WO2017002430A1

WO2017002430A1 - Actinic ray-sensitive or radiation-sensitive resin composition, actinic ray-sensitive or radiation-sensitive film, pattern molding method, and electronic device production method

Info

Publication number: WO2017002430A1
Application number: PCT/JP2016/062227
Authority: WO
Inventors: 研由後藤; 直也畠山; 啓太加藤; 惠瑜王
Original assignee: 富士フイルム株式会社
Priority date: 2015-07-01
Filing date: 2016-04-18
Publication date: 2017-01-05
Also published as: JP6571774B2; JPWO2017002430A1; TW201702743A

Abstract

Provided are: an actinic ray-sensitive or radiation-sensitive resin composition containing a resin (A) that includes a repeating unit (a) having an Si atom, a crosslinking agent (B), and a compound (C) that generates an acid upon irradiation with active light or radiation (with the caveat that a repeating unit having the Si atom has a structure in which a polar group is protected by a leaving group that is decomposed and removed by the action of the acid, and if the Si atom is only included in the leaving group, the repeating unit is not included in the repeating unit (a)); an actinic ray-sensitive or radiation-sensitive film that includes the actinic ray-sensitive or radiation-sensitive resin composition; a pattern molding method using the actinic ray-sensitive or radiation-sensitive resin composition; and an electronic device production method using the pattern molding method.

Description

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

The present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition, an actinic ray-sensitive or radiation-sensitive film, a pattern forming method, and an electronic device manufacturing method. More specifically, the present invention relates to an actinic ray-sensitive or radiation-sensitive material suitable for semiconductor manufacturing processes such as IC (Integrated Circuit), circuit boards such as liquid crystals and thermal heads, and other photofabrication lithography processes. The present invention relates to a photosensitive resin composition, an actinic ray-sensitive or radiation-sensitive film, a pattern forming method, and an electronic device manufacturing method.

Since the resist for KrF excimer laser (248 nm), an image forming method called chemical amplification has been used as an image forming method for a resist in order to compensate for sensitivity reduction due to light absorption. Explaining by taking a positive chemical amplification image forming method as an example, the acid generator in the exposed area is decomposed by exposure to generate an acid upon exposure, and the generated acid is reacted as a reaction catalyst in the post-exposure bake (Post Exposure Bake: PEB). Is used to change an alkali-insoluble group to an alkali-soluble group, and an exposed portion is removed by alkali development.

To reduce the size of semiconductor elements, the exposure light source has become shorter and the projection lens has a higher numerical aperture (high NA). Currently, an exposure machine using an ArF excimer laser having a wavelength of 193 nm as a light source has been developed. ing. When an ArF excimer laser is used as an exposure light source, a compound having an aromatic group essentially exhibits a large absorption in the 193 nm region. Therefore, an ArF excimer laser resist containing a resin having an alicyclic hydrocarbon structure has been developed. Yes. Further, as a technique for further increasing the resolving power, a method of filling a high refractive index liquid (hereinafter also referred to as “immersion liquid”) between the projection lens and the sample (ie, immersion method) has been proposed. In addition, EUV (Extreme Ultra Violet) lithography has been proposed in which exposure is performed with ultraviolet light having a shorter wavelength (13.5 nm).

In recent years, a negative image forming method including an organic solvent developing process in which development is performed using a developer containing an organic solvent (hereinafter also referred to as “organic solvent developer”) is being developed (for example, Patent Document 1). And 2).

JP 2012-13812 A JP 2011-100089 A

Integrated circuits are becoming more and more integrated, and accordingly, further improvements in resist pattern etching resistance and narrowing of resist pattern width and pitch are required. When the circuit line width is reduced, the difference in exposure amount (optical contrast) between the exposed area and the unexposed area decreases, and the dissolution rate of the developer in the low exposure area, intermediate exposure area, and high exposure area increases. The difference is reduced, resulting in degradation of contrast. Such deterioration of the contrast causes a line width variation (LWR) of a fine line pattern.

The present invention has been developed in view of the above circumstances, and is an actinic ray capable of forming a pattern excellent in etching resistance, having a high dissolution contrast between an exposed area and an unexposed area, and excellent in LWR performance. It aims at providing a photosensitive or radiation-sensitive resin composition and an actinic ray-sensitive or radiation-sensitive film. Another object of the present invention is to provide a pattern forming method using the actinic ray-sensitive or radiation-sensitive resin composition, and a method for producing an electronic device including the pattern forming method.

In one aspect, the present invention is as follows.
[1]
Actinic ray-sensitive or radiation-sensitive resin containing resin (A) containing repeating unit (a) having Si atom, crosslinking agent (B), and compound (C) that generates acid upon irradiation with actinic rays or radiation Composition. However, when the repeating unit having an Si atom has a structure in which a polar group is protected by a leaving group that decomposes and leaves by the action of an acid, and only the leaving group contains a Si atom, the repeating unit The unit is not included in the repeating unit (a).

[2]
The actinic ray-sensitive light according to [1], wherein the content of the resin (A) in the actinic ray-sensitive or radiation-sensitive resin composition is 50% by mass or more based on the total solid content in the composition. Or radiation sensitive resin composition.

[3]
The actinic ray-sensitive or radiation-sensitive resin composition according to [1] or [2], wherein the repeating unit (a) having an Si atom has a siloxane structure.

[4]
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [3], wherein the repeating unit (a) having an Si atom has a silsesquioxane structure.

[5]
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [4], wherein the content of Si atoms in the resin (A) is 10% by mass or more. However, when the resin (A) is a repeating unit having a structure in which a polar group is protected by a leaving group that is eliminated by the action of an acid, and the leaving group includes a repeating unit having a Si atom, Si atoms contained in the leaving group are not included in the content ratio of Si atoms.

[6]
The actinic ray-sensitive material according to any one of [1] to [5], wherein the resin (A) includes a repeating unit (d) having a crosslinkable reactive group capable of reacting with the crosslinker (B). Or a radiation sensitive resin composition. However, the repeating unit (d) having a crosslinkable reactive group may have a structure in which the crosslinkable reactive group is protected by a leaving group that decomposes and leaves by the action of an acid.

[7]
The crosslinking agent (B) includes at least one selected from melamine crosslinking agents, urea crosslinking agents, phenol crosslinking agents, epoxy crosslinking agents, vinyl ether crosslinking agents and glycoluril crosslinking agents, [1 ] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of items [6] to [6].

[8]
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [7], wherein the resin (A) contains a repeating unit (c) having an acid-decomposable group.

[9]
The actinic ray according to any one of [1] to [8], wherein the resin (A) contains a repeating unit (b) having at least one of a lactone structure, a sultone structure, and a cyclic carbonate structure. Or radiation sensitive resin composition.

[10]
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [9], which is for development using a developer containing an organic solvent.

[11]
[1] An actinic ray-sensitive or radiation-sensitive film comprising the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [10].

[12]
Forming an actinic ray-sensitive or radiation-sensitive film comprising the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [10],
Exposing the actinic ray sensitive or radiation sensitive film, and developing the actinic ray sensitive or radiation sensitive film after exposure using a developer containing an organic solvent to form a pattern;
A pattern forming method including:

[13]
The manufacturing method of an electronic device containing the pattern formation method as described in [12].

According to the present invention, an actinic ray-sensitive or radiation-sensitive resin composition capable of forming a pattern having excellent etching resistance, high dissolution contrast between exposed and unexposed areas, and excellent LWR performance, and It has become possible to provide an actinic ray-sensitive or radiation-sensitive film. Further, according to the present invention, it is possible to provide a pattern forming method using the actinic ray-sensitive or radiation-sensitive resin composition, and a method for manufacturing an electronic device including the pattern forming method.

Hereinafter, preferred embodiments of the present invention will be described in detail.
In the description of groups and atomic groups in the present specification, when substitution or non-substitution is not specified, both those having no substituent and those having a substituent are included. For example, an “alkyl group” that does not explicitly indicate substitution or unsubstituted includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). .

In the present invention, “active light” or “radiation” means, for example, an emission line spectrum of a mercury lamp, a deep ultraviolet ray represented by an excimer laser, an extreme ultraviolet ray (EUV light), an X-ray, an electron beam, an ion beam or other particle beam. Means. In the present invention, “light” means actinic rays or radiation.

In addition, the term “exposure” in the present specification is not limited to exposure to far ultraviolet rays, X-rays, extreme ultraviolet rays (EUV light) and the like represented by mercury lamps and excimer lasers. Drawing by particle beam such as is also included.

In this specification, “(meth) acrylate” means “at least one of acrylate and methacrylate”. “(Meth) acrylic acid” means “at least one of acrylic acid and methacrylic acid”.

In the present specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

[Actinic ray-sensitive or radiation-sensitive resin composition (resist composition)]
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention (hereinafter also referred to as “the composition of the present invention” or “the resist composition of the present invention”) is a repeating unit (a) having a Si atom (hereinafter referred to as “the composition of the present invention”). A resin (A) containing a “repeating unit (a)”, a crosslinking agent (B), and a compound (C) that generates an acid upon irradiation with actinic rays or radiation.

The first feature of the present invention is that the resin (A) containing the repeating unit (a) having Si atoms (hereinafter also referred to as “resin (A)”) and the crosslinking agent (B) are used in combination. To do.

Here, the repeating unit having an Si atom contained in the resin (A) has a structure in which a polar group is protected by a leaving group that is decomposed and eliminated by the action of an acid, and only in the leaving group. When a Si atom is included, this repeating unit is not included in the repeating unit (a).

That is, when the repeating unit having Si atoms is a repeating unit containing only Si atoms in the leaving group, the leaving group containing Si atoms is volatilized by exposure and subsequent heating (Post Exposure Bake: PEB). The content rate of Si atoms in the resulting pattern is low. On the other hand, in the repeating unit (a) having Si atoms, such a situation does not occur, so that the content of Si atoms in the obtained pattern is not reduced, and a pattern having excellent etching resistance is obtained. Is possible.

On the other hand, since organic molecules containing Si atoms have high hydrophobicity, when a negative pattern is formed using a resist composition containing a resin (A) containing a repeating unit (a) containing Si atoms, Then, due to the hydrophobicity of the repeating unit (a), the dissolution rate in the organic solvent developer is improved. On the other hand, since the composition of the present invention contains a cross-linking agent, a cross-linking reaction using the generated acid as a catalyst proceeds in the exposed area, and the permeability of the organic solvent developer is lowered, so that the dissolution rate is lowered. As a result of increasing the dissolution contrast between the exposed area and the unexposed area in this way, it is presumed that a pattern excellent in LWR can be obtained.

The composition of the present invention is typically a chemically amplified resist composition.
Hereinafter, each component contained in the composition of the present invention will be described.
[1] Resin (A)
Resin (A) contains the repeating unit (a) which has Si atom.
The content of Si atoms contained in the resin (A) is preferably 10% by mass or more, more preferably 12% by mass or more, and more preferably 15% by mass or more with respect to the total mass of the resin (A). More preferably, it is particularly preferably 18% by mass or more.

In one embodiment of the present invention, the content of Si atoms contained in the resin (A) is preferably 30% by mass or less, for example, with respect to the total mass of the resin (A).

Here, when the resin (A) is a repeating unit having a structure in which a polar group is protected by a leaving group that is removed by the action of an acid, and the leaving group includes a repeating unit having a Si atom, Si atoms contained in the leaving group are not included in the content of Si atoms.

In addition, in this specification, the repeating unit which has both Si atom and an acid-decomposable group corresponds to the repeating unit (a) which has Si atom, and the repeating unit which has an acid-decomposable group. For example, a resin composed of only a repeating unit having both an Si atom and an acid-decomposable group corresponds to a resin containing a repeating unit (a) having an Si atom and a repeating unit having an acid-decomposable group. The “acid-decomposable group” will be described later in the repeating unit (c) having an acid-decomposable group.

First, the repeating unit (a) having Si atoms will be described, and then the repeating unit that the resin (A) may contain will be described.

[1-1] Repeating unit having Si atom (a)
The repeating unit (a) having Si atoms is not particularly limited as long as it has Si atoms. For example, a repeating unit having a silane structure (—SiR ₂ —: R ₂ is an organic group), a repeating unit having a siloxane structure (—SiR ₂ —O—: R ₂ is an organic group), and a (meth) acrylate having a Si atom Examples thereof include a system repeating unit and a vinyl based repeating unit having a Si atom.

The repeating unit (a) having a Si atom preferably does not have an acid-decomposable group.

In one embodiment of the present invention, the repeating unit (a) having an Si atom preferably has a siloxane structure, and more preferably has a silsesquioxane structure. In addition, although it may have a siloxane structure or a silsesquioxane structure in a main chain or in a side chain, it is preferable to have in a side chain.

Examples of the silsesquioxane structure include a cage-type silsesquioxane structure, a ladder-type silsesquioxane structure (ladder-type silsesquioxane structure), a random-type silsesquioxane structure, and the like. Of these, a cage-type silsesquioxane structure is preferable.

Here, the cage silsesquioxane structure is a silsesquioxane structure having a cage structure. The cage silsesquioxane structure may be a complete cage silsesquioxane structure or an incomplete cage silsesquioxane structure, but may be a complete cage silsesquioxane structure. preferable.

The ladder-type silsesquioxane structure is a silsesquioxane structure having a ladder-like skeleton.

The random silsesquioxane structure is a silsesquioxane structure having a random skeleton.

The cage silsesquioxane structure is preferably a siloxane structure represented by the following formula (S).

In the above formula (S), R represents a monovalent substituent. A plurality of R may be the same or different.

The substituent is not particularly limited, and specific examples thereof include a halogen atom, a hydroxy group, a nitro group, a carboxy group, an alkoxy group, an amino group, a mercapto group, and a blocked mercapto group (for example, blocked (protected) with an acyl group). Mercapto groups), acyl groups, imide groups, phosphino groups, phosphinyl groups, silyl groups, vinyl groups, hydrocarbon groups optionally having heteroatoms, (meth) acryl group-containing groups and epoxy group-containing groups. Can be mentioned.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of the hetero atom of the hydrocarbon group that may have a hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom, and a phosphorus atom.

Examples of the hydrocarbon group that may have a hetero atom include an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group obtained by combining these.

The aliphatic hydrocarbon group may be linear, branched or cyclic. Specific examples of the aliphatic hydrocarbon group include a linear or branched alkyl group (particularly 1 to 30 carbon atoms), a linear or branched alkenyl group (particularly 2 to 30 carbon atoms), Examples thereof include a linear or branched alkynyl group (particularly 2 to 30 carbon atoms).

Examples of the aromatic hydrocarbon group include aromatic hydrocarbon groups having 6 to 18 carbon atoms such as a phenyl group, a tolyl group, a xylyl group, and a naphthyl group.

The repeating unit (a) having a Si atom is preferably represented by the following formula (I).

In the above formula (I), L represents a single bond or a divalent linking group.

Examples of the divalent linking group include an alkylene group, —COO—Rt— group, —O—Rt— group and the like. In the formula, Rt represents an alkylene group or a cycloalkylene group.

L is preferably a single bond or a —COO—Rt— group. Rt is preferably an alkylene group having 1 to 5 carbon atoms, more preferably a —CH ₂ — group, — (CH ₂ ) ₂ — group, or — (CH ₂ ) ₃ — group.

In the above formula (I), X represents a hydrogen atom or an organic group.

Examples of the organic group include an alkyl group which may have a substituent such as a fluorine atom and a hydroxyl group, and a hydrogen atom, a methyl group, a trifluoromethyl group, and a hydroxymethyl group are preferable.

In the above formula (I), A represents a Si-containing group. Of these, a group represented by the following formula (a) or (b) is preferable.

In the above formula (a), R represents a monovalent substituent. A plurality of R may be the same or different. Specific examples and preferred embodiments of R are the same as those in the above formula (S). * Represents a bonding position with L in the above formula (I). When A in the formula (I) is a group represented by the formula (a), the formula (I) is represented by the following formula (Ia).

In the formula (b), each R _b independently represents a hydrocarbon group that may have a hetero atom. Specific examples and preferred embodiments of the hydrocarbon group which may have a hetero atom are the same as R in the above-described formula (S). * Represents a bonding position with L in the above formula (I).

The repeating unit (a) having Si atoms contained in the resin (A) may be one kind or a combination of two or more kinds.

The content of the repeating unit (a) having Si atoms contained in the resin (A) (the total when there are a plurality of repeating units (a) having Si atoms) is the total repeating unit in the resin (A). On the other hand, it is preferably 1 to 70 mol%, more preferably 3 to 50 mol%.

[1-2] Repeating Unit Having Acid-Decomposable Group The resin (A) preferably contains a repeating unit having an acid-decomposable group (hereinafter also referred to as “repeating unit (c)”). The repeating unit (c) having an acid-decomposable group preferably has no Si atom.

Here, the acid-decomposable group refers to a group that decomposes by the action of an acid to generate a polar group.

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

The polar group is not particularly limited as long as it is a group that is hardly soluble or insoluble in a developer containing an organic solvent, and includes a phenolic hydroxyl group, a carboxyl group, a fluorinated alcohol group (preferably hexafluoroisopropanol group), and a sulfonic acid group. , Sulfonamide group, sulfonylimide group, (alkylsulfonyl) (alkylcarbonyl) methylene group, (alkylsulfonyl) (alkylcarbonyl) imide group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkyl Sulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, tris (alkylsulfonyl) methylene group and other acidic groups (2.38 mass% tetra, conventionally used as a resist developer) Methyl ammo Group dissociates in um hydroxide aqueous solution), or alcoholic hydroxyl group.

The alcoholic hydroxyl group is a hydroxyl group bonded to a hydrocarbon group and means a hydroxyl group other than a hydroxyl group directly bonded on an aromatic ring (phenolic hydroxyl group). Aliphatic alcohols substituted with a functional group (for example, fluorinated alcohol groups (such as hexafluoroisopropanol groups)) are excluded. The alcoholic hydroxyl group is preferably a hydroxyl group having a pKa (acid dissociation constant) of 12 or more and 20 or less.

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

A preferred group as the acid-decomposable group is a group in which the hydrogen atom of these groups is substituted with a group capable of leaving with an acid.

Examples of the group capable of leaving with an acid (leaving group) include —C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), —C (R ₃₆ ) (R ₃₇ ) (OR ₃₉ ), —C (R ₀₁₎ _(R 02) _(can be exemplified _{OR 39)} or the like.

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

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

The alkyl group of R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ is preferably an alkyl group having 1 to 8 carbon atoms, for example, methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, hexyl Group, octyl group and the like.

The cycloalkyl group of R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ may be monocyclic or polycyclic. The monocyclic type is preferably a cycloalkyl group having 3 to 8 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. The polycyclic type is preferably a cycloalkyl group having 6 to 20 carbon atoms. For example, an adamantyl group, norbornyl group, isobornyl group, camphanyl group, dicyclopentyl group, α-pinel group, tricyclodecanyl group, tetracyclododecyl group. Group, androstanyl group and the like. Note that at least one carbon atom in the cycloalkyl group may be substituted with a heteroatom such as an oxygen atom.

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

The aralkyl group of R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ is preferably an aralkyl group having 7 to 12 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 combining R ₃₆ and R ₃₇ is preferably a cycloalkyl group (monocyclic or polycyclic). The cycloalkyl group is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group or an adamantyl group. A monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferable, and a monocyclic cycloalkyl group having 5 carbon atoms is particularly preferable.

The acid-decomposable group is preferably a cumyl ester group, an enol ester group, an acetal ester group, a tertiary alkyl ester group or the like. More preferably, it is a tertiary alkyl ester group.

The resin (A) preferably has a repeating unit represented by the following general formula (AI) as the repeating unit (c) having an acid-decomposable group. The repeating unit represented by the general formula (AI) generates a carboxyl group as a polar group by the action of an acid, and in a plurality of carboxyl groups, shows a high interaction due to hydrogen bonding. The pattern can be more reliably insolubilized or hardly soluble in the solvent in the composition of the present invention described above.

In general formula (AI),
Xa ₁ represents a hydrogen atom, an alkyl group, a cyano group, or a halogen atom.

T represents a single bond or a divalent linking group.

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

Two of Rx ₁ to Rx ₃ may combine to form a ring structure.

Examples of the divalent linking group of T include an alkylene group, —COO—Rt— group, —O—Rt— group, phenylene group and the like. In the formula, Rt represents an alkylene group or a cycloalkylene group.

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

The alkyl group of _Xa1 may have a substituent, and examples of the substituent include a hydroxyl group and a halogen atom (preferably a fluorine atom).

The alkyl group for X _a1 is preferably an alkyl group having 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, and a methyl group is preferable.

X _a1 is preferably a hydrogen atom or a methyl group.

The alkyl group of Rx ₁ , Rx ₂ and Rx ₃ may be linear or branched, and is a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl. Group, t-butyl group and the like are preferable. The number of carbon atoms of the alkyl group is preferably 1 to 10, and more preferably 1 to 5.

Examples of the cycloalkyl group of Rx ₁ , Rx ₂ and Rx ₃ include polycyclic rings such as a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group and an adamantyl group. Are preferred.

The ring structure formed by combining two of Rx ₁ , Rx ₂ and Rx ₃ includes a monocyclic cycloalkane ring such as cyclopentyl ring and cyclohexyl ring, norbornane ring, tetracyclodecane ring, tetracyclododecane ring, adamantane ring A polycyclic cycloalkyl group such as is preferable. A monocyclic cycloalkane ring having 5 or 6 carbon atoms is particularly preferable.

Rx ₁ , Rx ₂ and Rx ₃ are preferably each independently an alkyl group, more preferably a linear or branched alkyl group having 1 to 4 carbon atoms.

Each of the above groups may have a substituent, and examples of the substituent include an alkyl group (1 to 4 carbon atoms), a cycloalkyl group (3 to 8 carbon atoms), a halogen atom, an alkoxy group (carbon 1 to 4), a carboxyl group, an alkoxycarbonyl group (2 to 6 carbon atoms), and the like, and 8 or less carbon atoms are preferable. Among these, from the viewpoint of further improving the dissolution contrast with respect to the developer containing an organic solvent before and after acid decomposition, a substituent having no hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom is more preferable (for example, More preferably, it is not an alkyl group substituted with a hydroxyl group, etc.), more preferably a group consisting of only a hydrogen atom and a carbon atom, and particularly preferably a linear or branched alkyl group or a cycloalkyl group. .

In general formula (AI), Rx ₁ to Rx ₃ are each independently an alkyl group, and it is preferable that two of Rx ₁ to Rx ₃ are not bonded to form a ring structure. As a result, an increase in the volume of the group represented by —C (Rx ₁ ) (Rx ₂ ) (Rx ₃ ) as a group capable of decomposing and leaving by the action of an acid can be suppressed, and after the exposure step and the exposure step In the post-exposure heating step that may be performed, the volume shrinkage of the exposed portion tends to be suppressed.

Specific examples of the repeating unit represented by the general formula (AI) are given below, but the present invention is not limited to these specific examples.

In specific examples, Rx represents a hydrogen atom, CH ₃ , CF ₃ , or CH ₂ OH. Rxa and Rxb each independently represents an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms). Xa ₁ represents a hydrogen atom, CH ₃ , CF ₃ , or CH ₂ OH. Z represents a substituent, and when a plurality of Zs are present, the plurality of Zs may be the same as or different from each other. p represents 0 or a positive integer. Specific examples and preferred examples of Z are the same as specific examples and preferred examples of the substituent that each group such as Rx ₁ to Rx ₃ may have.

In addition, the resin (A) preferably has a repeating unit described in paragraphs <0057> to <0071> of JP-A No. 2014-202969 as a repeating unit (c) having an acid-decomposable group.

In addition, the resin (A) has, as the repeating unit (c) having an acid-decomposable group, a repeating unit that generates an alcoholic hydroxyl group described in paragraphs <0072> to <0073> of JP-A No. 2014-202969. It may be.

One type of repeating unit (c) having an acid-decomposable group may be used, or two or more types may be used in combination.

When the resin (A) contains the repeating unit (c) having an acid-decomposable group, the content (the total when there are a plurality of repeating units (c)) is the total number of repetitions in the resin (A). The amount is preferably 20 to 90 mol%, more preferably 40 to 80 mol%, based on the unit. Among them, the resin (A) has a repeating unit represented by the above general formula (AI), and the content of the repeating unit represented by the above general formula (AI) with respect to all the repeating units of the resin (A) is 40 mol. % Or more is preferable.

[1-3] Repeating unit (d) having a crosslinkable reactive group capable of reacting with a crosslinking agent
The resin (A) preferably contains a repeating unit having a crosslinkable reactive group capable of reacting with the crosslinking agent contained in the composition of the present invention (hereinafter also referred to as “repeating unit (d)”).

Examples of the crosslinkable reactive group include an alcoholic hydroxyl group, a thiol group, an amino group, an epoxy group, an oxetane group, a vinyloxy group, a carboxyl group, and an ester group. From the viewpoints of crosslinking efficiency and ease of handling, the crosslinkable reactive group of the repeating unit (d) is preferably an alcoholic hydroxyl group or a carboxyl group.

When the resin (A) contains such a crosslinkable reactive group, the crosslinkable reactive group reacts with the crosslinker by the action of an acid in the exposed area, and the actinic ray-sensitive or radiation-sensitive film contains an organic solvent. Substantially insoluble in the developer.

In the present invention, the repeating unit (d) having a crosslinkable reactive group may have a structure in which the crosslinkable reactive group is protected by a leaving group that decomposes and leaves under the action of an acid.

Examples of the structure in which the crosslinkable reactive group is protected with a leaving group include, for example, a leaving group in which a carboxyl group that is a crosslinkable reactive group is a specific example of the aforementioned repeating unit (c) having an acid-decomposable group. And an acid-decomposable group protected with.

Examples of the structure in which the alcoholic hydroxyl group that is a crosslinkable reactive group is protected by a leaving group include structures such as a carbonate group, an acetal group, and a tertiary ether group, and preferably a carbonate group, an acetal. It is a group. In the case where the alcoholic hydroxyl group has a 1,2-diol or 1,3-diol structure, preferred examples include structures such as cyclic esters and cyclic orthoesters.

The repeating unit (d) having a crosslinkable reactive group that can be contained in the resin (A) may be one kind or a combination of two or more kinds.

When the resin (A) contains a repeating unit (d) having a crosslinkable reactive group, the content (the total when there are a plurality of repeating units (d)) is the total number of repeats in the resin (A). The amount is preferably 1 to 80 mol%, more preferably 5 to 80 mol%, based on the unit.

[1-4] Repeating unit (b) having at least one of lactone structure, sultone structure and cyclic carbonate structure
The resin (A) preferably contains a repeating unit having at least one of a lactone structure, a sultone structure, and a cyclic carbonate structure (hereinafter also referred to as “repeating unit (b)”).

Any lactone structure or sultone structure may be used as long as it has a lactone structure or sultone structure, preferably a 5- to 7-membered lactone structure or a 5- to 7-membered ring sultone structure, and a 5- to 7-membered structure. Other ring structures in which other ring structures are condensed in the form of forming a bicyclo structure or spiro structure in the ring lactone structure, or in the form of forming a bicyclo structure or a spiro structure in a 5- to 7-membered ring sultone structure More preferably, the ring is condensed. 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), More preferably, it has a repeating unit having A lactone structure or a sultone structure may be directly bonded to the main chain. Preferred lactone structures are (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-13), (LC1-14), (LC1-17), especially A preferred lactone structure is (LC1-4). By using such a specific lactone structure, LWR and development defects are improved.

The lactone structure portion or the sultone structure portion may or may not have a substituent (Rb ₂ ). Preferred substituents (Rb ₂ ) include alkyl groups having 1 to 8 carbon atoms, cycloalkyl groups having 4 to 7 carbon atoms, alkoxy groups having 1 to 8 carbon atoms, alkoxycarbonyl groups having 2 to 8 carbon atoms, and carboxyl groups. , Halogen atom, hydroxyl group, cyano group, acid-decomposable group and the like. More preferred are an alkyl group having 1 to 4 carbon atoms, a cyano group, and an acid-decomposable group. n ₂ represents an integer of 0 to 4. When n ₂ is 2 or more, the plurality of substituents (Rb ₂ ) may be the same or different. A plurality of substituents (Rb ₂ ) may be bonded to form a ring.

The repeating unit having a lactone structure or a sultone structure usually has an optical isomer, but any optical isomer may be used. One optical isomer may be used alone, or a plurality of optical isomers may be mixed and used. When one kind of optical isomer is mainly used, the optical purity (ee) thereof is preferably 90% or more, more preferably 95% or more.

The repeating unit having a lactone structure or a sultone structure is preferably a repeating unit represented by the following general formula (III).

In the general formula (III),
A represents an ester bond (a group represented by —COO—) or an amide bond (a group represented by —CONH—).

R ₀ represents an alkylene group, a cycloalkylene group, or a combination thereof independently when there are a plurality of R ₀ .

When there are a plurality of Z, each independently represents a single bond, an ether bond, an ester bond, an amide bond, or a urethane bond.

Or urea bond

Represents. Here, each R independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group.

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

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

R ₇ represents a hydrogen atom, a halogen atom or an alkyl group.

The alkylene group and cycloalkylene group represented by R ₀ may have a substituent.

Z is preferably an ether bond or an ester bond, and particularly preferably an ester bond.

The alkyl group for R ₇ is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and particularly preferably a methyl group.

The alkylene group of R ₀ , the cycloalkylene group, and the alkyl group in R ₇ may each be substituted. Examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom, a mercapto group, a hydroxyl group, Examples thereof include alkoxy groups such as methoxy group, ethoxy group, isopropoxy group, t-butoxy group and benzyloxy group, and acyloxy groups such as acetyloxy group and propionyloxy group.

R ₇ is preferably a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.

The preferred chain alkylene group for R ₀ is preferably a chain alkylene having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and examples thereof include a methylene group, an ethylene group, and a propylene group. A preferred cycloalkylene group is a cycloalkylene group having 3 to 20 carbon atoms, and examples thereof include a cyclohexylene group, a cyclopentylene group, a norbornylene group, and an adamantylene group. In order to exhibit the effect of the present invention, a chain alkylene group is more preferable, and a methylene group is particularly preferable.

The monovalent organic group having a lactone structure or a sultone structure represented by R ₈ is not limited as long as it has a lactone structure or a sultone structure, and specific examples thereof include general formulas (LC1-1) to (LC1-21). And a lactone structure or a sultone structure represented by any one of (SL1-1) to (SL1-3), and a structure represented by (LC1-4) is particularly preferable. In addition, n ₂ in (LC1-1) to (LC1-21) is more preferably an integer of 2 or less.

R ₈ is preferably a monovalent organic group having an unsubstituted lactone structure or sultone structure, or a monovalent organic group having a lactone structure or sultone structure having a methyl group, a cyano group or an alkoxycarbonyl group as a substituent. A monovalent organic group having a lactone structure (cyanolactone) having a cyano group as a substituent is more preferable.

Specific examples of the repeating unit having a group having a lactone structure or a sultone structure are shown below, but the present invention is not limited thereto.

In order to enhance the effect of the present invention, it is also possible to use a repeating unit having two or more lactone structures or sultone structures in combination.

When the resin (A) contains a repeating unit having a lactone structure or a sultone structure, the content of the repeating unit having a lactone structure or a sultone structure is 5 to 60 mol% with respect to all the repeating units in the resin (A). It is preferably 5 to 55 mol%, more preferably 10 to 50 mol%.

The resin (A) may have a repeating unit having a carbonate structure (cyclic carbonate structure).

The repeating unit having a cyclic carbonate structure is preferably a repeating unit represented by the following general formula (A-1).

In general formula (A-1), R _A ¹ represents a hydrogen atom or an alkyl group.

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

A represents a single bond or a divalent linking group.

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

N represents an integer of 0 or more.

The general formula (A-1) will be described in detail.

The alkyl group represented by R _A ¹ may have a substituent such as a fluorine atom. R _A ¹ preferably represents a hydrogen atom, a methyl group or a trifluoromethyl group, and more preferably represents a methyl group.

The substituent represented by R _A ² is, for example, an alkyl group, a cycloalkyl group, a hydroxyl group, an alkoxy group, an amino group, or an alkoxycarbonylamino group. Preferred is an alkyl group having 1 to 5 carbon atoms, for example, a linear alkyl group having 1 to 5 carbon atoms such as a methyl group, an ethyl group, a propyl group or a butyl group; an isopropyl group, an isobutyl group or a t-butyl group. Examples thereof include branched alkyl groups having 3 to 5 carbon atoms such as The alkyl group may have a substituent such as a hydroxyl group.

N is an integer of 0 or more representing the number of substituents. n is, for example, preferably 0 to 4, more preferably 0.

Examples of the divalent linking group represented by A include an alkylene group, a cycloalkylene group, an ester bond, an amide bond, an ether bond, a urethane bond, a urea bond, or a combination thereof. The alkylene group is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms, and examples thereof include a methylene group, an ethylene group, and a propylene group.

In one embodiment of the present invention, A is preferably a single bond or an alkylene group.

As the monocycle containing —O—C (═O) —O— represented by Z, for example, in the cyclic carbonate represented by the following general formula (a), n _A = 2 to 4 5 To 7-membered ring, preferably 5-membered ring or 6-membered ring (n _A = 2 or 3), more preferably 5-membered ring (n _A = 2).

Examples of the polycycle containing —O—C (═O) —O— represented by Z include, for example, a cyclic carbonate represented by the following general formula (a) together with one or more other ring structures: Examples include a structure forming a condensed ring and a structure forming a spiro ring. The “other ring structure” that can form a condensed ring or a spiro ring may be an alicyclic hydrocarbon group, an aromatic hydrocarbon group, or a heterocyclic ring. .

Monomers corresponding to the repeating units represented by the general formula (A-1) are, for example, Tetrahedron Letters, Vol. 27, no. 32 p. 3741 (1986), Organic Letters, Vol. 4, no. 15 p. 2561 (2002) and the like, and can be synthesized by a conventionally known method.

The resin (A) may contain one of repeating units represented by the general formula (A-1) alone, or may contain two or more kinds.

In the resin (A), the content of the repeating unit having a cyclic carbonate structure (preferably, the repeating unit represented by the general formula (A-1)) is based on the total repeating units constituting the resin (A). It is preferably 3 to 80 mol%, more preferably 3 to 60 mol%, and particularly preferably 3 to 40 mol%. By setting it as such a content rate, the developability as a resist, low defect property, low LWR (Line Width Roughness), low PEB (Post Exposure Bake) temperature dependence, a profile, etc. can be improved.

Specific examples of the repeating unit represented by formula (A-1) (repeating units (A-1a) to (A-1w)) are shown below, but the present invention is not limited thereto.

Incidentally, _R ^{A 1} in the following specific examples are the same meaning as _R ^{A 1} in the general formula (A-1).

[Other repeat units]
The resin (A) may have a repeating unit having a hydroxyl group or a cyano group. Examples of such repeating units include the repeating units described in paragraphs <0081> to <0084> of JP-A No. 2014-089921.

Further, the resin (A) may have a repeating unit having an alkali-soluble group. Examples of the alkali-soluble group include a carboxyl group, a sulfonamide group, a sulfonylimide group, a bissulfonylimide group, and an aliphatic alcohol (for example, a hexafluoroisopropanol group) in which the α-position is substituted with an electron withdrawing group. Examples of the repeating unit having an alkali-soluble group include the repeating units described in paragraphs <0085> to <0086> of JP-A No. 2014-098921.

Further, the resin (A) can further have a repeating unit that has an alicyclic hydrocarbon structure having no polar group (for example, an alkali-soluble group, a hydroxyl group, a cyano group, etc.) and does not exhibit acid decomposability. Examples of such a repeating unit include the repeating units described in paragraphs <0114> to <0123> of JP 2014-106299 A.

In addition, the resin (A) may contain, for example, repeating units described in paragraphs <0045> to <0065> of JP-A-2009-258586.

Resin (A) used in the method of the present invention, in addition to the above repeating structural unit, dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and resolving power which is a general necessary characteristic of resist, Various repeating structural units can be included for the purpose of adjusting heat resistance, sensitivity, and the like. Examples of such repeating structural units include, but are not limited to, repeating structural units corresponding to the following monomers.

Thereby, the performance required for the resin (A) used in the composition of the present invention, in particular, (1) solubility in a coating solvent, (2) film forming property (glass transition point), (3) alkali developability (4) Slip film (selection of hydrophilicity / hydrophobicity, alkali-soluble group), (5) Adhesion of unexposed part to substrate, (6) Dry etching resistance, etc. can be finely adjusted.

As such a monomer, for example, a compound having one addition polymerizable unsaturated bond selected from acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, etc. Etc.

In addition, any addition-polymerizable unsaturated compound that can be copolymerized with monomers corresponding to the above various repeating structural units may be copolymerized.

In the resin (A), the content molar ratio of each repeating structural unit is the resist dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and resolution, heat resistance, and sensitivity, which are general required performance of the resist. It is set appropriately in order to adjust etc.

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

Resin (A) is preferably a resin in which all repeating units are composed of (meth) acrylate repeating units. In this case, all of the repeating units are methacrylate repeating units, all of the repeating units are acrylate repeating units, or all of the repeating units are methacrylate repeating units and acrylate repeating units. It can be used, and the acrylate repeating unit is preferably 50 mol% or less of the total repeating units.

Resin (A) can be synthesized according to a conventional method (for example, radical polymerization). For example, as a general synthesis method, a monomer polymerization method in which a monomer species and an initiator are dissolved in a solvent and the polymerization is performed by heating, and a solution of the monomer species and the initiator is dropped into the heating solvent over 1 to 10 hours. The dropping polymerization method is added, and the dropping polymerization method is preferable. Examples of the reaction solvent include ethers such as tetrahydrofuran, 1,4-dioxane and diisopropyl ether, ketones such as methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as ethyl acetate, amide solvents such as dimethylformamide and dimethylacetamide, Furthermore, the solvent which melt | dissolves the composition of this invention like the below-mentioned propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and cyclohexanone is mentioned. More preferably, the polymerization is performed using the same solvent as the solvent used in the composition of the present invention. Thereby, generation | occurrence | production of the particle at the time of a preservation | save can be suppressed.

The polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon. As a polymerization initiator, a commercially available radical initiator (azo initiator, peroxide, etc.) is used to initiate the polymerization. As the radical initiator, an azo initiator is preferable, and an azo initiator having an ester group, a cyano group, or a carboxyl group is preferable. Preferred initiators include azobisisobutyronitrile, azobisdimethylvaleronitrile, dimethyl 2,2′-azobis (2-methylpropionate) and the like. If desired, an initiator is added or added in portions, and after completion of the reaction, it is put into a solvent and a desired polymer is recovered by a method such as powder or solid recovery. The concentration of the reaction is 5 to 50% by mass, preferably 10 to 30% by mass. The reaction temperature is usually 10 ° C. to 150 ° C., preferably 30 ° C. to 120 ° C., more preferably 60 to 100 ° C.

As described above, the content of Si atoms in the resin (A) is preferably 10% by mass or more.

However, when the above repeating unit having a Si atom has a structure in which a polar group is protected by a leaving group that decomposes and leaves by the action of an acid, and the leaving group has a Si atom, The content of Si atoms in (A) does not include the amount of Si atoms in the leaving group. That is, even if there are Si atoms in the leaving group, the amount of Si atoms is not included in the content of Si atoms in the resin (A).

For example, the repeating unit on the right side of the resin A-19 used in Comparative Example 4 described later has a Si atom derived from TMS (trimethylsilyl group), and the above repeating unit includes the following leaving group (*: bonding position). Since the polar group (—COOH) is protected, the amount of Si atoms derived from TMS in the leaving group is not included in the content of Si atoms in the resin. In addition, since the said repeating unit contains Si atom only in a leaving group, it does not correspond to the repeating unit (a) in this invention.

The weight average molecular weight of the resin (A) is preferably 1,000 to 200,000, more preferably 2,000 to 20,000, still more preferably 3,000 to 15,000, particularly preferably 3, 000 to 11,000. By setting the weight average molecular weight to 1,000 to 200,000, deterioration of heat resistance and dry etching resistance can be prevented, and developability is deteriorated, and viscosity is increased, resulting in deterioration of film forming property. Can be prevented.

The degree of dispersion (molecular weight distribution) is usually 1.0 to 3.0, preferably 1.0 to 2.6, more preferably 1.0 to 2.0, and particularly preferably 1.1 to 2.0. Those in the range are used. The smaller the molecular weight distribution, the better the resolution and the resist shape, and the smoother the side wall of the resist pattern, the better the roughness.

In addition, in this specification, a weight average molecular weight is a standard polystyrene conversion value calculated | required from the gel permeation chromatography (Gel Permeation Chromatography: GPC) of the following conditions.
Column type: TSK gel Multipore HXL-M (manufactured by Tosoh Corporation, 7.8 mm ID × 30.0 cm)
Developing solvent: THF (Tetrahydrofuran: tetrahydrofuran)
-Column temperature: 40 ° C
・ Flow rate: 1 ml / min
Sample injection volume: 10 μl
・ Device name: HLC-8120 (manufactured by Tosoh Corporation)
The content of the resin (A) in the total solid content of the composition of the present invention is preferably 50% by mass or more. The content of the resin (A) is more preferably 60% by mass or more, further preferably 65% by mass or more, and particularly preferably 70% by mass or more. The upper limit of the content of the resin (A) is not particularly limited, but in one embodiment of the present invention, it is preferably 95% by mass or less.
In the present invention, the resin (A) may be used alone or in combination.

[2] Crosslinking agent The composition of the present invention contains a compound having an acid crosslinking group (hereinafter also referred to as “crosslinking agent (B)” or “compound (B)”).
In one embodiment of the present invention, the crosslinking agent (B) is a compound selected from a melamine crosslinking agent, a urea crosslinking agent, a phenol crosslinking agent, an epoxy crosslinking agent, a vinyl ether crosslinking agent, and a glycoluril crosslinking agent. It is preferable that one of these may be used alone, or two or more of them may be used.

In another embodiment of the present invention, the crosslinking agent (B) is preferably a compound containing two or more hydroxymethyl groups or alkoxymethyl groups in the molecule. From the viewpoint of improving LWR, the compound (B) preferably contains a methylol group.

Compound (B) is preferably a hydroxymethylated or alkoxymethylated phenol compound, an alkoxymethylated melamine compound, an alkoxymethylglycoluril compound, and an alkoxymethylated urea compound. Particularly preferred compounds (B) include phenol derivatives and alkoxymethylglycolurils containing 3 to 5 benzene rings in the molecule and having two or more hydroxymethyl groups or alkoxymethyl groups, and having a molecular weight of 1200 or less. Derivatives.

The alkoxymethyl group is preferably a methoxymethyl group or an ethoxymethyl group.

Among the examples of the compound (B), a phenol derivative having a hydroxymethyl group can be obtained by reacting a corresponding phenol compound having no hydroxymethyl group with formaldehyde under a base catalyst. A phenol derivative having an alkoxymethyl group can be obtained by reacting a corresponding phenol derivative having a hydroxymethyl group with an alcohol in the presence of an acid catalyst.

Examples of another preferable compound (B) include compounds having an N-hydroxymethyl group or an N-alkoxymethyl group, such as an alkoxymethylated melamine compound, an alkoxymethylglycoluril compound, and an alkoxymethylated urea compound. Can be mentioned.

Examples of such compounds include hexamethoxymethyl melamine, hexaethoxymethyl melamine, tetramethoxymethyl glycoluril, 1,3-bismethoxymethyl-4,5-bismethoxyethylene urea, bismethoxymethyl urea, and the like. 133, 216A, West German Patent 3,634,671, West German Patent 3,711,264, EP 0,212,482A.

Further, examples of another preferable compound (B) include vinyl ether crosslinking agents such as ethylene glycol vinyl ether, trimethylolpropane trivinyl ether, 1,4-cyclohexanedimethanol divinyl ether.

Examples of another preferred compound (B) include bisphenol A / epichlorohydrin type epoxy resin, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, 1,6-hexanediol. Examples thereof include epoxy-based crosslinking agents such as diglycidyl ether, trimethylolpropane triglycidyl ether, sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl erythritol, diglycerol polyglycidyl ether.

Among the specific examples of the compound (B), those particularly preferred are listed below.

In the formula, L ₁ to L ₈ each independently represents a hydrogen atom, a hydroxymethyl group, a methoxymethyl group, an ethoxymethyl group, or an alkyl group having 1 to 6 carbon atoms.

In one embodiment of the present invention, the compound (B) is preferably a phenol compound represented by the following general formula (I).

In general formula (I),
R ₁ and R ₆ each independently represents a hydrogen atom or a hydrocarbon group having 5 or less carbon atoms.

R ₂ and R ₅ each independently represents an alkyl group, a cycloalkyl group, an aryl group, or an acyl group.

R ₃ and R ₄ each independently represent a hydrogen atom or an organic group having 2 or more carbon atoms. R ₃ and R ₄ may combine with each other to form a ring.

In one embodiment of the present invention, R ₁ and R ₆ are preferably a hydrocarbon group having 5 or less carbon atoms, more preferably a hydrocarbon group having 4 or less carbon atoms, and particularly preferably a methyl group, an ethyl group, Examples include a propyl group and an isopropyl group.

As the alkyl group represented by R ₂ and R ₅ , for example, an alkyl group having 1 to 6 carbon atoms is preferable, and as the cycloalkyl group, for example, a cycloalkyl group having 3 to 12 carbon atoms is preferable, and as the aryl group, For example, an aryl group having 6 to 12 carbon atoms is preferable, and as the acyl group, for example, an acyl group having 1 to 6 carbon atoms in the alkyl moiety is preferable.

In one embodiment of the present invention, R ₂ and R ₅ are preferably alkyl groups, more preferably alkyl groups having 1 to 6 carbon atoms, and particularly preferably methyl groups.

Examples of the organic group having 2 or more carbon atoms represented by R ₃ and R ₄ include an alkyl group having 2 or more carbon atoms, a cycloalkyl group, and an aryl group, and R ₃ and R ₄ are bonded to each other. It is preferable to form the ring described in detail below.

Examples of the ring formed by combining R ₃ and R ₄ with each other include, for example, an aromatic or non-aromatic hydrocarbon ring, an aromatic or non-aromatic heterocyclic ring, or a combination of two or more of these rings The polycyclic fused ring formed can be mentioned.

These rings may have a substituent. Examples of such a substituent include an alkyl group, a cycloalkyl group, an alkoxy group, a carboxyl group, an aryl group, an alkoxymethyl group, an acyl group, and an alkoxycarbonyl group. , A nitro group, a halogen atom, or a hydroxy group.

Specific examples of the ring formed by combining R ₃ and R ₄ with each other are given below. * In a formula represents a connection part with a phenol nucleus.

In one embodiment of the present invention, R ₃ and R ₄ in the general formula (I) are preferably bonded to form a polycyclic fused ring containing a benzene ring, and more preferably a fluorene structure is formed. preferable.

In the compound (B), for example, R ₃ and R _{4 in the} general formula (I) are preferably bonded to form a fluorene structure represented by the following general formula (Ia).

Where
R ₇ and R ₈ each independently represents a substituent. Examples of the substituent include an alkyl group, a cycloalkyl group, an alkoxy group, an aryl group, an alkoxymethyl group, an acyl group, an alkoxycarbonyl group, a nitro group, a halogen atom, and a hydroxy group.

N1 and n2 each independently represents an integer of 0 to 4, preferably 0 or 1.

* Represents a linking site with a phenol nucleus.

In one embodiment of the present invention, the compound (B) is preferably represented by the following general formula (Ib).

Where
R _1b and R _6b each independently represents an alkyl group having 5 or less carbon atoms.

R _2b and R _5b each independently represents an alkyl group having 6 or less carbon atoms or a cycloalkyl group having 3 to 12 carbon atoms.

Z represents an atomic group necessary for forming a ring together with the carbon atom in the formula.

The ring formed by Z together with the carbon atom in the formula is the same as that described for the ring formed by combining R ₃ and R ₄ with each other in the description of the general formula (I).

In one embodiment of the present invention, the compound (B) is preferably a compound having four or more aromatic rings and two alkoxymethyl groups and / or hydroxymethyl groups in the molecule.

Next, a method for producing the compound (B) represented by the general formula (I) will be described.

In general, the bisphenol compound serving as a mother nucleus of the compound (B) represented by the general formula (I) is generally a dehydration condensation reaction between two corresponding phenol compounds and one corresponding ketone in the presence of an acid catalyst. To be synthesized.

The obtained bisphenol compound is treated with paraformaldehyde and dimethylamine and aminomethylated to obtain an intermediate represented by the following general formula (IC). Subsequently, the target acid crosslinking agent is obtained through acetylation, deacetylation, and alkylation.

In formula, R < ₁ >, R < ₃ >, R < ₄ > and R < ₆ > are synonymous with each group in general formula (I).

This synthesis method has an effect of inhibiting particle formation because it is difficult to produce an oligomer as compared with a synthesis method via a hydroxymethyl compound under a basic condition (for example, JP 2008-273844 A). .

Specific examples of the compound (B) represented by the general formula (I) are shown below.

In the present invention, the compound (B) may be used alone or in combination of two or more. From the viewpoint of a good pattern shape, it is preferable to use a combination of two or more.

The compound (B) containing an acid crosslinkable group may be in the form of a resin containing a repeating unit having an acid crosslinkable group (hereinafter also referred to as compound (B ″)).

The content of the crosslinking agent (B) in the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention is preferably from 0.5 to the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition. 30% by mass, more preferably 1 to 15% by mass.
[3] Compound that generates acid upon irradiation with actinic ray or radiation The composition of the present invention comprises compound (C) that generates acid upon irradiation with actinic ray or radiation (hereinafter referred to as “acid generator” or “compound (C ) "). Although it does not specifically limit as an acid generator, It is preferable that it is a compound which generate | occur | produces an organic acid by irradiation of actinic light or a radiation. The acid generator may be a low-molecular compound or may be contained in a resin (for example, the above-described resin (A)).

As the acid generator, photo-initiator of photocation polymerization, photo-initiator of photo-radical polymerization, photo-decoloring agent of dyes, photo-discoloring agent, irradiation of actinic ray or radiation used for micro resist, etc. Known compounds that generate an acid and mixtures thereof can be appropriately selected and used. For example, compounds described in paragraphs <0039> to <0103> of JP-A-2010-61043, Examples thereof include compounds described in paragraphs <0284> to <0389> of Kaikai 2013-4820, but the present invention is not limited thereto.

Examples include diazonium salts, phosphonium salts, sulfonium salts, iodonium salts, imide sulfonates, oxime sulfonates, diazodisulfones, disulfones, and o-nitrobenzyl sulfonates.

As an acid generator which the composition of this invention contains, the compound (specific acid generator) which generate | occur | produces an acid by irradiation of the actinic ray or radiation represented by following General formula (3) suitably is mentioned, for example. it can.

(Anion)
In general formula (3),
Xf each independently 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, and when there are a plurality of R ₄ and R ₅ , R ₄ and R ₅ are the same But it can be different.

L represents a divalent linking group, and when there are a plurality of L, L may be the same or different.

W represents an organic group containing a cyclic structure.

O represents an integer of 1 to 3. p represents an integer of 0 to 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. The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms. The alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group.

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

The alkyl group as R ₄ and R ₅ may have a substituent and is preferably an alkyl group having 1 to 4 carbon atoms. R ₄ and R ₅ are preferably a hydrogen atom.

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

Examples of the divalent linking group include —COO — (— C (═O) —O—), —OCO—, —CONH—, —NHCO—, —CO—, —O—, —S—, — SO—, —SO ₂ —, an alkylene group (preferably having 1 to 6 carbon atoms), a cycloalkylene group (preferably having 3 to 10 carbon atoms), an alkenylene group (preferably having 2 to 6 carbon atoms), or a combination thereof And divalent linking groups. Among these, —COO—, —OCO—, —CONH—, —NHCO—, —CO—, —O—, —SO ₂ —, —COO-alkylene group—, —OCO-alkylene group—, —CONH— alkylene group - or -NHCO- alkylene group - are preferred, -COO -, - OCO -, - CONH -, - SO 2 -, - COO- alkylene group - or -OCO- alkylene group - is more preferable.

W represents an organic group containing a cyclic structure. Of these, a cyclic organic group is preferable.

Examples of the cyclic organic group include an alicyclic group, an aryl group, and a heterocyclic group.

The alicyclic group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include monocyclic cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. Examples of the polycyclic alicyclic group include polycyclic cycloalkyl groups such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group. Among these, 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 a PEB (heating after exposure) step It is preferable from the viewpoint of suppression of in-film diffusibility and improvement of MEEF (Mask Error Enhancement Factor).

The aryl group may be monocyclic or polycyclic. Examples of the aryl group include a phenyl group, a naphthyl group, a phenanthryl group, and an anthryl group. Among these, a naphthyl group having a relatively low light absorbance at 193 nm is preferable.

The heterocyclic group may be monocyclic or polycyclic, and polycyclic can suppress acid diffusion more. Moreover, the heterocyclic group may have aromaticity or may not have aromaticity. Examples of the heterocyclic ring having aromaticity include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Examples of the heterocyclic ring that does not have aromaticity include a tetrahydropyran ring, a lactone ring, a sultone ring, and a decahydroisoquinoline ring. As the heterocyclic ring in the heterocyclic group, a furan ring, a thiophene ring, a pyridine ring, or a decahydroisoquinoline ring is particularly preferable. Examples of the lactone ring and sultone ring include the lactone structure and sultone structure exemplified in the aforementioned resin (A).

The cyclic organic group may have a substituent. Examples of this substituent include an alkyl group (which may be linear or branched, preferably 1 to 12 carbon atoms), and a cycloalkyl group (monocyclic, polycyclic or spirocyclic). Well, preferably having 3 to 20 carbon atoms), aryl group (preferably having 6 to 14 carbon atoms), hydroxyl group, alkoxy group, ester group, amide group, urethane group, ureido group, thioether group, sulfonamide group, and sulfonic acid An ester group is mentioned. The carbon constituting the cyclic organic group (carbon contributing to ring formation) may be a carbonyl carbon.

In one embodiment, o in the general formula (3) is an integer of 1 to 3, p is an integer of 1 to 10, and q is preferably 0. Xf is preferably a fluorine atom, R ₄ and R ₅ are preferably both hydrogen atoms, and W is preferably a polycyclic hydrocarbon group. o is more preferably 1 or 2, and still more preferably 1. p is preferably an integer of 1 to 3, more preferably 1 or 2, and particularly preferably 1. W is more preferably a polycyclic cycloalkyl group, and further preferably an adamantyl group or a diamantyl group.
(Cation)
In the general formula (3), X ⁺ represents a cation.

X ⁺ is not particularly limited as long as it is a cation, and preferred embodiments include, for example, cations (parts other than Z ⁻ ) in the general formula (ZI), (ZII) or (ZIII) described later.
(Preferred embodiment)
As a suitable aspect of a specific acid generator, the compound represented by the following general formula (ZI), (ZII), or (ZIII) is mentioned, for example.

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

The organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.

Two of R ₂₀₁ to R ₂₀₃ may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group. Examples of the group formed by combining two _{members out} of R ₂₀₁ to R ₂₀₃ include an alkylene group (eg, butylene group, pentylene group).

Z ⁻ represents an anion in the general formula (3), and specifically represents the following anion.

Examples of the organic group represented by R ₂₀₁ , R ₂₀₂ and R ₂₀₃ include the corresponding groups in the compounds (ZI-1), (ZI-2), (ZI-3) and (ZI-4) described later. Can be mentioned.

In addition, the compound which has two or more structures represented by general formula (ZI) may be sufficient. For example, at least one of R ₂₀₁ to R ₂₀₃ of the compound represented by the general formula (ZI) is a single bond or at least one of R ₂₀₁ to R ₂₀₃ of the other compound represented by the general formula (ZI). It may be a compound having a structure bonded through a linking group.

More preferred (ZI) components include compounds (ZI-1), (ZI-2), (ZI-3) and (ZI-4) described below.

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

The 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 an aryl group, or a part of R ₂₀₁ to R ₂₀₃ may be an aryl group and the rest may be an alkyl group or a cycloalkyl group.

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

The aryl group of the arylsulfonium compound is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The aryl group may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom or the like. Examples of the heterocyclic structure include a pyrrole residue, a furan residue, a thiophene residue, an indole residue, a benzofuran residue, and a benzothiophene residue. When the arylsulfonium compound has two or more aryl groups, the two or more aryl groups may be the same or different.

The alkyl group or cycloalkyl group optionally possessed by the arylsulfonium compound is preferably a linear or branched alkyl group having 1 to 15 carbon atoms and a cycloalkyl group having 3 to 15 carbon atoms, such as a methyl group, Examples include an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, a cyclopropyl group, a cyclobutyl group, and a cyclohexyl group.

The aryl group, alkyl group, and cycloalkyl group of R ₂₀₁ to R ₂₀₃ are an alkyl group (for example, 1 to 15 carbon atoms), a cycloalkyl group (for example, 3 to 15 carbon atoms), an aryl group (for example, 6 to 14 carbon atoms). , An alkoxy group (for example, having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, and a phenylthio group may be substituted.

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 represents an organic group having no aromatic ring. Here, the aromatic ring includes an aromatic ring containing a hetero atom.

The organic group containing no 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, 2-oxocycloalkyl group, alkoxy group. A carbonylmethyl group, particularly preferably a linear or branched 2-oxoalkyl group.

The alkyl group and cycloalkyl group represented by R ₂₀₁ to R ₂₀₃ are preferably a linear or branched alkyl group having 1 to 10 carbon atoms (eg, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group), a carbon Examples thereof include cycloalkyl groups having a number of 3 to 10 (cyclopentyl group, cyclohexyl group, 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.

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

In general formula (ZI-3),
R _1c to R _5c are each independently a hydrogen atom, alkyl group, cycloalkyl group, aryl group, alkoxy group, aryloxy group, alkoxycarbonyl group, alkylcarbonyloxy group, cycloalkylcarbonyloxy group, halogen atom, hydroxyl group Represents a nitro group, an alkylthio group or an arylthio group.

R _6c and R _7c each independently represents 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 represents an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group, or a vinyl group.

Any two or more of R _1c to R _5c , R _5c and R _6c , R _6c and R _7c , R _5c and R _x , and R _x and R _y may be bonded to form a ring structure. In addition, this ring structure may 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 heterocyclic ring, or a polycyclic fused ring formed by combining two or more of these rings. Examples of the ring structure include 3- to 10-membered rings, preferably 4- to 8-membered rings, more preferably 5- or 6-membered rings.

Examples of the group 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.

The group formed by combining R _5c and R _6c and R _5c and R _x is preferably a single bond or an alkylene group, and examples of the alkylene group include a methylene group and an ethylene group. .

Zc ⁻ represents an anion in the general formula (3), specifically, as described above.

Specific examples of the alkoxy group in the alkoxycarbonyl group as R _1c ~ _{R 5c} are the same as specific examples of the alkoxy group as the _{_R} 1c _~ _R _5c.

Specific examples of the alkyl group in the alkylcarbonyloxy group and alkylthio group as R _1c ~ _{R 5c} are the same as specific examples of the alkyl group of the _{_R} 1c _~ _R _5c.

Specific examples of the cycloalkyl group in the cycloalkyl carbonyl group as R _1c ~ _{R 5c} are the same as specific examples of the cycloalkyl group of the _{_R} 1c _~ _R _5c.

Specific examples of the aryl group in the aryloxy group and arylthio group as R _1c ~ _{R 5c} are the same as specific examples of the aryl group of the _{_R} 1c _~ _R _5c.

Examples of the cation in the compound (ZI-2) or (ZI-3) in the present invention include cations described in paragraph <0036> and thereafter of US Patent Application Publication No. 2012/0076996.

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

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

In general formula (ZI-4),
R ₁₃ represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, or a group having a cycloalkyl group. These groups may have a substituent.

R ₁₄ is independently 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, when a plurality of R ₁₄ are present. Represents. These groups may have a substituent.

R ₁₅ each independently represents an alkyl group, a cycloalkyl group or a naphthyl group. These groups may have a substituent. Two R ₁₅ may be bonded to each other to form a ring. When two R ₁₅ 's are bonded to each other to form a ring, the ring skeleton may contain a hetero atom such as an oxygen atom or a nitrogen atom. In one embodiment, it is preferred that two R ₁₅ are alkylene groups and are bonded to each other to form a ring structure.

L represents an integer of 0-2.

R represents an integer from 0 to 8.

Z ⁻ represents an anion in the general formula (3), specifically as described above.

In general formula (ZI-4), the alkyl group of R ₁₃ , R ₁₄ and R ₁₅ is linear or branched, and is preferably an alkyl group having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, An n-butyl group, a t-butyl group and the like are preferable.

Examples of the cation of the compound represented by the general formula (ZI-4) in the present invention include paragraphs <0121>, <0123>, <0124> of JP 2010-256842 A, and JP 2011-76056 A. The cations described in paragraphs <0127>, <0129>, <0130>, etc.

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

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

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

The alkyl group and cycloalkyl group in R ₂₀₄ to R ₂₀₇ are preferably a linear or branched alkyl group having 1 to 10 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, pentyl group), carbon Examples thereof include cycloalkyl groups having a number of 3 to 10 (cyclopentyl group, cyclohexyl group, norbornyl group).

The aryl group, alkyl group, and cycloalkyl group of R ₂₀₄ to R ₂₀₇ may 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, having 1 to 15 carbon atoms) and a cycloalkyl group (eg, having 3 to 15 carbon atoms). ), Aryl groups (for example, having 6 to 15 carbon atoms), alkoxy groups (for example, having 1 to 15 carbon atoms), halogen atoms, hydroxyl groups, phenylthio groups, and the like.

The acid generator (including a specific acid generator; the same shall apply hereinafter) may be in the form of a low molecular compound or may be incorporated in a part of the polymer. Moreover, you may use together the form incorporated in a part of polymer and the form of a low molecular compound.

When the acid generator is in the form of a low molecular compound, the molecular weight is preferably 580 or more, more preferably 600 or more, further preferably 620 or more, and particularly preferably 640 or more. . Although an upper limit in particular is not restrict | limited, 3000 or less are preferable, 2000 or less are more preferable, and 1000 or less are still more preferable.

When the acid generator is incorporated in a part of the polymer, it may be incorporated in a part of the resin (A) described above or may be incorporated in a resin different from the resin (A).

The acid generator can be synthesized by a known method, for example, according to the method described in JP-A No. 2007-161707.

The acid generator can be used alone or in combination of two or more.

The content of the acid generator in the composition (the total when there are plural kinds) is preferably 0.1 to 30% by mass, more preferably 0.5 to 25% based on the total solid content of the composition. % By mass, more preferably 3 to 20% by mass, particularly preferably 3 to 15% by mass.

When the compound represented by the above general formula (ZI-3) or (ZI-4) is contained as the acid generator, the content of the acid generator contained in the composition (when there are plural kinds, the total thereof) Is preferably 5 to 35% by mass, more preferably 8 to 30% by mass, still more preferably 9 to 30% by mass, and particularly preferably 9 to 25% by mass based on the total solid content of the composition.

[4] Hydrophobic Resin The composition of the present invention may contain a hydrophobic resin (hereinafter also referred to as “hydrophobic resin (D)” or simply “resin (D)”). The hydrophobic resin (D) is preferably different from the resin (A).

The hydrophobic resin (D) is preferably designed to be unevenly distributed at the interface. However, unlike the surfactant, it is not always necessary to have a hydrophilic group in the molecule, and the polar / nonpolar substance is mixed uniformly. You don't have to contribute to

Examples of the effects of adding the hydrophobic resin include control of the static / dynamic contact angle of the resist film surface with respect to water, improvement of immersion liquid followability, and suppression of outgas.

The hydrophobic resin (D) is selected from any one of “fluorine atom”, “silicon atom”, and “CH ₃ partial structure contained in the side chain portion of the resin” from the viewpoint of uneven distribution in the film surface layer. It is preferable to have the above, and more preferable to have two or more.

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

When the hydrophobic resin (D) contains a fluorine atom, it is a resin having an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, or an aryl group having a fluorine atom as a partial structure having a fluorine atom. Preferably there is.

The alkyl group having a fluorine atom (preferably having 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms) is a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom. It may have a substituent other than.

A cycloalkyl group having a fluorine atom and an aryl group having a fluorine atom are a cycloalkyl group in which one hydrogen atom is substituted with a fluorine atom and an aryl group having a fluorine atom, respectively, and further a substituent other than a fluorine atom is substituted. You may have.

Preferred examples of the alkyl group having a fluorine atom, the cycloalkyl group having a fluorine atom, and the aryl group having a fluorine atom include groups represented by the following general formulas (F2) to (F4). The invention is not limited to this.

In general formulas (F2) to (F4),
R ₅₇ to R ₆₈ each independently represents a hydrogen atom, a fluorine atom or an alkyl group (straight or branched). Provided that at least one of R ₅₇ to R ₆₁ , at least one of R ₆₂ to R ₆₄ , and at least one of R ₆₅ to R ₆₈ are each independently a fluorine atom or at least one hydrogen atom is a fluorine atom. It represents a substituted alkyl group (preferably having 1 to 4 carbon atoms).

All of R ₅₇ to R ₆₁ and R ₆₅ to R ₆₇ are preferably fluorine atoms. R ₆₂ , R ₆₃ and R ₆₈ are preferably an alkyl group (preferably having 1 to 4 carbon atoms) in which at least one hydrogen atom is substituted with a fluorine atom, and preferably a perfluoroalkyl group having 1 to 4 carbon atoms. Further preferred. R ₆₂ and R ₆₃ may be connected to each other to form a ring.

The hydrophobic resin (D) may contain a silicon atom. The partial structure having a silicon atom is preferably a resin having an alkylsilyl structure (preferably a trialkylsilyl group) or a cyclic siloxane structure.

Examples of the repeating unit having a fluorine atom or a silicon atom include those exemplified in US Patent Application Publication No. 2012/0251948 [0519].

Further, as described above, the hydrophobic resin (D), it is also preferred to include CH ₃ partial structure side chain moiety.

Here, CH ₃ partial structure contained in the side chain moiety in the hydrophobic resin (D) (hereinafter, simply referred to as "side chain CH ₃ partial structure") The, CH ₃ partial structure an ethyl group, and a propyl group having Is included.

On the other hand, a methyl group directly bonded to the main chain of the hydrophobic resin (D) (for example, an α-methyl group of a repeating unit having a methacrylic acid structure) is caused by the influence of the main chain on the surface of the hydrophobic resin (D). Since the contribution to uneven distribution is small, it is not included in the CH ₃ partial structure in the present invention.

More specifically, the hydrophobic resin (D) is a repeating unit derived from a monomer having a polymerizable moiety having a carbon-carbon double bond, such as a repeating unit represented by the following general formula (M). In the case where R ₁₁ to R ₁₄ are CH ₃ “as is”, the CH ₃ is not included in the CH ₃ partial structure of the side chain moiety in the present invention.

Meanwhile, CH ₃ partial structure exists through some atoms from C-C backbone corresponds to CH ₃ partial structures in the present invention. For example, when R ₁₁ is an ethyl group (CH ₂ CH ₃ ), it has “one” CH ₃ partial structure in the present invention.

In the general formula (M),
R ₁₁ to R ₁₄ each independently represents a side chain portion.

Examples of R ₁₁ to R _{14 in the} side chain portion include a hydrogen atom and a monovalent organic group.

Examples of the monovalent organic group for R ₁₁ to R ₁₄ include an alkyl group, a cycloalkyl group, an aryl group, an alkyloxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, an alkylaminocarbonyl group, and a cycloalkylaminocarbonyl. Group, an arylaminocarbonyl group, and the like, and these groups may further have a substituent.

The hydrophobic resin (D) is preferably a resin having a repeating unit having a CH ₃ partial structure in the side chain portion, and as such a repeating unit, a repeating unit represented by the following general formula (II), and It is more preferable to have at least one repeating unit (x) among repeating units represented by the following general formula (III).

Hereinafter, the repeating unit represented by the general formula (II) will be described in detail.

In the general formula (II), X _b1 represents a hydrogen atom, an alkyl group, a cyano group or a halogen atom, R ₂ has one or more CH ₃ partial structure represents a stable organic radical to acid. Here, the organic group that is stable to acid is more preferably an organic group that does not have the “acid-decomposable group” described in the resin (A).

The alkyl group for _Xb1 is preferably an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, or a trifluoromethyl group, and is preferably a methyl group.

X _b1 is preferably a hydrogen atom or a methyl group.

Examples of R ₂ include an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group, and an aralkyl group having one or more CH ₃ partial structures. The above cycloalkyl group, alkenyl group, cycloalkenyl group, aryl group and aralkyl group may further have an alkyl group as a substituent.

R ₂ is preferably an alkyl group or an alkyl group-substituted cycloalkyl group having one or more CH ₃ partial structures.

The acid-stable organic group having one or more CH ₃ partial structures as R ₂ preferably has 2 or more and 10 or less CH ₃ partial structures, and more preferably 2 or more and 8 or less.

Preferred specific examples of the repeating unit represented by the general formula (II) are listed below. The present invention is not limited to this.

The repeating unit represented by the general formula (II) is preferably an acid-stable (non-acid-decomposable) repeating unit, and specifically, a group that decomposes by the action of an acid to generate a polar group. It is preferable that it is a repeating unit which does not have.

Hereinafter, the repeating unit represented by the general formula (III) will be described in detail.

In the above general formula (III), X _b2 represents a hydrogen atom, an alkyl group, a cyano group, or a halogen atom, R ₃ represents an acid-stable organic group having one or more CH ₃ partial structures, n represents an integer of 1 to 5.

The alkyl group for _Xb2 is preferably an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, or a trifluoromethyl group, and is preferably a methyl group.

X _b2 is preferably a hydrogen atom.

Since R ₃ is an organic group that is stable against acid, more specifically, R ₃ is preferably an organic group that does not have the “acid-decomposable group” described in the resin (A).

R ₃ includes an alkyl group having one or more CH ₃ partial structures.

The acid-stable organic group having one or more CH ₃ partial structures as R ₃ preferably has 1 or more and 10 or less CH ₃ partial structures, more preferably 1 or more and 8 or less, More preferably, it is 1 or more and 4 or less.

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

Preferred specific examples of the repeating unit represented by the general formula (III) are given below. The present invention is not limited to this.

The repeating unit represented by the general formula (III) is preferably an acid-stable (non-acid-decomposable) repeating unit, and specifically, a group that decomposes by the action of an acid to generate a polar group. It is preferable that it is a repeating unit which does not have.

In the case where the hydrophobic resin (D) contains a CH ₃ partial structure in the side chain portion, and particularly when it does not have a fluorine atom and a silicon atom, the repeating unit represented by the general formula (II), and The content of at least one repeating unit (x) among the repeating units represented by the general formula (III) is preferably 90 mol% or more based on all repeating units of the hydrophobic resin (D). More preferably, it is 95 mol% or more. Content is 100 mol% or less normally with respect to all the repeating units of hydrophobic resin (D).

The hydrophobic resin (D) comprises at least one repeating unit (x) among the repeating unit represented by the general formula (II) and the repeating unit represented by the general formula (III). ), The surface free energy of the hydrophobic resin (D) increases. As a result, the hydrophobic resin (D) is less likely to be unevenly distributed on the surface of the resist film, and the static / dynamic contact angle of the resist film with respect to water can be reliably improved and the immersion liquid followability can be improved. it can.

In addition, the hydrophobic resin (D) includes the following (x) to (z) regardless of whether (i) a fluorine atom and / or a silicon atom is included or (ii) a CH ₃ partial structure is included in the side chain portion. ) May have at least one group selected from the group of

(X) an acid group,
(Y) a group having a lactone structure, an acid anhydride group, or an acid imide group,
(Z) A group capable of decomposing 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 sulfonylimide 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 (alkyl) A carbonyl) methylene group, a tris (alkylsulfonyl) methylene group, and the like.

Preferred acid groups include fluorinated alcohol groups (preferably hexafluoroisopropanol), sulfonimide groups, and bis (alkylcarbonyl) methylene groups.

The repeating unit having an acid group (x) includes a repeating unit in which an acid group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid or methacrylic acid, or a resin having a linking group. Examples include a repeating unit in which an acid group is bonded to the main chain, and a polymerization initiator or chain transfer agent having an acid group can be introduced at the end of the polymer chain at the time of polymerization. preferable. The repeating unit having an acid group (x) may have at least one of a fluorine atom and a silicon atom.

The content of the repeating unit having an acid group (x) is preferably from 1 to 50 mol%, more preferably from 3 to 35 mol%, still more preferably from 5 to 5%, based on all repeating units in the hydrophobic resin (D). 20 mol%.

Specific examples of the repeating unit having an acid group (x) are shown below, but the present invention is not limited thereto. In the formula, Rx represents a hydrogen atom, CH ₃ , CF ₃ , or CH ₂ OH.

As the group having a lactone structure, the acid anhydride group, or the acid imide group (y), a group having a lactone structure is particularly preferable.

The repeating unit containing these groups is a repeating unit in which this group is bonded directly to the main chain of the resin, such as a repeating unit of acrylic ester and methacrylic ester. Alternatively, this repeating unit may be a repeating unit in which this group is bonded to the main chain of the resin via a linking group. Or this repeating unit may be introduce | transduced into the terminal of resin using the polymerization initiator or chain transfer agent which has this group at the time of superposition | polymerization.

Examples of the repeating unit having a group having a lactone structure include those similar to the repeating unit having a lactone structure described above in the section of the resin (A).

The content of the repeating unit having a group having a lactone structure, an acid anhydride group, or an acid imide group is preferably 1 to 100 mol% based on all repeating units in the hydrophobic resin (D), The content is more preferably 3 to 98 mol%, further preferably 5 to 95 mol%.

Examples of the repeating unit having a group (z) that is decomposed by the action of an acid in the hydrophobic resin (D) include the same repeating units as those having an acid-decomposable group listed for the resin (A). The repeating unit having a group (z) that decomposes by the action of an acid may have at least one of a fluorine atom and a silicon atom. In the hydrophobic resin (D), the content of the repeating unit having a group (z) that is decomposed by the action of an acid is preferably 1 to 80 mol% with respect to all the repeating units in the resin (D). The amount is preferably 10 to 80 mol%, more preferably 20 to 60 mol%.

The hydrophobic resin (D) may further have a repeating unit different from the above-described repeating unit.

The repeating unit containing a fluorine atom is preferably 10 to 100 mol%, more preferably 30 to 100 mol%, based on all repeating units contained in the hydrophobic resin (D). Further, the repeating unit containing a silicon atom is preferably 10 to 100 mol%, more preferably 20 to 100 mol% in all repeating units contained in the hydrophobic resin (D).

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

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

Further, the hydrophobic resin (D) may be used alone or in combination.

The content of the hydrophobic resin (D) in the composition is preferably 0.01 to 10% by mass, more preferably 0.05 to 8% by mass, based on the total solid content in the composition of the present invention.

In the hydrophobic resin (D), the residual monomer and oligomer components are preferably 0.01 to 5% by mass, more preferably 0.01 to 3% by mass. The molecular weight distribution (Mw / Mn, also referred to as dispersity) is preferably in the range of 1 to 5, more preferably in the range of 1 to 3.

As the hydrophobic resin (D), various commercially available products can be used, and the hydrophobic resin (D) can be synthesized according to a conventional method (for example, radical polymerization).
[5] Acid diffusion control agent The composition of the present invention preferably contains an acid diffusion control agent. The acid diffusion controller acts as a quencher that traps the acid generated from the acid generator or the like during exposure and suppresses the reaction of the acid-decomposable resin in the unexposed area due to excess generated acid. Examples of the acid diffusion controller include a basic compound, a low molecular compound having a nitrogen atom and a group capable of leaving by the action of an acid, a basic compound whose basicity is reduced or disappeared by irradiation with actinic rays or radiation, or An onium salt that is a weak acid relative to the acid generator can be used.

[5-1]
Preferred examples of the basic compound include compounds having a structure represented by the following formulas (A) to (E).

In general formulas (A) and (E),
R ²⁰⁰ , R ²⁰¹ and R ²⁰² may be the same or different and are a hydrogen atom, an alkyl group (preferably having a carbon number of 1 to 20), a cycloalkyl group (preferably having a carbon number of 3 to 20) or an aryl group (having a carbon number). 6-20), wherein 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 represents an alkyl group having 1 to 20 carbon atoms.

Regarding the alkyl group, the alkyl group having a substituent is preferably an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, or a cyanoalkyl group having 1 to 20 carbon atoms.

These alkyl groups in general formulas (A) and (E) are more preferably unsubstituted.

Preferred compounds include guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, piperidine and the like, and more preferred compounds include imidazole structure, diazabicyclo structure, onium hydroxide structure, onium carboxylate Examples thereof include a compound having a structure, a trialkylamine structure, an aniline structure or a pyridine structure, an alkylamine derivative having a hydroxyl group and / or an ether bond, and an aniline derivative having a hydroxyl group and / or an ether bond.

Specific examples of preferred compounds include those exemplified in US Patent Application Publication No. 2012/0219913 <0379>.

Preferred examples of the basic compound further include an amine compound having a phenoxy group, an ammonium salt compound having a phenoxy group, an amine compound having a sulfonic acid ester group, and an ammonium salt compound having a sulfonic acid ester group.

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

The composition of the present invention may or may not contain a basic compound. When it is contained, the content of the basic compound is usually 0.001 to 10 mass based on the solid content of the composition. %, Preferably 0.01 to 5% by mass.

The use ratio of the acid generator and the basic compound in the composition is preferably acid generator / basic compound (molar ratio) = 2.5 to 300, more preferably 5.0 to 200, still more preferably 7. 0-150.

[5-2]
A low molecular weight compound having a nitrogen atom and having a group capable of leaving by the action of an acid (hereinafter, also referred to as “compound (F)”) is an amine derivative having a group on the nitrogen atom that is leaving by the action of an acid. It is preferable that

As the group capable of leaving by the action of an acid, an acetal group, a carbonate group, a carbamate group, a tertiary ester group, a tertiary hydroxyl group, and a hemiaminal ether group are preferable, and a carbamate group and a hemiaminal ether group are particularly preferable. .

The molecular weight of the compound (F) is preferably 100 to 1000, more preferably 100 to 700, and particularly preferably 100 to 500.

Compound (F) may have a carbamate group having a protecting group on the nitrogen atom. The protecting group constituting the carbamate group can be represented by the following general formula (d-1).

In general formula (d-1),
Rb each independently represents a hydrogen atom, an alkyl group (preferably 1 to 10 carbon atoms), a cycloalkyl group (preferably 3 to 30 carbon atoms), an aryl group (preferably 3 to 30 carbon atoms), an aralkyl group ( Preferably, it represents 1 to 10 carbon atoms) or an alkoxyalkyl group (preferably 1 to 10 carbon atoms). Rb may be connected to each other to form a ring.

The alkyl group, cycloalkyl group, aryl group, and aralkyl group represented by Rb are substituted with a functional group such as hydroxyl group, cyano group, amino group, pyrrolidino group, piperidino group, morpholino group, oxo group, alkoxy group, or halogen atom. It may be. The same applies to the alkoxyalkyl group represented by Rb.

Rb is preferably a linear or branched alkyl group, cycloalkyl group, or aryl group. More preferably, it is a linear or branched alkyl group or cycloalkyl group.

Examples of the ring formed by connecting two Rb to each other include an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic hydrocarbon group, or a derivative thereof.

Specific examples of the group represented by the general formula (d-1) include the structures disclosed in US Patent Application Publication No. 2012/0135348 <0466>, but are not limited thereto. It is not something.

The compound (F) particularly preferably has a structure represented by the following general formula (6).

In the general formula (6), Ra represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. When l is 2, two Ras may be the same or different, and two Ras may be connected to each other to form a heterocyclic ring together with the nitrogen atom in the formula. This heterocycle may contain a heteroatom other than the nitrogen atom in the formula.

Rb has the same meaning as Rb in formula (d-1), and preferred examples are also the same.

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

In the general formula (6), the alkyl group, cycloalkyl group, aryl group and aralkyl group as Ra are described above as the groups in which the alkyl group, cycloalkyl group, aryl group and aralkyl group as Rb may be substituted. It may be substituted with a group similar to the group.

Specific examples of the Ra alkyl group, cycloalkyl group, aryl group, and aralkyl group (these alkyl group, cycloalkyl group, aryl group, and aralkyl group may be substituted with the above group) include: The same group as the specific example mentioned above about Rb is mentioned.

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

The compound represented by the general formula (6) can be synthesized based on JP2007-298569A, JP2009-199021A, and the like.

In the present invention, the low molecular compound (F) having a group capable of leaving by the action of an acid on the nitrogen atom can be used alone or in combination of two or more.

The content of the compound (F) in the composition of the present invention is preferably 0.001 to 20% by mass, more preferably 0.001 to 10% by mass, further based on the total solid content of the composition. Preferably, the content is 0.01 to 5% by mass.

[5-3]
A basic compound whose basicity decreases or disappears upon irradiation with actinic rays or radiation (hereinafter also referred to as “compound (PA)”) has a proton acceptor functional group and is irradiated with actinic rays or radiation. Is a compound whose proton acceptor properties are degraded, disappeared, or changed from proton acceptor properties to acidic properties.

The proton acceptor functional group is a group that can interact electrostatically with a proton or a functional group having an electron. For example, a functional group having a macrocyclic structure such as a cyclic polyether or a π-conjugated group. It means a functional group having a nitrogen atom with an unshared electron pair that does not contribute. The nitrogen atom having an unshared electron pair that does not contribute to π conjugation is, for example, a nitrogen atom having a partial structure represented by the following formula.

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

The compound (PA) is decomposed by irradiation with actinic rays or radiation to generate a compound whose proton acceptor property is lowered, disappeared, or changed from proton acceptor property to acidity. Here, the decrease or disappearance of the proton acceptor property or the change from the proton acceptor property to the acid is a change in the proton acceptor property caused by the addition of a proton to the proton acceptor functional group. Means that when a proton adduct is formed from a compound having a proton acceptor functional group (PA) and a proton, the equilibrium constant in the chemical equilibrium is reduced.

Proton acceptor properties can be confirmed by measuring pH.

In the present invention, the acid dissociation constant pKa of the compound generated by decomposition of the compound (PA) upon irradiation with actinic rays or radiation preferably satisfies pKa <−1, more preferably −13 <pKa <−1. More preferably, −13 <pKa <−3.

In the present invention, the acid dissociation constant pKa represents the acid dissociation constant pKa in an aqueous solution. For example, Chemical Handbook (II) (4th revised edition, 1993, edited by the Chemical Society of Japan, Maruzen Co., Ltd.) It shows that acid strength is so large that this value is low. Specifically, the acid dissociation constant pKa in an aqueous solution can be measured by measuring an acid dissociation constant at 25 ° C. using an infinitely diluted aqueous solution, and using the following software package 1, Hammett The values based on the substituent constants and the database of known literature values can also be obtained by calculation. The values of pKa described in this specification all indicate values obtained by calculation using this software package.

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

The compound (PA) generates, for example, a compound represented by the following general formula (PA-1) as the proton adduct generated by decomposition upon irradiation with actinic rays or radiation. Since the compound represented by the general formula (PA-1) has an acidic group together with the proton acceptor functional group, the proton acceptor property is reduced or disappeared compared to the compound (PA), or the proton acceptor property is reduced. It is a compound that has changed to acidic.

In general formula (PA-1),
Q represents —SO ₃ H, —CO ₂ H, or —W ₁ NHW ₂ R _f . Here, R _f represents an alkyl group (preferably having 1 to 20 carbon atoms), a cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group (preferably having 6 to 30 carbon atoms), and W ₁ and W ₂ each independently represents —SO ₂ — or —CO—.

A represents a single bond or a divalent linking group.

X represents —SO ₂ — or —CO—.

N represents 0 or 1.

B represents a single bond, an oxygen atom, or —N (R _x ) R _y —. Here, R _x represents a hydrogen atom or a monovalent organic group, and R _y represents a single bond or a divalent organic group. R _x may be bonded to R _y to form a ring, or R _x may be bonded to R to form a ring.

R represents a monovalent organic group having a proton acceptor functional group.

The compound (PA) is preferably an ionic compound. The proton acceptor functional group may be contained in either the anion portion or the cation portion, and is preferably contained in the anion portion.

In the present invention, a compound (PA) other than the compound that generates the compound represented by the general formula (PA-1) can be appropriately selected. For example, an ionic compound that has a proton acceptor moiety in the cation moiety may be used. More specifically, a compound represented by the following general formula (7) is exemplified.

In the formula, A represents a sulfur atom or an iodine atom.

M represents 1 or 2, and n represents 1 or 2. However, when A is a sulfur atom, m + n = 3, and when A is an iodine atom, m + n = 2.

R represents an aryl group.

R _N represents an aryl group substituted with a proton acceptor functional group. X ⁻ represents a counter anion.

Specific examples of X ⁻ include the same as the above-mentioned anion of the acid generator.

Specific examples of the aryl group of R and R _N is a phenyl group are preferably exemplified.

Specific examples of the proton acceptor functional group R _N are the same as those of the proton acceptor functional group described in the foregoing formula (PA-1).

Hereinafter, specific examples of the ionic compound having a proton acceptor site in the cation moiety may include compounds exemplified in US Patent Application Publication No. 2011/0269072 <0291>.

In addition, such a compound can be synthesized with reference to methods described in, for example, Japanese Patent Application Laid-Open No. 2007-230913 and Japanese Patent Application Laid-Open No. 2009-122623.

Compound (PA) may be used alone or in combination of two or more.

The content of the compound (PA) is preferably 0.1 to 10% by mass, more preferably 1 to 8% by mass, based on the total solid content of the composition.

[5-4]
In the composition of the present invention, an onium salt that becomes a weak acid relative to the acid generator can be used as an acid diffusion control agent.

When an acid generator and an onium salt that generates an acid that is a relatively weak acid with respect to the acid generated from the acid generator are mixed and used, it is generated from the acid generator by irradiation with actinic rays or radiation. When the acid collides with an onium salt having an unreacted weak acid anion, a weak acid is released by salt exchange to yield an onium salt having a strong acid anion. In this process, the strong acid is exchanged with a weak acid having a lower catalytic ability, so that the acid is apparently deactivated and the acid diffusion can be controlled.

The onium salt that is a weak acid relative to the acid generator is preferably a compound represented by the following general formulas (d1-1) to (d1-3).

In the formula, R ⁵¹ is an optionally substituted hydrocarbon group, and Z ^2c is an ^optionally substituted hydrocarbon group having 1 to 30 carbon atoms (provided adjacent to the S atom). R ⁵² is an organic group, Y ³ is a linear, branched or cyclic alkylene group or an arylene group, and Rf is a fluorine atom. It is a hydrocarbon group containing an atom, and each M ⁺ is independently a sulfonium cation or an iodonium cation.

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

Preferred examples of the anion moiety of the compound represented by the general formula (d1-1) include the structures exemplified in paragraph [0198] of JP2012-242799A.

Preferred examples of the anion moiety of the compound represented by the general formula (d1-2) include the structures exemplified in paragraph [0201] of JP2012-242799A.

Preferred examples of the anion moiety of the compound represented by the general formula (d1-3) include the structures exemplified in paragraphs [0209] and [0210] of JP2012-242799A.

The onium salt that is a weak acid relative to the acid generator is (C) a compound having a cation moiety and an anion moiety in the same molecule, and the cation moiety and the anion moiety being linked by a covalent bond (Hereinafter also referred to as “compound (CA)”).

The compound (CA) is preferably a compound represented by any one of the following general formulas (C-1) to (C-3).

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

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

-X ^- it ^{^is,} -COO ^_-, -SO 3 _- represents an anion portion selected from _{^{_{-R 4 -, -SO 2 -,}}} -N. R ₄ is a group having a carbonyl group: —C (═O) —, a sulfonyl group: —S (═O) ₂ —, and a sulfinyl group: —S (═O) — at the site of connection with the adjacent N atom. Represents a valent substituent.

R ₁ , R ₂ , R ₃ , R ₄ and L ₁ may be bonded to each other to form a ring structure. In the general formula (C-3), two of R ₁ to R ₃ may be combined to form a double bond with the N atom.

Examples of the substituent having 1 or more carbon atoms in R ₁ to R ₃ include alkyl group, cycloalkyl group, aryl group, alkyloxycarbonyl group, cycloalkyloxycarbonyl group, aryloxycarbonyl group, alkylaminocarbonyl group, cycloalkylamino A carbonyl group, an arylaminocarbonyl group, etc. are mentioned. Preferably, they are an alkyl group, a cycloalkyl group, and an aryl group.

L ₁ as the divalent linking group is a linear or branched alkylene group, cycloalkylene group, arylene group, carbonyl group, ether bond, ester bond, amide bond, urethane bond, urea bond, and two types thereof. Examples include groups formed by combining the above. L ₁ is more preferably an alkylene group, an arylene group, an ether bond, an ester bond, or a group formed by combining two or more of these.

Preferable examples of the compound represented by the general formula (C-1) include paragraphs [0037] to [0039] of JP2013-6827A and paragraphs [0027] to [0029] of JP2013-8020A. ] Can be mentioned.

Preferred examples of the compound represented by the general formula (C-2) include compounds exemplified in paragraphs [0012] to [0013] of JP2012-189977A.

Preferred examples of the compound represented by the general formula (C-3) include compounds exemplified in paragraphs [0029] to [0031] of JP 2012-252124 A.

The content of the onium salt that is a weak acid relative to the acid generator is preferably 0.5 to 10.0% by mass, and preferably 0.5 to 8.0% by mass based on the solid content of the composition. % Is more preferable, and 1.0 to 8.0% by mass is even more preferable.
[6] Solvent The composition of the present invention usually contains a solvent.

Solvents that can be used in preparing the composition include, for example, alkylene glycol monoalkyl ether carboxylates, alkylene glycol monoalkyl ethers, alkyl lactate esters, alkyl alkoxypropionates, cyclic lactones (preferably having 4 to 4 carbon atoms). 10), an organic solvent such as a monoketone compound (preferably having 4 to 10 carbon atoms) which may have a ring, alkylene carbonate, alkyl alkoxyacetate, alkyl pyruvate and the like.

Specific examples of these solvents include those described in US Patent Application Publication No. 2008/0187860 <0441> to <0455>.

In the present invention, a mixed solvent obtained by mixing a solvent containing a hydroxyl group in the structure and a solvent not containing a hydroxyl group may be used as the organic solvent.

As the solvent containing a hydroxyl group and the solvent not containing a hydroxyl group, the above-mentioned exemplary compounds can be selected as appropriate. As the solvent containing a hydroxyl group, alkylene glycol monoalkyl ether, alkyl lactate, etc. are preferable. Propylene glycol monomethyl ether (Propylene) Glycol monomethyl ether: PGME (also known as 1-methoxy-2-propanol), ethyl lactate, and methyl 2-hydroxyisobutyrate are more preferable. Further, as the solvent not containing a hydroxyl group, alkylene glycol monoalkyl ether acetate, alkyl alkoxypropionate, monoketone compound which may contain a ring, cyclic lactone, alkyl acetate and the like are preferable, and among these, propylene glycol monomethyl ether Particularly preferred are acetate (propylene monomethyl ether acetate: PGMEA, also known as 1-methoxy-2-acetoxypropane), ethylethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, butyl acetate, propylene glycol monomethyl ether acetate, ethyl Most preferred are ethoxypropionate and 2-heptanone.

The mixing ratio (mass) of the solvent containing a hydroxyl group and the solvent not containing a hydroxyl group is 1/99 to 99/1, preferably 10/90 to 90/10, more preferably 20/80 to 60/40. . A mixed solvent containing 50% by mass or more of a solvent not containing a hydroxyl group is particularly preferred from the viewpoint of coating uniformity.

The solvent preferably contains propylene glycol monomethyl ether acetate, and is preferably a propylene glycol monomethyl ether acetate single solvent or a mixed solvent of two or more containing propylene glycol monomethyl ether acetate.
[7] Surfactant The composition of the present invention may or may not further contain a surfactant. When it is contained, it contains a fluorine-based and / or silicon-based surfactant (fluorine-based surfactant, silicon-based surfactant). It is more preferable to contain any one of surfactants, surfactants having both fluorine atoms and silicon atoms, or two or more thereof.

When the composition of the present invention contains a surfactant, when using an exposure light source of 250 nm or less, particularly 220 nm or less, it is possible to provide a resist pattern with less adhesion and development defects with good sensitivity and resolution. Become.

Examples of the fluorine-based and / or silicon-based surfactant include surfactants described in paragraph <0276> of US Patent Application Publication No. 2008/0248425.

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

These surfactants may be used alone or in some combination.

When the composition of the present invention contains a surfactant, the amount of the surfactant used is preferably 0.0001 to 2% by mass, more preferably 0.0005 to 1%, based on the total solid content of the composition. % By mass.

On the other hand, by making the addition amount of the surfactant 10 ppm or less with respect to the total amount of the composition (excluding the solvent), the surface unevenness of the hydrophobic resin is increased, thereby making the resist film surface more hydrophobic. It is possible to improve water followability at the time of immersion exposure.
[8] Other additives The composition of the present invention may or may not contain a carboxylic acid onium salt. Examples of such carboxylic acid onium salts include those described in US Patent Application Publication No. 2008/0187860 <0605> to <0606>.

These carboxylic acid onium salts can be synthesized by reacting sulfonium hydroxide, iodonium hydroxide, ammonium hydroxide and carboxylic acid with silver oxide in a suitable solvent.

When the composition of the present invention contains a carboxylic acid onium salt, the content thereof is generally 0.1 to 20% by mass, preferably 0.5 to 10% by mass, based on the total solid content of the composition. More preferably, it is 1 to 7% by mass.

If necessary, the composition of the present invention may further include an acid proliferator, a dye, a plasticizer, a photosensitizer, a light absorber, an alkali-soluble resin, a dissolution inhibitor, and a compound that promotes solubility in a developer ( For example, a phenol compound having a molecular weight of 1000 or less, an alicyclic compound having a carboxyl group, or an aliphatic compound) can be contained.

Such phenol compounds having a molecular weight of 1000 or less are described in, for example, JP-A-4-122938, JP-A-2-28531, US Pat. No. 4,916,210, European Patent 219294, and the like. It can be easily synthesized by those skilled in the art with reference to the method described.

Specific examples of alicyclic or aliphatic compounds having a carboxyl group include carboxylic acid derivatives having a steroid structure such as cholic acid, deoxycholic acid, lithocholic acid, adamantane carboxylic acid derivatives, adamantane dicarboxylic acid, cyclohexane carboxylic acid, cyclohexane Examples include, but are not limited to, dicarboxylic acids.

The solid content concentration of the composition of the present invention is usually 1.0 to 10% by mass, preferably 2.0 to 5.7% by mass, and more preferably 2.0 to 5.3% by mass. By setting the solid content concentration within the above range, the resist solution can be uniformly applied on the substrate, and further, a resist pattern having excellent line width roughness can be formed. The reason for this is not clear, but perhaps the solid content concentration is 10% by mass or less, preferably 5.7% by mass or less, which suppresses aggregation of the material in the resist solution, particularly the photoacid generator. As a result, it is considered that a uniform resist film was formed.

The solid content concentration is a mass percentage of the mass of other resist components excluding the solvent with respect to the total mass of the composition.

The method for preparing the composition of the present invention is not particularly limited, but it is preferable to dissolve each of the above-described components in a predetermined organic solvent, preferably the above mixed solvent, and filter. 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 made of polytetrafluoroethylene, polyethylene, or nylon. In filter filtration, for example, as in JP-A-2002-62667, circulation filtration may be performed, or filtration may be performed by connecting a plurality of types of filters in series or in parallel. The composition may be filtered multiple times. Furthermore, you may perform a deaeration process etc. with respect to a composition before and behind filter filtration.

The composition of the present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition whose properties change upon irradiation with actinic rays or radiation. More specifically, the present invention relates to semiconductor manufacturing processes such as ICs, circuit boards such as liquid crystals and thermal heads, production of imprint mold structures, and other photofabrication processes, lithographic printing plates, acid-curing properties. The present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition used in the composition.

Moreover, this invention relates to the pattern formation method using such actinic-ray-sensitive or radiation-sensitive resin composition, and demonstrates the process which can be included in the pattern formation method of this invention below.
[Procedure of step (1)]
The procedure of step (1) is not particularly limited, but a method of applying the composition of the present invention on a substrate and subjecting it to a curing treatment (coating method) if necessary, or actinic ray sensitivity on a temporary support. Alternatively, a method of forming a radiation-sensitive film and transferring the actinic ray-sensitive or radiation-sensitive film onto the substrate can be used. Of these, the coating method is preferable in terms of excellent productivity.

The substrate is not particularly limited, and is an inorganic substrate of silicon, SiN, SiO ₂ or TiN, a coating inorganic substrate such as SOG (Spin on Glass), a semiconductor manufacturing process such as an IC, a circuit substrate such as a liquid crystal or a thermal head. In addition, a substrate generally used in the lithography process of other photofabrication processes can be used. Furthermore, if necessary, an antireflection film may be formed between the resist film and the substrate. As the antireflection film, a known organic or inorganic antireflection film can be appropriately used. Further, the pattern forming method of the present invention may be combined with a two-layer resist process as disclosed in, for example, Japanese Patent Application Laid-Open No. 2008-083384, and may be combined with exposure and exposure as disclosed in International Publication No. 2011/122336 pamphlet. It may be combined with a process having multiple developments. When combining the present invention and the process disclosed in WO 2011/122336 pamphlet, the pattern forming method of the present invention is used as the second negative pattern forming method in claim 1 of WO 2011/122336 pamphlet. It is preferable to apply.
[Actinic ray-sensitive or radiation-sensitive film]
The thickness of the actinic ray-sensitive or radiation-sensitive film is not particularly limited, but is preferably 1 to 500 nm and more preferably 1 to 100 nm because a fine pattern with higher accuracy can be formed. . Such a film thickness can be obtained by setting the solid content concentration in the composition to an appropriate range to give an appropriate viscosity and improving the coating property and film forming property.
[Step (2): Exposure step]
Step (2) is a step of irradiating (exposing) actinic rays or radiation to the film (actinic ray-sensitive or radiation-sensitive film) formed in step (1).

The light used for exposure is not particularly limited, and examples thereof include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-rays, and electron beams. Preferably, it is far ultraviolet light having a wavelength of 250 nm or less, more preferably 220 nm or less, and still more preferably 1 to 200 nm.

More specifically, KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ₂ excimer laser (157 nm), X-ray, EUV (13 nm), electron beam, and the like can be mentioned. ArF excimer laser, EUV or electron beam is preferable, and ArF excimer laser is more preferable.

In the exposure process, an immersion exposure method can be applied. The immersion exposure method can be combined with a super-resolution technique such as a phase shift method or a modified illumination method. The immersion exposure can be performed, for example, according to the method described in paragraphs <0594> to <0601> of JP2013-242397A.

In addition, when the receding contact angle of the actinic ray-sensitive or radiation-sensitive film formed using the composition of the present invention is too small, it cannot be suitably used for exposure through an immersion medium, and The effect of reducing water residue (watermark) defects cannot be fully exhibited. In order to realize a preferable receding contact angle, it is preferable to include the hydrophobic resin (D) in the composition. Alternatively, an immersion liquid poorly soluble film (hereinafter also referred to as “topcoat”) formed of the hydrophobic resin (D) may be provided on the actinic ray-sensitive or radiation-sensitive film. A top coat may be provided on the actinic ray-sensitive or radiation-sensitive film containing the hydrophobic resin (D). The functions necessary for the top coat are suitability for application to the actinic ray-sensitive or radiation-sensitive film upper layer, and poor immersion liquid solubility. It is preferable that the top coat is not mixed with the composition film and can be uniformly applied to the upper layer of the composition film.

The topcoat is not particularly limited, and a conventionally known topcoat can be formed by a conventionally known method. For example, based on the description in paragraphs <0072> to <0082> of JP-A-2014-059543 Can be formed.

It is preferable to form a topcoat containing a basic compound described in JP2013-61648A on the resist film.

Further, even when exposure is performed by a method other than the immersion exposure method, a top coat may be formed on the actinic ray-sensitive or radiation-sensitive film.

In the immersion exposure process, the immersion head needs to move on the wafer following the movement of the exposure head to scan the wafer at high speed to form the exposure pattern. The contact angle of the immersion liquid with the actinic ray-sensitive or radiation-sensitive film is important, and the ability to follow the high-speed scanning of the exposure head without remaining droplets is the actinic ray-sensitive or radiation-sensitive property. It is required for the resin composition.

After the step (2), before the step (3) described later, the film irradiated with the actinic ray or radiation in the step (2) may be subjected to heat treatment (PEB: Post Exposure Bake). By this step, the reaction of the exposed part is promoted. The heat treatment (PEB) may be performed a plurality of times.

The temperature of the heat treatment is preferably 70 to 130 ° C, more preferably 80 to 120 ° C.

The time for the heat treatment is preferably 30 to 300 seconds, more preferably 30 to 180 seconds, and further preferably 30 to 90 seconds.

The heat treatment can be performed by means provided in a normal exposure / developing machine, and may be performed using a hot plate or the like.
[Step (3): Development step]
The pattern formation process of this invention has a image development process. The developer is not particularly limited, and examples include a developer containing an alkali developer and an organic solvent.

The alkaline developer is preferably an alkaline aqueous solution containing an alkali. The type of the alkaline aqueous solution is not particularly limited. For example, an alkali containing a quaternary ammonium salt typified by tetramethylammonium hydroxide, an inorganic alkali, a primary amine, a secondary amine, a tertiary amine, an alcohol amine, a cyclic amine, or the like. An aqueous solution etc. are mentioned. Among these, an aqueous solution of a quaternary ammonium salt typified by tetramethylammonium hydroxide (TMAH) is preferable. An appropriate amount of alcohol, surfactant or the like may be added to the alkaline developer. The alkali concentration of the alkali developer is usually from 0.1 to 20% by mass. The pH of the alkaline developer is usually 10.0 to 15.0.

Step (3) is a step of developing the film irradiated with actinic rays or radiation in step (2) using a developer containing an organic solvent (hereinafter also referred to as “organic solvent developer”). Development is preferably performed using a developer containing an organic solvent in that the top coat can be peeled off and developed at the same time.

As the organic solvent developer, polar solvents such as ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents can be used. In addition to those described in paragraphs <0461> to <0463> of JP-A-048500, methyl 2-hydroxyisobutyrate, isobutyl isobutyrate, butyl propionate, butyl butanoate and isoamyl acetate can be mentioned.

A plurality of the above solvents may be mixed, or may be used by mixing with a solvent other than the above or water. However, in order to fully exhibit the effects of the present invention, the water content of the developer as a whole is preferably less than 10% by mass, and more preferably substantially free of moisture.

That is, the amount of the organic solvent used relative to the organic solvent developer is preferably 90% by mass or more and 100% by mass or less, and more preferably 95% by mass or more and 100% by mass or less, with respect to the total amount of the developer.

In particular, the organic solvent 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 and ether solvents. .

The vapor pressure of the organic solvent developer is preferably 5 kPa or less, more preferably 3 kPa or less, and particularly preferably 2 kPa or less at 20 ° C. By setting the vapor pressure of the organic solvent developer to 5 kPa or less, the evaporation of the developer on the substrate or in the developing cup is suppressed, and the temperature uniformity in the wafer surface is improved. As a result, the dimensions in the wafer surface are uniform. Sexuality improves.

An appropriate amount of a surfactant can be added to the organic solvent developer as necessary.

The surfactant is not particularly limited, and for example, an ionic or nonionic fluorine-based and / or silicon-based surfactant can be used. Examples of these fluorine and / or silicon surfactants include, for example, JP-A No. 62-36663, JP-A No. 61-226746, JP-A No. 61-226745, JP-A No. 62-170950, JP 63-34540 A, JP 7-230165 A, JP 8-62834 A, JP 9-54432 A, JP 9-5988 A, US Pat. No. 5,405,720, US US Pat. No. 5,360,692, US Pat. No. 5,529,881, US Pat. No. 5,296,330, US Pat. No. 5,346,098, US Pat. No. 5,576,143, US Pat. No. 5,294,511, US Pat. And surfactants described in the specification of US Pat. No. 5,824,451, preferably nonionic surfactants. A. Although it does not specifically limit as a nonionic surfactant, It is still more preferable to use a fluorochemical surfactant or a silicon-type surfactant.

The amount of the surfactant used 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 developer.

The organic solvent developer may contain a basic compound. Specific examples and preferred examples of the basic compound that can be contained in the organic solvent developer used in the present invention are the same as those in the basic compound that can be contained in the composition described above as the acid diffusion controller.

As a developing method, for example, a method in which a substrate is immersed in a tank filled with a developer 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 is left stationary for a certain time (paddle) Method), a method of spraying the developer on the substrate surface (spray method), a method of continuously discharging the developer while scanning the developer discharge nozzle on the substrate rotating at a constant speed (dynamic dispensing method) Etc. can be applied. The preferred range of the discharge pressure of the discharged developer and the method for adjusting the discharge pressure of the developer are not particularly limited. For example, paragraphs <0631> to <063 of JP 2013-242397 A 0636> can be used.

In the pattern formation method of the present invention, a step of developing using an organic solvent developer (organic solvent developing step) and a step of developing using an aqueous alkali solution (alkali developing step) may be used in combination. . Thereby, a finer pattern can be formed.

As the rinsing liquid in the rinsing treatment performed after alkali development, pure water can be used and an appropriate amount of a surfactant can be added.

In the present invention, a portion with low exposure intensity is removed by the organic solvent development step, but a portion with high exposure strength is also removed by further performing the alkali development step. In this way, by the multiple development process in which development is performed a plurality of times, a pattern can be formed without dissolving only the intermediate exposure intensity region, so that a finer pattern than usual can be formed (Japanese Patent Laid-Open No. 2008-292975 <0077). The same mechanism as>.

In the pattern forming method of the present invention, the order of the alkali development step and the organic solvent development step is not particularly limited, but it is more preferable to perform the alkali development before the organic solvent development step.

It is preferable that a step of washing with a rinsing solution is included after the step of developing with a developer containing an organic solvent.

The rinsing solution used in the rinsing step after the step of developing with a developer containing an organic solvent is not particularly limited as long as the resist pattern is not dissolved, and a solution containing a general organic solvent can be used. . As the rinsing liquid, a rinsing liquid containing at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents should be used. Is preferred.

Specific examples of the hydrocarbon solvent, ketone solvent, ester solvent, alcohol solvent, amide solvent and ether solvent are the same as those described in the developer containing an organic solvent.

More preferably, after the step of developing using a developer containing an organic solvent, at least one selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents, and hydrocarbon solvents. A step of washing with a rinsing liquid containing an organic solvent is performed, more preferably a step of washing with a rinsing liquid containing an alcohol solvent or an ester solvent, and particularly preferably a monohydric alcohol is contained. The washing step is performed using a rinse solution, and most preferably, the washing step is performed using a rinse solution containing a monohydric alcohol having 5 or more carbon atoms.

The rinsing liquid containing a hydrocarbon solvent is preferably a hydrocarbon compound having 6 to 30 carbon atoms, more preferably a hydrocarbon compound having 8 to 30 carbon atoms, and particularly preferably a hydrocarbon compound having 10 to 30 carbon atoms. Especially, pattern collapse is suppressed by using the rinse liquid containing a decane and / or undecane.

When an ester solvent is used as the organic solvent, a glycol ether solvent may be used in addition to the ester solvent (one or more). Specific examples in this case include using an ester solvent (preferably butyl acetate) as a main component and a glycol ether solvent (preferably propylene glycol monomethyl ether (PGME)) as a subcomponent. Thereby, a residue defect is suppressed more.

Here, examples of the monohydric alcohol used in the rinsing step include linear, branched, and cyclic monohydric alcohols. Specific examples include 1-butanol, 2-butanol, and 3-methyl-1-butanol. Tert-butyl alcohol, 1-pentanol, 2-pentanol, 1-hexanol, 4-methyl-2-pentanol, 1-heptanol, 1-octanol, 2-hexanol, cyclopentanol, 2-heptanol, 2 -Octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol and the like can be used, and particularly preferable monohydric alcohols having 5 or more carbon atoms are 1-hexanol, 2-hexanol, 4-methyl- Use 2-pentanol, 1-pentanol, 3-methyl-1-butanol, etc. Can.

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

The water content in the rinse liquid is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 3% by mass or less. By setting the water content to 10% by mass or less, good development characteristics can be obtained.

The vapor pressure of the rinsing solution used after the step of developing with a developer containing an organic solvent is preferably 0.05 kPa or more and 5 kPa or less, more preferably 0.1 kPa or more and 5 kPa or less at 20 ° C. 12 kPa or more and 3 kPa or less are the most preferable. By setting the vapor pressure of the rinse liquid to 0.05 kPa or more and 5 kPa or less, the temperature uniformity in the wafer surface is improved, and further, the swelling due to the penetration of the rinse solution is suppressed, and the dimensional uniformity in the wafer surface. Improves.

An appropriate amount of a surfactant can be added to the rinse solution.

In the rinsing step, the wafer that has been developed using the developer containing the organic solvent is cleaned using the rinse solution containing the organic solvent. The cleaning method is not particularly limited. For example, a method of continuing to discharge the rinse liquid onto the substrate rotating at a constant speed (rotary coating method), or immersing the substrate in a tank filled with the rinse liquid for a certain period of time. A method (dip method), a method of spraying a rinsing liquid onto the substrate surface (spray method), etc. can be applied. Among these, a cleaning process is performed by a spin coating method, and after cleaning, the substrate is rotated at a speed of 2000 rpm to 4000 rpm. It is preferable to rotate and remove the rinse liquid from the substrate. It is also preferable to include a heating step (Post Bake) after the rinsing step. The developing solution and the rinsing solution remaining between the patterns and inside the patterns are removed by baking. The heating step after the rinsing step is usually performed at 40 to 160 ° C., preferably 70 to 95 ° C., usually 10 seconds to 3 minutes, preferably 30 seconds to 90 seconds.

Various materials used in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention and the pattern forming method of the present invention (for example, a resist solvent, a developer, a rinse solution, an antireflection film-forming composition, a top The coating forming composition or the like) preferably does not contain impurities such as metals. The content of impurities contained in these materials is preferably 1 ppm or less, more preferably 10 ppb or less, still more preferably 100 ppt or less, particularly preferably 10 ppt or less, and substantially free (below the detection limit of the measuring device). Is most preferable.

As a method for removing impurities such as metals from the above various materials, for example, filtration using a filter can be mentioned. 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 a material of the filter, a filter made of polytetrafluoroethylene, polyethylene, or nylon is preferable. The filter may be a composite material obtained by combining these materials and ion exchange media. A filter that has been washed in advance 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. When a plurality of types of filters are used, filters having different pore diameters and / or materials may be used in combination. Moreover, various materials may be filtered a plurality of times, and the step of filtering a plurality of times may be a circulating filtration step.

Moreover, as a method for reducing impurities such as metals contained in the various materials, a raw material having a low metal content is selected as a raw material constituting the various materials, and filter filtration is performed on the raw materials constituting the various materials. For example, the inside of the apparatus may be lined with Teflon (registered trademark), and distillation may be performed under a condition in which contamination is suppressed as much as possible. The preferable conditions for filter filtration performed on the raw materials constituting the various materials are the same as those described above.

In addition to filter filtration, impurities may be removed by an adsorbent, or filter filtration and an adsorbent may be used in combination. As the adsorbent, known adsorbents can be used. For example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be used.

Organic processing liquids such as developer and rinse liquids contain conductive compounds to prevent chemical piping and various parts (filters, O-rings, tubes, etc.) from being damaged due to electrostatic charge and subsequent electrostatic discharge. It may be added. Although it does not restrict | limit especially as an electroconductive compound, For example, methanol is mentioned. The addition amount is not particularly limited, but is preferably 10% by mass or less, more preferably 5% by mass or less from the viewpoint of maintaining preferable development characteristics and rinse characteristics. Regarding chemical solution piping members, SUS (stainless steel) or various pipes coated with antistatic treated polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.) should be used. it can. Similarly, polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.) subjected to antistatic treatment can be used for the filter and O-ring.

A method for improving the surface roughness of the pattern may be applied to the pattern formed by the method of the present invention. Examples of the method for improving the surface roughness of the pattern include a method of treating a resist pattern with a plasma of a gas containing hydrogen disclosed in International Publication No. 2014/002808 pamphlet. In addition, JP 2004-235468 A, US Patent Application Publication No. 2010/0020297, JP 2008-83384 A, Proc. Of SPIE Vol. 8328 83280N-1 “EUV Resist Curing Technique for LWR Reduction and Etch Selectivity Enhancement” may be applied.

The pattern formation method of the present invention can also be used for guide pattern formation in DSA (Directed Self-Assembly) (see, for example, ACS Nano Vol. 4 No. 8, Pages 4815-4823).

Further, the resist pattern formed by the above method can be used as a core material (core) of a spacer process disclosed in, for example, Japanese Patent Application Laid-Open Nos. 3-270227 and 2013-164509.

The present invention also relates to an electronic device manufacturing method including the above-described pattern forming method of the present invention, and an electronic device manufactured by this manufacturing method.

The electronic device of the present invention is suitably mounted on electrical and electronic equipment (home appliances, OA (Office Automation) / media related equipment, optical equipment, communication equipment, etc.).

<Synthesis Example 1: Synthesis of Resin A-1>
Under a nitrogen stream, 214 g of cyclohexanone was placed in a three-necked flask and heated to 80 ° C. The monomer corresponding to each repeating unit of the resin A-1 described later was 67.3 g, 4.81 g, 35.33 g in this order from the left, and a polymerization initiator V-601 (manufactured by Wako Pure Chemicals, 2.28 g). And a solution prepared by dissolving 396 g in cyclohexanone was added dropwise over 6 hours. After completion of the dropwise addition, the obtained reaction solution was further reacted at 80 ° C. for 2 hours. The reaction solution was allowed to cool and then added dropwise to a methanol: water (9: 1) mixture over 20 minutes, and the precipitated powder was collected by filtration and dried to give the following resin A-1 (76 g) as an acid-decomposable resin. was gotten. The composition ratio (molar ratio) of repeating units determined by NMR (Nuclear Magnetic Resonance) method was 30/10/60. The obtained resin A-1 had a weight average molecular weight of 12,000 in terms of standard polystyrene under the above conditions, and a dispersity (Mw / Mn) of 1.7.

The same operations as in Synthesis Example 1 were performed to synthesize the resins A-2 to A-19 described below.
<Preparation of resist composition>
The components shown in Table 1 below were dissolved in the solvents shown in Table 1 so as to have the content shown in Table 1 (content in the total solid content), and a solution having a solid content concentration of 4.9% by mass was prepared for each. . Subsequently, the obtained solution was filtered through a polyethylene filter having a pore size of 0.1 μm to prepare an actinic ray-sensitive or radiation-sensitive resin composition (resist composition).

<Evaluation>
[Formation of resist film]
The prepared resist composition was applied on an 8-inch Si wafer (Si wafer having a diameter of 200 mm) coated with an organic antireflection film (ARC29A manufactured by Brewer) using a spin coater Act8 manufactured by Tokyo Electron Co., Ltd. The film was dried on a hot plate for 60 seconds to obtain an actinic ray-sensitive or radiation-sensitive film (resist film) having a film thickness of 140 nm.

[Formation of resist pattern using organic solvent developer]
(ArF immersion exposure)
An organic antireflection film ARC29SR (manufactured by Nissan Chemical Industries, Ltd.) was applied onto the silicon wafer and baked at 205 ° C. for 60 seconds to form an antireflection film having a thickness of 95 nm. The resist composition obtained thereon was applied, and baked (PB: Prebake) at 100 ° C. for 60 seconds to form a resist film having a thickness of 100 nm.

The obtained wafer was used with an ArF excimer laser immersion scanner (manufactured by ASML; XT1700i, NA1.20, C-Quad, outer sigma 0.900, inner sigma 0.812, XY deflection), pitch 90 nm, space width 35 nm. The line and space pattern was exposed through a 6% halftone mask. Ultra pure water was used as the immersion liquid.

Then, it heated at 105 degreeC for 60 second (PEB: Post Exposure Bake). Subsequently, the film was developed by paddle with an organic solvent developer (butyl acetate) for 30 seconds, and rinsed by paddle with a rinse solution [methyl isobutyl carbinol (MIBC)] for 30 seconds. Subsequently, the wafer was rotated at a rotational speed of 4000 rpm for 30 seconds to form a line and space pattern having a pitch of 90 nm and a space width of 35 nm.

[Evaluation of dissolution rate of exposed area]
For the evaluation of the dissolution rate of the exposed area, a resist composition was applied on an 8-inch Si wafer to a film thickness of 100 nm and baked at 90 ° C. for 60 seconds. The film was baked at overexposure (30 mJ) and 85 ° C. for 60 seconds to sufficiently deprotect it, soaked in a developer for 30 seconds, and then the film thickness of the remaining film was measured. The value obtained in (100 nm-residual film) / 30 seconds (nm / second) is the dissolution rate of the exposed area.

[LWR evaluation]
The obtained line-and-space pattern having a pitch of 90 nm and a space width of 35 nm was observed with a scanning microscope (S9380 manufactured by Hitachi, Ltd.), and the line width was measured at 50 points in the range of 2 μm in the longitudinal edge of the line pattern. The standard deviation was obtained for the measurement variation, and 3σ was calculated. A smaller value indicates better performance.

[Evaluation of etching resistance]
The obtained line and space pattern having a pitch of 90 nm and a space width of 35 nm was etched using a plasma etching apparatus (Hitachi ECR plasma etching apparatus U-621), and the etching rate was determined (plasma conditions: Ar 500 ml / min, N ₂ 500 ml / min, O ₂ 10 ml / min). In consideration of the stabilization of the plasma, the etching rate is the difference between the film thickness etched in 10 seconds after starting etching and the film thickness etched in 5 seconds after starting etching. I asked for it. The results are shown in Table 1.

In practice, the etching rate is preferably 7 nm / sec (seconds) or less, more preferably 5 nm / sec or less, and even more preferably 2 nm / sec or less.

(Etching rate) = {(film thickness etched in 10 seconds) − (film thickness etched in 5 seconds)} / 5
[Formation of resist pattern using alkaline developer]
For Examples 1 to 25, the above evaluation was performed under the same conditions except that the developer was changed to a 2.38 mass% tetramethylammonium hydroxide aqueous solution. Even in this case, it was confirmed that a good resist pattern was formed.

In Table 1, the structure of the resin (A) is as follows. Here, the composition ratio of the repeating units is a molar ratio. Me represents a methyl group, Et represents an ethyl group, and iBu represents an isobutyl group. The composition ratio of the repeating units, the weight average molecular weight (Mw) and the dispersity (Mw / Mn) of the resin were determined by the same method as that for the resin A-1.

In Table 1, the structure of the acid generator (C) is as follows.

In Table 1, the structure of the crosslinking agent (B) is as follows.

In Table 1, the structure of the acid diffusion controller (E) is as follows.

In Table 1, the structure of the hydrophobic resin (D) is as follows.

Table 2 below shows the composition ratio (molar ratio; corresponding in order from the left), weight average molecular weight (Mw), and dispersity (Mw / Mn) of each repeating unit for each hydrophobic resin. These were obtained by the same method as that for the resin A-1.

In Table 1, the solvents are as follows.

A1: Propylene glycol monomethyl ether acetate (PGMEA)
A2: Cyclohexanone A3: γ-Butyrolactone B1: Propylene glycol monomethyl ether (PGME)
B2: Ethyl lactate In Table 1, the surfactants are as follows.

W-1: Megafuck F176 (manufactured by DIC Corporation) (fluorine-based)
W-2: Megafuck R08 (manufactured by DIC Corporation) (fluorine and silicon)
W-3: PF6320 (manufactured by OMNOVA Solutions Inc.) (fluorine-based)

Claims

Actinic ray-sensitive or radiation-sensitive resin containing resin (A) containing repeating unit (a) having Si atom, crosslinking agent (B), and compound (C) that generates acid upon irradiation with actinic rays or radiation A composition; provided that the repeating unit having an Si atom has a structure in which a polar group is protected by a leaving group that decomposes and leaves by the action of an acid, and contains only a Si atom in the leaving group The repeating unit is not included in the repeating unit (a).
The actinic ray-sensitive light ray according to claim 1, wherein the content of the resin (A) in the actinic ray-sensitive or radiation-sensitive resin composition is 50% by mass or more based on the total solid content in the composition. Or radiation sensitive resin composition.
The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1 or 2, wherein the repeating unit (a) having Si atoms has a siloxane structure.
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 3, wherein the repeating unit (a) having an Si atom has a silsesquioxane structure.
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 4, wherein the content of Si atoms in the resin (A) is 10% by mass or more; When A) is a repeating unit having a structure in which a polar group is protected by a leaving group that is eliminated by the action of an acid, and the leaving group includes a repeating unit having a Si atom, Si atoms contained are not included in the content of Si atoms.
The actinic ray-sensitive or sensitization according to any one of claims 1 to 5, wherein the resin (A) comprises a repeating unit (d) having a crosslinkable reactive group capable of reacting with the crosslinker (B). Radiation resin composition; provided that the repeating unit (d) having a crosslinkable reactive group may have a structure in which the crosslinkable reactive group is protected by a leaving group that decomposes and leaves under the action of an acid. Good.
The cross-linking agent (B) includes at least one selected from melamine-based cross-linking agents, urea-based cross-linking agents, phenol-based cross-linking agents, epoxy-based cross-linking agents, vinyl ether-based cross-linking agents, and glycoluril-based cross-linking agents. The actinic ray-sensitive or radiation-sensitive resin composition according to any one of 1 to 6.
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 7, wherein the resin (A) contains a repeating unit (c) having an acid-decomposable group.
The actinic ray-sensitive or photosensitive resin according to any one of claims 1 to 8, wherein the resin (A) contains a repeating unit (b) having at least one of a lactone structure, a sultone structure and a cyclic carbonate structure. Radiation sensitive resin composition.
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 9, wherein the composition is for development using a developer containing an organic solvent.
An actinic ray-sensitive or radiation-sensitive film comprising the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 10.
Forming an actinic ray-sensitive or radiation-sensitive film comprising the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 10,
Exposing the actinic ray sensitive or radiation sensitive film, and developing the actinic ray sensitive or radiation sensitive film after the exposure using a developer containing an organic solvent to form a pattern; A pattern forming method.
An electronic device manufacturing method including the pattern forming method according to claim 12.