

(A) A resin having a repeating unit represented by the general formula (1), which is decomposed by the action of an acid and has an increased solubility in an alkaline developer,

In the general formula (1), R ₁ represents a hydrogen atom or a monovalent organic group. X ₁ represents a divalent linking group. Y ₁ and Z ₁ each independently represent a monovalent organic group. Y ₁ and Z ₁ may be connected to form a ring.

[13] A method for producing an actinic radiation-sensitive or radiation-sensitive resin composition, comprising the method for producing the resin described in [12].

[14] An actinic radiation-sensitive or radiation-sensitive film formed using the actinic radiation-sensitive or radiation-sensitive resin composition described in any one of [1] to [11].

[15] A method for forming a pattern, comprising: a resist film forming step of forming a resist film using the actinic radiation-sensitive or radiation-sensitive resin composition described in any one of [1] to [11] an exposing step of exposing the above-mentioned resist film; and a developing step of developing the exposed above-mentioned resist film using a developing solution.

[16] A method of manufacturing an electronic device, including the pattern forming method described in [15].

According to the present invention, it is possible to provide a photosensitized chemical having excellent resolution and roughness characteristics, suppressing the generation of scum, excellent CDU, and excellent stability over time. Linear or radiation-sensitive resin composition. According to the present invention, it is possible to provide a method for producing a resin for an actinic radiation-sensitive or radiation-sensitive resin composition, and an actinic radiation-sensitive or radiation-sensitive film and pattern using the above-mentioned actinic radiation-sensitive or radiation-sensitive resin composition Forming method and manufacturing method of electronic device.

Hereinafter, the present invention will be described in detail.

The description of the constituent elements described below may be based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.

"Actinic ray" or "radiation" in this specification refers to, for example, the bright line spectrum of mercury lamps, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV: Extreme Ultraviolet), X-rays, soft X-rays and Electron beam (EB: Electron Beam) and the like. "Light" in this specification refers to actinic rays or radiation. "Exposure" in this specification includes not only exposure using the bright line spectrum of a mercury lamp, extreme ultraviolet rays represented by excimer lasers, extreme ultraviolet rays, X-rays, and EUV, but also exposures using electron beams, unless otherwise specified. And the drawing of particle beams such as ion beams.

In this specification, "~" is used in the meaning which includes the numerical value described before and after it as a lower limit and an upper limit.

In this specification, (meth)acrylate means at least one of acrylate and methacrylate. Moreover, (meth)acrylic acid means at least 1 sort(s) of acrylic acid and methacrylic acid.

In this specification, the weight average molecular weight (Mw), number average molecular weight (Mn) and degree of dispersion (also referred to as molecular weight distribution) (Mw/Mn) of resins are defined as, based on GPC measurement by GPC (Gel Permeation Chromatography) device (HLC-8120GPC manufactured by TOSOH CORPORATION) (solvent: tetrahydrofuran, flow rate (sample injection volume): 10 μL, column: TSK gel manufactured by TOSOH CORPORATION Multipore HXL-M, column temperature: 40°C, flow rate: 1.0 mL/min, detector: polystyrene conversion value of differential refractive index detector (Refractive Index Detector).

Regarding the notation of a group (atomic group) in this specification, the notation of a substituted or unsubstituted notation includes a group having no substituent and a group having a substituent. For example, "alkyl" includes not only an alkyl group having no substituent (unsubstituted alkyl group), but also an alkyl group having a substituent (substituted alkyl group). Also, the "organic group" in the present specification refers to a group containing at least one carbon atom.

The actinic radiation-sensitive or radiation-sensitive resin composition of the present invention (hereinafter also referred to as the "composition of the present invention") is an actinic radiation-sensitive or radiation-sensitive resin composition containing the following (A) to (C) , in the actinic ray-sensitive or radiation-sensitive resin composition, the content of the compound whose conjugate acid pKa is 4.0 or more is 1 ppm on a mass basis relative to the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition (parts per million: parts per million) below.

(A) A resin having a repeating unit represented by the general formula (1), which is decomposed by the action of an acid and has an increased solubility in an alkaline developer

(B) Compounds that generate acids by irradiation with actinic rays or radiation

(C) A fluorine-containing compound having a group that is decomposed by the action of an alkaline developer and has an increased solubility in an alkaline developer

In the general formula (1), R ₁ represents a hydrogen atom or a monovalent organic group. X ₁ represents a divalent linking group. Y ₁ and Z ₁ each independently represent a monovalent organic group. Y ₁ and Z ₁ may be connected to form a ring.

The composition of the present invention is preferably a resist composition, and may be a positive resist composition or a negative resist composition. In addition, it may be a resist composition for alkaline development, or may be a resist composition for organic solvent development. Among them, a positive resist composition and a resist composition for alkaline development are preferable.

Also, the composition of the present invention is preferably a chemically amplified resist composition, more preferably a chemically amplified positive resist composition.

[Content of the compound whose pKa of the conjugate acid is 4.0 or more]

In the composition of the present invention, the content of the compound whose pKa of the conjugate acid is 4.0 or more is 1 ppm or less on a mass basis relative to the total solid content of the composition of the present invention (that is, 1×10 to the total solid content). ^-4 % by mass or less).

As described above, it can be inferred that by setting the content of the compound having a conjugate acid pKa of 4.0 or more in the composition of the present invention to 1 ppm or less on a mass basis with respect to the total solid content of the composition of the present invention, the content of the compound can be suppressed. The decomposition of the fluorine compound (C) can solve the above-mentioned problems.

pKa (acid dissociation constant) means pKa in an aqueous solution, and is defined in Chem. Handbook (II) (Revised 4th Edition, 1993, edited by the Chemical Society of Japan, Maruzen. Inc.). Lower pKa values indicate greater acid strength. Specifically, the pKa in an aqueous solution can be actually measured by measuring the acid dissociation constant at 25° C. using an infinitely diluted aqueous solution. Alternatively, the packaged software 1 described below can also be used to calculate the value based on Hammett's substituent constant and a database of known literature values. All the pKa values described in this specification represent the values obtained by calculation using the packaged software.

Package software 1: Advanced Chemistry Development (ACD/Labs) software V8.14 supports Solaris system (1994-2007 ACD/Labs).

The content of the compound whose conjugate acid has a pKa of 4.0 or more in the composition of the present invention is preferably 1 ppm or less, more preferably 0.5 ppm or less, and 0.3 ppm on a mass basis relative to the total solid content of the composition of the present invention The following are further preferred. In addition, the lower limit of the content of the compound whose pKa of the conjugate acid is 4.0 or more in the composition of the present invention is not particularly limited, for example, it is more than the detection limit of the measuring device (for example, 0.1 ppm or more).

The method for making the content of the compound having a conjugate acid pKa of 4.0 or more in the composition of the present invention to be 1 ppm or less on a mass basis relative to the total solid content of the composition of the present invention is not particularly limited, and may be Enumerate (1) wash the resin (A) with an acidic aqueous solution and use it in the composition of the present invention; (2) as the acid diffusion control agent used in the composition of the present invention, use a conjugate acid with a pKa of less than 4.0 ;Wait.

Regarding the above (1), in the present invention, as the resin (A), one having a repeating unit represented by the general formula (1), decomposed by the action of an acid and having an increased solubility in an alkaline developing solution is used. However, in the synthesis of the resin (A), an amine compound is usually used. In the past, since the amine compound used here was not specially treated and the resin was directly used for the preparation of the composition, the amine compound remained in the resin, and as a result, the pKa of the conjugate acid in the composition was 4.0 or more. The content of the compound exceeds 1 ppm on a mass basis with respect to the total solid content of the composition.

For example, by washing the synthesized resin (A) with an acidic aqueous solution and using it, the content of the compound whose pKa of the conjugate acid in the composition is 4.0 or more can be set to 1 ppm or less on a mass basis with respect to the total solid content .

The acidic aqueous solution is not particularly limited as long as it is an aqueous acidic solution. As the acid that can be used in the acidic aqueous solution, inorganic acids such as hydrochloric acid may be used, and organic acids such as oxalic acid may be used. The concentration of the acid in the acidic aqueous solution is not particularly limited, and when hydrochloric acid is used, the concentration is preferably 0.01 mol/L to 0.1 mol/L. When using oxalic acid, its concentration is preferably 0.05 mol/L to 0.5 mol/L.

There is no particular limitation on the cleaning method when cleaning the resin (A) with an acidic aqueous solution. For example, the powder of the resin (A) is dissolved in 30 times the amount of ethyl acetate, and the same amount of the solution is used for cleaning. After that, it is better to wash with the same amount of distilled water. It is preferable to wash with this distilled water in order to remove the acid originating in an acidic aqueous solution.

In addition, as the acid diffusion control agent of the above (2), those whose pKa of the conjugate acid is less than 4.0 will be described later.

[(A) A resin having a repeating unit represented by the general formula (1), decomposed by the action of an acid and having an increased solubility in an alkaline developer]

(A) Resin (also referred to as "resin (A)") which has a repeating unit represented by general formula (1), is decomposed by the action of acid and has increased solubility in an alkaline developer. illustrate.

The repeating unit represented by the general formula (1) is a repeating unit having a group (also referred to as "acid decomposable group") that decomposes to generate a polar group by the action of an acid. Since the resin (A) has a repeating unit represented by the general formula (1), it is decomposed by the action of an acid and has increased solubility in an alkaline developer.

In the general formula (1), R ₁ represents a hydrogen atom or a monovalent organic group. X ₁ represents a divalent linking group. Y ₁ and Z ₁ each independently represent a monovalent organic group. Y ₁ and Z ₁ may be connected to form a ring.

In the general formula (1), R ₁ represents a hydrogen atom or a monovalent organic group.

When R ₁ represents a monovalent organic group, the carbon number of the organic group is not particularly limited, but is preferably 1-20, more preferably 1-15, and still more preferably 1-8.

R ₁ preferably represents a hydrogen atom, an alkyl group or an alicyclic group, more preferably represents a hydrogen atom or an alkyl group.

The alkyl group for R1 is preferably _a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, second butyl group, hexyl group, 2-ethylhexyl group, octyl group, dodecyl group and the like with 20 carbon atoms The following alkyl group is more preferably an alkyl group having 8 or less carbon atoms, most preferably a methyl group.

_The alicyclic group for R1 may be monocyclic or polycyclic, and is preferably a monocyclic cycloalkyl group having 3 to 10 carbon atoms such as cyclopropyl, cyclopentyl, or cyclohexyl.

In the general formula (1), X ₁ represents a divalent linking group.

X ₁ preferably represents a keto group or a divalent aromatic ring group, and more preferably represents a divalent aromatic ring group.

、咪唑、苯并咪唑、三唑、噻二唑、噻唑等雜環之2價的芳香環基作為較佳例，最佳為伸苯基。 The divalent aromatic ring group includes, for example, arylylene groups having 6 to 18 carbon atoms such as phenylene, cresyl, and naphthyl, or, for example, thiophene, furan, pyrrole, benzothiophene, benzofuran, Benzopyrrole, three

, imidazole, benzimidazole, triazole, thiadiazole, thiazole and other heterocyclic divalent aromatic ring groups are preferred examples, most preferably phenylene groups.

In the general formula (1), Y ₁ represents a monovalent organic group.

The carbon number of the monovalent organic group represented by Y ₁ is not particularly limited, but is preferably 1-20, more preferably 1-15, and still more preferably 1-10.

The monovalent organic group represented by _Y1 is not particularly limited, but an alkyl group, an alicyclic group, and an aromatic group are preferable, and an alkyl group or alicyclic group is more preferable.

Specific examples of the alkyl group of _Y1 include methyl, ethyl, propyl, n-butyl, second-butyl, third-butyl, hexyl, and octyl.

The alicyclic group as _Y1 may be monocyclic or polycyclic, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, 1-adamantane group, 2-adamantyl group, etc.

The aromatic ring group as _Y1 may be an aryl group, an aralkyl group, a heterocyclic group, or the like. The aryl group is an aryl group having 6 to 15 carbon atoms, and specifically, phenyl, tolyl, naphthyl, anthracenyl and the like can be cited as preferable examples. As the aralkyl group, an aralkyl group having 6 to 20 carbon atoms is preferred, and an aralkyl group having 7 to 12 carbon atoms is more preferred. Specifically, a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group, etc. are mentioned. As the heterocyclic group, a heterocyclic group having 6 to 20 carbon atoms is preferred, and a heterocyclic group having 6 to 12 carbon atoms is more preferred.

From the viewpoint of etching resistance, Y ₁ preferably represents an alicyclic group having 3 to 10 carbon atoms, and more preferably represents an alicyclic group having 5 to 10 carbon atoms.

In the general formula (1), Z ₁ represents a monovalent organic group.

Examples of the monovalent organic group represented by Z ₁ include the same ones as those described above for the monovalent organic group represented by Y ₁ .

_In addition, the monovalent organic group represented by Z1 may be selected from the group including the alkyl group, alicyclic group, and aromatic group listed as the monovalent organic group represented by _Y1 above. The group consisting of alkenylene (for example, vinylene, propenyl, butylene, etc.), -S-, -O-, -CQ-, -SO ₂ -, -N(R ₀ )- or A group for linking with a divalent linking group obtained by combining a plurality of these. R ₀ is a hydrogen atom or an alkyl group (such as an alkyl group with 1 to 8 carbon atoms, specifically, methyl, ethyl, propyl, n-butyl, second butyl, hexyl, octyl, etc.) .

Z ₁ is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms.

In the general formula (1), Y ₁ and Z ₁ may be connected to form a ring. As the ring formed by connecting _Y1 and Z1, _an aliphatic oxygen-containing ring having 2 to 10 carbon atoms is preferable.

Although the specific example of the repeating unit represented by General formula (1) is shown below, it is not limited to these.

The repeating unit represented by the general formula (1) contained in the resin (A) may be one kind, or two or more kinds.

The content of the repeating unit represented by the general formula (1) in the resin (A) (total when multiple types are contained) is 5 mol% or more and 70 mol% with respect to all the repeating units in the resin (A) The following is preferred, more than 5 mol% and less than 60 mol% are more preferred, more than 10 mol% and less than 50 mol% are further preferred, and more than 10 mol% and less than 30 mol% are particularly preferred .

The resin (A) may contain repeating units other than the repeating unit represented by the general formula (1).

From the viewpoint of etching resistance, it is preferable that the resin (A) has a repeating unit represented by the following general formula (H-1).

In the general formula (H-1), R ₃₁ , R ₃₂ and R ₃₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. R ₃₃ may bond with Ar ₃ to form a ring, and R ₃₃ in this case represents an alkylene group.

X ₃ represents a single bond or a divalent linking group.

Ar ₃ represents an aromatic ring group with a valence of (n3+1), and when it is bonded to _R33 to form a ring, it represents an aromatic ring group with a valence of (n3+2).

n3 represents an integer from 1 to 4.

、咪唑、苯并咪唑、三唑、噻二唑、噻唑等雜環之芳香環基作為較佳例。 Ar ₃ represents an aromatic ring group having a valence of (n3+1). When n3 is 1, the divalent aromatic ring group includes, for example, arylylene groups having 6 to 18 carbon atoms such as phenylene, cresylylene, naphthylene, and anthracenyl, or, for example, thiophene, furan, pyrrole, etc. , benzothiophene, benzofuran, benzopyrrole, three

, imidazole, benzimidazole, triazole, thiadiazole, thiazole and other heterocyclic aromatic ring groups are preferred examples.

As a specific example of the (n3+1)-valent aromatic ring group when n3 is an integer of 2 or more, (n3-1) arbitrary hydrogens removed from the above-mentioned specific examples of the divalent aromatic ring group can be preferably mentioned. A group of atoms.

Examples of the divalent linking group of X ₃ include -COO- or -CONR ₆₄ -. R ₆₄ represents a hydrogen atom or an alkyl group.

The alkyl group of R ₆₄ in -CONR ₆₄ - of X ₃ includes the same ones as the alkyl groups of R ₆₁ to R ₆₃ .

X ₃ preferably represents a single bond, -COO- or -CONH-, more preferably represents a single bond or -COO-, and further preferably represents a single bond.

As Ar ₃ , an aromatic ring group having 6 to 18 carbon atoms is more preferable, and a phenyl ring group, a naphthalene ring group, and a biphenylene ring group are particularly preferable.

_Ar is preferably a phenyl ring group.

n3 represents an integer of 1 to 4, preferably representing 1 or 2, and more preferably representing 1.

Although the specific example of the repeating unit represented by General formula (H-1) is shown below, it is not limited to these. In the formula, a represents 1 or 2.

When the resin (A) contains the repeating unit represented by the general formula (H-1), the repeating unit represented by the general formula (H-1) contained in the resin (A) can be one kind, or two or more .

When the resin (A) contains a repeating unit represented by the general formula (H-1), the content of the repeating unit represented by the general formula (H-1) (total when multiple types are contained) relative to the resin (A) For all the repeating units in , the range of 3-98 mol% is preferred, the range of 10-90 mol% is more preferred, and the range of 25-85 mol% is further preferred.

Regarding the resin (A), in addition to the above-mentioned repeating structural unit, for the purpose of adjusting dry etching resistance, standard developer adaptability, substrate adhesion, resist profile (Profile), resolving power, heat resistance, sensitivity, etc. Various repeating units are possible.

Resin (A) can be synthesize|combined by a conventional method (for example, radical polymerization). As a general synthesis method, for example, there can be mentioned: (1) a blanket polymerization method in which polymerization is carried out by dissolving and heating a monomer type and an initiator in a solvent; The solution of the starter is added dropwise over 1 to 10 hours and then added to the heating solvent, such as the dropwise polymerization method.

The weight average molecular weight (Mw) of the resin (A) is preferably 1,000-200,000, more preferably 2,000-30,000, and still more preferably 3,000-25,000. The degree of dispersion (Mw/Mn) is usually 1.0-3.0, preferably 1.0-2.6, more preferably 1.0-2.0, and more preferably 1.1-2.0.

Resin (A) may be used individually by 1 type, and may use 2 or more types together.

In the composition, the content of the resin (A) is usually at least 20% by mass, preferably at least 40% by mass, more preferably at least 60% by mass, and still more preferably at least 80% by mass, based on the total solid content. The upper limit is not particularly limited, but is preferably at most 99.5% by mass, more preferably at most 99% by mass, and still more preferably at most 98% by mass.

In addition, the total solid content of the composition of the present invention refers to other components (components capable of constituting an actinic radiation-sensitive or radiation-sensitive film) other than the solvent.

[(B) Compounds that generate acid by irradiation with actinic rays or radiation]

(B) A compound (also referred to as a "photoacid generator") that generates an acid by irradiation with actinic rays or radiation will be described.

A photoacid generator is a compound that generates an acid upon irradiation with actinic rays or radiation.

As the photoacid generator, a compound that generates an organic acid by irradiation with actinic rays or radiation is preferable. For example, percite salt compounds, iodonium salt compounds, diazonium salt compounds, phosphonium salt compounds, imide sulfonate compounds, oxime sulfonate compounds, diazonium disulfide compounds, disulfide compounds, and o-nitrobenzyl sulfonates salt compounds.

As the photoacid generator, known compounds that generate acid upon irradiation with actinic rays or radiation can be appropriately selected and used alone or as a mixture thereof. For example, paragraphs <0125>~<0319> of US Patent Application Publication No. 2016/0070167A1, paragraphs <0086>~<0094> of US Patent Application Publication No. 2015/0004544A1 and US Patent Application Publication 2016 Known compounds disclosed in paragraphs <0323> to <0402> of Specification No. 0237190A1.

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

In the above general formula (ZI), R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represent an organic group.

The carbon numbers of the organic groups of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ are usually 1-30, preferably 1-20.

In addition, two of R ₂₀₁ to R ₂₀₃ may be bonded to form a ring structure, and an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group may also be included in the ring. As the group formed by bonding two of R ₂₀₁ to R ₂₀₃ , alkylene (for example, butylene, pentylene) and -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ - .

Z ^- represents anion (non-nucleophilic anion is preferred.).

As a preferred aspect of the cation in the general formula (ZI), the following compound (ZI-1), compound (ZI-2), the compound represented by the general formula (ZI-3) (compound (ZI- 3)) and the corresponding groups in the compound represented by the general formula (ZI-4) (compound (ZI-4)).

In addition, the photoacid generator may also be a compound having a plurality of structures represented by the general formula (ZI). For example, it is also possible to have at least one of R ₂₀₁ to R ₂₀₃ of the compound represented by general formula (ZI) and at least one of R ₂₀₁ to R ₂₀₃ of another compound represented by general formula (ZI) via A compound with a structure bonded by a single bond or a linker.

First, compound (ZI-1) will be described.

Compound (ZI-1) is an aryl permeicium compound in which at least one of R ₂₀₁ to R ₂₀₃ of the above general formula (ZI) is an aryl group, that is, a compound in which aryl permeicium is used as a cation.

In the aryl permeicium compound, all of R ₂₀₁ to R ₂₀₃ may be aryl groups, or a part of R ₂₀₁ to R ₂₀₃ may be aryl groups, and the remainder may be alkyl or cycloalkyl.

Examples of the aryl permeate compound include triaryl permedium compounds, diarylalkyl permeable compounds, aryl dialkyl permeable compounds, diarylcycloalkyl permeable compounds, and aryl dicycloalkyl permeable compounds.

As the aryl group contained in the aryl permeicium compound, phenyl or naphthyl is preferable, and phenyl is more preferable. The aryl group may also be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom, or the like. Examples of the heterocyclic structure include pyrrole residues, furan residues, thiophene residues, indole residues, benzofuran residues, and benzothiophene residues. When the aryl permeicium 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 that the aryl permeicium compound has as needed is a linear alkyl group with 1 to 15 carbons, a branched chain alkyl group with 3 to 15 carbons, or a cycloalkyl group with 3 to 15 carbons Preferable examples include methyl, ethyl, propyl, n-butyl, second-butyl, third-butyl, cyclopropyl, cyclobutyl, and cyclohexyl.

The aryl group, alkyl group and cycloalkyl group of _R201 ~ _R203 may also independently have an alkyl group (such as carbon number 1~15), cycloalkyl group (such as carbon number 3~15), aryl group ( For example, carbon number 6~14), alkoxy group (for example, carbon number 1~15), halogen atom, hydroxyl group or phenylthio group.

Next, compound (ZI-2) will be described.

Compound (ZI-2) is a compound in which R ₂₀₁ to R ₂₀₃ in formula (ZI) independently represent an organic group without an aromatic ring. Here, the aromatic ring refers to an aromatic ring containing heteroatoms.

The organic groups without an aromatic ring as R ₂₀₁ to R ₂₀₃ usually have 1 to 30 carbons, preferably 1 to 20 carbons.

R ₂₀₁ ~ R ₂₀₃ are independently preferably alkyl, cycloalkyl, allyl or vinyl, more preferably straight-chain or branched 2-oxoalkyl, 2-oxocycloalkane A group or an alkoxycarbonylmethyl group, more preferably a linear or branched 2-oxoalkyl group.

As the alkyl group and cycloalkyl group of R ₂₀₁ ~ R ₂₀₃ , preferably a linear alkyl group with 1 to 10 carbons or a branched chain alkyl group with 3 to 10 carbons (for example, methyl, ethyl, etc.) , propyl, butyl and pentyl) and cycloalkyl groups with 3 to 10 carbon atoms (such as cyclopentyl, cyclohexyl and norbornyl).

R ₂₀₁ ~R ₂₀₃ may be further substituted by halogen atoms, alkoxy groups (eg, carbon number 1~5), hydroxyl groups, cyano groups, and nitro groups.

Next, compound (ZI-3) will be described.

In the general formula (ZI-3), M represents an alkyl group, a cycloalkyl group or an aryl group. When having a ring structure, the above ring structure can include oxygen atoms, sulfur atoms, ester bonds, amide bonds and carbon-carbon double bonds. at least one of . R _1c and R _2c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an aryl group. R _1c and R _2c may be bonded to form a ring. R _x and R _y each independently represent an alkyl group, a cycloalkyl group or an alkenyl group. R _x and R _y may be bonded to form a ring. In addition, at least two selected from M, R _1c and R _2c may be bonded to form a ring structure, and the ring structure may contain a carbon-carbon double bond. Z ^- represents anion.

In the general formula (ZI-3), as the alkyl group and cycloalkyl group represented by M, straight-chain alkyl groups with 1 to 15 carbons (preferably 1 to 10 carbons), straight-chain alkyls with 3 to 15 carbons ( Preferably it is a branched chain alkyl group with 3 to 10 carbons) or a cycloalkyl group with 3 to 15 carbons (preferably 1 to 10 carbons), specifically, methyl, ethyl , propyl, n-butyl, second butyl, third butyl, cyclopropyl, cyclobutyl, cyclohexyl, and norbornyl, etc.

As the aryl group represented by M, phenyl or naphthyl is preferable, and phenyl is more preferable. The aryl group may be an aryl group having a heterocyclic structure containing an oxygen atom, a sulfur atom, or the like. Examples of the heterocyclic structure include a furan ring, a thiophene ring, a benzofuran ring, and a benzothiophene ring.

The aforementioned M may have a substituent. As this aspect, for example, benzyl group etc. are mentioned as M.

In addition, when M has a ring structure, the ring structure may contain at least one of an oxygen atom, a sulfur atom, an ester bond, an amide bond, and a carbon-carbon double bond.

Examples of the alkyl group, cycloalkyl group and aryl group represented by R _1c and R _2c include the same ones as those described above for M, and their preferred embodiments are also the same. Also, R _1c and R _2c may be bonded to form a ring.

Examples of the halogen atom represented by R _1c and R _2c include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Examples of the alkyl and cycloalkyl groups represented by R _x and R _y include the same ones as those described above for M, and their preferred embodiments are also the same.

As the alkenyl represented _by Rx and _Ry , allyl or vinyl is preferable.

The aforementioned R _x and R _y may have substituents. As this aspect, for example, 2-oxoalkyl group, alkoxycarbonylalkyl group, etc. are mentioned as R _x and R _y .

As the 2-oxoalkyl group represented by R _x and R _y , for example, those with 1 to 15 carbon atoms (preferably 1 to 10 carbon atoms), specifically 2-oxopropyl and 2-oxobutyl, etc.

Examples of the alkoxycarbonylalkyl group represented by R _x and R _y include those having 1 to 15 carbon atoms (preferably 1 to 10 carbon atoms). Also, R _x and R _y may be bonded to form a ring.

The ring structure formed by connecting R _x and R _y may contain oxygen atom, sulfur atom, ester bond, amide bond or carbon-carbon double bond.

In the general formula (ZI-3), M and R _1c may be bonded to form a ring structure, and the formed ring structure may contain a carbon-carbon double bond.

Among them, the above-mentioned compound (ZI-3)-based compound (ZI-3A) is preferred.

The compound (ZI-3A) is a compound represented by the following general formula (ZI-3A) and has a benzoylmethylconium salt structure.

[chemical 15]

In the general formula (ZI-3A), R _1c ~ R _5c 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, Cycloalkylcarbonyloxy, halogen atom, hydroxyl, nitro, alkylthio or arylthio.

R _6c and R _7c have the same meanings as R ₂ and R ₃ in the above-mentioned general formula (ZI-3), and their preferred embodiments are also the same.

R _x and R _y have the same meanings as R _x and R _y in the above general formula (ZI-3), and their preferred embodiments are also the same.

Any two or more of R _1c ~ R _5c , R _x and R _y can be bonded respectively to form a ring structure, and the ring structure can independently contain an oxygen atom, a sulfur atom, an ester bond, an amide bond or a carbon-carbon double bond. In addition, R _5c and R _6c , and R _5c and R _x may be bonded to each other to form a ring structure, and the ring structure may each independently contain a carbon-carbon double bond. Also, R _6c and R _7c may be bonded to each other to form a ring structure.

Examples of the ring structure include aromatic or nonaromatic hydrocarbon rings, aromatic or nonaromatic heterocycles, and polycyclic condensed rings in which two or more of these rings are combined. As the ring structure, 3-10-membered rings, 4-8-membered rings are preferable, and 5- or 6-membered rings are more preferable.

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.

Next, compound (ZI-4) will be described.

Compound (ZI-4) is represented by the following general formula (ZI-4).

In general formula (ZI-4), 1 represents the integer of 0-2.

r represents an integer from 0 to 8.

R ₁₃ represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, or a group having a monocyclic or polycyclic cycloalkyl skeleton. These groups may have substituents.

When there are multiple _R14 , each independently represents an alkyl group, a cycloalkyl group, an alkoxy group, an alkylsulfonyl group, a cycloalkylsulfonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, or a monocyclic or polycyclic The alkoxy group of the cycloalkyl skeleton. These groups may have substituents.

R ₁₅ each independently represent an alkyl group, a cycloalkyl group or a naphthyl group. These groups may have substituents. Two R ₁₅ may be bonded to each other to form a ring. When two R ₁₅ are bonded to each other to form a ring, a heteroatom such as an oxygen atom or a nitrogen atom may be included in the ring skeleton. In one aspect, two R ₁₅ are alkylene groups, and it is preferable to bond with each other to form a ring structure.

Z ^- represents anion.

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

Next, general formulas (ZII) and (ZIII) will be described.

In the general formulas (ZII) and (ZIII), R ₂₀₄ to R ₂₀₇ each independently represent an aryl group, an alkyl group or a cycloalkyl group.

As the aryl group for R ₂₀₄ to R ₂₀₇ , phenyl or naphthyl is preferred, and phenyl is more preferred. The aryl groups of R ₂₀₄ to R ₂₀₇ may also be aryl groups containing a heterocyclic structure having an oxygen atom, a nitrogen atom, or a sulfur atom. 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 ~ R ₂₀₇ , a straight chain alkyl group with 1 ~ 10 carbons or a branched chain alkyl group with 3 ~ 10 carbons (for example, methyl, ethyl, propyl, butyl, etc.) and pentyl) or cycloalkyls with 3 to 10 carbons (such as cyclopentyl, cyclohexyl, norbornyl) are preferred.

The aryl group, alkyl group, and cycloalkyl group of R ₂₀₄ to R ₂₀₇ may each independently have a substituent. As substituents that the aryl, alkyl, and cycloalkyl groups of R ₂₀₄ to R ₂₀₇ may have, for example, alkyl (such as 1 to 15 carbons), cycloalkyl (such as 3 to 15 carbons), aryl (such as carbon number 6~15), alkoxy group (such as carbon number 1~15), halogen atom, hydroxyl group and thiophenyl group, etc.

Z ^- represents anion.

As Z - in the general formula (ZI), Z ^- in the general formula (ZII), Zc ^- in the general formula (ZI-3) and Z ^- in the general formula (ZI ^- 4), the following general formula The anions represented by (3) are preferred.

In general formula (3), o represents the integer of 1-3. p represents an integer from 0 to 10. q represents an integer from 0 to 10.

Xf represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. The carbon number of the alkyl group is preferably 1-10, more preferably 1-4. Also, as the alkyl group substituted with at least one fluorine atom, perfluoroalkyl group is preferable.

Xf is preferably a fluorine atom or a perfluoroalkyl group with 1 to 4 carbon atoms, more preferably a fluorine atom or CF ₃ . In particular, both Xf-based fluorine atoms are further preferred.

R ₄ and R ₅ each independently represent a hydrogen atom, a fluorine atom, an alkyl group or an alkyl group substituted by at least one fluorine atom. When there are plural R ₄ and R ₅ , R ₄ and R ₅ may be the same or different.

The alkyl groups represented by R ₄ and R ₅ may have substituents, preferably having 1 to 4 carbon atoms. R ₄ and R ₅ are preferably hydrogen atoms.

Specific examples and preferred aspects of the alkyl group substituted with at least one fluorine atom are the same as the specific examples and preferred aspects of Xf in the general formula (3).

L represents a divalent linking group. When there are plural Ls, each L may be the same or different.

Examples of divalent linking groups include -COO-(-C(=O)-O-), -OCO-, -CONH-, -NHCO-, -CO-, -O-, -S-, -SO-, -SO ₂ -, alkylene (preferably 1~6 carbons), cycloalkylene (preferably 3~15 carbons), alkenylene (preferably 2~6 carbons ) and a divalent linking group formed by combining the plurality thereof. Among them, -COO-, -OCO-, -CONH-, -NHCO-, -CO-, -O-, -SO ₂ -, -COO-alkylene-, -OCO-alkylene-, - CONH-alkylene- or -NHCO-alkylene- is better, -COO-, -OCO-, -CONH-, -SO ₂ -, -COO-alkylene- or -OCO-alkylene- for better.

W represents an organic group including a ring structure. Among these, a cyclic organic group is preferable.

As a cyclic organic group, for example, an alicyclic group, an aryl group, and a heterocyclic group are mentioned preferably.

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, tricyclodecanyl, tetracyclodecanyl, tetracyclododecyl, and adamantyl. Among them, norbornyl, tricyclodecanyl, tetracyclodecanyl, tetracyclododecyl, adamantyl and other alicyclic groups having a bulky structure having 7 or more carbon atoms are preferred.

The aryl group may be monocyclic or polycyclic. Examples of the aryl group include phenyl, naphthyl, phenanthrenyl and anthracenyl.

The heterocyclic group may be monocyclic or polycyclic. The polycyclic form can inhibit the diffusion of acid more. Moreover, a heterocyclic group may or may not have aromaticity. As an aromatic heterocycle, a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring are mentioned, for example. As a non-aromatic heterocycle, a tetrahydropyran ring, a lactone ring, a sultone ring, and a decahydroisoquinoline ring are mentioned, for example. Examples of the lactone ring and the sultone ring include the lactone structure and the sultone structure exemplified in the aforementioned resins. As the heterocyclic ring in the heterocyclic group, a furan ring, a thiophene ring, a pyridine ring or a decahydroisoquinoline ring is particularly preferable.

The above-mentioned cyclic organic group may have a substituent. As the substituent, for example, an alkyl group (which may be any of straight chain and branched chain, preferably having 1 to 12 carbon atoms), cycloalkyl group (which may be monocyclic, polycyclic and spirocyclic) Any one of them, carbon number 3~20 is better), aryl group (carbon number 6~14 is better), hydroxyl group, alkoxyl group, ester group, amido group, urethane group, urea group , sulfide group, sulfonamide group and sulfonate group. In addition, the carbon constituting the cyclic organic group (the carbon contributing to the formation of the ring) may be carbonyl carbon.

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

In one aspect, as Z - in the general formula (ZI), Z ^- in the general formula (ZII), Zc ^- in the general formula (ZI-3), and Z ^- in the general formula (ZI ^- 4), Anions represented by the following general formula (4) are preferred.

In the general formula (4), X ^B1 and X ^B2 each independently represent a hydrogen atom or a monovalent organic group not having 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 of X ^B3 and X ^B4 are a fluorine atom or a monovalent organic group having a fluorine atom. . Both of X ^B3 and X ^B4 are more preferably alkyl groups substituted with fluorine atoms.

L, q and W are the same as the general formula (3).

Z in general formula (ZI), Z ⁱⁿ general formula (ZII), Zc ⁱⁿ general formula (ZI ^- 3) and Z in general formula (ZI ^- 4) can be benzenesulfonic acid anion, Benzenesulfonic acid anion substituted by branched alkyl or cycloalkyl is preferred.

As Z - in the general formula (ZI), Z ^- in the general formula (ZII), Zc ^- in the general formula (ZI-3) and Z ^- in the general formula (ZI ^- 4), the following general formula An aromatic sulfonic acid anion represented by (SA1) is also preferable.

In the formula (SA1), Ar represents an aryl group, and may have substituents other than the sulfonic acid anion and the -(D-B) group. As a substituent which may have, a fluorine atom, a hydroxyl group, etc. are mentioned.

n represents an integer of 0 or more. As n, 1-4 are preferable, 2-3 are more preferable, and 3 is still more preferable.

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 arylene group, an arylene group, a sulfonate group, an ester group, and a combination of two or more of these groups.

B represents a hydrocarbon group.

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

Preferred examples of the percite cation in the general formula (ZI) and the iodonium cation in the general formula (ZII) are shown below.

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

The above-mentioned cations and anions can be combined arbitrarily and used as a photoacid generator.

The photoacid generator may be in the form of a low-molecular compound, or may be incorporated into a part of the polymer. Moreover, the form of a low-molecular-weight compound and the form incorporated into a part of polymer can also be used together.

The photoacid generator is preferably in the form of a low-molecular compound.

When the photoacid generator is in the form of a low molecular weight 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 is in the form of being incorporated into a part of the polymer, it may be incorporated into one of the aforementioned resins (A), or may be incorporated into a resin different from the resin (A).

A photoacid generator may be used individually by 1 type, and may use 2 or more types together.

In the composition of the present invention, the content of the photoacid generator (total when there are a plurality of them) is preferably 0.1 to 35% by mass, more preferably 0.5 to 25% by mass, based on the total solid content of the composition. 1-20 mass % is more preferable, and 1-15 mass % is especially preferable.

As the photoacid generator, when the compound represented by the above-mentioned general formula (ZI-3) or (ZI-4) is contained, the content of the photoacid generator contained in the composition (total when there are plural kinds) is equal to or equal to Based on the total solid content of the composition, 1 to 35% by mass is preferred, and 1 to 30% by mass is more preferred.

[(C) Fluorine-containing compound having a group that is decomposed by the action of alkaline developer and has increased solubility in alkaline developer]

(C) A fluorine-containing compound (also referred to as "fluorine-containing compound (C)") having a group which is decomposed by the action of an alkaline developer and whose solubility in an alkaline developer is increased will be described.

The fluorine-containing compound (C) can locally exist on the surface of the actinic radiation-sensitive or radiation-sensitive film of the present invention by including fluorine, and can exhibit desired performance.

The group that is decomposed by the action of an alkaline developer and has increased solubility in an alkaline developer is also called a "polarity conversion group". As specific examples, a lactone group, a carboxylate group (- COO-), acid anhydride group (-C(O)OC(O)-), acid imide group (-NHCONH-), carboxylic acid thioester group (-COS-), carbonate group (-OC(O) O-), sulfate group (-OSO ₂ O-), sulfonate group (-SO ₂ O-), etc.

In addition, as in acrylate, etc., among the ester groups directly bonded to the main chain of the repeating unit, it is decomposed by the action of the alkaline developer to increase the solubility of the alkaline developer. Therefore, it is not included in the polarity switching group in the present invention.

From the viewpoint of surface locality, it is preferable that the fluorine-containing compound (C) has a fluoroalkyl group.

A fluorine-containing compound (C)-based resin (also referred to as "resin (C)") is more preferable.

The fluorine-containing compound (C) is more preferably a resin comprising a repeating unit having a polarity switching group (also referred to as "repeating unit (c)").

As the repeating unit (c), for example, a repeating unit represented by the general formula (K0) can be cited.

In the general formula (K0), R _k1 represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an aryl group, or a group containing a polarity conversion group.

R _k2 represents an alkyl group, a cycloalkyl group, an aryl group, or a group containing a polarity switching group.

Among them, at least one of R _k1 and R _k2 has a polarity switching group.

In addition, the ester group directly bonded to the main chain of the repeating unit represented by the general formula (K0) is not included in the polarity conversion group in the present invention as described above.

As the polarity converting group, a group represented by X in the partial structure represented by the general formula (KA-1) or (KB-1) is preferable.

That is, the repeating unit (c) has at least one of the partial structures represented by the general formulas (KA-1) and (KB-1), and the polarity switching group is represented by the general formulas (KA-1) or (KB-1) X in the partial structure shown is preferable.

X in general formula (KA-1) or (KB-1) represents carboxylate group: -COO-, acid anhydride group: -C(O)OC(O)-, acid imide group: -NHCONH-, Carboxylic acid thioester group: -COS-, carbonate group: -OC(O)O-, sulfate ester group: -OSO ₂ O-, sulfonate group: -SO ₂ O-.

Y ¹ and Y ² may be the same or different, and represent electron-attracting groups.

In addition, the repeating unit (c) contains a group having a partial structure represented by the general formula (KA-1) or (KB-1), thereby having a preferable polar conversion group, but as shown by the general formula (KA-1 ) and the partial structure represented by (KB-1) when Y ¹ and Y ² are monovalent, when the above partial structure does not have a bond, the group having the above partial structure has the ability to remove At least one group of a monovalent or higher group of an arbitrary hydrogen atom in the above-mentioned partial structure.

The partial structure represented by the general formula (KA-1) or (KB-1) is connected to the main chain of the resin (C) via a substituent at an arbitrary position.

The partial structure represented by the general formula (KA-1) forms a ring structure together with a group as X.

X in the general formula (KA-1) is preferably a carboxylate group (that is, when KA-1 forms a lactone ring structure), an acid anhydride group, or a carbonate group. More preferred is a carboxylate group.

The ring structure represented by the general formula (KA-1) may have a substituent, for example, may have nka substituents Z _ka1 .

When Z _ka1 exists in plural, each independently represents an alkyl group, a cycloalkyl group, an ether group, a hydroxyl group, an amido group, an aryl group, a lactone ring group or an electron-attracting group.

Z _ka1 can be connected to each other to form a ring. Examples of rings formed by linking _Zka1 to each other include cycloalkyl rings and heterocycles (cyclic ether rings, lactone rings, etc.).

nka represents an integer from 0 to 10. It is preferably an integer of 0-8, more preferably an integer of 0-5, further preferably an integer of 1-4, most preferably an integer of 1-3.

The electron-attracting group as Z _ka1 is the same as the electron-attracting groups as ^Y1 and ^Y2 described later, represented by a halogen atom.

In addition, the above electron-attracting groups may be substituted with other electron-attracting groups.

Z _ka1 is preferably an alkyl group, a cycloalkyl group, an ether group, a hydroxyl group or an electron-attracting group, more preferably an alkyl group, a cycloalkyl group or an electron-attracting group. Moreover, as an ether group, what is substituted with an alkyl group, a cycloalkyl group, etc., that is, an alkylether group etc. are preferable. Preferable examples of the electron-attracting group are the same as the electron-attracting groups for ^Y1 and ^Y2 described later.

Examples of the halogen atom in Z _ka1 include fluorine atom, chlorine atom, bromine atom and iodine atom, among which fluorine atom is preferred.

The alkyl group as Z _ka1 may not have a substituent, and may be either a straight chain or a branched chain. The linear alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, for example, methyl, ethyl, n-propyl, n-butyl, second-butyl, and third-butyl , n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, etc. The branched chain alkyl group preferably has 3 to 30 carbon atoms, more preferably 3 to 20 carbon atoms, for example, isopropyl, isobutyl, tert-butyl, isopentyl, tert-amyl, Base, tertiary hexyl, isoheptyl, tertiary heptyl, isooctyl, tertiary octyl, isononyl, tertiary decanyl, etc. Methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl and other groups with 1 to 4 carbon atoms are preferred.

The cycloalkyl group as Z _ka1 may have a substituent, may be a monocyclic type, may be a polycyclic type, or may be a bridged type. For example, a cycloalkyl group may have a bridged structure. As a monocyclic type, a cycloalkyl group having 3 to 8 carbon atoms is preferable, and examples thereof include cyclopropyl, cyclopentyl, cyclohexyl, cyclobutyl, and cyclooctyl. As the polycyclic type, groups having a bicyclic, tricyclic, and tetracyclic structure with 5 or more carbon atoms can be mentioned, and cycloalkyl groups with 6 to 20 carbon atoms are preferred, for example, adamantyl, norbornyl , Isocamyl, Camphenyl, Dicyclopentyl, α-Pinenyl, Tricyclodecanyl, Tetracyclododecyl, Androstanyl, etc. As the cycloalkyl group, the following structures are also preferable. In addition, some of the carbon atoms in the cycloalkyl group may be substituted with heteroatoms such as oxygen atoms.

[chem 25]

Preferred examples of the aforementioned alicyclic moieties include adamantyl, noradamantyl, decahydronaphthyl, tricyclodecanyl, tetracyclododecyl, norbornyl, cedrol, cyclohexyl, cyclohexyl, Heptyl, cyclooctyl, cyclodecyl, cyclododecyl. More preferred are adamantyl, decahydronaphthyl, norbornyl, cedrol, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, cyclododecyl, and tricyclodecanyl.

As a substituent of such an alicyclic structure, an alkyl group, a halogen atom, a hydroxyl group, an alkoxy group, a carboxyl group, and an alkoxycarbonyl group are mentioned. As the alkyl group, lower alkyl groups such as methyl, ethyl, propyl, isopropyl, and butyl are preferred, and methyl, ethyl, propyl, and isopropyl are further preferred. As the above-mentioned alkoxy group, preferably methoxy, ethoxy, propoxy, Those with 1 to 4 carbons such as butoxy. Examples of substituents that the alkyl group and the alkoxy group may have include a hydroxyl group, a halogen atom, an alkoxy group (preferably having 1 to 4 carbon atoms), and the like.

Examples of the lactone ring group of Z _ka1 include groups obtained by removing a hydrogen atom from the structure represented by any one of (KA-1-1) to (KA-1-17) described below.

Examples of the aryl group in Z _ka1 include phenyl and naphthyl.

As substituents that the alkyl, cycloalkyl and aryl groups of Z _ka1 may further have include hydroxyl, halogen atoms (fluorine, chlorine, bromine, iodine), nitro, cyano, the above-mentioned alkyl, methoxy, Ethoxy, hydroxyethoxy, propoxy, hydroxypropoxy, n-butoxy, isobutoxy, second butoxy, third butoxy and other alkoxy, methoxycarbonyl, ethyl Alkoxycarbonyl such as oxycarbonyl, aralkyl such as benzyl, phenethyl, and cumyl, aralkyloxy, formyl, acetyl, butyryl, benzoyl, cyanamide acyl group such as pentyloxy group, acyloxy group such as butyryloxy group, alkenyloxy group such as above-mentioned alkenyl group, vinyloxy group, propyleneoxy group, allyloxy group, butenyloxy group, above-mentioned aryl group, phenoxy group Aryloxy groups such as benzoyloxy groups, aryloxycarbonyl groups such as benzoyloxy groups, etc.

X in the general formula (KA-1) is a carboxylate group, and the partial structure shown in the general formula (KA-1) is preferably a lactone ring, more preferably a 5-7 membered lactone ring.

In addition, as in the following (KA-1-1) to (KA-1-17), other ring structures form bicyclic structures and spiro structures and 5, which is a partial structure represented by the general formula (KA-1). The ~7-membered cyclic lactone ring is preferably ring-condensed.

Regarding the ring structure that can be bonded to the periphery of the ring structure represented by the general formula (KA-1), for example, those in the following (KA-1-1) to (KA-1-17) can be listed or referred to as standard.

As a structure containing a lactone ring structure represented by general formula (KA-1), a structure represented by any one of the following (KA-1-1) to (KA-1-17) is more preferable. In addition, the lactone structure may be directly bonded to the main chain. As the preferred structural system (KA-1-1), (KA-1-4), (KA-1-5), (KA-1-6), (KA-1-13), (KA-1- 14), (KA-1-17).

The structure containing the above-mentioned lactone ring structure may have a substituent or may not have a substituent. As a preferable substituent, the thing similar to the substituent which the ring structure represented by said General formula (KA-1) has is mentioned.

An optically active substance may exist in the lactone structure, but any optically active substance may be used. In addition, one kind of optically active substance may be used alone, or a plurality of optically active substances may be mixed and used. When one optically active substance is mainly used, the optical purity (ee) is preferably above 90%, more preferably above 95%, most preferably above 98%.

As X of general formula (KB-1), carboxylate group (-COO-) can be mentioned preferably.

Y ¹ and Y ² in the general formula (KB-1) each independently represent an electron attracting group.

The electron-attracting group is preferably a partial structure represented by the following formula (EW). * in the formula (EW) represents a bond directly bonded to (KA-1) or a bond directly bonded to X in (KB-1).

In the formula ( _EW ), new is the repeating number of the linker represented by -C(R _ew1 )(R _ew2 )-, and represents an integer of 0 or 1. When n _ew is 0, it means a single bond, which means that Y _ew1 is directly bonded.

Examples of Y _ew1 include a halogen atom, a cyano group, a nitrile group, a nitro group, a halogenated (cyclo)alkyl group, a halogenated aryl group, and an oxy group represented by -C(R _f1 )(R _f2 )-R _f3 described later. , carbonyl, sulfonyl, sulfinyl and combinations thereof, the electron-attracting group can be, for example, the following structure. In addition, "halo(cyclo)alkyl" means an alkyl group and a cycloalkyl group at least partially halogenated. R _ew3 and R _ew4 each independently represent an arbitrary structure. In any of the structures of R _ew3 and R _ew4 , the partial structure represented by the formula (EW) has electron-withdrawing properties, for example, can be connected to the main chain of the resin, but is preferably an alkyl group, a cycloalkyl group, or a fluoroalkyl group.

When Y _ew1 is a group having a valence of 2 or more, the remaining bonds form bonds with arbitrary atoms or substituents. At least any one of Y _ew1 , R _ew1 , and R _ew2 is further connected to the main chain of the resin (C) via a substituent.

Y _ew1 is preferably a halogen atom or a halogenated (cyclo)alkyl or halogenated aryl group represented by -C(R _f1 )(R _f2 )-R _f3 .

R _ew1 and R _ew2 each independently represent an arbitrary substituent, for example, a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group.

At least two of Re _ew1 , Re _ew2 and _{Ye ew1} may be connected to each other to form a ring.

Here, R _f1 represents a halogen atom, a perhaloalkyl group, a perhalocycloalkyl group or a perhaloaryl group, more preferably a fluorine atom, a perfluoroalkyl group or a perfluorocycloalkyl group, further preferably a fluorine atom or Trifluoromethyl.

R _f2 and R _f3 independently represent a hydrogen atom, a halogen atom or an organic group, and R _f2 and R _f3 may be connected to form a ring. The organic group includes, for example, an alkyl group, a cycloalkyl group, an alkoxy group, etc., which may be substituted by a halogen atom (preferably a fluorine atom), and R _f2 and R _f3 are more preferably (halogenated) alkyl groups. R _f2 represents the same group as R _f1 , or it is more preferable that it can be linked with R _f3 to form a ring.

R _f1 and R _f3 may be connected to form a ring, and examples of the formed ring include (halogenated) cycloalkyl rings, (halogenated) aryl rings, and the like.

Examples of the (halogenated) alkyl group in R _f1 to R _f3 include the alkyl group in the aforementioned Z _ka1 and the halogenated structure of the alkyl group.

As the (per)fluorocycloalkyl group and (per)fluoroaryl group in R _f1 to R _f3 , or in the ring formed by R _f2 and R _f3 being connected, for example, the cycloalkyl group in the aforementioned Z _ka1 is halogenated The resulting structure is more preferably a fluorocycloalkyl group represented by -C _(n) F _(2n-2) H and a perfluoroaryl group represented by -C _(n) F _(n-1) . Here, the carbon number n is not particularly limited, but 5-13 is preferable, and 6 is more preferable.

The ring formed by linking at least two of R _ew1 , R _ew2 and _{Ye ew1} to each other is preferably a cycloalkyl group or a heterocyclic group, and a heterocyclic lactone ring group is preferred. As a lactone ring, the structure represented by said formula (KA-1-1)-(KA-1-17) is mentioned, for example.

In addition, the repeating unit (c) may have a plurality of partial structures represented by the general formula (KA-1), a plurality of partial structures represented by the general formula (KB-1), or may have the general formula (KA Both the partial structure of -1) and the partial structure of general formula (KB-1).

In addition, part or all of the partial structure of the general formula (KA-1) may also serve as an electron-attracting group as Y ¹ or Y ² in the general formula (KB-1). For example, when X in the general formula (KA-1) is a carboxylate group, the carboxylate group can also function as an electron-attracting group of ^Y1 or ^Y2 in the general formula (KB-1).

The repeating unit (c) may be a repeating unit (c') having a fluorine atom and a polarity switching group on a side chain, or a repeating unit (c*) having a polarity switching group and no fluorine atom, or A repeating unit (c") having a polarity switching group on one side chain and a fluorine atom on a side chain different from the above-mentioned side chain in the same repeating unit, but the resin (C) has a repeating unit as the repeating unit (c) (c') is more preferable. That is, it is more preferable that the repeating unit (c) having at least one polarity switching group has a fluorine atom.

In addition, when the resin (C) has a repeating unit (c*), it is preferably a copolymer with a repeating unit having a fluorine atom (repeating unit (c1) described later). Also, the side chain with the polar conversion group and the side chain with the fluorine atom in the repeating unit (c") are bonded to the same carbon atom in the main chain, that is, the positional relationship of the following formula (K1) is: better.

In the formula, B1 represents a partial structure having a polarity switching group, and B2 represents a partial structure having a fluorine atom.

Also, in the repeating unit (c*) and the repeating unit (c"), it is more preferable that the polarity switching group is a partial structure represented by -COO- in the structure represented by the general formula (KA-1).

The hydrolysis rate of the resin (C) relative to the alkaline developer is preferably at least 0.001 nm/sec, more preferably at least 0.01 nm/sec, more preferably at least 0.1 nm/sec, most preferably at least 1 nm/sec.

Here, the hydrolysis rate of the resin (C) with respect to the alkaline developer is at 23°C with respect to TMAH (tetramethylammonium hydroxide aqueous solution) (2.38% by mass), when a resin film is formed only from the resin (C) The rate at which the film thickness decreases.

The resin (C) of the present invention contains a repeating unit (c) having at least two polarity switching groups, and is preferably a resin (C1) having a fluorine atom.

When the repeating unit (c) has at least two polarity switching groups, the repeating unit (c) has a moiety represented by the following general formula (KY-1) having two polarity switching groups The structure is better. In addition, when the structure represented by the general formula (KY-1) does not have a bond, it is a monovalent or higher group obtained by removing at least one arbitrary hydrogen atom in the above structure.

In the general formula (KY-1), R _ky1 and R _ky4 independently represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, a carbonyl group, a carbonyloxy group, an oxycarbonyl group, an ether group, a hydroxyl group, a cyano group, an acyl group amino or aryl. Alternatively, R _ky1 and R _ky4 may be bonded to the same atom to form a double bond, for example, R _ky1 and R _ky4 may be bonded to the same oxygen atom to form a part of a carbonyl group (=O).

R _ky2 and R _ky3 are independently electron-attracting groups, or R _ky1 and R _ky2 are connected to form a lactone ring and R _ky3 is an electron-attracting group. As the formed lactone ring, the above-mentioned structures of (KA-1-1) to (KA-1-17) are preferable. Examples of the electron-attracting group include the same ones as Y ¹ and Y ² in the above formula (KB-1), preferably a halogen atom or a halogen represented by the above-C(R _f1 )(R _f2 )-R _f3 Substituted (cyclo)alkyl or halogenated aryl. Preferably, R _ky3 is a halogen atom or a halogenated (cyclo)alkyl or halogenated aryl group represented by the above-C(R _f1 )(R _f2 )-R _f3 , and R _ky2 is connected to R _ky1 to form A lactone ring or an electron-attracting group without a halogen atom.

R _ky1 , R _ky2 , and R _ky4 may be connected to each other to form a monocyclic or polycyclic structure.

Specifically, R _ky1 and R _ky4 include the same groups as Z _ka1 in the formula (KA-1).

As R _ky1 and R _ky2 are connected to form a lactone ring, the structures of (KA-1-1) to (KA-1-17) above are preferable. Examples of the electron-attracting group include the same ones as Y ¹ and Y ² in the above formula (KB-1).

As the structure represented by the general formula (KY-1), a structure represented by the following general formula (KY-2) is more preferable. In addition, the structure represented by the general formula (KY-2) is a monovalent or higher group obtained by removing at least one arbitrary hydrogen atom in the above structure.

In formula (KY-2), R _ky6 ~ R _ky10 independently represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, a carbonyl group, a carbonyloxy group, an oxycarbonyl group, an ether group, a hydroxyl group, a cyano group, and an amido group or aryl.

Two or more of R _ky6 to R _ky10 may be connected to each other to form a single-ring or polycyclic structure.

R _ky5 represents an electron attracting group. The electron-attracting group can be the same as those of the above-mentioned Y ¹ and Y ² , preferably a halogen atom or a halogenated (cyclo)alkyl or halogen represented by the above-C(R _f1 )(R _f2 )-R _f3 Substituted aryl.

Specific examples of R _ky5 to R _ky10 include the same groups as Z _ka1 in formula (KA-1).

The structure represented by the formula (KY-2) is more preferably a partial structure represented by the following general formula (KY-3).

In the formula (KY-3), Z _ka1 and nka have the same meanings as in the above general formula (KA-1). R _ky5 has the same meaning as in the above formula (KY-2).

L _ky represents an alkylene group, an oxygen atom or a sulfur atom. Examples of the alkylene group of L _ky include a methylene group, an ethylene group, and the like. L _ky is preferably an oxygen atom or a methylene group, more preferably a methylene group.

The repeating unit (c) is not limited as long as it is a repeating unit obtained by polymerization such as addition polymerization, polycondensation, and addition condensation, but a repeating unit obtained by addition polymerization of a carbon-carbon double bond is preferred. . Examples include acrylate-based repeating units (including systems having substituents at the α- and β-positions), styrene-based repeating units (including systems having substituents at the α- and β-positions), vinyl ether-based Repeating units, norcamphene-based repeating units, repeating units of maleic acid derivatives (maleic anhydride and its derivatives, maleimide, etc.), acrylate-based repeating units, styrene repeating units, vinyl ether repeating units, and norbornene repeating units are preferred, and acrylic acid Ester-based repeating units, vinyl ether-based repeating units, and norbornene-based repeating units are more preferred, and acrylate-based repeating units are most preferred.

As a more specific structure of the repeating unit (c), a repeating unit having a partial structure shown below is preferable.

The repeating unit (c) may be a repeating unit having a partial structure shown below.

In the general formula (cc), when there are a plurality of Z ₁ , each independently represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond, or a urea bond, preferably an ester bond.

When there are a plurality of Z ₂ , each independently represents a chain or cyclic alkylene group, preferably an alkylene group having 1 or 2 carbon atoms or a cycloalkylene group having 5 to 10 carbon atoms.

Ta independently represents an alkyl group, a cycloalkyl group, an alkoxyl group, a nitrile group, a hydroxyl group, an amido group, an aryl group or an electron-attracting group (with ^Y1 and ^Y2 in the above-mentioned general formula (KB-1) Electron-attracting group has the same meaning), preferably represents an alkyl group, a cycloalkyl group, and an electron-attracting group, and further preferably represents an electron-attracting group. When there are plural Ta, Ta may be bonded to each other to form a ring.

L ₀ represents a single bond or an m+1-valent hydrocarbon group (preferably having 20 or less carbon atoms), preferably a single bond. The single bond that is L ₀ is the case where m is 1. The m+1-valent hydrocarbon group as _L0 means, for example, an m+1-valent hydrocarbon group obtained by removing m-1 arbitrary hydrogen atoms from an alkylene group, a cycloalkylene group, a phenylene group, or a combination thereof.

L each independently represents a carbonyl group, a carbonyloxy group or an ether group.

Tc represents a hydrogen atom, an alkyl group, a cycloalkyl group, a nitrile group, a hydroxyl group, an amido group, an aryl group, or an electron-attracting group (with the electron-attracting group of ^Y1 and ^Y2 in the above-mentioned general formula (KB-1) have the same meaning).

* indicates a bond to the main chain or side chain of the resin. That is, the partial structure represented by the formula (cc) may be directly bonded to the main chain, or the partial structure represented by the formula (cc) may be bonded to the side chain of the resin. In addition, the bond to the main chain is a bond to atoms existing in the bonds constituting the main chain, and the bond to the side chain is a bond to atoms other than the bonds constituting the main chain. Knot.

m represents the integer of 1-28, Preferably it is the integer of 1-3, More preferably, it is 1.

k represents an integer of 0 to 2, preferably 1.

q represents the repetition number of the group (Z ₂ -Z ₁ ), and represents an integer of 0-5, preferably 0-2.

r represents an integer from 0 to 5.

In addition, instead of -(L)r-Tc, the above-mentioned -L ₀ -(Ta)m may be substituted.

It is also preferable to have a fluorine atom at the end of the sugar lactone and also have a fluorine atom on a side chain different from that on the sugar lactone side in the same repeating unit (repeating unit (c")).

When the chain chain alkylene as Z2 is a straight chain alkylene, it is preferably ₁ to 30 carbons, more preferably 1 to 20, and when it is a branched chain, it is preferably 3 to 30 carbons, and further Preferably it is 3~20. Specific examples of the chain-like alkylene group for R2 include groups in which one arbitrary _hydrogen atom has been removed from the specific examples of the alkyl group as _Zka1 above.

The cyclic alkylene group as Z2 preferably has ₃ to 8 carbon atoms, and a specific example thereof includes a group obtained by removing one arbitrary hydrogen atom from the cycloalkyl group as _Zka1 above.

Desirable carbon numbers and specific examples of the alkyl and cycloalkyl groups as Ta and Tc are the same as those described for the alkyl group and cycloalkyl group as Z _ka1 above.

The alkoxy group of Ta preferably has 1 to 8 carbon atoms, and examples thereof include methoxy, ethoxy, propoxy, butoxy and the like.

The aryl group of Ta and Tc is preferably an aryl group having 6 to 12 carbon atoms, and examples thereof include phenyl and naphthyl.

Desirable carbon numbers and specific examples of the alkylene group and cycloalkylene group as _L0 are the same as those described for the chain alkylene group and cyclic alkylene group as _Z2 .

As a more specific structure of the repeating unit (c), a repeating unit having a partial structure shown below is preferable.

In the general formulas (ca-2) and (cb-2), n represents an integer of 0-11, preferably represents an integer of 0-5, more preferably represents 1 or 2.

p represents an integer of 0-5, preferably represents an integer of 0-3, more preferably represents 1 or 2.

Tb independently represents an alkyl group, a cycloalkyl group, an alkoxy group, a nitrile group, a hydroxyl group, an amido group, an aryl group, or an electron-attracting group (with electrons as ^Y1 and ^Y2 in the above general formula (KB-1) Attracting group has the same meaning), preferably represents an alkyl group, a cycloalkyl group, and an electron-attracting group. When there are a plurality of Tbs, Tbs may be bonded to each other to form a ring.

* indicates a bond to the main chain or side chain of the resin. That is, the partial structure represented by formula (ca-2) or (cb-2) can be directly bonded to the main chain, or can be bonded on the side chain of the resin. Formula (ca-2) or (cb- 2) Part of the structure represented.

Z ₁ , Z ₂ , Ta, Tc, L, *, m, q, r have the same meanings as those in the general formula (cc), and the preferred ones are also the same.

In the general formula (KY-4), R ₂ represents a chain or cyclic alkylene group, and when there are plural R ₂ , they may be the same or different.

R ₃ represents a linear, branched or cyclic hydrocarbon group in which some or all of the hydrogen atoms constituting carbon are substituted with fluorine atoms.

R ₄ represents a halogen atom, a cyano group, a hydroxyl group, an amido group, an alkyl group, a cycloalkyl group, an alkoxy group, a phenyl group, an acyl group, an alkoxycarbonyl group or by RC(=O)- or RC(=O)O - the group represented (R represents an alkyl group or a cycloalkyl group.). When there are plural R ₄ , they may be the same or different, and two or more R ₄ may be bonded to form a ring.

X represents an alkylene group, an oxygen atom or a sulfur atom.

When Z and Za exist in plural, each independently represents a single bond, ether bond, ester bond, amide bond, urethane bond, or urea bond. When Z and Za exist in plural, they may be the same or different.

* indicates a bond to the main chain or side chain of the resin.

o is a substituent base, representing an integer of 1 to 7.

m is the number of substituents, representing an integer of 0-7.

n represents the number of repetitions, representing an integer of 0 to 5.

The -R ₂ -Z ^- structure is preferably represented by -(CH ₂ ) _l -COO- (l represents an integer of 1 to 5).

Preferred carbon number ranges and specific examples of the chain or cyclic alkylene group as R2 are the same as those described for the chain and cyclic alkylene groups in Z2 in the general _formula (cc ₎ .

Regarding the carbon number of the linear, branched or cyclic hydrocarbon group as _R3 , when it is linear, it is preferably 1 to 30, more preferably 1 to 20, and when it is branched, Preferably it is 3-30, More preferably, it is 3-20, When it is cyclic, it is 6-20. Specific examples of R ₃ include specific examples of the alkyl and cycloalkyl groups that are Z _{ka 1} described above. Preferred carbon numbers and specific examples of R ₄ and R in the alkyl and cycloalkyl groups are the same as those described above for the alkyl and cycloalkyl groups in Z _ka1 .

As the acyl group of R ₄ , those having 1 to 6 carbon atoms are preferable, for example, formyl, acetyl, propionyl, butyryl, isobutyryl, pentyl, trimethylacetyl and the like can be mentioned.

As the alkyl moiety in the alkoxy group and alkoxycarbonyl group of R ₄ , straight-chain, branched or cyclic alkyl moieties can be cited, and the preferred carbon number and specific examples of the alkyl moiety are the same as the above-mentioned Z _ka1 The descriptions of the alkyl group and cycloalkyl group are the same.

Examples of the alkylene group for X include chain or cyclic alkylene groups, and preferred carbon numbers and specific examples thereof are the same as those described for the chain and cyclic alkylene groups as R ₂ .

More preferably, it is a repeating unit having a partial structure represented by general formula (KY-5).

In the general formula (KY-5), R ₂ represents a chain or cyclic alkylene group, and when there are plural R ₂ , they may be the same or different.

R ₃ represents a linear, branched or cyclic hydrocarbon group in which some or all of the hydrogen atoms constituting carbon are substituted with fluorine atoms.

R ₄ represents a halogen atom, a cyano group, a hydroxyl group, an amido group, an alkyl group, a cycloalkyl group, an alkoxy group, a phenyl group, an acyl group, an alkoxycarbonyl group or by RC(=O)- or RC(=O)O - the group represented (R represents an alkyl group or a cycloalkyl group.). When there are plural R ₄ , they may be the same or different, and two or more R ₄ may be bonded to form a ring.

X represents an alkylene group, an oxygen atom or a sulfur atom.

Z represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond, or a urea bond, and when there are plural Zs, they may be the same or different.

* indicates a bond to the main chain or side chain of the resin.

n represents the number of repetitions, representing an integer of 0 to 5.

m is the number of substituents, representing an integer of 0-7.

The preferred ranges and specific examples of the carbon numbers in R ₂ to R ₄ and X are the same as those described in the general formula (KY-4).

The -R ₂ -Z ^- structure is preferably represented by -(CH ₂ ) _l -COO- (l represents an integer of 1 to 5).

In the general formulas (rf-1) and (rf-2), X' represents an electron-withdrawing substituent, preferably a carbonyloxy group, an oxycarbonyl group, an alkylene group substituted by a fluorine atom, and an alkene group substituted by a fluorine atom. Cycloalkyl.

A represents a single bond or a divalent linking group represented by -C(R _x )(R _y )-. Among them, R _x and R _y independently represent a hydrogen atom, a fluorine atom, an alkyl group (preferably having 1 to 6 carbon atoms, and may be substituted by a fluorine atom, etc.) or a cycloalkyl group (preferably having 5 to 12 carbon atoms). , and may be substituted by fluorine atoms, etc.). R _x and R _y are preferably a hydrogen atom, an alkyl group, or an alkyl group substituted with a fluorine atom.

X represents an electron-attracting group, preferably a fluorinated alkyl group, a fluorinated cycloalkyl group, an aryl group substituted by fluorine or a fluorinated alkyl group, or an aralkyl group substituted by fluorine or a fluorinated alkyl group.

* indicates a bond to the main chain or side chain of the resin. That is, it means a bond bonded to the main chain of the resin via a single bond or a linker.

In addition, when X' is carbonyloxy or oxycarbonyl, A is not a single bond.

The alkylene group in the alkylene group substituted with a fluorine atom as X', when it is a straight chain alkylene group, preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and is a branched chain alkylene group When , the carbon number is preferably 3-30, more preferably 3-20. Specific examples of the above-mentioned alkylene group include groups obtained by removing one arbitrary hydrogen atom from the specific examples of the above-mentioned Z _ka1 alkyl group. As the alkylene group substituted with a fluorine atom, a perfluoroalkylene group is preferable.

The cycloalkylene group in the cycloalkylene group substituted by a fluorine atom as X' preferably has 3 to 8 carbon atoms. As its specific example, the following specific examples of the cycloalkyl group except Z _ka1 above can be cited. A group of any hydrogen atom. As the cycloalkylene group substituted with a fluorine atom, a perfluorocycloalkylene group is preferred.

As the alkyl group in the fluorinated alkyl group of X, when it is a straight chain alkyl group, it is preferably 1 to 30 carbons, and more preferably 1 to 20 carbons, and when it is a branched chain alkyl group, it is preferably 3 to 3 carbons. 30, more preferably 3-20. Specific examples of the above-mentioned alkyl group include specific examples of the above-mentioned _Zka1 alkyl group. As the fluorinated alkyl group, perfluoroalkyl group is preferred.

The cycloalkyl group in the fluorinated cycloalkyl group as X preferably has 3 to 8 carbon atoms, and specific examples thereof include the specific examples of the cycloalkyl group as Z _ka1 described above. As the fluorinated cycloalkyl group, perfluorocycloalkyl group is preferred.

The aryl group in the aryl group substituted with fluorine or a fluorinated alkyl group as X is preferably an aryl group having 6 to 12 carbon atoms, and examples thereof include phenyl and naphthyl. Also, as the fluorinated alkyl Specific examples of the fluorinated alkyl group in the aryl group are the same as those described for the fluorinated alkyl group as X.

The aralkyl group in the aralkyl group substituted by fluorine or a fluorinated alkyl group as X is preferably an aralkyl group having 6 to 12 carbon atoms, for example, benzyl, phenethyl, naphthylmethyl, naphthalene Ethyl, naphthylbutyl, etc. Further, specific examples of the fluorinated alkyl group in the aralkyl group substituted with a fluorinated alkyl group are the same as those described for the fluorinated alkyl group as X.

The resin (C) preferably has a repeating unit represented by the following general formula (2) as the repeating unit (c).

In the general formula (2), R ₂₁ represents a hydrogen atom or a monovalent organic group. X ₂ represents a divalent linking group. R ₂₂ and R ₂₃ each independently represent a fluoroalkyl group. R ₂₄ represents a hydrogen atom, a fluorine atom, or a monovalent organic group.

As the divalent linking group represented by X ₂ in the general formula (2), a divalent linking group having the aforementioned polarity conversion group is preferable, and a lactone structure is particularly preferable.

In the general formula (2), _R21 is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or an alkyl group with 1 to 5 carbon atoms.

In the general formula (2), R ₂₂ and R ₂₃ independently represent a fluoroalkyl group, preferably a fluoroalkyl group having 1 to 10 carbon atoms, and more preferably a fluoroalkyl group having 1 to 5 carbon atoms.

In the general formula (2), _R24 preferably represents a hydrogen atom, a fluorine atom, or a fluoroalkyl group with 1 to 10 carbons, and more preferably represents a hydrogen atom, a fluorine atom, or a fluoroalkyl group with 1 to 5 carbons.

Although the specific example of the repeating unit (c) which has a polarity conversion group is shown, it is not limited to these.

Ra represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.

Relative to all the repeating units in the resin (C), the content of the repeating unit (c) in the resin (C) is preferably 10-100 mol%, more preferably 20-100 mol%, further preferably It is 30~100 mol%, and the best is 40~100 mol%.

Relative to all the repeating units in the resin (C), the content of the repeating unit (c') is preferably 10-100 mol%, more preferably 20-100 mol%, further preferably 30-100 mol%. ear%, the best is 40~100 mole%.

Relative to all the repeating units in the resin (C), the content of the repeating unit (c*) is preferably 5-70 mol %, more preferably 5-60 mol %, further preferably 10-50 mol % ear%, the best is 10~40 mole%. Relative to all the repeating units in the resin (C), the content of the repeating unit having a fluorine atom used together with the repeating unit (c*) is preferably 10-95 mol%, more preferably 15-85 mol%. mol%, further preferably 20-80 mol%, most preferably 25-75 mol%.

Relative to all the repeating units in the resin (C), the content of the repeating unit (c") is preferably 10-100 mol%, more preferably 20-100 mol%, further preferably 30-100 mol% ear%, the best is 40~100 mole%.

The fluorine atoms in the resin (C) may exist in the main chain of the resin, or may be substituted on the side chain.

The resin (C) may also have other repeating units. Preferred aspects of other repeating units are listed below.

(cy1) A repeating unit that has a fluorine atom, is stable to acids, and is hardly soluble or insoluble in an alkaline developer.

(cy2) A repeating unit that does not have a fluorine atom, is stable to acids, and is hardly soluble or insoluble in an alkaline developing solution.

(cy3) A repeating unit having a fluorine atom and a polar group.

(cy4) A repeating unit having no fluorine atom and having a polar group.

In the repeating units of (cy1) and (cy2), poorly soluble or insoluble in alkaline developer means that (cy1) and (cy2) do not contain alkali-soluble groups and are produced by the action of acid or alkaline developer Alkali-soluble groups (such as acid decomposable groups or polarity conversion groups).

The repeating units (cy1) and (cy2) preferably have an alicyclic hydrocarbon structure without a polar group.

Preferred aspects of repeating units (cy1) to (cy4) are shown below.

As repeating units (cy1) and (cy2), repeating units represented by the following general formula (CIII) are preferable.

In the general formula (CIII), R _c31 represents a hydrogen atom, an alkyl group which may be substituted by a fluorine atom, a cyano group or a -CH ₂ -OR _ac2 group. In the formula, R _ac2 represents a hydrogen atom, an alkyl group or an acyl group. R _c31 is preferably a hydrogen atom, a methyl group, a hydroxymethyl group, or a trifluoromethyl group, and particularly preferably a hydrogen atom or a methyl group.

R _c32 represents a group having an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group or an aryl group. These groups may be substituted with groups containing silicon atoms, fluorine atoms, and the like.

L _c3 represents a single bond or a divalent linking group.

The alkyl group of R _c32 in the general formula (CIII) is preferably a straight-chain or branched-chain alkyl group with 3 to 20 carbon atoms.

The cycloalkyl group is preferably a cycloalkyl group with 3 to 20 carbon atoms.

The alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms.

The cycloalkenyl group is preferably a cycloalkenyl group having 3 to 20 carbon atoms.

The aryl group is preferably a phenyl group and a naphthyl group having 6 to 20 carbon atoms, and these may have a substituent.

R _c32 is preferably an unsubstituted alkyl group or an alkyl group substituted by fluorine atoms. The divalent linking group of L _c3 is preferably an alkylene group (preferably having 1 to 5 carbon atoms), an oxy group, a phenylene group, and an ester bond (a group represented by -COO-).

As the repeating unit (cy1) and (cy2), a repeating unit represented by the following general formula (C4) or (C5) is preferable.

In the general formulas (C4), (C5), R _c5 represents a hydrocarbon group having at least one cyclic structure and not having any of a hydroxyl group and a cyano group.

Rac represents a hydrogen atom, an alkyl group substituted by a fluorine atom, a cyano group or a -CH ₂ -O-Rac ₂ group. In the formula, Rac ₂ represents a hydrogen atom, an alkyl group or an acyl group. Rac is preferably a hydrogen atom, a methyl group, a hydroxymethyl group, or a trifluoromethyl group, and a hydrogen atom or a methyl group is particularly preferable.

The cyclic structure of R _c5 includes monocyclic hydrocarbon groups and polycyclic hydrocarbon groups. Examples of the monocyclic hydrocarbon group include a cycloalkyl group having 3 to 12 carbon atoms and a cycloalkenyl group having 3 to 12 carbon atoms. A preferred monocyclic hydrocarbon group is a monocyclic hydrocarbon group having 3 to 7 carbon atoms.

The polycyclic hydrocarbon group includes a ring-assembled hydrocarbon group and a cross-linked cyclic hydrocarbon group. Examples of the crosslinked cyclic hydrocarbon ring include bicyclic hydrocarbon rings, tricyclic hydrocarbon rings, and tetracyclic hydrocarbon rings. In addition, the cross-linked cyclic hydrocarbon ring also includes a condensed cyclic hydrocarbon ring (for example, a condensed ring formed by condensing a plurality of 5- to 8-membered naphthenic rings). Preferable cross-linked cyclic hydrocarbon rings include norbornyl and adamantyl.

These alicyclic hydrocarbon groups may have a substituent, and preferable substituents include a halogen atom, an alkyl group, a hydroxyl group protected by a protecting group, an amino group protected by a protecting group, and the like. Preferable halogen atoms include bromine, chlorine, and fluorine atoms, and preferable alkyl groups include methyl, ethyl, butyl, and t-butyl. The above-mentioned alkyl group may have a substituent, and examples of the substituent that may have include a halogen atom, an alkyl group, a hydroxyl group protected by a protecting group, and an amine group protected by a protecting group.

As a protecting group, an alkyl group, a cycloalkyl group, an aralkyl group, a substituted methyl group, a substituted ethyl group, an alkoxycarbonyl group, and an aralkyloxycarbonyl group are mentioned, for example. Preferred alkyl groups include alkyl groups with 1 to 4 carbon atoms, and preferred substituted methyl groups include methoxymethyl, methoxythiomethyl, benzyloxymethyl, tert-butyl Oxymethyl, 2-methoxyethoxymethyl, as preferred substituted ethyl, can enumerate 1-ethoxyethyl, 1-methyl-1-methoxyethyl, as preferred The acyl group can include aliphatic acyl groups with 1 to 6 carbons such as formyl, acetyl, propionyl, butyryl, isobutyryl, pentyl, and trimethylacetyl, as an alkoxycarbonyl group, Examples thereof include an alkoxycarbonyl group having 2 to 4 carbon atoms.

R _c6 represents an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkoxycarbonyl group, or an alkylcarbonyloxy group. These groups may be substituted by fluorine atoms and silicon atoms.

The alkyl group of R _c6 is preferably a straight-chain or branched-chain alkyl group with 1 to 20 carbon atoms. The cycloalkyl group is preferably a cycloalkyl group with 3 to 20 carbon atoms.

The alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms.

The cycloalkenyl group is preferably a cycloalkenyl group having 3 to 20 carbon atoms.

The alkoxycarbonyl group is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms.

Alkylcarbonyloxy is preferably an alkylcarbonyloxy group having 2 to 20 carbon atoms.

n represents an integer from 0 to 5. When n is 2 or more, a plurality of R _c6 may be the same or different.

R _c6 is preferably an unsubstituted alkyl group or an alkyl group substituted by a fluorine atom, especially preferably trifluoromethyl or tert-butyl.

(cy1) and (cy2) are also preferably repeating units represented by the following general formula (CII-AB).

In the formula (CII-AB), R _c11 ' and R _c12 ' each independently represent a hydrogen atom, a cyano group, a halogen atom or an alkyl group.

Zc' includes two carbon atoms (C-C) bonded, and represents an atomic group for forming an alicyclic structure.

Moreover, it is more preferable that the above general formula (CII-AB) is the following general formula (CII-AB1) or general formula (CII-AB2).

In the formulas (CII-AB1) and (CII-AB2), R _c13 ' to R _c16 ' each independently represent a hydrogen atom, a halogen atom, an alkyl group or a cycloalkyl group.

In addition, at least two of R _c13 ' to R _c16 ' may be bonded to form a ring.

n represents 0 or 1.

Specific examples of (cy1) and (cy2) are listed below, but the present invention is not limited thereto. In the formula, Ra represents H, CH ₃ , CH ₂ OH, CF ₃ or CN.

(cy3) and (cy4) are preferably repeating units having a hydroxyl group or a cyano group as a polar group. Thereby, developer affinity is improved. The repeating unit having a hydroxyl group or a cyano group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted by a hydroxyl group or a cyano group. Among the alicyclic hydrocarbon structures substituted by hydroxyl or cyano groups, the adamantyl, diadamantyl and norbornyl groups are preferred as the alicyclic hydrocarbon structure. As preferred hydroxyl or cyano substituted alicyclic hydrocarbon structures, monohydroxyadamantyl, dihydroxyadamantyl, monohydroxydiamantyl, dihydroxyadamantyl, and norbornyl substituted by cyano Wait.

Examples of the repeating unit having the above atomic group include repeating units represented by the following general formulas (CAIIa) to (CAIId).

In the general formulas (CAIIa)~(CAIId), R ₁ c represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.

R ₂ c to R ₄ c each independently represent a hydrogen atom, a hydroxyl group or a cyano group. Wherein, at least one of R ₂ c to R ₄ c represents a hydroxyl group or a cyano group. Preferably, one or two of R ₂ c to R ₄ c are hydroxyl groups, and the rest are hydrogen atoms. In the general formula (CAIIa), more preferably, two of R ₂ c to R ₄ c are hydroxyl groups, and the rest are hydrogen atoms.

Specific examples of the repeating unit represented by (cy3) and (cy4) are listed below, but the present invention is not limited thereto.

Relative to all the repeating units in the resin (C), the content rate of the repeating units represented by (cy1)~(cy4) is preferably 5~40mol%, more preferably 5~30mol%, further preferably 10 ~25mol%.

The resin (C) may have a plurality of repeating units represented by (cy1) to (cy4).

The content of the fluorine atoms in the resin (C) is preferably from 5 to 80% by mass, more preferably from 10 to 80% by mass, based on the molecular weight of the resin (C). Moreover, it is preferable that the repeating unit containing a fluorine atom is 10-100 mass % with respect to all the repeating units in resin (C), and it is more preferable that it is 30-100 mass %.

The molecular weight of the fluorine-containing compound (C) is preferably 1,000 to 100,000 from the viewpoint of improving localized presence.

The weight average molecular weight of the resin (C) is preferably from 1,000 to 100,000, more preferably from 1,000 to 50,000, further preferably from 2,000 to 15,000.

The molecular weight distribution (Mw/Mn, also known as dispersion) of the resin (C) is preferably in the range of 1 to 3, more preferably 1 to 2, further preferably 1 to 1.8, and most preferably 1 to 1.5 scope.

Resin (C) can also use various commercial items, and can synthesize|combine by a conventional method (for example, radical polymerization) similarly to resin (A).

The fluorine-containing compound (C) can be used alone or in combination of two or more.

From an analytical point of view, the content of the fluorine-containing compound (C) in the composition of the present invention is preferably 0.01 to 10% by mass, more preferably 0.1% by mass, based on the total solid content of the composition of the present invention. ~10% by mass, more preferably 0.1~5% by mass.

[Acid Diffusion Control Agent]

The composition of the present invention preferably contains an acid diffusion controller. The acid diffusion control agent functions as a quencher that traps acid generated from a photoacid generator or the like during exposure, and suppresses the reaction of the acid-decomposable resin in the unexposed portion due to excess generated acid.

The composition of the present invention preferably contains an acid diffusion controller whose pKa of the conjugate acid is less than 4.0.

From an analytical point of view, the pKa of the conjugate acid of the acid diffusion inhibitor is preferably -2.5 or more and less than 4.0, more preferably 0.0 or more and less than 4.0, and still more preferably 1.0 or more and 3.0 or less.

As the acid diffusion control agent, for example, a basic compound (DA), a basic compound (DB) whose basicity is reduced or disappeared by irradiation with actinic rays or radiation, and an onium salt that becomes a relatively weak acid relative to the acid generator can be used. (DC), having a nitrogen atom and having A low-molecular compound (DD) of a group detached by the action of an acid, an onium salt compound (DE) having a nitrogen atom in a cationic portion, etc. are used as an acid diffusion control agent. In the composition of the present invention, known acid diffusion controllers can be suitably used. For example, paragraphs <0627>~<0664> of US Patent Application Publication No. 2016/0070167A1, paragraphs <0095>~<0187> of US Patent Application Publication No. 2015/0004544A1, US Patent Application Publication 2016 The well-known compounds disclosed in paragraphs <0403>~<0423> of specification No./0237190A1 and paragraphs <0259>~<0328> of specification US Patent Application Publication No. 2016/0274458A1 are used as acid diffusion control agents.

As the basic compound (DA), compounds having structures represented by the following general formulas (A) to (E) are preferred.

In the general formulas (A) and (E), R ²⁰⁰ , R ²⁰¹ and R ²⁰² may be the same or different, and each independently represent a hydrogen atom, an alkyl group (preferably having 1 to 20 carbon atoms), a cycloalkyl group (more preferably Preferably it is carbon number 3~20) or aryl group (carbon number 6~20). R ²⁰¹ and R ²⁰² may also be bonded to each other to form a ring.

R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ and R ²⁰⁶ may be the same or different, and each independently represents an alkyl group having 1 to 20 carbon atoms.

The alkyl groups in the general formulas (A) and (E) may have a substituent or may be unsubstituted.

Regarding the above-mentioned alkyl group, as the alkyl group having a substituent, an aminoalkyl group having 1 to 20 carbons, a hydroxyalkyl group having 1 to 20 carbons, or a cyanoalkyl group having 1 to 20 carbons are preferred.

It is more preferable that the alkyl groups in the general formulas (A) and (E) are unsubstituted.

、胺基嗎福林、胺基烷基嗎啉、哌啶或具有該等結構之化合物為較佳，具有噻唑結構、苯并噻唑結構、噁唑結構、苯并噁唑結構、咪唑結構、二吖雙環結構、鎓氫氧化物結構、羧酸鎓鹽結構、三烷基胺結構、苯胺結構或吡啶結構之化合物、具有羥基和/或醚鍵之烷基胺衍生物或具有羥基和/或醚鍵之苯胺衍生物等為更佳。 As basic compounds (DA), thiazole, benzothiazole, oxazole, benzoxazole, guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperidine

, aminomorphine, aminoalkylmorpholine, piperidine or compounds with these structures are preferred, with thiazole structure, benzothiazole structure, oxazole structure, benzoxazole structure, imidazole structure, di Compounds with acryl ring structure, onium hydroxide structure, carboxylate onium salt structure, trialkylamine structure, aniline structure or pyridine structure, alkylamine derivatives with hydroxyl and/or ether bond or hydroxyl and/or ether Bonded aniline derivatives etc. are more preferable.

A basic compound (DB) (hereinafter, also referred to as a "compound (DB)") whose alkalinity is reduced or disappeared by irradiation with actinic rays or radiation has a proton-accepting functional group and is activated by actinic radiation. A compound whose proton-accepting property decreases, disappears, or changes from proton-accepting to acidic after being decomposed by radiation or radiation exposure.

The proton-accepting functional group refers to a functional group having a group or electrons capable of electrostatically interacting with protons, such as a functional group having a macrocyclic structure such as cyclic polyether, or a functional group containing The functional group of the nitrogen atom that acts on the unshared electron pair. The nitrogen atom having an unshared electron pair that does not contribute to π-conjugation means, for example, a nitrogen atom having a partial structure represented by the following formula.

結構等。 As a preferable partial structure of the proton-accepting functional group, for example, a crown ether structure, an azacrown ether structure, a primary amine to a tertiary amine structure, a pyridine structure, an imidazole structure, and a pyridine structure are listed.

structure etc.

Compound (DB) yields a compound whose proton-accepting property decreases, disappears, or changes from proton-accepting property to acidity when decomposed by irradiation with actinic rays or radiation. Among them, the reduction or disappearance of proton accepting properties or the change from proton accepting properties to acidity refers to the change of proton accepting properties caused by the addition of protons to proton accepting functional groups. When the proton-accepting functional group compound (DB) forms a proton adduct with a proton, the equilibrium constant in the chemical equilibrium decreases.

Proton accepting properties can be confirmed by performing pH measurements.

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

The acid dissociation constant pKa represents the acid dissociation constant pKa in an aqueous solution, and is defined, for example, by ChemHandbook (II) (revised 4th edition, 1993, edited by the Chemical Society of Japan, Maruzen.Inc.). The lower the value representing the acid dissociation constant pKa, the greater the acid strength. Specifically, the acid dissociation constant pKa in an aqueous solution can be actually measured from the acid dissociation constant at 25° C. using an infinitely diluted aqueous solution. Alternatively, the following packaged software 1 can be used to obtain the value based on the database of Hammett's substituent constants and known literature values by calculation. All the pKa values described in this specification represent the values obtained by calculation using the packaged software.

Package software 1: Advanced Chemistry Development (ACD/Labs) software V8.14 supporting the Solaris system (1994-2007 ACD/Labs).

In the composition of the present invention, an onium salt (DC) which is a relatively weak acid relative to the photoacid generator can be used as an acid diffusion control agent.

When a photoacid generator and an onium salt that generates an acid that is a relatively weak acid relative to the acid generated by the photoacid generator are used in combination, if the acid generated by the photoacid generator is Collision with an onium salt with an unreacted weak acid anion releases the weak acid by salt exchange to produce an onium salt with a strong acid anion. In this process the strong acid is exchanged for a weaker acid with lower catalytic energy, thus visually inactivating the acid and enabling control of acid diffusion.

Compounds represented by the following general formulas (d1-1) to (d1-3) are preferable as onium salts that are relatively weak acids with respect to the photoacid generator.

In the formula, ^R51 is a hydrocarbon group that may have a substituent, ^Z2c is a hydrocarbon group with a carbon number of 1 to 30 that may have a substituent (wherein, the carbon adjacent to S is not substituted by a fluorine atom), ^R52 is an organic group, ^Y3 is a linear, branched or cyclic alkylene or arylylene group, Rf is a hydrocarbon group containing a fluorine atom, and M ⁺ are independently ammonium cations, percite cations or iodonium cations.

Preferable examples of the persubium cation or the odonium cation represented by M ⁺ include percite cations exemplified by the general formula (ZI) and odonium cations exemplified by the general formula (ZII).

The onium salt (DC) which becomes a relatively weak acid with respect to the photoacid generator may also be a compound having a cation site and an anion site in the same molecule and the cation site and the anion site are linked by a covalent bond (hereinafter also referred to as "" Compound (DCA)".).

As the compound (DCA), a compound represented by any one of the following general formulas (C-1) to (C-3) is preferable.

In the general formulas (C-1) to (C-3), R ₁ , R ₂ and R ₃ each independently represent a substituent having 1 or more carbon atoms.

L ₁ represents a divalent linking group or a single bond connecting the cation site and the anion site.

-X ^- represents an anion site selected from -COO ^- , -SO ₃ ^- , -SO ₂ ^- , -N ^- -R ₄ . R ₄ represents a carbonyl group (-C(=O)-), a sulfonyl group (-S(=O) ₂ -), and a sulfinyl group (-S(=O) -) at least one monovalent substituent.

R ₁ , R ₂ , R ₃ , R ₄ , and L ₁ may be bonded to each other to form a ring structure. Also, in the general formula (C-3), two of R ₁ to R ₃ may together represent a divalent substituent, and be bonded to an N atom through a double bond.

Examples of substituents having 1 or more carbon atoms in R ₁ to R ₃ include alkyl, cycloalkyl, aryl, alkoxycarbonyl, cycloalkoxycarbonyl, aryloxycarbonyl, alkylaminocarbonyl, ring Alkylaminocarbonyl and arylaminocarbonyl, etc. Preferably it is an alkyl group, a cycloalkyl group or an aryl group.

Examples of L ₁ of the divalent linking group include linear or branched alkylene groups, cycloalkylene groups, arylylene groups, carbonyl groups, ether linkages, ester linkages, amide linkages, and urethane linkages. , a urea bond, and a group obtained by combining two or more of these. L ₁ is more preferably an alkylene group, an arylylene group, an ether bond, an ester bond, or a combination of two or more thereof.

A low-molecular compound (DD) having a nitrogen atom and a group detached by the action of an acid (hereinafter also referred to as "compound (DD)") has a group detached by the action of an acid on the nitrogen atom. Amine derivatives of the group are preferred.

As the group detached by the action of acid, acetal group, carbonate group, carbamate group, tertiary ester group, tertiary hydroxyl group or half amine acetal ether group are preferred, carbamate Group or half amine acetal ether group is more preferred.

The molecular weight of the compound (DD) is preferably 100-1000, more preferably 100-700, and still more preferably 100-500.

Compound (DD) may also have a carbamate group having a protecting group on the nitrogen atom. As a protecting group constituting a urethane group, it can be represented by the following general formula (d-1).

In the general formula (d-1), R _b independently represent a hydrogen atom, an alkyl group (preferably having 1 to 10 carbons), a cycloalkyl group (preferably having 3 to 30 carbons), an aryl group (preferably 3-30 carbons), aralkyl (preferably 1-10 carbons) or alkoxyalkyl (preferably 1-10 carbons). R _b may be bonded to each other to form a ring.

The alkyl group, cycloalkyl group, aryl group and aralkyl group represented by R _b can be independently replaced by functional groups such as hydroxyl group, cyano group, amino group, pyrrolidinyl group, piperidinyl group, morpholinyl group, oxo group, etc. Alkoxy, halogen atom substitution. The same applies to the alkoxyalkyl group represented by R _b .

As R _b , a linear or branched alkyl group, cycloalkyl group or aryl group is preferred, and a linear or branched alkyl group or cycloalkyl group is more preferred.

Examples of the ring formed by linking 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 the general formula (d-1), the structure disclosed in paragraph <0466> of US Patent Publication No. US2012/0135348A1 may be mentioned, but it is not limited thereto.

Compound (DD) preferably has a structure represented by the following general formula (6).

In the general formula (6), l represents an integer of 0 to 2, m represents an integer of 1 to 3, and l+m=3 is satisfied.

R _a represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. When l is 2, the two R _a can be the same or different, and the two R _a can also be connected to each other to form a heterocyclic ring together with the nitrogen atom in the formula. The heterocyclic ring may contain heteroatoms other than the nitrogen atom in the formula.

R _b is defined the same as R _b in the above general formula (d-1), and preferred examples are also the same.

In the general formula (6), the alkyl group, cycloalkyl group, aryl group and aralkyl group as R _a may be independently substituted by the same group as the aforementioned group as the following group, which is represented as The alkyl group, cycloalkyl group, aryl group, and aralkyl group of R _b may be substituted.

Specific examples of the alkyl group, cycloalkyl group, aryl group, and aralkyl group (these groups may be substituted by the above-mentioned groups) of the above-mentioned R _a include the same groups as those described above for R _b .

Specific examples of the particularly preferred compound (DD) in the present invention include compounds disclosed in paragraph <0475> of US Patent Application Publication No. 2012/0135348A1, but are not limited thereto.

The onium salt compound (DE) (hereinafter also referred to as "compound (DE)") having a nitrogen atom in the cation portion is preferably a compound having a basic site containing a nitrogen atom in the cation portion. The basic part is preferably an amine group, more preferably an aliphatic amine group. It is further preferred that all atoms adjacent to the nitrogen atom in the basic site are hydrogen atoms or carbon atoms. Also, from the viewpoint of increasing the basicity, it is preferable that an electron-withdrawing functional group (carbonyl group, sulfonyl group, cyano group, halogen atom, etc.) is not directly bonded to a nitrogen atom.

Preferable specific examples of the compound (DE) include compounds disclosed in paragraph <0203> of US Patent Application Publication No. 2015/0309408A1, but are not limited thereto.

In the present invention, as the acid diffusion control agent, it is better to be an alkaline compound (DA), wherein, a compound having a structure represented by the general formula (C) is more preferred, especially, by the following general formula (DAC1 ) or (DAC2) is preferred.

In the general formulas (DAC1) and (DAC2), Ar ^D1 and Ar ^D2 each independently represent an aromatic group.

Ar ^D1 and Ar ^D2 preferably represent an aryl group, and more preferably represent a phenyl group.

The aromatic groups represented by Ar ^D1 and Ar ^D2 may have a substituent, and examples of the substituent include an alkyl group, an alkoxy group, an ester group, etc., and a methoxy group is particularly preferable.

Preferred examples of acid diffusion controllers are shown below.

[Chemical 56]

In the composition of the present invention, one kind of acid diffusion controller may be used alone, or two or more kinds may be used in combination.

The content of the acid diffusion control agent in the composition of the present invention (total when there are plural types) is preferably 1.0×10 ^-4 mass% or less, 1.0×10 ^-5 mass % relative to the total solid content of the composition % or less is preferable, 1.0×10 ^-6 mass % or less is more preferred, 1.0×10 ^-7 mass % or less is particularly preferred, and 1.0×10 ^-8 mass % or less is most preferable.

[solvent]

It is preferable that the composition of the present invention contains a solvent.

In the composition of the present invention, known resist solvents can be appropriately used. For example, paragraphs <0665>~<0670> of US Patent Application Publication No. 2016/0070167A1 specification, US Patent Application Publication No. 2015/0004544A1 specification can be preferably used <0210>~<0235> of the book, <0424>~<0426> of the US patent application publication 2016/0237190A1 specification and <0357>~<0366> of the US patent application publication 2016/0274458A1 specification Known solvents disclosed.

Examples of solvents that can be used in the preparation of the composition include alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, alkyl lactate, alkyl alkoxypropionate , cyclic lactones (preferably having 4-10 carbon atoms), monoketone compounds which may have a ring (preferably having 4-10 carbon atoms), alkylene carbonates, alkyl alkoxy acetates and alkyl pyruvates Organic solvents such as base esters.

As the organic solvent, a mixed solvent obtained by mixing a solvent having a hydroxyl group in the structure and a solvent not having a hydroxyl group in the structure can be used.

As a solvent with a hydroxyl group and a solvent without a hydroxyl group, the aforementioned exemplified compounds can be appropriately selected. As a solvent containing a hydroxyl group, alkylene glycol monoalkyl ether or alkyl lactate is preferred, and propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether (PGEE), methyl 2-hydroxyisobutyrate or ethyl lactate are more preferred. Also, as a solvent not having a hydroxyl group, there are alkylene glycol monoalkyl ether acetates, alkyl alkoxy propionates, monoketone compounds that may contain rings, cyclic lactones, or alkyl acetates, etc. Preferably, among these, propylene glycol monomethyl ether acetate (PGMEA), ethoxy ethyl propionate, 2-heptanone, γ-butyrolactone, cyclohexanone, cyclopentanone or butyl acetate More preferably, propylene glycol monomethyl ether acetate, γ-butyrolactone, ethyl ethoxypropionate, cyclohexanone, cyclopentanone or 2-heptanone are further more preferable. Propylene carbonate is also preferable as the solvent not having a hydroxyl group.

The mixing ratio (mass ratio) of the solvent having a hydroxyl group to the solvent not having a hydroxyl group is 1/99-99/1, preferably 10/90-90/10, more preferably 20/80-60/40. In terms of coating uniformity, a mixed solvent containing 50% by mass or more of a solvent not having a hydroxyl group is preferable.

It is preferable that the solvent contains propylene glycol monomethyl ether acetate, and may be a single solvent of propylene glycol monomethyl ether acetate, or may be a mixed solvent containing two or more kinds of propylene glycol monomethyl ether acetate.

[Surfactant]

The composition of the present invention may further contain a surfactant. By containing a surfactant, when using an exposure light source with a wavelength below 250nm, especially below 220nm, it is possible to form a pattern with good sensitivity and resolution and fewer developing defects.

As the surfactant, it is particularly preferable to use a fluorine-based and/or silicon-based surfactant.

Examples of the fluorine-based and/or silicon-based surfactant include those described in <0276> of US Patent Application Publication No. 2008/0248425. Also, EFTOP EF301 or EF303 (manufactured by Shin-Akita Kasei Co., Ltd.); FLUORAD FC430, 431 or 4430 (manufactured by Sumitomo 3M Limited); MEGAFACE F171, F173, F176, F189, F113, F110, F177, F120 can be used or R08 (manufactured by DIC CORPORATION); SURFLON S-382, SC101, 102, 103, 104, 105 or 106 (manufactured by ASAHI GLASS CO., LTD.); Troy Sol S-366 (manufactured by Troy Chemical Industries Inc.); GF -300 or GF-150 (manufactured by TOAGOSEI CO., LTD.), SURFLON S-393 (SEIMI CHEMICAL CO.,LTD.); EFTOP EF121, EF122A, EF122B, RF122C, EF125M, EF135M, EF351, EF352, EF801, EF802 or EF601 (Gemco co.,ltd.); PF636, PF656, PF6320 or PF6520 (OMNOVA SOLUTIONS INC.); or FTX-204G, 208G, 218G, 230G, 204D, 208D, 212D, 218D or 222D (by NEOS COMPANY LIMITED). In addition, polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon-based surfactant.

In addition, the surfactant can be obtained by short-chain polymerization method (telomerization method) (also called short-chain polymer method (telomer method)) or oligomerization method (oligomerization method) ( Also known as oligomer method) to produce fluoroaliphatic compounds for synthesis. Specifically, a polymer having a fluoroaliphatic group derived from the fluoroaliphatic compound can be used as a surfactant. The fluoroaliphatic compound can be synthesized, for example, by the method described in JP-A-2002-090991.

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

These surfactants may be used alone or in combination of two or more.

When the composition of the present invention includes a surfactant, its content is based on the total solid content of the composition, preferably 0-2% by mass, more preferably 0.0001-2% by mass, further preferably 0.0005-1% by mass %.

[Other additives]

The composition of the present invention may suitably contain, in addition to the components described above, a dissolution inhibiting compound having a molecular weight of 3000 or less described in Proceeding of SPIE, 2724, 355 (1996), dyes, carboxylic acids, carboxylate onium salts, etc. Plasticizers, photosensitizers, light absorbers, antioxidants, etc.

In particular, carboxylic acids can also be preferably used for performance improvement. As the carboxylic acid, aromatic carboxylic acids such as benzoic acid and naphthoic acid are preferable.

When the composition of the present invention contains a carboxylic acid, the content of the carboxylic acid is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass, and even more preferably 0.01 to 3% by mass relative to the total solid content of the composition. %.

From the point of view of improving resolution, it is better to use the actinic radiation-sensitive or radiation-sensitive resin composition in the present invention with a film thickness of 10-250 nm, more preferably with a film thickness of 20-200 nm, and with a film thickness of 30-200 nm. The use of 100nm is further preferred. Such a film thickness can be obtained by setting the solid content concentration in the composition in an appropriate range and maintaining an appropriate viscosity to improve applicability and film-forming properties.

The solid content concentration of the actinic radiation-sensitive or radiation-sensitive resin composition in the present invention is usually 1.0 to 10% by mass, preferably 2.0 to 5.7% by mass, further preferably 2.0 to 5.3% by mass. By setting the solid content concentration within the above-mentioned range, the resist solution can be uniformly applied on the substrate, and a resist pattern excellent in line width roughness can be formed.

The solid content concentration is the percentage by mass of the mass of other components except the solvent relative to the total mass of the actinic radiation-sensitive or radiation-sensitive resin composition.

[use]

The composition of the present invention relates to an actinic radiation-sensitive or radiation-sensitive resin composition that reacts and changes properties when irradiated with actinic rays or radiation. More specifically, the composition of the present invention is related to a semiconductor manufacturing process used in IC (Integrated Circuit: integrated circuit), manufacturing of circuit substrates such as liquid crystal or thermal head, and manufacturing of mold structures for imprinting. , and other actinic radiation-sensitive or radiation-sensitive resin compositions used in photosensitive etching processing steps or in the manufacture of lithographic printing plates or acid-hardening compositions. The pattern formed in the present invention can be used in etching steps, ion implantation steps, bump electrode formation steps, rewiring formation steps, MEMS (Micro Electro Mechanical Systems: Micro Electro Mechanical Systems) and the like.

[actinic radiation or radiation sensitive film]

The present invention also relates to an actinic radiation-sensitive or radiation-sensitive film (preferably a resist film) formed from the actinic radiation-sensitive or radiation-sensitive composition of the present invention. Such a film is formed, for example, by applying the composition of the present invention on a support such as a substrate. The thickness of the film is preferably 0.02 to 0.1 μm. As the method of coating on the substrate, it is coated on the substrate by an appropriate coating method such as spin coating, roll coating, flow coating, dip coating, spray coating, doctor blade coating, but the spin coating is Preferably, the rotation speed is 1000~3000rpm (rotations per minute: revolutions per minute). The coating film is baked at 60-150° C. for 1-20 minutes, preferably at 80-120° C. for 1-10 minutes to form a thin film.

The material constituting the substrate to be processed and its outermost layer is, for example, a silicon wafer when it is a semiconductor wafer. Examples of the material used as the outermost layer include Si, SiO ₂ , SiN, SiON, TiN, WSi, BPSG, SOG, Organic anti-reflection film, etc.

An anti-reflection film may be pre-coated on the substrate before forming the resist film.

As the antireflection film, any of inorganic film types such as titanium, titanium dioxide, titanium nitride, chromium oxide, carbon, and amorphous silicon, and organic film types including light absorbers and polymer materials can be used. In addition, commercially available organic antireflection films such as DUV30 series and DUV-40 series manufactured by Brewer Science, Inc., AR-2, AR-3, and AR-5 manufactured by Shipley Japan, Ltd. can also be used as the organic antireflection film. Reflective film.

In addition, in the pattern forming method of the present invention, a top coat layer may be formed on the upper layer of the resist film. It is preferable that the top coat layer is not mixed with the resist film and can be evenly applied to the upper layer of the resist film.

The top coat layer is not particularly limited, and a conventionally known top coat layer can be formed by a conventionally known method, for example, the top coat layer can be formed according to the description in paragraphs 0072 to 0082 of JP-A-2014-059543.

For example, it is preferable to form a top coat layer containing a basic compound described in JP 2013-061648 A on a resist film. Specific examples of the basic compound that can be included in the top coat layer are the same as those described above for the acid diffusion inhibitor.

Also, it is preferable that the top coat layer contains a compound containing at least one group or bond selected from the group consisting of ether bond, thioether bond, hydroxyl group, thiol group, carbonyl bond and ester bond.

Also, it is preferable that the top coat layer contains a resin. The resin that can contain the top coat layer is not particularly limited, and the same hydrophobic resin that can be contained in the actinic radiation-sensitive or radiation-sensitive composition can be used.

As the hydrophobic resin, it is possible to refer to paragraphs <0017>~<0023> of Japanese Patent Laid-Open No. 2013-061647 (corresponding to paragraphs <0017>~<0023> of U.S. Laid-Open Patent Publication No. 2013/244438) and Japanese Patent Laid-Open The records in paragraphs <0016> to <0165> of Publication No. 2014-056194 can be incorporated into the description of this application.

The top coat layer preferably comprises a resin containing repeating units having an aromatic ring. By including a repeating unit having an aromatic ring, the generation efficiency of secondary electrons and the acid generation efficiency from compounds that generate acid by actinic rays or radiation become high especially at the time of electron beam or EUV exposure, and at the time of pattern formation Effects of high sensitivity and high resolution can be expected.

When the top coat layer contains several kinds of resins, it is preferable to contain at least one resin (XA) having fluorine atoms and/or silicon atoms. The top coat composition includes at least one resin (XA) having fluorine atoms and/or silicon atoms, and a resin (XB) having a smaller content of fluorine atoms and/or silicon atoms than the resin (XA) is more preferable. Thereby, when the top coat film is formed, the resin (XA) is locally present on the surface of the top coat film, so performances such as developing characteristics and immersion liquid followability can be improved.

In addition, the top coat layer may contain an acid generator and a crosslinking agent.

The top coat layer is typically formed from a composition for forming a top coat layer.

In the composition for forming a top coat layer, each component is preferably dissolved in a solvent and filtered through a filter. As a filter, the pore size is below 0.1 μm (more preferably 0.05 μm or less, more preferably 0.03 μm or less), those made of polytetrafluoroethylene, polyethylene or nylon are preferred. Also, when the solid content concentration of the 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, more preferably 0.5 μm or less, and 0.3 μm or less. Further better. The filter is preferably made of polytetrafluoroethylene, polyethylene or nylon. When performing filter filtration, for example, as disclosed in Japanese Patent Application Publication No. 2002-062667 (Japanese Patent Application Laid-Open No. 2002-062667 ), cyclic filtration can be performed, or multiple types of filters can be connected in series or in parallel to perform filtration. In addition, the composition may be filtered multiple times. In addition, the composition may be degassed before and after filtering through the filter.

It is preferable that the composition for forming a top coat layer does not contain impurities such as metals. The content of metal components contained in these materials is preferably 10 ppm or less, more preferably 5 ppm or less, still more preferably 1 ppm or less, and particularly preferably substantially free (below the detection limit of the measuring device).

In the manufacturing process (including the process of synthesizing raw materials, etc.) of the raw materials (resin, photoacid generator, etc.) The content of metal impurities in the agent composition (for example, mass ppm level) is also preferred. Such a method is described, for example, in Chemical Industry Daily on December 21, 2017.

When the exposure described later is immersion exposure, the top coat layer is disposed between the resist film and the immersion liquid and functions as a layer that prevents the resist film from directly contacting the immersion liquid. In this case, as the top coat (top coat forming composition) has Its preferred properties are coating suitability to resist film, transparency to radiation, especially 193nm, and poor solubility to immersion liquid (preferably water). In addition, it is preferable that the top coat layer is not mixed with the resist film, and can be evenly applied to the surface of the resist film.

In addition, in order to uniformly coat the surface of the resist film with the composition for forming the top coat layer without dissolving the resist film, it is preferable that the composition for forming the top coat layer contains a solvent that does not dissolve the resist film. good. As the solvent which does not dissolve the resist film, it is more preferable to use a solvent having a different component from a developer (organic developer) containing an organic solvent described in detail below.

The coating method of the composition for forming a top coat layer is not particularly limited, and conventionally known spin coating methods, spray methods, roll coating methods, dipping methods, and the like can be used.

The film thickness of the top coat layer is not particularly limited. From the viewpoint of transparency to the exposure light source, the film thickness is usually 5 nm to 300 nm, preferably 10 nm to 300 nm, more preferably 20 nm to 200 nm, and further preferably 30 nm. ~100nm thickness formed.

After the top coat is formed, the substrate is optionally heated (PB).

From an analytical point of view, it is preferable that the refractive index of the top coat layer is close to that of the resist film.

The top coat is preferably insoluble in the dipping solution, more preferably insoluble in water.

Regarding the receding contact angle of the top coat, the receding contact angle (23° C.) of the immersion liquid relative to the top coat is preferably 50 to 100 degrees, more preferably 80 to 100 degrees, from the viewpoint of the followability of the immersion liquid.

In liquid immersion exposure, it is necessary for the immersion liquid to move on the wafer following the action of scanning the exposure head on the wafer at high speed and forming an exposure pattern, so the contact angle of the immersion liquid to the top coat layer in the dynamic state becomes Importantly, in order to obtain better resist performance, it is preferable to have a receding contact angle within the above-mentioned range.

When stripping the top coat, an organic developer can be used, or a stripper can be used alone. As a stripping agent, a solvent having little penetration into a resist film is preferable. From the viewpoint of simultaneously performing the peeling of the top coat layer and the development of the resist film, it is preferable that the top coat layer can be peeled off with an organic developer. The organic developing solution used for the stripping is not particularly limited as long as the low-exposed portion of the resist film can be dissolved and removed.

From the viewpoint of peeling by the organic developer, the dissolution rate of the top coat layer in the organic developer is preferably 1-300 nm/sec, more preferably 10-100 nm/sec.

Here, the dissolution rate of the top coat layer in an organic developer refers to the film thickness reduction rate when the top coat layer is formed into a film and exposed to a developer solution. In the present invention, it is butyl acetate soaked at 23°C. time speed.

By setting the dissolution rate of the top coat layer in the organic developer at least 1 nm/sec, preferably at least 10 nm/sec, there is an effect of reducing development defects after developing the resist film. Also, by setting it to 300nm/sec or less, preferably 100nm/sec, the line edge roughness of the pattern after developing the resist film may be further reduced due to the influence of the reduction of exposure unevenness during liquid immersion exposure. good effect.

For the top coat layer, other well-known developing solutions can also be used, for example, it can be removed using an alkaline aqueous solution or the like. As a basic aqueous solution which can be used, the aqueous solution of tetramethylammonium hydroxide is mentioned concretely.

[Pattern Formation Method]

The present invention also relates to a pattern forming method, comprising: a resist film forming step of forming a resist film using the actinic radiation-sensitive or radiation-sensitive resin composition of the present invention; and an exposing step of exposing the resist film. ; and a developing step of developing the exposed resist film using a developing solution.

In the present invention, the above-mentioned exposure is preferably performed using electron beams, ArF excimer lasers, or extreme ultraviolet rays, more preferably electron beams or extreme ultraviolet rays.

In the manufacture of precision integrated circuit elements, etc., for the exposure on the resist film (patterning step), first, ArF excimer laser, electron beam or extreme ultraviolet (EUV) is applied to the resist film of the present invention in a pattern form. Irradiation is better. In the case of ArF excimer laser, the exposure is performed with an exposure amount of about 1~100mJ/cm ² , preferably about 20~60mJ/cm ² , and in the case of an electron beam, the exposure amount is 0.1~ Expose at about 20μC/cm ² , preferably about 3~10μC/cm ² , in the case of extreme ultraviolet rays, the exposure amount becomes about 0.1~20mJ/cm ² , preferably 3~15mJ/cm ² exposure in a left-right manner.

Next, heat on a heating plate preferably at 60-150°C for 5 seconds to 20 minutes (post-exposure baking), more preferably at 80-120°C for 15 seconds-10 minutes Then heat (post-exposure baking), and then develop, rinse, and dry to form a pattern. Here, after exposure, heating is performed by resin (A) having The acid decomposability of the repeating unit having an acid decomposable group is properly adjusted. When the acid decomposability is low, it is also preferable that the temperature of heating after exposure is 110° C. or higher, and the heating time is 45 seconds or longer.

The developer can be appropriately selected, but it is preferable to use an alkaline developer (usually an alkaline aqueous solution) or a developer containing an organic solvent (also referred to as an organic developer). When the developer is an alkaline aqueous solution, 0.1 to 5% by mass of tetramethylammonium hydroxide (TMAH), tetrabutylammonium hydroxide (TBAH), etc., preferably 2 to 3% by mass, of an alkaline aqueous solution is used. The development is carried out for 0.1 to 3 minutes, preferably 0.5 to 2 minutes, by a conventional method such as a dip method, a puddle method, and a spray method. An appropriate amount of alcohols and/or surfactants can also be added to the alkaline developer. In this way, when a negative pattern is formed, the film of the unexposed part dissolves, and the exposed part is difficult to dissolve in the developing solution; when a positive pattern is formed, the film of the exposed part dissolves, and the film of the unexposed part hardly dissolves The developing solution can form the target pattern on the substrate.

When the pattern forming method of the present invention has a step of developing using an alkaline developing solution, as the alkaline developing solution, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia water can be used and other inorganic bases, primary amines such as ethylamine and n-propylamine, secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, dimethylethanolamine, tertiary amines such as Alcoholamines such as ethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctyl ammonium hydroxide Ammonium Hydroxide, Ethyl Trimethyl Ammonium Hydroxide, Butyl Trimethyl Ammonium Hydroxide, Methyl Tripentyl Ammonium Hydroxide, Dibutyl Dipentyl Ammonium Hydroxide, Tetraalkyl Ammonium Hydroxide, Trimethyl phenyl ammonium hydroxide, trimethylbenzyl hydroxide Ammonium, triethylbenzyl ammonium hydroxide, dimethyl bis(2-hydroxyethyl) ammonium hydroxide and other quaternary ammonium salts, pyrrole, piperidine and other cyclic amines and other alkaline aqueous solutions.

In addition, an appropriate amount of alcohols and surfactants may be added to the above-mentioned alkaline aqueous solution and used.

The alkali concentration of an alkaline developer is normally 0.1-20 mass %.

The pH of alkaline developer is usually 10.0~15.0.

In particular, a 2.38% by mass aqueous solution of tetramethylammonium hydroxide is preferable.

It is also possible to use pure water and add a suitable amount of surfactant as a rinse liquid in the rinse process performed after alkali image development.

In addition, after the development treatment or the rinse treatment, it is possible to perform a process of removing the developing solution or the rinse solution adhering to the pattern with a supercritical fluid.

When the pattern forming method of the present invention has a step of developing using a developer containing an organic solvent, as the developer in the above step (hereinafter also referred to as an organic developer), a ketone-based solvent, an ester-based developer, or a ketone-based developer can be used. Solvents, alcohol solvents, amide solvents, ether solvents and other polar solvents and hydrocarbon solvents.

In the present invention, an ester solvent is a solvent having an ester group in the molecule, a ketone solvent is a solvent having a ketone group in the molecule, an alcohol solvent is a solvent having an alcoholic hydroxyl group in the molecule, and an amide solvent is a solvent having an alcoholic hydroxyl group in the molecule. A solvent having an amide group in the molecule, and an ether solvent is a solvent having an ether bond in the molecule. Among these, there are also solvents having a plurality of types of the above-mentioned functional groups in one molecule, and in this case, any solvent type containing the functional groups that the solvent has is applicable. For example, diethylene glycol monomethyl ether is regarded as any one of alcohol-based solvents and ether-based solvents in the above classification. In addition, the hydrocarbon solvent system does not have substitution Based hydrocarbon solvents.

In particular, a developer containing at least one solvent selected from ketone-based solvents, ester-based solvents, alcohol-based solvents, and ether-based solvents is preferable.

From the viewpoint of being able to suppress the swelling of the resist film, the developer used has a carbon number of 7 or more (preferably 7-14, more preferably 7-12, and more preferably 7-10) and has a heteroatom number of 2 The following ester solvents are preferred.

The heteroatoms of the above-mentioned ester-based solvent are atoms other than carbon atoms and hydrogen atoms, and examples thereof include oxygen atoms, nitrogen atoms, sulfur atoms, and the like. The number of heteroatoms is preferably 2 or less.

Preferred examples of ester-based solvents having 7 or more carbon atoms and 2 or less heteroatoms include amyl acetate, isopentyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, acetic acid Hexyl ester, pentyl propionate, hexyl propionate, heptyl propionate, butyl butyrate, isobutyl isobutyrate, etc., particularly preferably isoamyl acetate or isobutyl isobutyrate.

The developer may be a mixed solvent of the above-mentioned ester solvent and the above-mentioned hydrocarbon solvent or a mixed solvent of the above-mentioned ketone solvent and the above-mentioned hydrocarbon solvent instead of the above-mentioned ester solvent having 7 or more carbon atoms and 2 or less heteroatoms. In this case, swelling of the resist film is effectively suppressed.

When using an ester-based solvent and a hydrocarbon-based solvent in combination, it is preferable to use isoamyl acetate as the ester-based solvent. Also, as the hydrocarbon solvent, a saturated hydrocarbon solvent (for example, octane, nonane, decane, dodecane, undecane, hexadecane, etc.) is used from the viewpoint of the solubility of the resist film. is better.

Examples of ketone solvents include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methyl amyl ketone), 4-heptanone, 1-hexanone Ketone, 2-hexanone, diiso Butyl ketone, 2,5-dimethyl-4-hexanone, diisobutyl ketone, cyclohexanone, methyl cyclohexanone, propiophenone, methyl ethyl ketone, methyl isobutyl ketone, ethyl Diisobutyl ketone, 2,5-Dimethyl-4-hexanone is particularly preferred.

Examples of ester-based solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl 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, methyl 2-hydroxyisobutyrate, etc.

Examples of alcohol-based solvents include methanol, ethanol, n-propanol, isopropanol, n-butanol, secondary butanol, 4-methyl-2-pentanol, tertiary butanol, isobutanol, n-hexane Alcohols such as alcohol, n-heptanol, n-octanol, and n-decyl alcohol; glycol-based solvents such as ethylene glycol, diethylene glycol, and triethylene glycol; ethylene glycol monomethyl ether, propylene glycol monomethyl ether, and ethylene glycol Glycol ether solvents such as monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, or methoxymethyl butanol; etc.

Examples of ether solvents include anisole, dioxane, tetrahydrofuran, and the like in addition to the above-mentioned glycol ether solvents.

As an amide-based solvent, for example, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, hexamethylphosphoric acid triamide or 1,3-Dimethyl- 2-imidazolidinone, etc.

Examples of the hydrocarbon-based solvent include aromatic hydrocarbon-based solvents such as toluene and xylene, and aliphatic hydrocarbon-based solvents such as pentane, hexane, octane, decane, and undecane.

In addition, in the aliphatic hydrocarbon solvent which is a hydrocarbon solvent, it may be a mixture of compounds having the same carbon number and different structures. For example, when decane is used as an aliphatic hydrocarbon solvent, 2-methylnonane, 2,2-dimethyloctane, 4-ethyloctane, and isooctane, which are compounds with the same carbon number but different structures, etc. may also be included in the aliphatic hydrocarbon solvent.

In addition, the above-mentioned compounds having the same carbon number and different structures may contain only one kind, or may contain plural kinds as described above.

The above-mentioned solvents may be mixed in plural, and may be used in admixture with solvents other than the above-mentioned ones or water. However, in order to fully exhibit the effects of the present invention, the water content of the entire developer is preferably less than 10% by mass, and it is more preferably substantially free of water.

The concentration of the organic solvent (total when mixing multiple types) in the organic developer is preferably at least 50% by mass, more preferably 50 to 100% by mass, further preferably 85 to 100% by mass, still more preferably 90% by mass. ~100% by mass, preferably 95~100% by mass. Optimal is the case where virtually only organic solvents are included. In addition, the case where only an organic solvent is actually included includes a case where a trace amount of a surfactant, an antioxidant, a stabilizer, an antifoaming agent, and the like are included.

In particular, an organic developer containing at least one organic solvent selected from the group consisting of ketone-based solvents, ester-based solvents, alcohol-based solvents, amide-based solvents, and ether-based solvents is preferred.

The vapor pressure of the organic developer is preferably below 5kPa at 20°C, 3 It is still more preferable that it is below kPa, and it is especially preferable that it is below 2 kPa. By setting the vapor pressure of the organic developer below 5kPa, the evaporation of the developer on the substrate or in the developing cup is suppressed, the temperature uniformity in the wafer surface is improved, and the dimensional uniformity in the wafer surface is optimized as a result.

Specific examples having a vapor pressure of 5 kPa or less include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 2-heptanone (methyl amyl ketone), 4-heptanone, Ketone solvents such as 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, propiophenone, methyl isobutyl ketone, butyl acetate, pentyl acetate, isoamyl 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 ester, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, butyl formate, propyl formate, lactic acid Ethyl ester, butyl lactate, propyl lactate and other ester solvents, n-propanol, isopropanol, n-butanol, secondary butanol, tertiary butanol, isobutanol, n-hexanol, n-heptanol, n-octyl alcohol Alcohol-based solvents such as alcohol and n-decyl alcohol, glycol-based solvents such as ethylene glycol, diethylene glycol, and triethylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether , diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methoxymethyl butanol and other glycol ether solvents, tetrahydrofuran and other ether solvents, N-methyl-2-pyrrolidone, N,N -Amide-based solvents such as dimethylacetamide and N,N-dimethylformamide, aromatic hydrocarbon-based solvents such as toluene and xylene, and aliphatic hydrocarbon-based solvents such as octane and decane.

Specific examples of a vapor pressure of 2 kPa or less in an especially preferable range include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 2-heptanone, 4-heptanone, and 2-hexanone. Ketones, diisobutyl ketone, cyclohexanone, methylcyclohexanone, propiophenone and other ketone solvents, butyl acetate, acetic acid Amyl ester, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropane Esters, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl lactate, butyl lactate, propyl lactate and other ester solvents, n-butanol, Secondary butanol, tertiary butanol, isobutanol, n-hexanol, n-heptanol, n-octanol, n-decyl alcohol and other alcohol solvents, ethylene glycol, diethylene glycol, triethylene glycol and other glycols Solvent, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methoxymethyl butanol and other glycol ethers N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide and other amide-based solvents, xylene and other aromatic hydrocarbon-based solvents, Aliphatic hydrocarbon solvents such as octane, decane, and undecane.

The organic developer may also contain a basic compound. Specific examples and preferred examples of the basic compound that can be contained in the developer used in the present invention are the same as those of the basic compound that can be contained in the above-mentioned actinic radiation-sensitive or radiation-sensitive composition.

An appropriate amount of surfactant can be added to the organic developer solution as required.

The surfactant is not particularly limited, and for example, ionic or nonionic fluorine-based and/or silicon-based surfactants can be used. As such fluorine and/or silicon-based surfactants, for example, JP-A-62-036663, JP-A-61-226746, JP-A-61-226745, JP-A 62-170950, JP-A-63-034540, JP-H7-230165, JP-8-062834, JP-9-054432, JP-9-005988 Gazette, U.S. Patent No. 5,405,720 specification, U.S. Patent No. 5,360,692 specification, U.S. Patent No. 5,529,881 The surfactants described in the specification, US Patent No. 5,296,330, US Patent No. 5,436,098, US Patent No. 5,576,143, US Patent No. 5,294,511, and US Patent No. 5,824,451 are preferably nonionic of surfactants. Although it does not specifically limit as a nonionic surfactant, It is more preferable to use a fluorine type surfactant or a silicon type surfactant.

The amount of the surfactant used is preferably 0.0001 to 2% by mass, more preferably 0.0001 to 1% by mass, and most preferably 0.0001 to 0.1% by mass relative to the total amount of the developer.

As the developing method, for example, the following methods can be applied: a method of immersing the substrate in a tank filled with a developer for a certain period of time (dipping method), and a method of developing by stacking the developer on the surface of the substrate by surface tension and standing still for a certain period of time (paddle method), method of spraying the developer on the surface of the substrate (spray method), or method of continuously spraying the developer while scanning the developer spray nozzle at a constant speed on the substrate rotating at a constant speed (dynamic allocation method), etc.

When the above-mentioned various developing methods include the step of ejecting the developer from the developing nozzle of the developing device to the resist film, the ejection pressure of the ejected developer (the flow rate per unit area of the ejected developer) is preferably 2 mL /sec/mm ² or less, more preferably 1.5 mL/sec/mm ² or less, further preferably 1 mL/sec/mm ² or less. There is no particular lower limit for the flow rate, but considering the throughput, it is preferably 0.2 mL/sec/mm ² or more.

By setting the ejection pressure of the ejected developing solution within the above-mentioned range, it is possible to remarkably reduce pattern defects due to resist residue after image development.

The details of the mechanism are not clear, but it is thought that the reason is that by injecting The pressure is set to the above range, so that the pressure exerted by the developer on the resist film becomes smaller, and the resist film becomes smaller. Inadvertent chipping or collapse of the resist pattern is suppressed.

In addition, the discharge pressure (mL/sec/mm ² ) of the developer is a value at the outlet of the developing nozzle in the developing device.

As a method of adjusting the discharge pressure of the developer, for example, a method of adjusting the discharge pressure by using a pump or the like, or a method of changing the discharge pressure by adjusting the pressure with supply from a pressurizing tank, etc. are mentioned.

Moreover, after the process of developing using the developing solution containing an organic solvent, you may implement the process of stopping development, replacing with another solvent.

After the step of developing using a developing solution containing an organic solvent, a step of washing with a rinse solution may also be included, but from the viewpoint of the throughput (productivity) and the amount of rinse solution used, etc., it may not include the step of using a rinse solution. Cleaning steps.

The rinsing solution used in the rinsing step after the step of developing using a developing solution 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 above-mentioned rinsing solution, it is preferable to use the following rinsing solution, which contains at least an organic solvent.

Specific examples of hydrocarbon-based solvents, ketone-based solvents, ester-based solvents, alcohol-based solvents, amide-based solvents, and ether-based solvents include the same ones as those described in the developer containing organic solvents. In particular, preferred Examples thereof include butyl acetate and methyl isobutyl carbinol.

After the step of developing using a developing solution containing an organic solvent, it is more preferable to carry out Perform the step of cleaning using the following rinse solution, the rinse solution contains at least one organic solvent selected from the group consisting of ester solvents, alcohol solvents, and hydrocarbon solvents, and it is further preferred to use an alcohol solvent or The cleaning step is carried out with the rinse solution of hydrocarbon solvent.

As the organic solvent contained in the rinsing liquid, it is also preferable to use a hydrocarbon-based solvent among the organic solvents, and it is more preferable to use an aliphatic hydrocarbon-based solvent. As the aliphatic hydrocarbon solvent used in the rinsing liquid, from the viewpoint of further improving its effect, aliphatic hydrocarbon solvents with 5 or more carbon atoms (for example, pentane, hexane, octane, decane, undecane , dodecane, hexadecane, etc.) are preferred, aliphatic hydrocarbon solvents having 8 or more carbon atoms are preferred, and aliphatic hydrocarbon solvents having 10 or more carbon atoms are more preferred.

Moreover, the upper limit of the carbon number of the said aliphatic hydrocarbon solvent is not specifically limited, For example, 16 or less are mentioned, Preferably it is 14 or less, More preferably, it is 12 or less.

Among the above-mentioned aliphatic hydrocarbon solvents, decane, undecane, and dodecane are particularly preferable, and undecane is most preferable.

As described above, by using a hydrocarbon-based solvent (especially an aliphatic hydrocarbon-based solvent) as the organic solvent contained in the rinse solution, the developer solution that has slightly permeated into the resist film after development is rinsed, further suppressing swelling, And the effect of suppressing pattern collapse is further exhibited.

The above-mentioned components may be mixed in plural, and may be used in admixture with organic solvents other than the above-mentioned ones.

The water content in the flushing liquid is preferably at most 10% by mass, more preferably at most 5% by mass, and most preferably at most 3% by mass. By setting the moisture content to 10% by mass Under this condition, good developing properties can be obtained.

The vapor pressure of the rinse solution used after the development step using a developer containing an organic solvent is preferably 0.05 kPa to 5 kPa at 20°C, more preferably 0.1 kPa to 5 kPa, and 0.12 More than kPa and less than 3kPa are the best. By setting the vapor pressure of the rinsing liquid above 0.05kPa and below 5kPa, the temperature uniformity in the wafer surface is improved, the swelling caused by the penetration of the rinsing liquid is further suppressed, and the dimensional uniformity in the wafer surface is optimized.

It can also be used by adding an appropriate amount of surfactant to the rinse solution.

In the rinsing step, the wafer developed using the developing solution containing the organic solvent is cleaned using the rinsing solution containing the above-mentioned organic solvent. The method of cleaning treatment is not particularly limited, and for example, the following methods can be applied: a method of continuously spraying a rinse solution on a substrate rotating at a constant speed (spin coating method), and a method of immersing a substrate in a tank filled with a rinse solution for a certain period of time. method (dipping method), or a method of spraying a rinsing liquid on the substrate surface (spraying method), etc., wherein the cleaning treatment is performed by a spin coating method, and after cleaning, the substrate is rotated at a speed of 2000 rpm to 4000 rpm, and the rinsing liquid is sprayed from Substrate removal is preferred. In addition, it is also preferable to include a heating step (Post Bake) after the rinsing step. The developer and rinse solution remaining between the patterns and inside the patterns are removed by baking. The heating step after the rinsing step is usually performed at 40 to 160° C. (preferably 70 to 95° C.) for 10 seconds to 3 minutes (preferably 30 seconds to 90 seconds).

When there is no step of washing with a rinse solution, for example, the development treatment method described in paragraphs [0014] to [0086] of JP-A-2015-216403 can be used.

Moreover, the pattern formation method of this invention may have the image development process which used the organic developer, and the image development process which used the alkaline developer. The portion with weak exposure intensity can be removed by development using an organic developer, and the portion with strong exposure intensity can be removed by development using an alkaline developer. In this way, by performing the multiple development process of developing multiple times, it is possible to form a pattern without dissolving only the region of the intermediate exposure intensity, so it is possible to form a finer pattern than usual (with JP-A-2008-292975 <0077> same mechanism).

The actinic radiation-sensitive or radiation-sensitive composition in the present invention and various materials used in the pattern forming method of the present invention (for example, resist solvent, developing solution, rinse solution, composition for forming an antireflection film, top, etc.) The composition for forming a coating layer, etc.) preferably does not contain impurities such as metals, metal salts including halogens, acids, alkalis, components including sulfur atoms or phosphorus atoms. Among them, examples of impurities containing metal atoms include Na, K, Ca, Fe, Cu, Mn, Mg, Al, Cr, Ni, Zn, Ag, Sn, Pb, Li, or salts thereof.

The content of impurities contained in these materials is preferably 1ppm or less, more preferably 1ppb or less, further preferably 100ppt (parts per trillion: parts per trillion) or less, and particularly preferably 10ppt or less. Actually, it does not contain (Below the detection limit of the measuring device) is the best.

As a method of removing impurities such as metals from various materials, for example, filtration using a filter can be mentioned. The pore size of the filter is preferably at most 10 nm, more preferably at most 5 nm, and still more preferably at most 3 nm. As a material of the filter, a filter made of polytetrafluoroethylene, polyethylene, or nylon is preferable. filter also It may be a composite material combining these materials with an ion exchange medium. Filters can also be pre-cleaned with organic solvents. In the filter filtration step, a plurality of types of filters can be used by connecting them in series or in parallel. When using multiple types of filters, filters with different pore diameters and/or materials can also be used in combination. In addition, various materials may be filtered multiple times, and the step of performing multiple times of filtration may also be a circulating filtration step.

In addition, as a method of reducing impurities such as metals contained in various materials, the following methods can be listed: selecting raw materials with low metal content as raw materials constituting various materials, filtering raw materials constituting various materials, and using TEFLON (registered trademark) lining, etc., under the conditions of suppressing contamination as much as possible, such as distillation. Preferable conditions in filter filtration of raw materials constituting various materials are the same as the above-mentioned conditions.

In addition to filter filtration, adsorption materials can also be used to remove impurities, and filter filtration and adsorption materials can also be used in combination. As the adsorbent, known adsorbents can be used, for example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be used.

In addition, as a method of reducing impurities such as metals contained in the organic treatment liquid of the present invention, the following methods can be cited: selecting raw materials with low metal content as raw materials constituting various materials, and filtering the raw materials constituting various materials. , Lining the inside of the device with TEFLON (registered trademark), etc., and performing distillation under conditions that suppress contamination as much as possible. Preferable conditions in filter filtration of raw materials constituting various materials are the same as the above-mentioned conditions.

In addition to filter filtration, it is also possible to remove impurities using adsorption materials, Combinations of filter filtration and adsorption materials are also possible. As the adsorbent, known adsorbents can be used, for example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be used.

[container]

An organic solvent for pattern formation using a chemically amplified or non-chemically amplified resist film stored in a container as an organic solvent (also referred to as an "organic treatment solution") that can be used in a developing solution and a rinse solution Liquid storage containers are preferred. As the storage container, for example, the inner wall of the storage part in contact with the organic treatment liquid is made of a resin different from any of polyethylene resin, polypropylene resin, and polyethylene-polypropylene resin, or rust-proof/ The storage container for the organic processing liquid for patterning the resist film formed of the metal elution preventing treatment is preferable. A predetermined organic solvent used as an organic treatment liquid for patterning a resist film is stored in the storage portion of the storage container, and what is discharged from the storage portion can be used when forming a pattern of the resist film.

When the storage container further has a sealing portion for sealing the storage portion, the sealing portion is also made of one or more resins selected from the group consisting of polyethylene resin, polypropylene resin, and polyethylene-polypropylene resin. It is preferable to form it with a resin, or a metal treated with antirust/metal elution treatment.

Here, the sealing part refers to a member capable of blocking the housing part from the outside air, and a gasket, an O-ring, and the like can be preferably mentioned.

Resin-based perfluororesins different from one or more resins selected from the group consisting of polyethylene resins, polypropylene resins, and polyethylene-polypropylene resins are preferred.

Examples of perfluororesins include tetrafluoroethylene resin (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer resin (FEP), tetrafluoroethylene- Ethylene copolymer resin (ETFE), chlorotrifluoroethylene-ethylene copolymer resin (ECTFE), vinylidene chloride resin (PVDF), chlorotrifluoroethylene copolymer resin (PCTFE), vinyl fluoride resin (PVF), etc.

Particularly preferred perfluororesins include tetrafluoroethylene resins, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymers, and tetrafluoroethylene-hexafluoropropylene copolymer resins.

Examples of metals in metals subjected to rust prevention/metal elution prevention treatment include carbon steel, alloy steel, nickel-chromium steel, nickel-chromium-molybdenum steel, chromium steel, chromium-molybdenum steel, manganese steel, and the like.

As anti-rust/metal elution prevention treatment, it is better to apply coating technology.

Coating technology is roughly divided into three types: metal coating (various electroplating), inorganic coating (various chemical conversion treatments, glass, cement, ceramics, etc.), and organic coating (antirust oil, paint, rubber, plastic).

As a preferred coating technology, surface treatment using anti-rust oil, anti-rust agent, preservative, chelating compound, peelable plastic, and lining agent can be listed.

Among them, various chromates, nitrites, silicates, phosphates, oleic acid, dimer acid, naphthenic acid and other carboxylic acids, carboxylic acid metal soaps, sulfonates, amine salts, esters (glycerin of higher fatty acids) ester or phosphate), chelating compounds such as ethylenediaminetetraacetic acid, gluconic acid, nitrilotriacetic acid, hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, and fluororesin lining better. The best is phosphate treatment and fluororesin lining.

In addition, compared with direct coating treatment, although it is not for direct rust prevention, as a treatment method for prolonging the rust prevention period by coating treatment, it is adopted as a method related to rust prevention. "Pretreatment" of the stage before the treatment is also preferable.

As a specific example of such pretreatment, a treatment for removing various corrosion factors such as chlorides and sulfates present on the metal surface by cleaning or polishing can be preferably mentioned.

Specific examples of the container include the following.

． Fluoro Pure PFA compound cartridge made by Entegris, Inc. (wetted inner surface; PFA resin lining)

． JFE steel tank (inner surface in contact with liquid; zinc phosphate coating)

In addition, as a storage container that can be used in the present invention, the <0013>-<0030> paragraphs of JP-A-11-021393 and the <0012>-<0024> paragraphs of JP-A-10-045961 can also be cited. Recorded container.

In order to prevent electrostatic charging and failure of chemical piping or various components (filters, O-rings, hoses, etc.) associated with continued electrostatic discharge, conductive compounds can be added to the organic treatment liquid of the present invention. It does not specifically limit as a conductive compound, For example, methanol is mentioned. The amount added is not particularly limited, but from the viewpoint of maintaining good image development properties, it is preferably 10% by mass or less, more preferably 5% by mass or less. As for the chemical piping components, various pipings coated with SUS (stainless steel) or antistatic treated polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.) can be used. For filters and O-rings, antistatic-treated polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.) can also be used in the same manner.

In addition, in general, developer and rinse solution are stored through piping after use. in the waste tank. At this time, when a hydrocarbon-based solvent is used as the rinse solution, the resist dissolved in the developer is precipitated. In order to prevent adhesion to the back of the wafer or the side of the pipe, there is a method of passing the solvent that dissolves the resist through the pipe again. As a method of passing through the piping, there may be mentioned a method of washing the back surface or side of the substrate with a solvent that dissolves the resist after cleaning with a rinse solution; or flowing a solvent that dissolves the resist without contacting the resist, In order to pass through the piping method.

The solvent passing through the piping is not particularly limited as long as it can dissolve the resist. For example, the above-mentioned organic solvents are mentioned, and propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, Propyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol mono Methyl ether (PGME), propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-heptanone, ethyl lactate, 1-propanol, acetone, etc. Among them, PGMEA, PGME, and cyclohexanone can be preferably used.

[Manufacturing method of electronic device]

Moreover, the present invention also relates to a method of manufacturing an electronic device including the above pattern forming method. The electronic device manufactured by the method for manufacturing an electronic device of the present invention is suitably mounted on electrical and electronic equipment (for example, home appliances, OA (Office Automation) related equipment, media related equipment, optical equipment, communication equipment, etc.) .

[Manufacturing method of resin for actinic radiation-sensitive or radiation-sensitive resin composition]

The present invention also relates to a method for producing a resin for an actinic radiation-sensitive or radiation-sensitive resin composition, which comprises the step of washing the following (A) with an acidic aqueous solution.

(A) A resin having a repeating unit represented by the general formula (1), which is decomposed by the action of an acid and has an increased solubility in an alkaline developer

In the general formula (1), R ₁ represents a hydrogen atom or a monovalent organic group. X ₁ represents a divalent linking group. Y ₁ and Z ₁ each independently represent a monovalent organic group. Y ₁ and Z ₁ may be connected to form a ring.

About resin (A) and acidic aqueous solution, it is as above-mentioned.

A compound capable of making the pKa of the conjugate acid in the actinic or radiation sensitive resin composition be 4.0 or more by using the resin produced by the above-mentioned method for producing a resin for an actinic or radiation sensitive resin composition The content of is set to 1 ppm or less on a mass basis with respect to the total solid content.

[Manufacturing method of actinic radiation-sensitive or radiation-sensitive resin composition]

The present invention also relates to a method for producing an actinic radiation-sensitive or radiation-sensitive resin composition including the method for producing the above-mentioned resin (A).

The actinic radiation-sensitive or radiation-sensitive resin composition is as described above.

[Example]

The present invention will be described in further detail below based on examples. Materials, usage amounts, ratios, processing contents, processing procedures, and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. However, the scope of the present invention should not be limitedly interpreted by the examples shown below.

<Resin (A)>

<Synthesis Example 1: Synthesis of Resin (A-3)>

(Synthesis of Chloroethers)

25.0 g of 1-adamantanecarbaldehyde, 24.2 g of trimethyl orthoformate, 353 mg of camphorsulfonic acid, and 125 mL of hexane were added to a 500 mL eggplant-shaped flask, and stirred at 25° C. for 1 hour. 1.5 g of triethylamine was added and stirred, and the organic phase was washed three times with 200 mL of distilled water. Hexane was removed under reduced pressure to obtain 33.0 g of Compound 1 shown below as an acetal compound.

Next, 28.6 g of acetyl chloride (AcCl) was added to 31.8 g of the obtained compound 1, and stirred in a water bath at 40° C. for 5 hours. After returning to 25° C., unreacted acetyl chloride was removed under reduced pressure to obtain 36.2 g of Compound 2 shown below as a chloroether compound.

(Synthesis of Resin (A-3))

18.0 g of poly(p-hydroxystyrene) (VP-2500, manufactured by NIPPON SODA CO., LTD.) was dissolved in 120 g of tetrahydrofuran (THF), and 3.46 g of triethylamine was added thereto, followed by stirring in an ice-water bath. Compound 2 (6.12 g) obtained above was added dropwise to the reaction liquid, followed by stirring for 4 hours. A small amount of the reaction solution was taken and the result of ¹ H-NMR was measured. The protection rate was 18.2%. Then, a small amount of compound 2 was added and stirred for 4 hours, and the operation of measuring ¹ H-NMR was repeated, and the reaction was stopped by adding distilled water to the etch where the protection rate exceeded 20.0% which was the target value. THF was distilled off under reduced pressure, and the reactant was dissolved in ethyl acetate. After the obtained organic phase was washed 5 times with distilled water, the organic phase was added dropwise to 1.5 L of hexane. The obtained precipitate was separated by filtration and washed with a small amount of hexane. 10 g of the obtained powder was dissolved in 20 g of propylene glycol monomethyl ether acetate (PGMEA), and 300 g of ethyl acetate was added thereto. The solution was transferred to a separatory funnel, and 300 g of an acidic aqueous solution was added and washed. After repeating this washing operation 3 times, it washed 4 times with 300 g of distilled water. At this time, a 0.1 mol/L aqueous hydrochloric acid solution or a 0.5 mol/L oxalic acid aqueous solution was used as the acidic aqueous solution. After the solvent was distilled off under reduced pressure, it was dissolved in 30 g of PGMEA. The low boiling point solvent was removed from the obtained solution with the evaporator, and the PGMEA solution (30.1 mass %) of 26.3 g of resin (A-3) was obtained.

Regarding the obtained resin (A-3), the repeating unit content was measured by ¹³ C-NMR (nuclear magnetic resonance: nuclear magnetic resonance) or ¹ H-NMR. In addition, the weight average molecular weight (Mw) and dispersity (Mw/Mn) of resin were measured by GPC (carrier: tetrahydrofuran (THF)) (it was the amount in terms of polystyrene).

Regarding the other resin (A) used, by carrying out the same process as resin (A-3) operation to synthesize. The structure of the repeating unit of the resin (A) used and its content (molar ratio), weight average molecular weight (Mw) and degree of dispersion (Mw/Mn) are shown.

<Acid Generator>

The structures of the acid generators used are shown below.

<Resin (C)>

Regarding the resin (C) used, the structure of the repeating unit and its content (molar ratio), weight average molecular weight (Mw) and degree of dispersion (Mw/Mn) are shown.

In addition, the weight average molecular weight (Mw) and degree of dispersion (Mw/Mn) of the resin were measured in the same manner as the resin (A).

[chem 62]

<Acid Diffusion Control Agent>

The structure of the acid diffusion controller used is shown below.

<Surfactant>

As surfactants, the following W-1 to W-4 were used.

W-1: MEGAFACE R08 (manufactured by Dainippon Ink and Chemicals, Inc.; fluorine and silicon)

W-2: polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.; silicon-based)

W-3: Troy Sol S-366 (manufactured by Troy Chemical Industries Inc.; fluorine-based)

W-4: PF6320 (manufactured by OMNOVA SOLUTIONS INC.; fluorine-based)

<solvent>

The solvents used are shown below.

S-1: Propylene Glycol Monomethyl Ether Acetate (PGMEA)

S-2: Propylene Glycol Monomethyl Ether (PGME)

S-3: Ethyl Lactate (EL)

S-4: Ethyl 3-ethoxypropionate (EEP)

S-5: 2-Heptanone (MAK)

S-6: Methyl 3-methoxypropionate (MMP)

S-7: 3-methoxybutyl acetate

[Preparation and application of coating solution of resist composition]

The components shown in the following Table 1 were dissolved in the solvents shown in the following Table 1, and a solution with a solid content concentration shown in the following Table 1 was prepared, and the solution was made of polyethylene with a pore size of 0.02 μm. Filtering was performed to obtain resist compositions R-1 to R-17.

These resist compositions were coated on a 6-inch Si wafer previously treated with hexamethyldisilazane (HMDS) using a spin coater Mark 8 manufactured by Tokyo Electron Limited, and heated at 100° C. Drying was carried out on a hot plate for 60 seconds to obtain a resist film with a film thickness of 150 nm.

Among them, 1 inch is 0.0254m.

In addition, even if the Si wafer described above was changed to a chromium substrate, the same result was obtained.

[EB exposure and development]

The wafer coated with the resist film obtained above was subjected to pattern irradiation using an electron beam drawing apparatus (HL750 manufactured by Hitachi, Ltd., acceleration voltage: 50 KeV). At this time, it is drawn in such a way that a 1:1 line and space are formed. After electron beam drawing, after heating on a hot plate at 100°C for 60 seconds, 2.38% by mass of tetramethylammonium hydroxide aqueous solution was applied for 30 seconds to develop, rinsed with pure water, and then rotated at 4000rpm. After the wafer was rotated for 30 seconds, it was heated at 95° C. for 60 seconds, thereby obtaining a resist pattern of a 1:1 line and space pattern with a line width of 50 nm.

[Evaluation]

(1) Sensitivity

The cross-sectional shape of the obtained pattern was observed with a scanning electron microscope (S-4300 manufactured by Hitachi, Ltd.). The exposure amount (electron beam irradiation amount) when analyzing a 1:1 line-space resist pattern with a line width of 50 nm was defined as sensitivity (Eop).

(2) LS resolution

The limit resolution (line and space (line: Space=1:1) The minimum line width for separation and analysis) is set as L/S resolution (nm).

(3) Analysis power of isolated space patterns

Calculate the limit resolution (minimum space width for separate analysis of line and space) of the isolated space (line:space=100:1) in the above-mentioned sensitivity. And, let this value be "isolated space pattern resolution (nm)". The smaller the value, the better the performance.

(4) Line edge roughness (LER)

The above-mentioned 50 nm line pattern (line: space = 1:1) was observed with a scanning electron microscope (S-4300 manufactured by Hitachi, Ltd.). Furthermore, the distance between the reference line that should have an edge and the actual edge was measured for 30 points at equal intervals included in the longitudinal direction of 50 μm. Then, the standard deviation of the distance is obtained, and 3σ is calculated. Then, let this 3σ be "LER (nm)".

(5) Scum

In the evaluation of the isolated space pattern resolving power described above, scum was evaluated as follows.

A: No scum was seen at all.

B: Scum is seen in the line width near the limit resolving power.

C: Scum was seen in a line width wider than the limit resolution.

(6)CDU

[In-plane uniformity (CDU) evaluation method of line width]

Measure the line width (CD) of 100 line patterns in each line pattern at an exposure dose at which the line width of the line-space 1:1 pattern becomes 50nm, and obtain three times the standard deviation (σ) of the average value calculated from the measurement results (3σ) and the in-plane uniformity (CDU) of CD was evaluated. The 3σ obtained from the above means that the smaller the value, the better the surface of each line CD formed on the resist film. The higher the internal uniformity (CDU).

(7) LS resolution after 3 months (stability over time)

The resist composition was stored at 25° C. for 3 months, and the L/S resolution was measured using the stored resist composition as described above.

(8) Content of the compound whose conjugate acid pKa is 4.0 or more in the resist composition (ratio to the total solid content of the resist composition (mass basis))

149 mg of triethylamine manufactured by Wako Pure Chemical Industries, Ltd. was dissolved in 10 mL of EL/PGME/PGMEA (mass ratio 6/2/2). This solution was further diluted 100-fold, collected in a 50 μL sample container for a pyrolysis device, and allowed to dry naturally. This sample was subjected to gas chromatography mass spectrometry analysis by gas chromatography mass spectrometry analyzer GCMS-QP2010 manufactured by Shimadzu Corporation connected to Frontier Laboratories Ltd. pyrolysis apparatus PY2020D, and the peak surface area of triethylamine was obtained from the spectrum (S ₀ ).

Thermal decomposition conditions in gas chromatography mass spectrometry are shown below.

Injection and interface temperature: 300°C

Column: thermal decomposition device column Frontier Laboratories Ltd. UA-5 (30m×0.25mmD film thickness 0.25μm)

Column temperature sequence: 50°C (2 minutes) → 15°C/min → 280°C (15 minutes)

Split ratio: 1/23.5

Detector: 0.8kV

Thermal decomposition furnace temperature: 300°C

The resist composition was collected in a 50 μL sample container for a thermal decomposition device and allowed to dry naturally. The sample is subjected to gas chromatography mass spectrometry analysis by the above-mentioned gas chromatography mass spectrometry device, and the sum of the spectral peak surface areas (S ₁ ) of the compound corresponding to the pKa of the conjugate acid of 4.0 or more is obtained, in the following formula Calculate the contained mass (mg) of the compound whose conjugate acid pKa is 4.0 or more.

Containing mass (mg) of the compound whose conjugate acid pKa is 4.0 or more=149×1.0×10 ^-3 ×5.0×10 ^-2 ×S ₁ /S ₀

Furthermore, by dividing this by the total solid content contained in 50 μL of the resist composition, the mass of the compound whose pKa of the conjugate acid is 4.0 or more relative to the total solid content of the resist composition is obtained Benchmark content (ppm).

In addition, in the following Table 1, the content (mass %) of each component other than the solvent means the content ratio with respect to the total solid content. Moreover, the content rate (mass %) of the solvent used with respect to all the solvents is described in following Table 1.

[Extreme Ultraviolet (EUV) Exposure]

Resist compositions R-1 to R-17 were coated on a 6-inch Si wafer previously treated with hexamethyldisilazane (HMDS) using a spin coater Mark8 manufactured by Tokyo Electron Limited. It was dried on a hot plate at 100° C. for 60 seconds to obtain a resist film with a film thickness of 150 nm.

The above-mentioned The wafer of the obtained resist film was subjected to pattern exposure. After exposure, it was heated on a hot plate at 100° C. for 90 seconds, then immersed in a 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds, and then rinsed with water for 30 seconds. Then, the wafer was rotated at 4000 rpm for 30 seconds, and then baked at 95° C. for 60 seconds to obtain a resist pattern of a 1:1 line and space pattern with a line width of 50 nm.

[Evaluation]

(1) Sensitivity

The cross-sectional shape of the obtained pattern was observed using a scanning electron microscope (S-4300 manufactured by Hitachi, Ltd.). The exposure amount (EUV irradiation amount) when analyzing a 1:1 line-space resist pattern with a line width of 50 nm was defined as sensitivity (Eop).

(2) LS resolution

Let the limit resolving power (minimum line width at which line and space (line: space = 1:1) are separated and analyzed) at the exposure amount showing the above-mentioned sensitivity be L/S resolving power (nm).

(3) Analysis power of isolated space patterns

Calculate the limit resolution (minimum space width for separate analysis of line and space) of the isolated space (line:space=100:1) in the above-mentioned sensitivity. And, let this value be "isolated space pattern resolution (nm)". The smaller the value, the better the performance.

(4) Line edge roughness (LER)

The above-mentioned 50 nm line pattern (line: space = 1:1) was observed with a scanning electron microscope (S-4300 manufactured by Hitachi, Ltd.). Furthermore, the distance between the reference line that should have an edge and the actual edge was measured for 30 points at equal intervals included in the longitudinal direction of 50 μm. Then, the standard deviation of the distance is obtained, and 3σ is calculated. Then, let this 3σ be "LER (nm)".

(5) Scum

In the evaluation of the isolated space pattern resolving power described above, scum was evaluated as follows.

A: No scum was seen at all.

B: Scum is seen in the line width near the limit resolving power.

C: Scum was seen in a line width wider than the limit resolution.

(6)CDU

[In-plane uniformity (CDU) evaluation method of line width]

Measure the line width (CD) of 100 line patterns in each line pattern at an exposure dose at which the line width of the line-space 1:1 pattern becomes 50nm, and obtain three times the standard deviation (σ) of the average value calculated from the measurement results (3σ) and the in-plane uniformity (CDU) of CD was evaluated. The 3σ obtained above indicates that the smaller the value, the higher the in-plane uniformity (CDU) of each line CD formed in the resist film.

(7) LS resolution after 3 months (stability over time)

The resist composition was stored at 25° C. for 3 months, and the L/S resolution was measured using the stored resist composition as described above.

(8) Content of the compound whose conjugate acid pKa is 4.0 or more in the resist composition (ratio to the total solid content of the resist composition (mass basis))

149 mg of triethylamine manufactured by Wako Pure Chemical Industries, Ltd. was dissolved in 10 mL of EL/PGME/PGMEA (6/2/2). This solution was further diluted 100 times, collected in a 50 µL sample container for a thermal decomposition device, and allowed to dry naturally. This sample was subjected to gas chromatography mass spectrometry analysis with a gas chromatography mass spectrometry analyzer GCMS-QP2010 manufactured by Shimadzu Corporation connected to a pyrolysis apparatus PY2020D produced by Frontier Laboratories Ltd., and the peak of triethylamine was obtained from the spectrum Surface area (S ₀ ).

Thermal decomposition conditions in gas chromatography mass spectrometry are shown below.

Injection and interface temperature: 300°C

Column: thermal decomposition device column Frontier Laboratories Ltd. UA-5 (30m×0.25mmD film thickness 0.25μm)

Column temperature sequence: 50°C (2 minutes) → 15°C/min → 280°C (15 minutes)

Split ratio: 1/23.5

Detector: 0.8kV

Thermal decomposition furnace temperature: 300°C

The resist composition was collected in a 50 μL sample container for a thermal decomposition device and allowed to dry naturally. The sample is subjected to gas chromatography mass spectrometry analysis by the above-mentioned gas chromatography mass spectrometry device, and the sum of the spectral peak surface areas (S ₁ ) of the compound corresponding to the pKa of the conjugate acid of 4.0 or more is obtained, in the following formula The contained mass (mg) of the compound whose pKa is 4.0 or more was calculated.

Containing mass (mg) of the compound whose conjugate acid pKa is 4.0 or more=149×1.0×10 ^-3 ×5.0×10 ^-2 ×S ₁ /S ₀

Furthermore, by dividing this by the total solid content contained in 50 μL of the resist composition, the mass of the compound whose pKa of the conjugate acid is 4.0 or more relative to the total solid content of the resist composition is obtained Baseline content (ppm).

From the results of Table 2 and Table 3, it can be seen that the resist compositions of the examples are excellent in resolution and roughness characteristics during pattern formation, can suppress generation of scum, have excellent CDU, and excellent stability over time.

Claims (15)

An actinic radiation-sensitive or radiation-sensitive resin composition, which contains the following (A) to (C), in the actinic radiation-sensitive or radiation-sensitive resin composition, the pKa of the conjugate acid is 4.0 or more The content is 1 ppm or less on a mass basis relative to the total solid content of the actinic radiation-sensitive or radiation-sensitive resin composition, and (A) has a repeating unit represented by general formula (1) and is carried out by the action of an acid A resin that decomposes and has an increased solubility in an alkaline developer; (B) a compound that generates an acid by irradiation with actinic rays or radiation; (C) has the ability to decompose by the action of an alkaline developer and The fluorine-containing compound of the group whose solubility in the developer is increased, the compound that generates an acid by irradiation with actinic rays or radiation relative to the total solid content of the actinic radiation-sensitive or radiation-sensitive resin composition (B ) content is 0.1~35% by mass, the content of the fluorine-containing compound (C) is 0.1~10% by mass,

In the general formula (1), R ₁ represents a hydrogen atom, an alkyl group with 1 to 20 carbons, or an alicyclic group with 3 to 10 carbons; X ₁ represents a keto group, a divalent aromatic ring group with 6 to 18 carbons or a divalent aromatic ring group including a heterocycle; _Y1 and Z1 independently represent an alkyl group with ₁ to 20 carbons, an alicyclic group with 3 to 10 carbons, an aryl group with 6 to 15 carbons, a carbon An aralkyl group with 6-20 carbons or a heterocyclic group with 6-20 carbons; Y ₁ and Z ₁ can be connected to form an aliphatic oxygen-containing ring with 2-10 carbons. The actinic radiation-sensitive or radiation-sensitive resin composition as described in claim 1, wherein the fluorine-containing compound (C) has a fluoroalkyl group. The actinic radiation-sensitive or radiation-sensitive resin composition as described in claim 1, wherein the fluorine-containing compound (C) has a repeating unit represented by general formula (2),

In the general formula (2), R ₂₁ represents a hydrogen atom or a monovalent organic group; X ₂ represents a divalent linking group; R ₂₂ and R ₂₃ independently represent a fluoroalkyl group; R ₂₄ represents a hydrogen atom, a fluorine atom or 1-valent organic group. The actinic radiation-sensitive or radiation-sensitive resin composition as described in claim 3, wherein X ₂ in the general formula (2) has a lactone structure. The actinic radiation-sensitive or radiation-sensitive resin composition as described in any one of the claims 1 to 4, wherein the molecular weight of the fluorine-containing compound (C) is 1,000-100,000. The actinic radiation-sensitive or radiation-sensitive resin composition as described in any one of the claims 1 to 4, wherein The content of the fluorine-containing compound (C) is 0.1 to 5% by mass relative to the total solid content of the actinic radiation-sensitive or radiation-sensitive resin composition. The actinic radiation-sensitive or radiation-sensitive resin composition as described in any one of the claims 1 to 4, wherein the resin (A) also has the following general formula (H-1) the repeating unit,

In the general formula (H-1), R ₃₁ , R ₃₂ and R ₃₃ independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group; R ₃₃ can be bonded to Ar ₃ to form When forming a ring, _R33 at this time represents an alkylene group, _X3 represents a single bond or a divalent linking group, and _Ar3 represents an aromatic ring group with a valence of (n3+1), and is bonded to _R33 to form a ring Represents an aromatic ring group with a valence of (n3+2), and n3 represents an integer of 1 to 4. The actinic radiation-sensitive or radiation-sensitive resin composition as described in any one of the first to fourth items of the scope of the patent application, wherein Y in the general formula ( ₁ ) is an alicyclic ring with 3 to 10 carbon atoms base. The actinic radiation-sensitive or radiation-sensitive resin composition described in any one of items 1 to 4 of the scope of the patent application, which contains a conjugate acid with a pKa of less than 4.0 Acid diffusion controller. The actinic radiation-sensitive or radiation-sensitive resin composition described in any one of items 1 to 4 of the patent claims is a chemically amplified positive resist composition. A method for producing a resin for an actinic radiation-sensitive or radiation-sensitive resin composition, comprising the step of washing the following (A) with an acidic aqueous solution, (A) having a repeating unit represented by general formula (1), A resin that is decomposed by the action of an acid and has an increased solubility in an alkaline developer,

In the general formula (1), R ₁ represents a hydrogen atom, an alkyl group with 1 to 20 carbons, or an alicyclic group with 3 to 10 carbons; X ₁ represents a keto group, a divalent aromatic ring group with 6 to 18 carbons or a divalent aromatic ring group including a heterocycle; _Y1 and Z1 independently represent an alkyl group with ₁ to 20 carbons, an alicyclic group with 3 to 10 carbons, an aryl group with 6 to 15 carbons, a carbon An aralkyl group with 6-20 carbons or a heterocyclic group with 6-20 carbons; Y ₁ and Z ₁ can be connected to form an aliphatic oxygen-containing ring with 2-10 carbons. A method for producing an actinic radiation-sensitive or radiation-sensitive resin composition, which includes the method for producing the resin described in item 11 of the patent application. An actinic radiation-sensitive or radiation-sensitive film, which uses the actinic radiation-sensitive or radiation-sensitive film described in any one of items 1 to 10 of the patent application Formed from a linear resin composition. A pattern forming method, which includes: a resist film forming step, using the actinic radiation-sensitive or radiation-sensitive resin composition described in any one of the claims 1 to 10 to form a resist an exposing step of exposing the resist film; and a developing step of developing the exposed resist film using a developing solution. A method of manufacturing an electronic device, which includes the pattern forming method described in item 14 of the patent application.