KR102469463B1 - Actinic ray-sensitive or radiation-sensitive resin composition, resist film, pattern formation method, and electronic device manufacturing method - Google Patents

Abstract

Provision of an actinic ray-sensitive or radiation-sensitive resin composition capable of imparting a pattern with excellent resolution, a resist film using the actinic ray-sensitive or radiation-sensitive resin composition, a pattern forming method, and an electronic device manufacturing method do. An actinic ray-sensitive or radiation-sensitive resin composition is used for forming a pattern having a film thickness of 1 μm or more, contains a resin, and contains an impurity having absorption at a wavelength of 248 nm, which is 1.00% by mass or less relative to the resin.

Description

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

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

Since the resist for KrF excimer laser (248 nm), an image forming method called chemical amplification has been used as a resist image forming method to compensate for the decrease in sensitivity due to light absorption. For example, as a positive chemical amplification image formation method, exposure to excimer laser, electron beam, extreme ultraviolet light, etc. decomposes the photoacid generator in the exposed area to generate acid, and post-exposure bake (PEB: Post Exposure Bake ), an image forming method in which an alkali-insoluble group is changed into an alkali-soluble group by using the generated acid as a reaction catalyst, and the exposed portion is removed by an alkali developer.

As such a resist composition, Patent Literature 1 describes, for example, a positive type resist composition containing a resin having p-hydroxystyrene-based repeating units.

Patent Document 1: Japanese Unexamined Patent Publication No. 2000-147772

On the other hand, at present, miniaturization using the wavelength of an exposure light source is facing a limit, and in particular, in the ion implantation process process and NAND memory (NOT AND memory), for the purpose of increasing the capacity, three-dimensionalization of the memory layer is becoming mainstream. Since the three-dimensionalization of the memory layer requires an increase in the number of processing steps in the vertical direction, the resist film is required to be thickened from the conventional nanoscale to micron scale.

The present inventors prepared a thick (1 μm or more) resist film using a resin having a p-hydroxystyrene-based repeating unit described in Patent Document 1, and examined the performance of the pattern after exposure and development. It turns out that this is not necessarily sufficient and there is room for further improvement.

Therefore, this invention makes it a subject to provide the actinic ray-sensitive or radiation-sensitive resin composition which can provide the pattern excellent in resolution.

Moreover, this invention makes it a subject to provide the resist film using the said actinic-ray sensitive or radiation-sensitive resin composition, the pattern formation method, and the manufacturing method of an electronic device.

The inventors of the present invention, as a result of intensive studies to achieve the above object, found that the object of the present invention can be solved by setting the content of an impurity having absorption at a wavelength of 248 nm in an actinic ray-sensitive or radiation-sensitive resin composition to a predetermined amount or less. found that there is, and completed the present invention.

That is, it was found that the above object can be achieved by the following structures.

[1] An actinic ray-sensitive or radiation-sensitive resin composition used for forming a pattern having a film thickness of 1 μm or more,

contains resin;

An actinic ray-sensitive or radiation-sensitive resin composition in which the content of impurities having absorption at a wavelength of 248 nm is 1.00% by mass or less with respect to the resin.

[2] The actinic ray-sensitive or radiation-sensitive resin composition according to [1], wherein the resin contains a repeating unit having a group that is decomposed by an action of acid to increase polarity.

[3] The actinic ray-sensitive or radiation-sensitive resin composition according to [1] or [2], wherein the resin contains a repeating unit having a phenolic hydroxyl group.

[4] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [3], wherein the impurity is an aromatic compound.

[5] The resin contains a repeating unit represented by general formula (I) described later,

The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [4], wherein the impurity is a compound represented by general formula (X) described later.

[6] The resin is a resin synthesized in the presence of a basic compound,

The actinic ray-sensitive or radiation-sensitive resin composition according to [5], wherein the content of the basic impurity derived from the basic compound is 0.10% by mass or less with respect to the resin.

[7] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [6], further containing a photoacid generator.

[8] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [7], having a viscosity of 100 to 500 mPa·s.

[9] A resist film formed of the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [8].

[10] A resist film forming step of forming a resist film having a film thickness of 1 μm or more using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [8];

an exposure step of exposing the resist film;

A pattern formation method comprising a developing step of developing the exposed resist film using a developing solution.

[11] A method for manufacturing an electronic device, including the pattern formation method according to [10].

ADVANTAGE OF THE INVENTION According to this invention, the actinic ray-sensitive or radiation-sensitive resin composition which can provide a pattern with excellent resolution can be provided.

Moreover, according to this invention, the resist film using the said actinic-ray sensitive or radiation-sensitive resin composition, the pattern formation method, and the manufacturing method of an electronic device can be provided.

1 is a SEM image of a cross section of a wafer after development (judgment N).
2 is a SEM image of a cross section of a wafer after development (judgment B).
3 is a SEM image of a cross section of a wafer after development (judgment A).

Hereinafter, the present invention will be described in detail.

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

Regarding the notation of a group (atomic group) in this specification, the notation that does not describe substitution and unsubstitution includes groups having no substituents as well as groups having no substituents. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). In addition, "organic group" in this specification refers to a group containing at least one carbon atom.

In this specification, "active ray" or "radiation" means, for example, the bright line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV light: Extreme Ultraviolet), X-rays, and electron beams (EB: Electron Beam), etc. "Light" in this specification means actinic light or radiation.

Unless otherwise specified, "exposure" in this specification means not only exposure by a bright line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV light), and X-rays, but also electron beams, ion beams, etc. Drawing by a particle beam of is also included.

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

In this specification, (meth)acrylate represents acrylate and methacrylate.

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

[Active ray sensitive or radiation sensitive resin composition]

The actinic ray-sensitive or radiation-sensitive resin composition of the present invention (hereinafter also simply referred to as "the composition of the present invention") is an actinic ray-sensitive or radiation-sensitive resin composition used for forming a pattern having a film thickness of 1 µm or more. ,

contains resin;

The content of impurities having absorption at a wavelength of 248 nm is 1.00% by mass or less with respect to the resin.

The composition of the present invention is a so-called resist composition, and may be a positive resist composition or a negative resist composition. Further, it may be a resist composition for alkali development or a resist composition for organic solvent development.

The composition of the present invention is typically a chemically amplified resist composition.

The composition of the present invention is excellent in resolution when a pattern is formed by setting it as the above structure.

The inventors of the present invention found that as the thickness of the formed resist film (actinic ray-sensitive or radiation-sensitive film) increases, the effect of impurities, which was not a problem in the conventional lithography process of a resist film with a nano-scale film thickness, significantly occurs. found something Specifically, during exposure, light is absorbed by impurities contained in the resist film of the thick film, and a phenomenon in which light does not reach the deep part of the thick film becomes remarkable. As a result, it was confirmed that the resolution of the formed pattern deteriorated and the desired shape could not be obtained.

The inventors of the present invention conducted further studies on the above-mentioned impurities, and found that the resolution of the formed pattern was excellent, particularly by setting the content of impurities having absorption at a wavelength of 248 nm in the resist film to 1.00% by mass or less with respect to the resin.

<impurities>

In the present invention, impurities are intended to be components other than resins, photoacid generators, acid diffusion controllers, surfactants, solvents, hydrophobic resins, and crosslinking agents that may be included in the composition of the present invention, and include, for example, each of the above Components such as raw materials brought into the composition through components (for example, unreacted monomers brought in from the resin and modified products of the unreacted monomers, basic compounds used in the deprotection reaction in the synthesis of the resin, etc.) can be heard

(an impurity having absorption at a wavelength of 248 nm)

In the composition of the present invention, among impurities, in particular, the content of impurities having absorption at a wavelength of 248 nm is 1.00% by mass or less with respect to the resin.

An impurity having absorption at a wavelength of 248 nm is not particularly limited as long as it has absorption at a wavelength of 248 nm, and among these, those having an absorption peak at a wavelength of 220 to 280 nm are preferable. In particular, when the impurity is an aromatic compound (for example, a compound having a benzene ring), it is preferably removed by purification because it has high absorption derived from the aromatic ring near the wavelength of 248 nm.

The impurity having absorption at the wavelength of 248 nm is, for example, a resin (for example, a repeating unit having a group that is decomposed by the action of an acid and increases polarity (in particular, a phenolic hydroxyl group decomposed by the action of an acid and desorbed) An unreacted monomer that is a synthetic raw material for a resin having a repeating unit having a structure protected by a leaving group (acid-decomposable group) and/or a repeating unit having a phenolic hydroxyl group (particularly, a repeating unit derived from hydroxystyrene) and modified products of unreacted monomers. Unreacted monomers and modified products of unreacted monomers are carried into the composition through resin. Therefore, in the case of using the above resin, it is necessary to reduce unreacted monomers and modified substances of unreacted monomers by purification treatment.

Examples of the impurity having absorption at the wavelength of 248 nm include compounds represented by the general formula (X). In particular, when the resin contains a repeating unit having a phenolic hydroxyl group (particularly, a repeating unit represented by the general formula (I)), the compound represented by the general formula (X) is easily carried in as an impurity.

[Formula 1]

In General Formula (X), the definitions of X ₄ , L ₄ and Ar ₄ are synonymous with the definitions of each group in General Formula (I) described later.

In addition, R _a represents a group represented by general formula (Y1) or a group represented by general formula (Y2). The definitions of R ₄₁ , R ₄₂ and R ₄₃ in General Formula (Y1) and General Formula (Y2) are synonymous with the definitions of each group in General Formula (I) described later.

R ₄₄ represents an alkyl group. 1-5 are preferable, as for carbon number of an alkyl group, 1-3 are more preferable, and 1 is still more preferable.

R _b represents a hydrogen atom or a protecting group. As a protecting group, an alkyl group or -CO- _Rc etc. are mentioned.

R _c represents an alkyl group.

1-5 are preferable, as for carbon number of the alkyl group represented by _Rb and the alkyl group represented by _Rc , 1-3 are more preferable, and 1 is still more preferable.

* indicates a binding position.

In the composition of the present invention, the content of the impurity having absorption at a wavelength of 248 nm is 1.00% by mass or less with respect to the resin (total mass of the resin), and from the viewpoint of better resolution of the pattern, the content is preferably 0.95% by mass or less, and 0.80% by mass. Mass % or less is more preferable, 0.60 mass % or less is more preferable, and 0 mass % is especially preferable.

That is, the compound having absorption at a wavelength of 248 nm is not contained in the composition of the present invention, or when it is contained (when the content of the compound having absorption at a wavelength of 248 nm is more than 0% by mass with respect to the resin), 1.00% by mass below

The content of impurities having absorption at a wavelength of 248 nm in the composition of the present invention can be identified by liquid chromatography.

(basic impurity)

In the composition of the present invention, it is preferable that the content of basic impurities among impurities is reduced with respect to the resin. This is because when the composition of the present invention contains a basic impurity, the acid generated from the photoacid generator is deactivated by irradiation with radiation or actinic rays.

Here, basic impurities, such as an amine compound and a metal hydroxide (as a metal, an alkali metal ion etc.), are intended with a basic impurity.

In the case where a basic impurity has absorption at a wavelength of 248 nm, the basic impurity corresponds to the above "impurity having absorption at a wavelength of 248 nm" and is not included in the "basic impurity".

When the composition of the present invention contains a resin having a repeating unit having a phenolic hydroxyl group (particularly, a repeating unit represented by the general formula (I)), the basic impurity is carried in through the resin in many cases. A resin having a repeating unit having a phenolic hydroxyl group, for example, a resin having a repeating unit derived from hydroxystyrene is generally synthesized using acetoxystyrene as a raw material. For this reason, it is necessary to undergo a deprotection reaction to deprotect an acetoxy group into a phenolic hydroxyl group in the presence of a basic compound either during the synthesis of the monomer or after the synthesis of the resin. That is, basic compounds, such as the said amine compound and a metal hydroxide, are mainly derived from the basic compound used at the time of this deprotection. Therefore, in the case of using the above resin, it is necessary to remove the basic compound used at the time of deprotection by purification treatment.

When the composition of the present invention contains a resin synthesized in the presence of a basic compound, the content of basic impurities derived from the basic compound is preferably 0.10% by mass or less relative to the resin. When the content of the basic impurity derived from the basic compound is 0.10% by mass or less with respect to the resin, the resolution of the pattern is more excellent. The content of the basic impurity derived from the basic compound is more preferably 0.05% by mass or less, more preferably 0.01% by mass or less, and particularly preferably 0% by mass relative to the resin.

That is, the basic impurity is not contained in the composition of the present invention, or when it is contained (when the content of the basic impurity is more than 0% by mass relative to the resin), it is preferably 0.10% by mass or less.

Examples of the amine compound include triethylamine, N,N-dimethyl-4-aminopyridine, and diazabicycloundecene. Moreover, sodium hydroxide, potassium hydroxide, etc. are mentioned as said metal hydroxide.

The content of the basic impurity in the composition of the present invention can be identified/quantified by gas chromatography, capillary electrophoresis, neutralization titration or the like.

<Resin (A)>

The composition of the present invention contains a resin.

The resin contains a resin (hereinafter also referred to as "acid-decomposable resin" or "resin (A)") having a group that is decomposed by the action of an acid and increases polarity (hereinafter, also referred to as "acid-decomposable group"). It is desirable to do

In this case, in the pattern formation method of the present invention, typically, a positive pattern is suitably formed when an alkali developer is employed as the developer, and a negative pattern is suitably formed when an organic developer is employed as the developer. it is formed

Resin (A) preferably has a repeating unit having an acid decomposable group.

As resin (A), well-known resin can be used suitably. For example, paragraphs <0055> to <0191> of US Patent Application Publication 2016/0274458A1, paragraphs <0035> to <0085> of US Patent Application Publication 2015/0004544A1, and US Patent Application Publication 2016/0147150A1. Known resins disclosed in paragraphs <0045> to <0090> can be suitably used as the resin (A).

The acid-decomposable group preferably has a structure protected by a group (leaving group) that decomposes and leaves the polar group by the action of an acid.

As the polar group, a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group, a sulfonic acid group, a sulfonamide group, a sulfonylmide group, (alkylsulfonyl) (alkylcarbonyl) methylene group, (alkylsulfonyl) (alkylcarbonyl) Imide group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, and tris acidic groups (groups that dissociate in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide) such as (alkylsulfonyl)methylene groups; alcoholic hydroxyl groups; and the like.

Further, the alcoholic hydroxyl group is a hydroxyl group bonded to a hydrocarbon group, and refers to a hydroxyl group other than a hydroxyl group (phenolic hydroxyl group) directly bonded to an aromatic ring, and an aliphatic alcohol in which the α-position as a hydroxyl group is substituted with an electron withdrawing group such as a fluorine atom (eg For example, hexafluoroisopropanol group, etc.) are excluded. As the alcoholic hydroxyl group, a hydroxyl group having a pKa (acid dissociation constant) of 12 or more and 20 or less is preferable.

Preferred polar groups include a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), and a sulfonic acid group.

Groups preferable as acid decomposable groups are groups in which the hydrogen atoms of these groups are substituted with groups that leave by the action of an acid (leaving group).

Examples of the group (leaving group) that leaves by the action of an acid include -C(R ₃₆ )(R ₃₇ )(R ₃₈ ), -C(R ₃₆ )(R ₃₇ )(OR ₃₉ ), and -C (R ₀₁ ) (R ₀₂ ) (OR ₃₉ ); and the like.

In the formula, R ₃₆ to R ₃₉ each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. R ₃₆ and R ₃₇ may combine with each other to form a ring.

R ₀₁ and R ₀₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.

The alkyl group of R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ is preferably an alkyl group having 1 to 8 carbon atoms, and examples thereof include methyl, ethyl, propyl, n-butyl, sec-butyl, hexyl, and jade. A til group etc. are mentioned.

The cycloalkyl groups of R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ may be monocyclic or polycyclic. As a monocyclic cycloalkyl group, a C3-C8 cycloalkyl group is preferable, and a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group etc. are mentioned, for example. As the polycyclic cycloalkyl group, a cycloalkyl group having 6 to 20 carbon atoms is preferable. For example, adamantyl group, norbornyl group, isobornyl group, campanyl group, dicyclopentyl group, α-pinene group, tricyclodecanyl group, tetra A cyclododecyl group, an androstanyl group, etc. are mentioned. In addition, at least one carbon atom in the cycloalkyl group may be substituted with a hetero atom such as an oxygen atom.

The aryl group for R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include a phenyl group, a naphthyl group and an anthryl group.

The aralkyl group of R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ is preferably an aralkyl group having 7 to 12 carbon atoms, and examples thereof include a benzyl group, a phenethyl group, and a naphthylmethyl group.

The alkenyl group of R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ is preferably an alkenyl group having 2 to 8 carbon atoms, and examples thereof include a vinyl group, an allyl group, a butenyl group, and a cyclohexenyl group.

The ring formed by bonding R ₃₆ and R ₃₇ to each other is preferably a cycloalkyl group (monocyclic or polycyclic). The cycloalkyl group is preferably a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group, and adamantyl group.

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

Resin (A) preferably has a repeating unit represented by the following general formula (AI) as a repeating unit having an acid-decomposable group.

[Formula 2]

In the general formula (AI),

Xa ₁ represents a hydrogen atom, a halogen atom, or a monovalent organic group.

T represents a single bond or a divalent linking group.

Rx ₁ to Rx ₃ each independently represent an alkyl group or a cycloalkyl group.

Any two of Rx ₁ to Rx ₃ may or may not form a ring structure by bonding.

Examples of the divalent linking group for T include an alkylene group, an arylene group, -COO-Rt-, and -O-Rt-. In formula, Rt represents an alkylene group, a cycloalkylene group, or an arylene group.

T is preferably a single bond or -COO-Rt-. Rt is preferably a chain alkylene group having 1 to 5 carbon atoms, and more preferably -CH ₂ -, -(CH ₂ ) ₂ -, or -(CH ₂ ) ₃ -. T is more preferably a single bond.

Xa ₁ is preferably a hydrogen atom or an alkyl group.

The alkyl group for Xa ₁ may have a substituent, and examples of the substituent include a hydroxyl group and a halogen atom (preferably a fluorine atom).

The alkyl group of Xa ₁ preferably has 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group and a trifluoromethyl group. The alkyl group for Xa ₁ is preferably a methyl group.

The alkyl group for Rx ₁ , Rx ₂ and Rx ₃ may be linear or branched, and is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, etc. this is preferable As carbon number of an alkyl group, 1-10 are preferable, 1-5 are more preferable, and 1-3 are still more preferable. In the alkyl group of Rx ₁ , Rx ₂ and Rx ₃ , a part of the carbon-to-carbon bond may be a double bond.

Examples of the cycloalkyl group for Rx ₁ , Rx ₂ and Rx ₃ include monocyclic cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group, or a cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group. A cycloalkyl group of the ring is preferred.

As the ring structure formed by combining two of Rx ₁ , Rx ₂ and Rx ₃ , a monocyclic cycloalkane ring such as a cyclopentyl ring, a cyclohexyl ring, a cycloheptyl ring, and a cyclooctane ring, or a norbornene ring; Polycyclic cycloalkyl rings, such as a tetracyclodecane ring, a tetracyclododecane ring, and an adamantane ring, are preferable. Especially, a cyclopentyl ring, a cyclohexyl ring, or an adamantane ring is more preferable. As the ring structure formed by bonding of two of Rx ₁ , Rx ₂ and Rx ₃ , structures shown below are also preferable.

[Formula 3]

Although the specific example of the monomer corresponding to the repeating unit represented by general formula (AI) below is given, this invention is not limited to these specific examples. The following specific examples correspond to the case where Xa ₁ in Formula (AI) is a methyl group, but Xa ₁ can be optionally substituted with a hydrogen atom, a halogen atom, or a monovalent organic group.

[Formula 4]

The resin (A) also preferably has a repeating unit described in paragraphs <0336> to <0369> of US Patent Application Publication No. 2016/0070167A1 as a repeating unit having an acid-decomposable group.

In addition, the resin (A) is a repeating unit having an acid-decomposable group, which is decomposed by the action of an acid described in paragraphs <0363> to <0364> of US Patent Application Publication No. 2016/0070167A1 and contains a group that generates an alcoholic hydroxyl group. It may have a repeating unit.

Resin (A) may contain the repeating unit which has an acid-decomposable group individually by 1 type, or may contain it in combination of 2 or more types.

The content of the repeating unit having an acid-decomposable group contained in the resin (A) (the sum of repeating units having a plurality of acid-decomposable groups) is 10 to 90 mol% with respect to all repeating units of the resin (A). It is preferable, 20 to 80 mol% is more preferable, and 30 to 70 mol% is more preferable.

It is preferable that resin (A) has a repeating unit which has at least 1 sort(s) selected from the group which consists of a lactone structure, a sultone structure, and a carbonate structure.

As the lactone structure or the sultone structure, it is sufficient to have a lactone structure or a sultone structure, and a 5- to 7-membered ring lactone structure or a 5- to 7-membered ring sultone structure is preferable. Among them, those in which another ring structure is condensed in a 5- to 7-membered ring lactone structure in the form of forming a bicyclo structure or spiro structure, or a 5- to 7-membered ring sultone structure in the form of forming a bicyclo structure or spiro structure. It is more preferable that other ring structures are condensed.

Resin (A) has a lactone structure represented by any of the following general formulas (LC1-1) to (LC1-21) or a sultone structure represented by any of the following general formulas (SL1-1) to (SL1-3) It is more preferable to have repeating units. Moreover, the lactone structure or the sultone structure may be directly bonded to the main chain. As a preferable structure, general formula (LC1-1), general formula (LC1-4), general formula (LC1-5), general formula (LC1-8), general formula (LC1-16), or general formula (LC1- 21), or a sultone structure represented by general formula (SL1-1).

[Formula 5]

The lactone structure part or the sultone structure part may or may not have a substituent (Rb ₂ ). Preferred substituents (Rb ₂ ) include an alkyl group of 1 to 8 carbon atoms, a cycloalkyl group of 4 to 7 carbon atoms, an alkoxy group of 1 to 8 carbon atoms, an alkoxycarbonyl group of 2 to 8 carbon atoms, a carboxyl group, a halogen atom, a hydroxyl group, and between An ano group, an acid decomposable group, etc. are mentioned, A C1-C4 alkyl group, a cyano group, or an acid decomposable group is preferable. n ₂ represents an integer of 0 to 4. When n ₂ is 2 or more, a plurality of substituents (Rb ₂ ) may be the same or different. In addition, a plurality of substituents (Rb ₂ ) may be bonded to each other to form a ring.

As the repeating unit having a lactone structure or a sultone structure, a repeating unit represented by the following general formula (III) is preferable.

[Formula 6]

In the above general formula (III),

A represents an ester bond (group represented by -COO-) or an amide bond (group represented by -CONH-).

n is a repeating number of a structure represented by -R ₀ -Z-, represents an integer of 0 to 5, and is preferably 0 or 1, more preferably 0. When n is 0, -R ₀ -Z- does not exist and it becomes a single bond.

R ₀ represents an alkylene group, a cycloalkylene group, or a combination thereof. When a plurality of R ₀ exist, R ₀ each independently represents an alkylene group, a cycloalkylene group, or a combination thereof.

Z represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond. When a plurality of Z's are present, Z's each independently represent a single bond, an ether bond, an ester bond, an amide bond, a urethane bond, or a urea bond.

R ₈ represents a monovalent organic group having a lactone structure or a sultone structure.

R ₇ represents a hydrogen atom, a halogen atom or a monovalent organic group (preferably a methyl group).

The alkylene group or cycloalkylene group of R ₀ may have a substituent.

As Z, an ether bond or an ester bond is preferable, and an ester bond is more preferable.

The resin (A) may have a repeating unit having a carbonate structure. The carbonate structure is preferably a cyclic carbonic acid ester structure.

It is preferable that the repeating unit which has a cyclic carbonic acid ester structure is a repeating unit represented by the following general formula (A-1).

[Formula 7]

In general formula (A-1), R _A ¹ represents a hydrogen atom, a halogen atom or a monovalent organic group (preferably a methyl group).

n represents an integer greater than or equal to 0;

R _A ² represents a substituent. When n is 2 or more, R _A ² each independently represents a substituent.

A represents a single bond or a divalent linking group.

Z represents an atomic group forming a monocyclic structure or a polycyclic structure together with a group represented by -O-C(=O)-O- in the formula.

The resin (A) is a repeating unit having at least one selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure, and is a repeating unit described in paragraphs <0370> to <0414> of US Patent Application Publication No. 2016/0070167A1. It is also desirable to have a unit.

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

Although the specific example of the monomer corresponding to the repeating unit represented by general formula (III) below, and the specific example of the monomer corresponding to the repeating unit represented by general formula (A-1) are given, the present invention is limited to these specific examples It doesn't work. The following specific examples correspond to the case where R ₇ in general formula (III) and R _A ¹ in general formula (A-1) are methyl groups, but R ₇ and R _A ¹ are hydrogen atoms, It can be arbitrarily substituted with a rosen atom or a monovalent organic group.

[Formula 8]

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

[Formula 9]

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

Resin (A) preferably has a repeating unit having a polar group.

As a polar group, a hydroxyl group, a cyano group, a carboxyl group, a fluorinated alcohol group, etc. are mentioned.

As the repeating unit having a polar group, a repeating unit having an alicyclic hydrocarbon structure substituted with a polar group is preferable. Moreover, it is preferable that the repeating unit which has a polar group does not have an acid-decomposable group. As the alicyclic hydrocarbon structure in the alicyclic hydrocarbon structure substituted with a polar group, an adamantyl group or a norbornene group is preferable.

Although the specific example of the monomer corresponding to the repeating unit which has a polar group is given below, this invention is not limited to these specific examples.

[Formula 10]

In addition, specific examples of the repeating unit having a polar group include the repeating units disclosed in paragraphs <0415> to <0433> of US Patent Application Publication No. 2016/0070167A1.

Resin (A) may have the repeating unit which has a polar group individually by 1 type, and may have it in combination of 2 or more types.

The content of the repeating unit having a polar group is preferably 5 to 40 mol%, more preferably 5 to 30 mol%, still more preferably 10 to 25 mol%, based on all the repeating units in the resin (A).

The resin (A) may further have a repeating unit having neither an acid decomposable group nor a polar group. It is preferable that the repeating unit having neither an acid-decomposable group nor a polar group has an alicyclic hydrocarbon structure. As a repeating unit having neither an acid-decomposable group nor a polar group, the repeating unit described in paragraph <0236> - <0237> of US Patent Application Publication 2016/0026083A1 is mentioned, for example. Preferred examples of the monomer corresponding to the repeating unit having neither an acid-decomposable group nor a polar group are shown below.

[Formula 11]

In addition, specific examples of the repeating unit having neither an acid-decomposable group nor a polar group include the repeating unit disclosed in paragraph <0433> of US Patent Application Publication No. 2016/0070167A1.

The resin (A) may have a repeating unit having neither an acid-decomposable group nor a polar group alone or in combination of two or more.

The content of the repeating unit having neither an acid-decomposable group nor a polar group is preferably 5 to 40 mol%, more preferably 5 to 30 mol%, and 5 to 25 mol% based on all repeating units in the resin (A). more preferable

In addition to the above repeating structural units, the resin (A) further includes various repeating structural units for the purpose of adjusting dry etching resistance, standard developer aptitude, substrate adhesion, resist profile, or resolution, heat resistance, sensitivity, etc., which are general necessary characteristics of resists. You may have it.

Examples of such repeating structural units include, but are not limited to, repeating structural units corresponding to predetermined monomers.

As the predetermined monomer, for example, one addition polymerizable unsaturated bond selected from acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, etc. The compound etc. which have are mentioned.

In addition, addition polymerizable unsaturated compounds copolymerizable with monomers corresponding to the various repeating structural units described above may be used.

In the resin (A), the content molar ratio of each repeating structural unit is appropriately set in order to adjust various performances.

When the composition of the present invention is for exposure to ArF, it is preferable that the resin (A) does not substantially have an aromatic group from the viewpoint of transmittance to ArF light. More specifically, with respect to all the repeating units in the resin (A), the number of repeating units having an aromatic group is preferably 5 mol% or less, more preferably 3 mol% or less, and ideally 0 mol%, that is, aromatic group-containing repeating units. It is more preferable to have no repeating unit. Moreover, it is preferable that resin (A) has a monocyclic or polycyclic alicyclic hydrocarbon structure.

In the resin (A), it is preferable that all of the repeating units are composed of (meth)acrylate-based repeating units. In this case, all of the repeating units are methacrylate-based repeating units, all of the repeating units are acrylate-based repeating units, and all of the repeating units are methacrylate-based repeating units and acrylate-based repeating units. Any of these can be used, but it is preferable that the acrylate-based repeating unit is 50 mol% or less with respect to all the repeating units of the resin (A).

When the composition of the present invention is for KrF exposure, EB exposure or EUV exposure, the resin (A) preferably contains a repeating unit (a) having an aromatic hydrocarbon group.

As the repeating unit (a) having an aromatic hydrocarbon group, a repeating unit (a1) having a phenolic hydroxyl group is preferable.

・Repeating unit (a1) having a phenolic hydroxyl group

In this specification, a phenolic hydroxyl group is a group obtained by substituting a hydrogen atom of an aromatic hydrocarbon group with a hydroxyl group. The aromatic ring of the aromatic hydrocarbon group is a monocyclic or polycyclic aromatic ring, and examples thereof include a benzene ring and a naphthalene ring.

As a repeating unit (a1) which has a phenolic hydroxyl group, the repeating unit represented by the following general formula (I) is mentioned, for example.

[Formula 12]

during the ceremony,

R ₄₁ , R ₄₂ and R ₄₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. However, R ₄₂ may be bonded to Ar ₄ to form a ring, in which case R ₄₂ represents a single bond or an alkylene group.

X ₄ represents a single bond, -COO-, or -CONR ₆₄ -, and R ₆₄ represents a hydrogen atom or an alkyl group.

L ₄ represents a single bond or a divalent linking group.

Ar ₄ represents a (n+1) valent aromatic hydrocarbon group, and when combined with R ₄₂ to form a ring, represents an (n+2) valent aromatic hydrocarbon group.

n represents the integer of 1-5.

It is also preferable that n is an integer of 2 or more, or X ₄ is -COO-, or -CONR ₆₄ - for the purpose of increasing the polarity of the repeating unit represented by general formula (I).

Examples of the alkyl group represented by R ₄₁ , R ₄₂ , and R ₄₃ in the general formula (I) include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a hexyl group which may have a substituent. , 2-ethylhexyl group, an octyl group, and a C20 or less alkyl group such as a dodecyl group is preferable, a C8 or less alkyl group is more preferable, and a C3 or less alkyl group is still more preferable.

The cycloalkyl group represented by R ₄₁ , R ₄₂ , and R ₄₃ in the general formula (I) may be monocyclic or polycyclic. A monocyclic cycloalkyl group having 3 to 8 carbon atoms, such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group, which may have a substituent, is preferable.

Examples of the halogen atom represented by R ₄₁ , R ₄₂ , and R ₄₃ in the general formula (I) include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferable.

The alkyl group contained in the alkoxycarbonyl group represented by R ₄₁ , R ₄₂ , and R ₄₃ in the general formula (I) is preferably the same as the alkyl group described above for R ₄₁ , R ₄₂ , and R ₄₃ .

Preferable substituents for each group include, for example, an alkyl group, a cycloalkyl group, an aryl group, an amino group, an amide group, a ureido group, a urethane group, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group, a thioether group, An acyl group, an acyloxy group, an alkoxycarbonyl group, a cyano group, a nitro group, etc. are mentioned, and as for carbon number of a substituent, 8 or less are preferable.

Ar ₄ represents a (n+1) valent aromatic hydrocarbon group. The divalent aromatic hydrocarbon group in the case where n is 1 may have a substituent, for example, an arylene group having 6 to 18 carbon atoms such as a phenylene group, a tolylene group, a naphthylene group, and an anthracenylene group, or an example For example, aromatic hydrocarbons including heterocycles such as thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, and thiazole Giga is preferred.

As a specific example of the (n+1) valent aromatic hydrocarbon group in the case where n is an integer of 2 or more, a divalent aromatic hydrocarbon group is a group formed by removing (n-1) arbitrary hydrogen atoms from the above specific examples. can be suitably

The (n+1) valent aromatic hydrocarbon group may further have a substituent.

Examples of the substituents that the above-described alkyl group, cycloalkyl group, alkoxycarbonyl group, and (n+1) valent aromatic hydrocarbon group may have are the alkyl groups listed as R ₄₁ , R ₄₂ , and R ₄₃ in the general formula (I). ; alkoxy groups such as a methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, a hydroxypropoxy group, and a butoxy group; Aryl groups, such as a phenyl group; etc. can be mentioned.

Examples of the alkyl group of R ₆₄ in -CONR ₆₄ - (R ₆₄ represents a hydrogen atom or an alkyl group) represented by X ₄ include a methyl group, an ethyl group, a propyl group, an isopropyl group, and an n-view which may have a substituent. An alkyl group having 20 or less carbon atoms, such as a ethyl group, a sec-butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, and a dodecyl group, is preferable, and an alkyl group with 8 or less carbon atoms is more preferable.

As X ₄ , a single bond, -COO-, or -CONH- is preferable, and a single bond or -COO- is more preferable.

The divalent linking group as L ₄ is preferably an alkylene group, and the alkylene group may have 1 to 8 carbon atoms such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, and an octylene group, which may have a substituent. An alkylene group of is preferred.

As Ar ₄ , an aromatic hydrocarbon group having 6 to 18 carbon atoms, which may have a substituent, is preferable, and a benzene ring group, a naphthalene ring group, or a biphenylene ring group is more preferable. Especially, it is preferable that the repeating unit represented by General formula (I) is a repeating unit derived from hydroxystyrene. That is, Ar ₄ is preferably a benzene ring group.

Specific examples of the repeating unit (a1) having a phenolic hydroxyl group are shown below, but the present invention is not limited thereto. In formula, a represents 1 or 2.

[Formula 13]

Resin (A) may have 1 type of repeating unit (a1) which has a phenolic hydroxyl group independently, and may have it in combination of 2 or more types.

The content of the repeating unit (a1) having a phenolic hydroxyl group is preferably 10 to 95 mol%, more preferably 20 to 90 mol%, and 30 to 85 mol% based on all repeating units of the resin (A). more preferable

As the repeating unit (a) having an aromatic hydrocarbon group, a repeating unit (a2) having a structure (acid-decomposable group) protected by a leaving group in which a phenolic hydroxyl group is decomposed and released by the action of an acid is preferably exemplified.

Repeating unit (a2) having a structure (acid-decomposable group) protected by a leaving group in which the phenolic hydroxyl group is decomposed and released by the action of acid

As a leaving group decomposed by the action of an acid and desorbed, groups represented by formulas (Y1) to (Y4) are exemplified.

Equation (Y1): -C(Rx ₁ )(Rx ₂ )(Rx ₃ )

Equation (Y2): -C(=O)OC(Rx ₁ )(Rx ₂ )(Rx ₃ )

Formula (Y3): -C(R ₃₆ )(R ₃₇ )(OR ₃₈ )

Formula (Y4): -C(Rn)(H)(Ar)

In formulas (Y1) and (Y2), Rx ₁ to Rx ₃ each independently represent an alkyl group (straight or branched) or a cycloalkyl group (monocyclic or polycyclic). However, when all of Rx ₁ to Rx ₃ are alkyl groups (linear or branched), it is preferable that at least two of Rx ₁ to Rx ₃ are methyl groups.

Among them, it is more preferable that Rx ₁ to Rx ₃ are repeating units each independently representing a linear or branched alkyl group, and Rx ₁ to Rx ₃ are repeating units each independently representing a linear or branched alkyl group. It is more preferable to be

Two of Rx ₁ to Rx ₃ may combine to form a monocyclic or polycyclic ring.

As the alkyl group for Rx ₁ to Rx ₃ , an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and t-butyl is preferable.

Examples of the cycloalkyl group for Rx ₁ to Rx ₃ include a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group. desirable.

Examples of the cycloalkyl group formed by combining two of Rx ₁ to Rx ₃ include a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, or a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group. Polycyclic cycloalkyl groups such as these are preferable. Especially, a C5-C6 monocyclic cycloalkyl group is more preferable.

In the cycloalkyl group formed by combining two of Rx ₁ to Rx ₃ , for example, one of the methylene groups constituting the ring may be substituted with a group having a hetero atom such as an oxygen atom or a hetero atom such as a carbonyl group. .

In the groups represented by formulas (Y1) and (Y2), for example, an embodiment in which Rx ₁ is a methyl group or an ethyl group and Rx ₂ and Rx ₃ are bonded to form the above-mentioned cycloalkyl group is preferable.

In Formula (Y3), R ₃₆ to R ₃₈ each independently represent a hydrogen atom or a monovalent organic group. R ₃₇ and R ₃₈ may combine with each other to form a ring. As a monovalent organic group, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, etc. are mentioned. R ₃₆ is preferably a hydrogen atom.

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

As the repeating unit (a2), it is preferable to have a structure in which a hydrogen atom in a phenolic hydroxyl group is protected by a group represented by formulas (Y1) to (Y4).

As the repeating unit (a2), a repeating unit represented by the following general formula (AII) is preferable.

[Formula 14]

Among the general formula (AII),

R ₆₁ , R ₆₂ and R ₆₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. However, R ₆₂ may be bonded to Ar ₆ to form a ring, in which case R ₆₂ represents a single bond or an alkylene group.

X ₆ represents a single bond, -COO-, or -CONR ₆₄ -. R ₆₄ represents a hydrogen atom or an alkyl group.

L ₆ represents a single bond or an alkylene group.

Ar ₆ represents a (n+1) valent aromatic hydrocarbon group, and when combined with R ₆₂ to form a ring, represents an (n+2) valent aromatic hydrocarbon group.

Y ₂ , in the case of n≥2, each independently represents a hydrogen atom or a group that leaves by the action of an acid. However, at least one of Y ₂ represents a group that leaves by the action of an acid. It is preferable that the group which desorbs by the action _of an acid as Y2 is formula (Y1) - (Y4).

n represents the integer of 1-4.

Each said group may have a substituent, and as a substituent, for example, an alkyl group (C 1-4), a halogen atom, a hydroxyl group, an alkoxy group (C 1-4), a carboxyl group, and an alkoxycarbonyl group (C 2-6 ) etc., and a C8 or less thing is preferable.

Specific examples of the repeating unit (a2) are shown below, but the present invention is not limited thereto.

[Formula 15]

[Formula 16]

Resin (A) may have repeating unit (a2) individually by 1 type, and may have it in combination of 2 or more types.

The content of the repeating unit (a2) in the resin (A) (the total amount when a plurality of types are contained) is preferably 5 to 80 mol%, and preferably 5 to 75 mol, based on all the repeating units in the resin (A). % is more preferable, and 10 to 65 mol% is more preferable.

In addition, in the present specification, the repeating unit having an acid-decomposable group and an aromatic hydrocarbon group corresponds to both a repeating unit having an acid-decomposable group and a repeating unit having an aromatic hydrocarbon group.

<Suji (B)>

When the composition of the present invention contains a crosslinking agent (G) described later, the composition of the present invention preferably contains an alkali-soluble resin (B) having a phenolic hydroxyl group (hereinafter also referred to as “resin (B)”). . Resin (B) preferably has a repeating unit having a phenolic hydroxyl group.

In this case, typically, a negative pattern is suitably formed.

The crosslinking agent (G) may be in a form supported by the resin (B).

The resin (B) may have the acid decomposable group described above.

As the repeating unit having a phenolic hydroxyl group in the resin (B), a repeating unit represented by the following general formula (II) is preferable.

[Formula 17]

In general formula (II),

R ₂ represents a hydrogen atom, an alkyl group (preferably a methyl group), or a halogen atom (preferably a fluorine atom).

B' represents a single bond or a divalent linking group.

Ar' represents an aromatic ring group.

m represents an integer greater than or equal to 1;

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

As resin (B), the resin disclosed in paragraph <0142> - <0347> of US Patent Application Publication No. 2016/0282720A1 is mentioned suitably.

The composition of the present invention may contain both resin (A) and resin (B).

The polymerization method of the resin is not particularly limited, and a known method can be used.

However, during production of the resin, it is necessary to sufficiently perform a purification treatment in order to further reduce impurities (for example, impurities having absorption at a wavelength of 248 nm, basic impurities, etc.) mixed from the resin into the composition.

As a purification method for reducing the impurities (particularly impurities having absorption at a wavelength of 248 nm), a method (precipitation purification) in which a resin-containing solution dissolved in a good solvent is brought into contact with a poor solvent to precipitate a solid is exemplified. It is preferred to repeat the precipitation purification a plurality of times.

In addition, it is not specifically limited as long as it is a solvent in which resin, an unreacted monomer, etc. dissolve as said good solvent. Moreover, it will not specifically limit if it is a solvent which precipitates resin as said poor solvent.

Examples of purification methods for reducing the impurities (especially basic impurities) include a method of washing the resin using a solution containing a weak acid such as dilute hydrochloric acid, and a method of removing basic impurities by washing with water.

In the composition of the present invention, the content of the resin (A) and/or the resin (B) (the total content when both are contained) is generally 30% by mass or more, and is often 40% by mass or more, relative to the total solid content. This is preferable, and 50 mass % or more is more preferable. The upper limit is not particularly limited, and is preferably 99% by mass or less, more preferably 90% by mass or less, and still more preferably 85% by mass or less.

<Photoacid Generator (C)>

The composition of the present invention preferably preferably contains a photoacid generator (hereinafter, also referred to as “photoacid generator (C)”).

A photoacid generator is a compound which generates an acid by 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, sulfonium salt compounds, iodonium salt compounds, diazonium salt compounds, phosphonium salt compounds, imide sulfonate compounds, oxime sulfonate compounds, diazodisulfone compounds, disulfone compounds, and o-nitrobenzyl A sulfonate compound is mentioned.

As the photoacid generator, a known compound that generates an acid when irradiated with actinic light or radiation can be appropriately selected and used alone or as a mixture thereof. For example, paragraphs <0125> to <0319> of US Patent Application Publication 2016/0070167A1, paragraphs <0086> to <0094> of US Patent Application Publication 2015/0004544A1, and US Patent Application Publication 2016/0237190A1. Known compounds disclosed in paragraphs <0323> to <0402> can be suitably used as the photoacid generator (C).

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

[Formula 18]

In the above general formula (ZI),

R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represent an organic group.

The number of carbon atoms of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is generally 1 to 30, preferably 1 to 20.

Further, 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 be included in the ring. Examples of the group formed by combining two of R ₂₀₁ to R ₂₀₃ include an alkylene group (eg, a butylene group and a pentylene group) and -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -.

Z ^- represents an anion.

Preferred embodiments of the cation in the general formula (ZI) include the corresponding groups in the compounds (ZI-1), compounds (ZI-2), compounds (ZI-3) and compounds (ZI-4) described later. can

Further, the photoacid generator (C) may be a compound having a plurality of structures represented by general formula (ZI). For example, at least one of R _{201 to R 203 of the compound represented by the general formula (ZI) and at least one of R 201 to R 203 of another} compound represented by the general formula (ZI) form a single bond or a linking group. It may be a compound having a structure bonded through.

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

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

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

Examples of the arylsulfonium compound include triarylsulfonium compounds, diarylalkylsulfonium compounds, aryldialkylsulfonium compounds, diarylcycloalkylsulfonium compounds, and aryldicycloalkylsulfonium compounds.

As an aryl group contained in an arylsulfonium compound, a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable. The aryl group may be an aryl group having a heterocyclic structure containing an oxygen atom, a nitrogen atom, or a sulfur atom. As a heterocyclic structure, a pyrrole residue, a furan residue, a thiophene residue, an indole residue, a benzofuran residue, a benzothiophene residue, etc. are mentioned. When the arylsulfonium compound has two or more aryl groups, the two or more existing aryl groups may be the same or different.

The alkyl group or cycloalkyl group that the arylsulfonium compound has as necessary is preferably a straight-chain alkyl group of 1 to 15 carbon atoms, a branched chain alkyl group of 3 to 15 carbon atoms, or a cycloalkyl group of 3 to 15 carbon atoms, for example, a methyl group. , ethyl group, propyl group, n-butyl group, sec-butyl group, t-butyl group, cyclopropyl group, cyclobutyl group, and cyclohexyl group.

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

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

Compound (ZI-2) is a compound in which R ₂₀₁ to R ₂₀₃ in formula (ZI) each independently represent an organic group having no aromatic ring. An aromatic ring here also includes an aromatic ring containing a hetero atom.

The organic group without an aromatic ring as R ₂₀₁ to R ₂₀₃ generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.

R ₂₀₁ to R ₂₀₃ are each independently, preferably an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group, more preferably a linear or branched 2-oxoalkyl group, a 2-oxocycloalkyl group, or an alkoxy group. A carbonylmethyl group, more preferably a linear or branched 2-oxoalkyl group.

As the alkyl group and cycloalkyl group of R ₂₀₁ to R ₂₀₃ , preferably, a straight-chain alkyl group having 1 to 10 carbon atoms or a branched-chain alkyl group having 3 to 10 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, and a pen ethyl group), and a cycloalkyl group having 3 to 10 carbon atoms (for example, a cyclopentyl group, a cyclohexyl group, and a norbornyl group).

R ₂₀₁ to R ₂₀₃ may be further substituted with a halogen atom, an alkoxy group (for example, having 1 to 5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group.

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

Compound (ZI-3) is represented by the following general formula (ZI-3) and is a compound having a phenacylsulfonium salt structure.

[Formula 19]

Among the general formula (ZI-3),

R _1c to R _5c are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a cycloalkylcarbonyloxy group, a halogen atom, a hydroxyl group, represents a nitro group, an alkylthio group or an arylthio group.

R _6c and R _7c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an aryl group.

R _x and R _y each independently represent an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group or a vinyl group.

Any two or more of R _1c to R _5c , R _5c and R _6c , R _6c and R _7c , R _5c and R _x , and R _x and R _y may combine to form a ring structure, respectively, and this ring structure may each independently contain an oxygen atom, a sulfur atom, a ketone group, an ester bond, or an amide bond.

Examples of the ring structure include an aromatic or non-aromatic hydrocarbon ring, an aromatic or non-aromatic heterocycle, and a polycyclic condensed ring formed by a combination of two or more of these rings. As a ring structure, a 3- to 10-membered ring is mentioned, a 4- to 8-membered ring is preferable, and a 5- or 6-membered ring is more preferable.

Examples of groups formed by combining any two or more of R _1c to R _5c , R _6c and R _7c , and R _x and R _y include a butylene group and a pentylene group.

As a group formed by combining R _5c and R _6c and R _5c and R _x , a single bond or an alkylene group is preferable. As an alkylene group, a methylene group, an ethylene group, etc. are mentioned.

Zc ^- represents an anion.

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

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

[Formula 20]

Among the general formula (ZI-4),

l represents an integer from 0 to 2;

r represents an integer from 0 to 8;

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

R ₁₄ represents a group having a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a cycloalkyl group. These groups may have a substituent. When a plurality of R ₁₄ are present, each independently represents a group such as a hydroxyl group.

R ₁₅ each independently represents an alkyl group, a cycloalkyl group or a naphthyl group. These groups may have a substituent. 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, it is preferable that two R ₁₅ are alkylene groups, and bonded to each other to form a ring structure.

Z ^- represents an anion.

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

Next, general formulas (ZII) and (ZIII) are described.

In 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 , a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable. The aryl group for R ₂₀₄ to R ₂₀₇ may be an aryl group having a heterocyclic structure containing an oxygen atom, a nitrogen atom, or a sulfur atom. Examples of the skeleton of an aryl group having a heterocyclic structure include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene.

As the alkyl group and cycloalkyl group of R ₂₀₄ to R ₂₀₇ , a straight-chain alkyl group having 1 to 10 carbon atoms or a branched-chain alkyl group having 3 to 10 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group), or A cycloalkyl group having 3 to 10 carbon atoms (for example, a cyclopentyl group, a cyclohexyl group, and a norbornyl group) is preferable.

The aryl group, alkyl group, and cycloalkyl group of R ₂₀₄ to R ₂₀₇ may each independently have a substituent. Examples of the substituent that the aryl group, alkyl group, and cycloalkyl group of R ₂₀₄ to R ₂₀₇ may have include an alkyl group (eg, 1 to 15 carbon atoms), a cycloalkyl group (eg, 3 to 15 carbon atoms), an aryl group ( For example, a C6-C15), an alkoxy group (eg C1-C15), a halogen atom, a hydroxyl group, and a phenylthio group etc. are mentioned.

Z ^- represents an 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), Anions represented by the following general formula (3) are preferred.

[Formula 21]

In formula (3),

o represents the integer of 1-3. p represents the integer of 0-10. q represents an integer of 0 to 10.

Xf represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. 1-10 are preferable and, as for carbon number of this alkyl group, 1-4 are more preferable. Moreover, as an alkyl group substituted with at least 1 fluorine atom, a perfluoroalkyl group is preferable.

Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, and more preferably a fluorine atom or CF ₃ . In particular, it is more preferable that both Xf's are fluorine atoms.

R ₄ and R ₅ each independently represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom. When a plurality of R ₄ and R ₅ exist, R ₄ and R ₅ may be the same or different, respectively.

The alkyl group represented by R ₄ and R ₅ may have a substituent and preferably has 1 to 4 carbon atoms. R ₄ and R ₅ are preferably hydrogen atoms.

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

L represents a divalent linking group. When a plurality of L's exist, L's may be the same or different, respectively.

As a divalent linking group, for example -COO-(-C(=O)-O-), -OCO-, -CONH-, -NHCO-, -CO-, -O-, -S-, -SO- , -SO ₂ -, an alkylene group (preferably 1 to 6 carbon atoms), a cycloalkylene group (preferably 3 to 15 carbon atoms), an alkenylene group (preferably 2 to 6 carbon atoms), and a combination of a plurality thereof A divalent linking group etc. are mentioned. Among these, -COO-, -OCO-, -CONH-, -NHCO-, -CO-, -O-, -SO ₂ -, -COO-alkylene group-, -OCO-alkylene group-, -CONH-alkyl A rene group- or a -NHCO-alkylene group- is preferable, and a -COO-, -OCO-, -CONH-, -SO ₂ -, -COO-alkylene group- or -OCO-alkylene group- is more preferable.

W represents an organic group containing a cyclic structure. Among these, it is preferable that it is a cyclic organic group.

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

The alicyclic group may be monocyclic or polycyclic. As a monocyclic alicyclic group, monocyclic cycloalkyl groups, such as a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group, are mentioned, for example. Examples of the polycyclic alicyclic group include polycyclic cycloalkyl groups such as norbornyl group, tricyclodecanyl group, tetracyclodecanyl group, tetracyclododecanyl group, and adamantyl group. Among them, an alicyclic group having a bulky structure having 7 or more carbon atoms, such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group, is preferable.

The aryl group may be monocyclic or polycyclic. As this aryl group, a phenyl group, a naphthyl group, a phenanthryl group, and an anthryl group are mentioned, for example.

The heterocyclic group may be monocyclic or polycyclic. The diffusion of acid can be suppressed more than a polycyclic type. In addition, the heterocyclic group may or may not have aromaticity. As a heterocyclic ring which has aromaticity, 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 heterocyclic ring which does not have aromaticity, a tetrahydropyran ring, a lactone ring, a sultone ring, and a decahydroisoquinoline ring are mentioned, for example. As an example of a lactone ring and a sultone ring, the lactone structure and sultone structure illustrated in the resin mentioned above are mentioned. As the heterocycle in the heterocyclic group, a furan ring, a thiophene ring, a pyridine ring, or a decahydroisoquinoline ring is particularly preferred.

The cyclic organic group may have a substituent. As this substituent, for example, an alkyl group (either linear or branched chain may be used, preferably having 1 to 12 carbon atoms) or a cycloalkyl group (which may be monocyclic, polycyclic, or spirocyclic, and having 3 to 20 carbon atoms) is preferred), an aryl group (preferably having 6 to 14 carbon atoms), a hydroxyl group, an alkoxy group, an ester group, an amide group, a urethane group, a ureido group, a thioether group, a sulfonamide group, and a sulfonic acid ester group. have. In addition, carbonyl carbon may be sufficient as the carbon constituting the cyclic organic group (carbon contributing to ring formation).

Examples of anions represented by Formula (3) include SO ₃ ^- -CF ₂ -CH ₂ -OCO-(L)q'-W and 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. Here, L, q and W are the same as in General Formula (3). q' represents the integer of 0-10.

In one aspect, Z - in the general formula (ZI), Z ^- in the general formula (ZII), Zc ^- in the general formula (ZI ^- 3), and in the general formula (ZI-4) As Z ^- of , an anion represented by the following general formula (4) is also preferable.

[Formula 22]

In formula (4),

X ^B1 and X ^B2 each independently represent a hydrogen atom or a monovalent organic group having no fluorine atom. X ^B1 and X ^B2 are preferably hydrogen atoms.

X ^B3 and X ^B4 each independently represent a hydrogen atom or a monovalent organic group. 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. It is more preferable that both X ^B3 and X ^B4 are alkyl groups substituted with a fluorine atom.

L, q and W are the same as in General Formula (3).

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), It may be a benzenesulfonic acid anion, preferably a benzenesulfonic acid anion substituted with a branched alkyl group or cycloalkyl group.

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), An aromatic sulfonic acid anion represented by the following general formula (SA1) is also preferable.

[Formula 23]

In formula (SA1),

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

n represents an integer greater than or equal to 0. 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, a sulfoxide group, a sulfone group, a sulfonic acid ester group, an ester group, and a group composed of 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 an isopropyl group or a cyclohexyl group.

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

[Formula 24]

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

[Formula 25]

Any combination of the above cations and anions may be used as the photoacid generator.

The photoacid generator may be in the form of a low-molecular compound or a form contained in a part of a polymer. Moreover, you may use together the form of a low molecular weight compound, and the form contained in a part of a polymer.

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

When the photoacid generator is in the form of a low molecular weight compound, the molecular weight is preferably 3,000 or less, more preferably 2,000 or less, and still more preferably 1,000 or less.

When the photoacid generator is in the form of being included in a part of the polymer, it may be included in a part of the resin (A) described above, or may be included in 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 (the sum of the photoacid generators when there are multiple species) 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 to 20% by mass is more preferable, and 1 to 15% by mass is particularly preferable.

In the case of containing the compound represented by the general formula (ZI-3) or (ZI-4) as the photo-acid generator, the content of the photo-acid generator contained in the composition (the sum of the photo-acid generators in the case of multiple species) is the total amount of the composition. Based on the solid content, 1 to 35% by mass is preferable, and 1 to 30% by mass is more preferable.

<Acid Diffusion Controlling Agent (D)>

The composition of the present invention preferably contains an acid diffusion controller (D). The acid diffusion control agent (D) traps acid generated from a photoacid generator or the like during exposure, and acts as a quencher to suppress the reaction of the acid-decomposable resin in the unexposed area due to the excess acid generated. For example, a basic compound (DA), a basic compound (DB) whose basicity is reduced or lost by irradiation with actinic rays or radiation, an onium salt (DC) that becomes a relatively weak acid with respect to an acid generator, and a nitrogen atom , a low-molecular-weight compound (DD) having a group that leaves by the action of an acid, or an onium salt compound (DE) having a nitrogen atom in the cation portion, etc. can be used as the acid diffusion control agent. In the composition of the present invention, known acid diffusion controllers can be used as appropriate. For example, paragraphs <0627> to <0664> of US Patent Application Publication 2016/0070167A1, paragraphs <0095> to <0187> of US Patent Application Publication 2015/0004544A1, paragraphs of US Patent Application Publication 2016/0237190A1 Known compounds disclosed in <0403> to <0423> and paragraphs <0259> to <0328> of US Patent Application Publication No. 2016/0274458A1 can be suitably used as the acid diffusion control agent (D).

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

[Formula 26]

Among the general formulas (A) and (E),

R ²⁰⁰ , R ²⁰¹ and R ²⁰² may be the same or different, and are each independently a hydrogen atom, an alkyl group (preferably 1 to 20 carbon atoms), a cycloalkyl group (preferably 3 to 20 carbon atoms), or an aryl group (carbon atoms) 6 to 20). R ²⁰¹ and R ²⁰² may combine with each other to form a ring.

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

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

As for the alkyl group having a substituent, an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, or a cyanoalkyl group having 1 to 20 carbon atoms is preferable.

As for the alkyl group in general formula (A) and (E), it is more preferable that it is unsubstituted.

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

The basic compound (DB) whose basicity is reduced or lost by irradiation with actinic rays or radiation (hereinafter, also referred to as “compound (DB)”) has a proton acceptor functional group and furthermore, by irradiation with actinic rays or radiation It is a compound that is decomposed and the proton acceptor property is reduced or lost, or the proton acceptor property is changed to an acidic state.

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

[Formula 27]

As a preferable partial structure of a proton acceptor functional group, a crown ether structure, an aza crown ether structure, primary-tertiary amine structure, a pyridine structure, an imidazole structure, and a pyrazine structure etc. are mentioned, for example.

The compound (DB) is decomposed by irradiation with actinic light or radiation to generate a compound whose proton acceptor property is reduced or lost, or whose proton acceptor property is changed to an acidic state. Here, the decrease or loss of proton acceptor property or the change from proton acceptor property to acidic is a change in proton acceptor property due to the addition of a proton to a proton acceptor functional group, and specifically, proton acceptor property. This means that when a proton adduct is generated from a proton and a compound (DB) having a functional group, the equilibrium constant in the chemical equilibrium decreases.

Proton acceptor property can be confirmed by performing pH measurement.

The acid dissociation constant pKa of the compound resulting from decomposition of the compound (DB) by irradiation with actinic light or radiation preferably satisfies pKa<-1, more preferably satisfies -13<pKa<-1, It is more preferable to satisfy -13<pKa<-3.

The acid dissociation constant pKa represents the acid dissociation constant pKa in an aqueous solution, and is defined, for example, in Chemical Handbook (II) (revised 4th edition, 1993, edited by the Chemical Society of Japan, Maruzen Co., Ltd.). The lower the value of the acid dissociation constant pKa, the higher the acid strength. The acid dissociation constant pKa in an aqueous solution can be specifically measured by measuring the acid dissociation constant at 25°C using an infinitely dilute aqueous solution. Alternatively, using the following software package 1, values based on the database of Hammett's substituent constants and known literature values may be obtained by calculation. The values of pKa described in this specification all show the value calculated|required by calculation using this software package.

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

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

In the case of using a mixture of a photoacid generator and an onium salt that generates an acid that is a relatively weak acid with respect to the acid generated from the photoacid generator, the acid generated from the photoacid generator by irradiation with actinic light or radiation generates unreacted weak acid anions. When it collides with an onium salt having a strong acid anion, a weak acid is released by salt exchange to generate an onium salt having a strong acid anion. Since the strong acid is exchanged for a weak acid having a lower catalytic activity in this process, apparently, the acid is deactivated and the acid diffusion can be controlled.

As the onium salt that becomes a relatively weak acid with respect to the photoacid generator, compounds represented by the following general formulas (d1-1) to (d1-3) are preferable.

[Formula 28]

In the formula, R ₅₁ is a hydrocarbon group which may have a substituent, and Z ^2c is a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent (provided that no fluorine atom is substituted on the carbon adjacent to S). ), R ⁵² is an organic group, Y ³ is a linear, branched or cyclic alkylene or arylene group, Rf is a hydrocarbon group containing a fluorine atom, M ⁺ are each independently an ammonium cation, sulfonium cation or iodonium cation.

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

Onium salt (DC), which is a relatively weak acid with respect to a photoacid generator, is a compound having a cation moiety and an anion moiety in the same molecule and in which the cation moiety and anion moiety are covalently linked (hereinafter referred to as "compound (DCA)"). )") may also be used.

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

[Formula 29]

Among 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 single bond connecting the cation site and the anion site.

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

R ₁ , R ₂ , R ₃ , R ₄ , and L ₁ may combine with each other to form a ring structure. Further, in the general formula (C-3), two of R ₁ to R ₃ are combined to represent one divalent substituent, which may be bonded to the N atom through a double bond.

As a substituent having 1 or more carbon atoms in R ₁ to R ₃ , an alkyl group, a cycloalkyl group, an aryl group, an alkyloxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, an alkylaminocarbonyl group, a cycloalkylaminocarbonyl group, and An arylaminocarbonyl group etc. are mentioned. Preferably, it is an alkyl group, a cycloalkyl group, or an aryl group.

L ₁ as a divalent linking group is a linear or branched chain alkylene group, a cycloalkylene group, an arylene group, a carbonyl group, an ether bond, an ester bond, an amide bond, a urethane bond, a urea bond, or a combination of two or more thereof. and groups formed by doing so. L ₁ is preferably an alkylene group, an arylene group, an ether bond, an ester bond, or a group formed by combining two or more of these.

The low-molecular-weight compound (DD) having a nitrogen atom and a group that leaves by the action of an acid (hereinafter also referred to as "compound (DD)") is an amine derivative having a group that leaves by the action of an acid on the nitrogen atom. desirable.

As the group that leaves by the action of an acid, an acetal group, a carbonate group, a carbamate group, a tertiary ester group, a tertiary hydroxyl group, or a hemiaminal ether group is preferable, and a carbamate group or a hemiaminal ether group is more preferable

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

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

[Formula 30]

In the general formula (d-1),

R _b is, each independently, a hydrogen atom, an alkyl group (preferably having 1 to 10 carbon atoms), a cycloalkyl group (preferably having 3 to 30 carbon atoms), an aryl group (preferably having 3 to 30 carbon atoms), an aralkyl group (preferably having 3 to 30 carbon atoms), preferably 1 to 10 carbon atoms) or an alkoxyalkyl group (preferably 1 to 10 carbon atoms). R _b may be linked to each other to form a ring.

The alkyl group, cycloalkyl group, aryl group, and aralkyl group represented by R _b are each independently a hydroxyl group, a cyano group, an amino group, a pyrrolidino group, a piperidino group, a morpholino group, a functional group such as an oxo group, or an alkoxy group. It may be substituted with a group or a halogen atom. 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 preferable, and a linear or branched chain alkyl group or cycloalkyl group is more preferable.

Examples of the ring formed by connecting two R _bs include alicyclic hydrocarbons, aromatic hydrocarbons, heterocyclic hydrocarbons and derivatives thereof.

As a specific structure of the group represented by general formula (d-1), although the structure disclosed in Paragraph <0466> of US Patent Publication US2012/0135348A1 is mentioned, it is not limited to this.

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

[Formula 31]

In formula (6),

l represents an integer of 0 to 2, m represents an integer of 1 to 3, and satisfies l+m=3.

R _a represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. When l is 2, the two R _{a '} s may be the same or different, and the two R _{a '} s may be connected to each other to form a heterocycle together with the nitrogen atom in the formula. This heterocycle may contain heteroatoms other than the nitrogen atom in the formula.

R _b is synonymous with R _b in the 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 are each independently the above-mentioned group as the alkyl group, cycloalkyl group, aryl group, and aralkyl group as R _b may be substituted. It may be substituted with the same group as the group.

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

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

The onium salt compound (DE) having a nitrogen atom in the cation portion (hereinafter also referred to as "compound (DE)") is preferably a compound having a basic moiety containing a nitrogen atom in the cation portion. It is preferable that it is an amino group, and, as for a basic site|part, it is more preferable that it is an aliphatic amino group. It is more preferable that all the atoms adjacent to the nitrogen atom in the basic site are hydrogen atoms or carbon atoms. Further, from the viewpoint of improving basicity, it is preferable that no electron-withdrawing functional group (such as a carbonyl group, a sulfonyl group, a cyano group, and a halogen atom) is directly connected to the nitrogen atom.

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

Preferred examples of the acid diffusion controller (D) are shown below.

[Formula 32]

[Formula 33]

In the composition of the present invention, the acid diffusion controller (D) may be used alone or in combination of two or more.

The content of the acid diffusion control agent (D) in the composition (the total amount when there are multiple species) is preferably 0.1 to 10% by mass, more preferably 0.1 to 5% by mass, based on the total solid content of the composition.

<Hydrophobic Resin (E)>

The composition of the present invention preferably contains a hydrophobic resin (E). Moreover, it is preferable that hydrophobic resin (E) is resin different from resin (A) and resin (B).

When the composition of the present invention contains the hydrophobic resin (E), the static/dynamic contact angle on the surface of the actinic ray-sensitive or radiation-sensitive film can be controlled. This makes it possible to improve development characteristics, suppress outgassing, improve immersion liquid followability in liquid immersion exposure, and reduce liquid immersion defects.

The hydrophobic resin (E) is preferably designed to be unevenly distributed on the surface of the resist film, but unlike a surfactant, it does not necessarily have a hydrophilic group in its molecule and does not need to contribute to uniformly mixing polar/non-polar substances.

The hydrophobic resin (E) is at least one member selected from the group consisting of "fluorine atom", "silicon atom", and "CH ₃ partial structure contained in the side chain portion of the resin" from the viewpoint of localization to the film surface layer. It is preferably a resin having a repeating unit having.

When the hydrophobic resin (E) contains a fluorine atom and/or a silicon atom, the fluorine atom and/or silicon atom in the hydrophobic resin (E) may be contained in the main chain of the resin or in the side chain. There may be.

When the hydrophobic resin (E) contains a fluorine atom, it is preferably a resin having a fluorine-containing partial structure, a fluorine-containing alkyl group, a fluorine-containing cycloalkyl group, or a fluorine-containing aryl group.

The hydrophobic resin (E) preferably has at least one group selected from the group of (x) to (z) below.

(x) acidity

(y) A group that is decomposed by the action of an alkali developer and increases its solubility in an alkali developer (hereinafter also referred to as a polarity converter)

(z) a group that is decomposed by the action of an acid

As the acid group (x), a phenolic hydroxyl group, a carboxylic acid group, a fluorinated alcohol group, a sulfonic acid group, a sulfonamide group, a sulfonylmide group, (alkylsulfonyl)(alkylcarbonyl)methylene group, (alkylsulfonyl)(alkyl Carbonyl) imide group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group , and a tris(alkylsulfonyl)methylene group.

As the acid group, a fluorinated alcohol group (preferably hexafluoroisopropanol), a sulfonimide group, or a bis(alkylcarbonyl)methylene group is preferable.

Examples of the group (y) which is decomposed by the action of an alkali developer and increases solubility in an alkali developer include a lactone group, a carboxylic acid ester group (-COO-), an acid anhydride group (-C(O)OC(O) -), acid imide group (-NHCONH-), carboxylic acid thioester group (-COS-), carbonic acid ester group (-OC(O)O-), sulfuric acid ester group (-OSO ₂ O-), and sulfonic acid ester group (-SO ₂ O-) etc. are mentioned, and a lactone group or a carboxylic acid ester group (-COO-) is preferable.

As a repeating unit containing these groups, it is a repeating unit in which these groups are directly couple|bonded with the main chain of resin, for example, the repeating unit by acrylic acid ester and methacrylic acid ester, etc. are mentioned. In this repeating unit, these groups may be bonded to the main chain of the resin through a linking group. Alternatively, this repeating unit may be introduced into the terminal of the resin by using a polymerization initiator or chain transfer agent having these groups at the time of polymerization.

As a repeating unit which has a lactone group, the same thing as the repeating unit which has a lactone structure previously demonstrated by the term of resin (A) is mentioned, for example.

The content of the repeating unit having a group (y) that is decomposed by the action of an alkali developer and increases its solubility in an alkali developer is preferably 1 to 100 mol% with respect to all repeating units in the hydrophobic resin (E), and 3 -98 mol% is more preferable, and 5-95 mol% is still more preferable.

In the hydrophobic resin (E), the repeating unit having a group (z) decomposed by the action of an acid is the same as the repeating unit having an acid-decomposable group exemplified for the resin (A). The repeating unit having a group (z) that is decomposed by the action of an acid may have at least either a fluorine atom or a silicon atom. The content of the repeating unit having a group (z) decomposed by the action of acid is preferably 1 to 80 mol%, more preferably 10 to 80 mol%, based on all repeating units in the hydrophobic resin (E). 20 to 60 mol% is more preferable.

Hydrophobic resin (E) may further have a repeating unit different from the repeating unit mentioned above.

10-100 mol% is preferable with respect to all the repeating units in hydrophobic resin (E), and, as for the repeating unit containing a fluorine atom, 30-100 mol% is more preferable. Moreover, 10-100 mol% is preferable with respect to all the repeating units in hydrophobic resin (E), and, as for the repeating unit containing a silicon atom, 20-100 mol% is more preferable.

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

1,000-100,000 are preferable and, as for the weight average molecular weight of standard polystyrene conversion of hydrophobic resin (E), 1,000-50,000 are more preferable.

0.01-5 mass % is preferable and, as for the total content of the residual monomer and/or oligomer component contained in hydrophobic resin (E), 0.01-3 mass % is more preferable. Further, the degree of dispersion (Mw/Mn) is preferably in the range of 1 to 5, more preferably in the range of 1 to 3.

As the hydrophobic resin (E), a known resin can be appropriately selected and used alone or as a mixture thereof. For example, a known resin disclosed in paragraphs <0451> to <0704> of US Patent Application Publication No. 2015/0168830A1 and paragraphs <0340> to <0356> of US Patent Application Publication No. 2016/0274458A1 may be used as a hydrophobic resin (E ) can be used suitably. In addition, the repeating units disclosed in paragraphs <0177> to <0258> of US Patent Application Publication No. 2016/0237190A1 are also preferable as repeating units constituting the hydrophobic resin (E).

Preferable examples of the monomer corresponding to the repeating unit constituting the hydrophobic resin (E) are shown below.

[Formula 34]

[Formula 35]

Hydrophobic resin (E) may be used individually by 1 type, and may use 2 or more types together.

It is preferable to mix and use two or more types of hydrophobic resins (E) having different surface energies from the viewpoint of both immersion liquid followability and development characteristics in immersion lithography.

The content of the hydrophobic resin (E) in the composition is preferably 0.01 to 10% by mass, and more preferably 0.05 to 8% by mass with respect to the total solid content in the composition of the present invention.

<Solvent (F)>

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

In the composition of the present invention, known resist solvents can be appropriately used. For example, paragraphs <0665> to <0670> of US Patent Application Publication 2016/0070167A1, paragraphs <0210> to <0235> of US Patent Application Publication 2015/0004544A1, paragraphs of US Patent Application Publication 2016/0237190A1 <0424> to <0426> and the known solvents disclosed in paragraphs <0357> to <0366> of US Patent Application Publication No. 2016/0274458A1 can be suitably used.

As a solvent that can be used when preparing the composition, for example, an alkylene glycol monoalkyl ether carboxylate, an alkylene glycol monoalkyl ether, an alkyl lactate ester, an alkyl alkoxypropionate, a cyclic lactone (preferably having 4 carbon atoms) to 10), monoketone compounds which may have a ring (preferably having 4 to 10 carbon atoms), organic solvents such as alkylene carbonate, alkyl alkoxyacetate, and alkyl pyruvate.

As the organic solvent, a mixed solvent obtained by mixing a solvent having a hydroxyl group in the structure and a solvent having no hydroxyl group may be used.

As the solvent having a hydroxyl group and the solvent not having a hydroxyl group, the exemplary compounds described above can be appropriately selected. As the solvent containing a hydroxyl group, an alkylene glycol monoalkyl ether or an alkyl lactate is preferable, and propylene glycol Colmonomethyl ether (PGME), propylene glycol monoethyl ether (PGEE), methyl 2-hydroxyisobutyrate, or ethyl lactate is more preferred. Moreover, as a solvent which does not have a hydroxyl group, an alkylene glycol monoalkyl ether acetate, an alkyl alkoxy propionate, a monoketone compound which may have a ring, a cyclic lactone, or an alkyl acetate is preferable, and among these, propylene glycol Lycol monomethyl ether acetate (PGMEA), ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, cyclopentanone or butyl acetate are more preferred, and propylene glycol monomethyl Ether acetate, γ-butyrolactone, ethylethoxypropionate, cyclohexanone, cyclopentanone or 2-heptanone is more preferred. As a solvent which does not have a hydroxyl group, propylene carbonate is also preferable.

The mixing ratio (mass ratio) of the solvent having a hydroxyl group and the solvent not having a hydroxyl group is preferably 1/99 to 99/1, more preferably 10/90 to 90/10, and still more preferably 20/80 to 60/40. desirable. A mixed solvent containing 50% by mass or more of a solvent having no hydroxyl group is preferable from the viewpoint of application uniformity.

The solvent preferably contains propylene glycol monomethyl ether acetate, and may be a single solvent of propylene glycol monomethyl ether acetate, or a mixed solvent of two or more types containing propylene glycol monomethyl ether acetate. may be

<Crosslinking agent (G)>

The composition of the present invention may contain a compound that crosslinks the resin by the action of an acid (hereinafter also referred to as a crosslinking agent (G)). As a crosslinking agent (G), a well-known compound can be used suitably. For example, a known compound disclosed in paragraphs <0379> to <0431> of US Patent Application Publication No. 2016/0147154A1 and paragraphs <0064> to <0141> of US Patent Application Publication No. 2016/0282720A1 may be used as a crosslinking agent (G) can be suitably used as

The crosslinking agent (G) is a compound having a crosslinkable group capable of crosslinking a resin, and examples of the crosslinkable group include a hydroxymethyl group, an alkoxymethyl group, an acyloxymethyl group, an alkoxymethyl ether group, an oxirane ring, and an oxetane ring. can be heard

It is preferable that a crosslinkable group is a hydroxymethyl group, an alkoxymethyl group, an oxirane ring, or an oxetane ring.

It is preferable that a crosslinking agent (G) is a compound (including resin) which has 2 or more crosslinkable groups.

It is more preferable that the crosslinking agent (G) is a phenol derivative, a urea-based compound (a compound having a urea structure) or a melamine-based compound (a compound having a melamine structure) having a hydroxymethyl group or an alkoxymethyl group.

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

The content of the crosslinking agent (G) is preferably 1 to 50% by mass, preferably 3 to 40% by mass, more preferably 5 to 30% by mass, based on the total solid content of the resist composition.

<Surfactant (H)>

When the composition of the present invention contains a surfactant preferably containing a surfactant, a fluorine-based and/or silicon-based surfactant (specifically, a fluorine-based surfactant, a silicone-based surfactant, or both fluorine atoms and silicon atoms) surfactant) is preferred.

By containing the surfactant in the composition of the present invention, when an exposure light source of 250 nm or less, particularly 220 nm or less, is used, a pattern with good sensitivity and resolution and little adhesion and development defects can be obtained.

As the fluorine-based and/or silicone-based surfactant, the surfactant described in paragraph <0276> of US Patent Application Publication No. 2008/0248425 can be mentioned.

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

These surfactants may be used individually by 1 type, and may use 2 or more types together.

When the composition of the present invention contains a surfactant, the content of the surfactant is preferably 0.0001 to 2% by mass, and more preferably 0.0005 to 1% by mass with respect to the total solid content of the composition.

On the other hand, when the content of the surfactant is 10 ppm or more with respect to the total solid content of the composition, the surface unevenness of the hydrophobic resin (E) is increased. In this way, the surface of the actinic ray-sensitive or radiation-sensitive film can be made more hydrophobic, and followability to water during immersion exposure is improved.

(other additives)

The composition of the present invention may further contain an acid increasing agent, a dye, a plasticizer, a photosensitizer, a light absorber, an alkali-soluble resin, a dissolution inhibitor, or a dissolution accelerator.

<Preparation method>

The solid content concentration of the composition of the present invention is usually preferably 1.0 to 50% by mass, more preferably 10 to 50% by mass, still more preferably 30 to 50% by mass. Solid content concentration is the mass percentage of the mass of the other resist components excluding the solvent with respect to the total mass of the composition.

Further, the film thickness of the actinic ray-sensitive or radiation-sensitive film comprising the composition of the present invention is 1 μm or more, and for the purpose of increasing the number of processing steps, 3 μm or more is preferable, 5 μm or more is more preferable, and 10 μm or more is still more preferable. do. Although an upper limit is not specifically limited, For example, it is 100 micrometers or less.

Also, as will be described later, a pattern can be formed from the composition of the present invention.

The film thickness of the pattern to be formed is 1 μm or more, and for the purpose of increasing the number of processing steps, it is preferably 3 μm or more, more preferably 5 μm or more, and still more preferably 10 μm or more. The upper limit is not particularly limited, and is, for example, 100 μm or less.

The composition of the present invention is used by dissolving the above components in a predetermined organic solvent, preferably the above mixed solvent, filtering the above components, and then applying the composition onto a predetermined support (substrate). The pore size of the filter used for filter filtration is preferably 0.1 μm or less, more preferably 0.05 μm or less, and still more preferably 0.03 μm or less. It is preferable that this filter is made of polytetrafluoroethylene, polyethylene, or nylon. In filter filtration, as disclosed in, for example, Japanese Patent Application Laid-Open No. 2002-062667 (Japanese Patent Application Publication No. 2002-062667), cyclic filtration may be performed, or a plurality of types of filters are connected in series or parallel, You may perform filtration. Moreover, you may filter a composition multiple times. In addition, you may perform degassing treatment etc. with respect to a composition before and after filter filtration.

It is preferable that the viscosity of the composition of this invention is 100-500 mPa*s. The viscosity of the composition of the present invention is more preferably 100 to 300 mPa·s from the viewpoint of more excellent applicability.

In addition, a viscosity can be measured with an E-type viscometer.

<Use>

The composition of the present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition whose properties change in response to irradiation with actinic ray or radiation. More specifically, the composition of the present invention is used in semiconductor manufacturing processes such as IC (Integrated Circuit), manufacturing of circuit boards such as liquid crystals or thermal heads, manufacturing of imprint mold structures, other photofabrication processes, or lithographic printing plates. Or, it relates to an actinic ray-sensitive or radiation-sensitive resin composition used in the manufacture of an acid-curable composition. The pattern formed in the present invention can be used in an etching process, an ion implantation process, a bump electrode formation process, a rewiring formation process, MEMS (Micro Electro Mechanical Systems), and the like.

[Pattern formation method]

The present invention also relates to a pattern formation method using the actinic ray-sensitive or radiation-sensitive resin composition. Hereinafter, the pattern formation method of the present invention will be described. Moreover, together with description of the pattern formation method, the actinic ray sensitive or radiation sensitive film of this invention is also demonstrated.

The pattern formation method of the present invention,

(i) a step of forming a resist film (actinic ray-sensitive or radiation-sensitive film) on a support with the above-described actinic ray-sensitive or radiation-sensitive resin composition (resist film forming step);

(ii) a step of exposing the resist film (irradiating with actinic rays or radiation) (exposure step), and

(iii) a step of developing the exposed resist film using a developing solution (development step).

The pattern formation method of the present invention is not particularly limited as long as it includes the steps (i) to (iii), and may further include the following steps.

In the pattern formation method of the present invention, the exposure method in the (ii) exposure step may be immersion exposure.

The pattern formation method of the present invention preferably includes (iv) a preheating (PB: PreBake) step before the (ii) exposure step.

The pattern formation method of the present invention preferably includes a (v) Post Exposure Bake (PEB) process after (ii) the exposure process and before (iii) the development process.

The pattern formation method of the present invention may include the (ii) exposure step a plurality of times.

The pattern formation method of the present invention may include the (iv) preheating step a plurality of times.

The pattern formation method of the present invention may include (v) a post-exposure heating step a plurality of times.

In the pattern formation method of the present invention, the above-described (i) film formation step, (ii) exposure step, and (iii) development step can be performed by generally known methods.

Further, if necessary, a resist underlayer film (for example, SOG (Spin On Glass), SOC (Spin On Carbon), and antireflection film) may be formed between the resist film and the support. As a material constituting the resist underlayer film, known organic or inorganic materials can be appropriately used.

A protective film (top coat) may be formed on the upper layer of the resist film. As a protective film, a well-known material can be used suitably. For example, US Patent Application Publication No. 2007/0178407, US Patent Application Publication No. 2008/0085466, US Patent Application Publication No. 2007/0275326, US Patent Application Publication No. 2016/0299432, US Patent Application Publication No. The composition for forming a protective film disclosed in Publication No. 2013/0244438 and International Patent Application Publication No. 2016/157988A can be suitably used. As the composition for forming a protective film, it is preferable to contain the acid diffusion control agent described above.

A protective film may be formed on the upper layer of the resist film containing the hydrophobic resin described above.

The support is not particularly limited, and substrates commonly used in the manufacturing process of semiconductors such as ICs, the manufacturing process of circuit boards such as liquid crystals or thermal heads, and other photofabrication lithography processes can be used. As a specific example of a support body, inorganic substrates, such as silicon, SiO2 _, and SiN, etc. are mentioned.

The heating temperature is preferably 70 to 130°C, and more preferably 80 to 120°C, also in any of the (iv) pre-heating step and (v) post-exposure heating step.

The heating time is preferably 30 to 300 seconds, more preferably 30 to 180 seconds, and even more preferably 30 to 90 seconds, also in any of the (iv) pre-heating step and (v) post-exposure heating step.

Heating can be performed by means provided in the exposure apparatus and developing apparatus, and may be performed using a hot plate or the like.

The wavelength of the light source used in the exposure step is not limited, and examples thereof include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light (EUV), X-rays, and electron beams. Among these, far ultraviolet light is preferable. The wavelength is preferably 250 nm or less, more preferably 220 nm or less, and still more preferably 1 to 200 nm. Specifically, KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ₂ excimer laser (157 nm), X-ray, EUV (13 nm), electron beam, etc., KrF excimer laser, ArF excimer laser, EUV or electron beam This is preferable, and a KrF excimer laser is more preferable.

(iii) In the developing step, an alkaline developing solution may be used or a developing solution containing an organic solvent (hereinafter also referred to as an organic-based developing solution) may be used.

As the alkaline developer, a quaternary ammonium salt typified by tetramethylammonium hydroxide is usually used, but besides this, inorganic alkalis, primary to tertiary amines, alcohol amines, and alkaline aqueous solutions such as cyclic amines can also be used.

Moreover, the said alkaline developing solution may contain alcohol and/or surfactant in an appropriate amount. The alkali concentration of the alkali developing solution is usually 0.1 to 20% by mass. The pH of an alkaline developing solution is 10-15 normally.

The time for developing using an alkali developing solution is usually 10 to 300 seconds.

The alkali concentration of the alkali developing solution, pH, and developing time can be appropriately adjusted according to the pattern to be formed.

The organic developer is preferably a developer containing at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents.

Examples of the ketone solvent include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methyl amyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetonyl acetone, ionone, diacetonyl alcohol, acetyl carbinol, acetophenone, methyl naphthyl ketone, isophorone, and propylene carbonate; and the like.

Examples of the ester solvent include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isopentyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, and 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, isoamyl acetate, isobutyl isobutyrate, and butyl propionate, etc. can be heard

As the alcohol-based solvent, the amide-based solvent, the ether-based solvent, and the hydrocarbon-based solvent, the solvents disclosed in paragraphs <0715> to <0718> of US Patent Application Publication No. 2016/0070167A1 can be used.

A plurality of the above solvents may be mixed, or may be mixed with solvents or water other than the above. The moisture content of the entire developing solution is preferably less than 50% by mass, more preferably less than 20% by mass, still more preferably less than 10% by mass, and particularly preferably substantially free of moisture.

The content of the organic solvent relative to the organic developer is preferably 50 to 100% by mass, more preferably 80 to 100% by mass, still more preferably 90 to 100% by mass, and 95 to 100% by mass with respect to the total amount of the developing solution. % is particularly preferred.

The organic developer may contain an appropriate amount of a known surfactant as required.

The content of the surfactant is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and more preferably 0.01 to 0.5% by mass with respect to the total amount of the developing solution.

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

As the developing method, for example, a method in which the substrate is immersed in a tank filled with a developing solution for a certain period of time (dip method), a method in which the developer is raised on the surface of the substrate by surface tension and stopped for a certain period of time (puddle method), A method of spraying a developer solution (spray method), or a method of continuously discharging a developer solution while scanning a developer ejection nozzle at a constant speed on a substrate rotating at a constant speed (dynamic dispensing method), and the like.

You may combine the process of developing using an alkaline aqueous solution (alkaline developing process) and the process of developing using the developing solution containing an organic solvent (organic solvent developing process). By this, since pattern formation can be performed without dissolving only the region of intermediate exposure intensity, a finer pattern can be formed.

(iii) It is preferable to include a step of washing with a rinse liquid (rinse step) after the developing step.

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

The rinsing liquid used in the rinsing step after the developing process using a developing solution containing an organic solvent is not particularly limited as long as it does not dissolve the pattern, and a solution containing a general organic solvent can be used. As the rinse liquid, it is preferable to use a rinse liquid containing at least one organic solvent selected from the group consisting of hydrocarbon-based solvents, ketone-based solvents, ester-based solvents, alcohol-based solvents, amide-based solvents, and ether-based solvents do.

Specific examples of the hydrocarbon-based solvent, ketone-based solvent, ester-based solvent, alcohol-based solvent, amide-based solvent, and ether-based solvent include those similar to those described for the developing solution containing an organic solvent.

As the rinse liquid used in the rinse step in this case, a rinse liquid containing a monohydric alcohol is more preferable.

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

A plurality of each component may be mixed, or may be used in combination with an organic solvent other than the above.

The water content in the rinse liquid is preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 3% by mass or less. When the water content is 10% by mass or less, good developing characteristics are obtained.

The rinse liquid may contain an appropriate amount of surfactant.

In the rinsing step, a substrate subjected to development using an organic developer is cleaned using a rinsing solution containing an organic solvent. The method of cleaning treatment is not particularly limited, and for example, a method of continuously discharging a rinse liquid onto a substrate rotating at a constant speed (rotation coating method), a method of immersing a substrate in a bath filled with a rinse liquid for a certain period of time ( dip method), or a method of spraying a rinse liquid on the substrate surface (spray method), and the like. Among them, it is preferable to perform the cleaning treatment by a spin coating method, and to rotate the substrate at a rotational speed of 2,000 to 4,000 rpm (revolution per minute) after cleaning to remove the rinse liquid from the substrate. In addition, it is also preferable to include a heating process (Post Bake) after the rinsing process. By this heating process, the developer and rinse liquid remaining between the patterns and inside the patterns are removed. In the heating step after the rinse step, the heating temperature is usually 40 to 160°C, preferably 70 to 95°C, and the heating time is usually 10 seconds to 3 minutes, preferably 30 seconds to 90 seconds.

The actinic ray-sensitive or radiation-sensitive resin composition of the present invention and various materials used in the pattern formation method of the present invention (eg, resist solvent, developer, rinse, composition for forming an antireflection film, or topcoat formation compositions) preferably do not contain impurities such as metal components, isomers, and residual monomers. The content of these impurities contained in the various materials described above is preferably 1 ppm or less, more preferably 100 ppt or less, still more preferably 10 ppt or less, and particularly not substantially contained (below the detection limit of the measuring device). desirable.

As a method of removing impurities such as metal from the various materials described above, filtration using a filter is exemplified. The pore size of the filter is preferably 10 nm or less, more preferably 5 nm or less, and still more preferably 3 nm or less. As the material of the filter, a filter made of polytetrafluoroethylene, polyethylene, or nylon is preferable. As the filter, one previously washed with an organic solvent may be used. In the filter filtration step, a plurality of types of filters may be connected in series or in parallel and used. In the case of using a plurality of types of filters, filters having different pore diameters and/or materials may be used in combination. Moreover, you may filter various materials multiple times, and the process of filtering multiple times may be a circulation filtration process. As the filter, one in which eluents are reduced as disclosed in Japanese Patent Application Laid-Open No. 2016-201426 (Japanese Patent Publication No. 2016-201426) is preferable.

In addition to filter filtration, impurities may be removed by an adsorbent, or a combination of filter filtration and adsorbent may be used. As the adsorbent, known adsorbents can be used, and for example, inorganic adsorbents such as silica gel or zeolite, or organic adsorbents such as activated carbon can be used. As a metal adsorption agent, what is disclosed by Unexamined-Japanese-Patent No. 2016-206500 (Japanese Unexamined Patent Publication No. 2016-206500) is mentioned, for example.

In addition, as a method for reducing impurities such as metal contained in the various materials, a raw material having a low metal content is selected as a raw material constituting the various materials, filter filtration is performed on the raw material constituting the various materials, or an apparatus is used. Methods such as performing distillation under conditions in which contamination is suppressed as much as possible by lining the inside with Teflon (registered trademark) are exemplified. Preferable conditions in the filter filtration performed with respect to raw materials constituting various materials are the same as the above conditions.

It is preferable to store the above various materials in a container described in US Patent Application Publication No. 2015/0227049, Japanese Patent Application Publication No. 2015-123351 (Japanese Patent Application Publication No. 2015-123351), etc., in order to prevent contamination of impurities. do.

A method for improving surface roughness of the pattern may be applied to the pattern formed by the pattern forming method of the present invention. As a method of improving the surface roughness of a pattern, the method of processing a pattern with the plasma of the gas containing hydrogen disclosed, for example in US Patent Application Publication No. 2015/0104957 is mentioned. In addition, Japanese Patent Application Publication No. 2004-235468 (Japanese Patent Application Publication No. 2004-235468), US Patent Application Publication No. 2010/0020297, Proc. of SPIE Vol. 8328 83280N-1 "EUV Resist Curing Technique for LWR Reduction and Etch Selectivity Enhancement" may be applied.

In addition, the pattern formed by the above method is the core of the spacer process disclosed in, for example, Japanese Patent Application Laid-Open No. 1991-270227 (Japanese Patent Laid-Open No. 3-270227) and US Patent Application Laid-Open No. 2013/0209941. ) can be used as

[Method of manufacturing electronic device]

Moreover, this invention also relates to the manufacturing method of an electronic device including the pattern formation method mentioned above. The electronic device manufactured by the electronic device manufacturing method of the present invention is suitable for electrical and electronic equipment (e.g., home appliances, OA (Office Automation) related equipment, media related equipment, optical equipment, communication equipment, etc.) it is mounted

Example

The present invention will be described in more detail below based on examples. The materials, usage amount, ratio, processing contents, processing procedures, etc. shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limitedly interpreted by the examples shown below.

[Synthesis of Resin]

Various resins were synthesized according to the following procedure.

<Synthesis of Resin 1A>

Resin 1A was synthesized by the following method (hereinafter also referred to as "PACST method").

[Formula 36]

60 g of propylene glycol monomethyl ether acetate (PGMEA) was put into a four-necked flask equipped with a thermometer, a gas blowing tube, a cooling tube, a stirrer, and a water bath, and the temperature was raised to 80°C after nitrogen substitution. In addition, 200.31 g of paraacetoxystyrene (manufactured by Tosoh), 67.55 g of t-butyl methacrylate (manufactured by Wako Pure Chemical Industries), 33.48 g of benzyl methacrylate (manufactured by Wako Pure Chemical Industries), and V-601 (polymerization initiator, manufactured by Wako Pure Chemical Industries) A mixed solution in which 13.12 g of Kuze) was dissolved in 241.1 g of PGMEA was added dropwise over 4 hours. After dripping, it stirred at 80 degreeC for 3 hours, and obtained the polymer fluid (1A-1).

The obtained polymer solution (1A-1) was transferred to a 5 L three-necked flask, and 300 g of propylene glycol monomethyl ether, 600 g of methanol, 35 g of pure water, and 149.96 g of triethylamine were added thereto, and an oil bath set at 80°C ( Oil bath) and reacted for 12 hours. 1H ^- NMR (nuclear magnetic resonance) confirmed that the acetyl group protection had been removed, and the reaction solution was cooled to room temperature. The reaction solution was transferred to a separatory funnel, and ethyl acetate and dilute hydrochloric acid were added thereto, and the extraction operation was repeated three times (removal of basic impurities). Subsequently, after washing the organic layer about three times with pure water, heptane was added to the viscous liquid concentrated by evaporation to precipitate a solid (first precipitation purification). The powder obtained by decantation of the supernatant was dissolved in ethyl acetate, and the ethyl acetate solution was slowly added dropwise into heptane to perform precipitation purification (second precipitation purification). The precipitated powder was filtered, washed with heptane, and dried under reduced pressure at 40°C. Obtaining the target resin 1A was confirmed by ¹ H-NMR and GPC.

<Synthesis of Resin 1B>

Resin 1B was synthesized by the following method (hereinafter also referred to as "PHS method").

[Formula 37]

According to the method described in Journal of the American Chemical Society, 131, 13949 (2009), parahydroxystyrene was synthesized in good yield by hydrolyzing paraacetoxystyrene as a starting material under sodium hydroxide conditions.

60 g of propylene glycol monomethyl ether acetate (PGMEA) was put into a four-necked flask equipped with a thermometer, a gas blowing tube, a cooling tube, a stirrer, and a water bath, and the temperature was raised to 80°C after nitrogen substitution. In addition, 276.35 g of parahydroxystyrene, 67.55 g of t-butyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.), 33.48 g of benzyl methacrylate (manufactured by Wako Pure Chemical Industries), and 13.12 g of V-601 (polymerization initiator, manufactured by Wako Pure Chemical Industries) A mixed solution dissolved in 241.1 g of PGMEA was added dropwise over 4 hours. After dripping, the reaction solution stirred at 80°C for 3 hours was transferred to a separatory funnel, and ethyl acetate and dilute hydrochloric acid were added thereto, and the extraction operation was repeated three times (to remove basic impurities). Subsequently, after washing the organic layer about three times with pure water, heptane was added to the viscous liquid concentrated by evaporation to precipitate a solid (first precipitation purification). The powder obtained by decantation of the supernatant was dissolved in ethyl acetate, and the ethyl acetate solution was slowly added dropwise into heptane to perform precipitation purification (second precipitation purification). The precipitated powder was filtered, washed with heptane, and dried under reduced pressure at 40°C. Obtaining the target Resin 1B was confirmed by ¹ H-NMR and GPC.

<Synthesis of Resin 2A>

Resin 2A having the following structure was synthesized by the same method except for changing the monomer species in the synthesis method of Resin 1A (PACST method) described above. Obtaining the target resin 2A was confirmed by ¹ H-NMR and GPC.

<Synthesis of Resin 2B>

Resin 2B having the following structure was synthesized by the same method except for changing the monomer species in the synthesis method of Resin 1B (PHS method) described above. Obtaining the target Resin 2B was confirmed by ¹ H-NMR and GPC.

[Formula 38]

<Synthesis of Resin 3A>

Resin 3A having the following structure was synthesized by the same method except for changing the monomer species in the synthesis method of Resin 1A (PACST method) described above. Obtaining the target resin 3A was confirmed by ¹ H-NMR and GPC.

<Synthesis of Resin 3B>

Resin 3B having the following structure was synthesized by the same method except for changing the monomer species in the synthesis method of Resin 1B (PHS method) described above. Obtaining the target Resin 3B was confirmed by ¹ H-NMR and GPC.

[Formula 39]

<Synthesis of Resin 4>

Resin 4 was synthesized by the following method (polymer reaction).

[Formula 40]

According to the method described in Journal of the American Chemical Society, 131, 13949 (2009), parahydroxystyrene was synthesized in good yield by hydrolyzing paraacetoxystyrene as a starting material under sodium hydroxide conditions.

Dissolve 210 g of parahydroxystyrene and 45 g of t-butylvinyl ether in 1000 mL of dehydrated tetrahydrofuran (THF) in a four-necked flask equipped with a thermometer, gas blowing tube, cooling tube, stirrer and water bath, and there 1 g of dehydrated p-toluenesulfonic acid was added thereto, and 30 g of a molecular sieve 3A was further added as a dehydrating agent, followed by stirring at room temperature for 4 hours. After filtering the reaction solution, the filtrate was poured into 3 liters of water (to remove basic impurities), and the precipitated powder was collected by filtration (first precipitation purification). The obtained powder was dried at room temperature under reduced pressure, dissolved in 2 liters of ethyl acetate, added dropwise to 50 L of heptane, and purified by precipitation (second precipitation purification). Obtaining the target Resin 4 was confirmed by ¹ H-NMR and GPC.

<Synthesis of Resin 5>

Resin 5 having the following structure was synthesized by the same method except for changing the monomer species in the synthesis method of Resin 1B (PHS method) described above. Obtaining the target Resin 5 was confirmed by ¹ H-NMR and GPC.

[Formula 41]

<Synthesis of Resin 1A'>

Resin 1A' was synthesized in the same manner as in the synthesis method of Resin 1A (PACST method) described above, except that precipitation purification was carried out once.

<Synthesis of Resin 3B'>

Resin 3B' was synthesized in the same manner as in the synthesis method of Resin 3B (PHS method) described above, except that basic impurities were not removed and precipitation purification was carried out once.

<Synthesis of Resin 2A'>

Resin 2A' was synthesized in the same manner as in the synthesis method of Resin 2A (PACST method) described above, except that basic impurities were not removed.

<Synthesis of Resin 4'>

Resin 4 was synthesized in the same manner as in the method for synthesizing Resin 4 (polymer reaction) described above, except that basic impurities were not removed.

Table 1 shows the molar ratio of repeating units, weight average molecular weight (Mw), and degree of dispersion (Mw/Mn) in the synthesized various resins. In addition, the weight average molecular weight (Mw) and dispersion degree (Mw/Mn) of various resins shown in Table 1 were measured by GPC (carrier: THF) (polystyrene equivalent). In addition, the composition ratio (mol% ratio) of resin was measured by ¹³ C-NMR.

In addition, the resin 1A', resin 2A', resin 3B', and resin 4' have the same molar ratios of repeating units, Mw, and Mw/Mn as those of Resin 1A, Resin 2A, Resin 3B, and Resin 4, respectively. showed up

[Table 1]

[Preparation of actinic ray-sensitive or radiation-sensitive resin composition]

Below, the various components contained in the actinic ray-sensitive or radiation-sensitive resin composition shown in the 2nd table|surface are shown.

<Suzy>

As the resin shown in Table 2, the resin synthesized in the upper stage was used.

<mine generator>

The structure of the photo-acid generator shown in Table 2 is shown below.

[Formula 42]

<Acid Diffusion Controlling Agent>

The structure of the acid diffusion control agent shown in Table 2 is shown below.

[Formula 43]

<Surfactant>

Surfactant shown in a 2nd table|surface is shown below.

W-1: The thing of the following structure was used.

[Formula 44]

<Solvent>

The solvent shown in the 2nd table|surface is shown below.

PGME: propylene glycol monomethyl ether

PGMEA: propylene glycol monomethyl ether acetate

<Preparation of actinic ray-sensitive or radiation-sensitive resin composition>

Each component shown in Table 2 was mixed by adjusting the solid content so that the film thickness after pattern formation described later became 11 µm. Next, the obtained liquid mixture was filtered in the order of a polyethylene filter having a pore diameter of 50 nm, then a nylon filter having a pore diameter of 10 nm, and finally a polyethylene filter having a pore diameter of 5 nm in this order, thereby forming an actinic ray-sensitive or radiation-sensitive resin composition. (hereinafter also referred to as a resin composition) was prepared. In addition, in a resin composition, solid content means all components other than a solvent. The obtained resin composition was used in Examples and Comparative Examples.

In addition, 25 types (Na, K, Ca, Fe, Cu, Mg, Mn, Al, Li, Cr, Ni, Sn, Zn, Ag, As, Au, Ba, Cd, Co, Pb, Ti, V, W, Mo, Zr) was measured with an ICP-MS device (inductively coupled plasma mass spectrometer) "Agilent 7500cs" manufactured by Agilent Technologies, and the content of each metal species was less than 10 ppb, respectively.

<Identification of impurities having absorption at 248 nm>

The type and content (% by mass) of impurities having absorption at a wavelength of 248 nm contained in the actinic ray-sensitive or radiation-sensitive resin composition were measured. In the actinic ray-sensitive or radiation-sensitive resin compositions of Examples 1 to 8 and Comparative Examples 1 to 4, compounds a to e shown in the column "Impurities having absorption at a wavelength of 248 nm" in Table 2, respectively, were observed. It became. The structures and contents of compounds a to e were identified by liquid chromatography.

In addition, compounds a to e are para-hydroxystyrene and its modified products (compounds a and c), para-acetoxystyrene and its modified products (compounds b and d), and 4-(tert-butoxy), respectively. It is styrene (compound e), and it is estimated that all are derived from the raw material component of resin.

The specific structure of compounds a-e is shown below.

[Formula 45]

<Identification of basic impurities>

The type and content (% by mass) of basic impurities contained in the actinic ray-sensitive or radiation-sensitive resin composition were measured. In the actinic ray-sensitive or radiation-sensitive resin compositions of Examples 1 to 8 and Comparative Examples 1 to 4, compounds x and z shown in the "basic impurity" column in Table 2 were respectively observed. The structures and contents of compounds x and z were identified by capillary electrophoresis.

In addition, compounds x and z are triethylamine and sodium hydroxide, respectively, and it was presumed that all of them are derived from basic compounds used in deprotection of the resin.

A 2nd table|surface is shown below.

In addition, in the table|surface, content of each component corresponds to content (mass %) with respect to the total amount of solid content.

[Table 2]

[Pattern Formation and Various Evaluations]

<Pattern Formation: KrF Exposure, Alkali Development>

Using Tokyo Electron spin coater ACT-8, the resin composition prepared above was applied on a Si substrate (manufactured by Advanced Materials Technology Co., Ltd.) subjected to hexamethyldisilasein treatment without providing an antireflection layer, while the substrate was still. Dropped. After dropping, the substrate was rotated, and the rotational speed was maintained at 500 rpm for 3 seconds, then at 100 rpm for 2 seconds, further at 500 rpm for 3 seconds, and again at 100 rpm for 2 seconds. It was raised to the set rotation speed (1200 rpm) and maintained for 60 seconds. Thereafter, heat drying was performed on a hot plate at 130° C. for 60 seconds to form a positive resist film having a film thickness of 11 μm. For this resist film, a KrF excimer laser scanner (manufactured by ASML, PAS5500/850C, wavelength 248 nm), pattern exposure was carried out under exposure conditions of NA = 0.60 and σ = 0.75. It baked at 120 degreeC for 60 second after irradiation, and immersed for 60 second using the 2.38 mass % tetramethylammonium hydroxide (TMAH) aqueous solution. Thereafter, it was rinsed with pure water for 30 seconds and dried to form an isolated space pattern having a space width of 5 μm and a pitch width of 25 μm.

The pattern exposure is exposure through a mask having a line-and-space pattern having a space width of 5 μm and a pitch width of 25 μm after reduction projection exposure, and the exposure amount is an isolated space pattern having a space width of 5 μm and a pitch width of 25 μm. It was set as the optimal exposure amount (sensitivity) (mJ/cm ² ) to form . In determining the sensitivity, a scanning electron microscope (SEM) (9380II manufactured by Hitachi High-Technologies Corporation) was used to measure the space width of the pattern.

(performance evaluation)

The obtained pattern was evaluated by the method shown below.

From the SEM results of the cross section of the wafer after development, those that were not resolved to the substrate were evaluated as N, those that were resolved to the substrate but with bad linearity of the pattern, and those with good linearity of the pattern were evaluated as A. Examples of determination are shown in FIGS. 1 to 3 . 1 is an example in which the judgment is N, FIG. 2 is an example in which the judgment is B, and FIG. 3 is an example in which the judgment is A.

An evaluation result is shown to a 3rd table|surface.

[Table 3]

When the actinic ray-sensitive or radiation-sensitive resin composition of Examples 1-8 was used, it was confirmed that all were resolved to the board|substrate.

On the other hand, when the actinic ray-sensitive or radiation-sensitive resin compositions of Comparative Examples 1 to 4 were used, it was confirmed that they were not resolved to the substrate due to the influence of impurities having absorption at a wavelength of 248 nm and basic impurities.

Claims (11)

A resist film forming step of forming a resist film having a film thickness of 1 µm or more using an actinic ray-sensitive or radiation-sensitive resin composition;
an exposure step of exposing the resist film;
A pattern formation method comprising a developing step of developing the exposed resist film using a developing solution;
The actinic ray-sensitive or radiation-sensitive resin composition contains a resin and a photo-acid generator represented by any of the following general formulas (ZI), (ZII) and (ZIII),
The resin contains 65 to 80 mol% of a repeating unit represented by the following general formula (I) based on all repeating units,
The content of impurities having absorption at a wavelength of 248 nm is 1.00% by mass or less with respect to the resin,
The resin is a resin obtained by synthesis in the presence of a basic compound, and is a resin obtained by including a step of washing with a solution containing a weak acid,
The pattern formation method, wherein the content of basic impurities derived from the basic compound is 0.10% by mass or less with respect to the resin.

[In general formula (ZI),
R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represent an organic group, and two of R ₂₀₁ to R ₂₀₃ may be bonded to form a ring structure.
In formulas (ZII) and (ZIII), R ₂₀₄ to R ₂₀₇ each independently represent an aryl group, an alkyl group, or a cycloalkyl group.
In formulas (ZI) and (ZII), Z ^- represents an anion represented by formula (3) or formula (4).]

[In formula (3),
o represents the integer of 1-3. p represents the integer of 0-10. q represents an integer of 0 to 10.
Xf represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
R ₄ and R ₅ each independently represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom. When a plurality of R ₄ and R ₅ exist, R ₄ and R ₅ may be the same or different, respectively.
L represents a divalent linking group. When a plurality of L's exist, L's may be the same or different, respectively.
W represents an organic group containing a cyclic structure.]

[In formula (4),
X ^B1 and X ^B2 each independently represent a hydrogen atom or a monovalent organic group having no fluorine atom.
X ^B3 and X ^B4 each independently represent a hydrogen atom or a monovalent organic group.
L represents a divalent linking group. When a plurality of L's exist, L's may be the same or different, respectively.
q represents an integer of 0 to 10;
W represents an organic group containing a cyclic structure.]

[In formula (I),
R ₄₁ , R ₄₂ and R ₄₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. However, R ₄₂ may be bonded to Ar ₄ to form a ring, in which case R ₄₂ represents a single bond or an alkylene group.
X ₄ represents a single bond.
L ₄ represents a single bond.
Ar ₄ represents a (n+1) valent aromatic hydrocarbon group, and when combined with R ₄₂ to form a ring, represents an (n+2) valent aromatic hydrocarbon group.
n represents an integer of 1 to 5.] The method of claim 1,
The pattern formation method according to claim 1 , wherein the resin contains a repeating unit having a group whose polarity is increased by being decomposed by an action of an acid. delete According to claim 1 or claim 2,
The pattern formation method in which the impurity having absorption at the wavelength of 248 nm is an aromatic compound. According to claim 1 or claim 2,
The pattern formation method, wherein the impurity having absorption at a wavelength of 248 nm is a compound represented by general formula (X).

R _a represents a group represented by general formula (Y1) or a group represented by general formula (Y2).
R ₄₄ represents an alkyl group.
R _b represents a hydrogen atom or a protecting group. * indicates a binding position. A method for manufacturing an electronic device, including the pattern formation method according to claim 1. delete delete delete delete delete

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