JPWO2017169626A1 - Actinic ray-sensitive or radiation-sensitive resin composition, pattern forming method, and electronic device manufacturing method - Google Patents

Abstract

An object of the present invention is to provide an actinic ray-sensitive or radiation-sensitive resin composition capable of forming a pattern excellent in dry etching resistance and collapse resistance, and a pattern forming method and an electronic device manufacturing method using the same Is to provide. The actinic ray-sensitive or radiation-sensitive resin composition of the present invention comprises a resin (A) containing a repeating unit (a1) having a group represented by the general formula (1), and an acid by irradiation with actinic rays or radiation. And a generated compound (B).
* -L ₁ -W- (L ₂ -R ₂ ) _n (1)
In general formula (1), L ₁ is a single bond or a divalent linking group, W is an n + 1 valent alicyclic hydrocarbon group or an n + 1 valent aromatic group, L ₂ is a divalent linking group, and R ₂ is A specific substituent, n represents an integer of 1 or more. When n is 2 or more, the plurality of L ₂ may be the same as or different from each other, and the plurality of R ₂ may be the same as or different from each other.

Description

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

  In microfabrication using a resist composition, it is required to form an ultrafine pattern as the integrated circuit is highly integrated. Therefore, there is a trend towards shorter exposure wavelengths, such as from g-line to i-line and from KrF excimer laser to ArF excimer laser. At present, for example, development of lithography technology using electron beams. Is progressing.

  As such a resist composition, for example, Patent Document 1 discloses a negative resist composition containing a polymer compound (resin) containing a repeating unit having a naphthalene ring (Claim 1).

JP 2011-170316 A

  In order to form a fine pattern using the resist composition (actinic ray-sensitive or radiation-sensitive resin composition), the dry etching resistance of the pattern obtained using the resist film is required.

The present inventors have examined a resin containing a repeating unit having a naphthalene ring as described in Patent Document 1, and have found that the dry etching resistance is improved by having a naphthalene ring. .
However, when the present inventors further studied, depending on the type of substituent of the naphthalene ring, the solubility of the resist film after exposure to a developer (particularly, a developer containing an organic solvent) is too high, It was found that the formed pattern swells and pattern collapse occurs (decrease in fall resistance).

  Accordingly, the present invention provides an actinic ray-sensitive or radiation-sensitive resin composition capable of forming a pattern having excellent dry etching resistance and collapse resistance, and a pattern forming method and an electronic device manufacturing method using the same. The purpose is to provide.

As a result of intensive studies on the above problems, the inventor of the present invention uses actinic ray-sensitive or radiation-sensitive resin composition containing a resin containing a repeating unit (a1) having a group having a specific structure. The inventors have found that a pattern having excellent collapse resistance can be formed, and have reached the present invention.
That is, the present inventor has found that the above problem can be solved by the following configuration.

[1]
A resin (A) containing a repeating unit (a1) having a group represented by the general formula (1);
A compound (B) that generates an acid upon irradiation with actinic rays or radiation; and
An actinic ray-sensitive or radiation-sensitive resin composition containing
* -L ₁ -W- (L ₂ -R ₂ ) _n (1)
In the general formula (1), L ₁ represents a single bond or a divalent linking group.
W represents an n + 1 valent alicyclic hydrocarbon group or an n + 1 valent aromatic group.
L ₂ represents a divalent linking group.
R ₂ represents a substituent having at least one group selected from the group consisting of a group having a lactone structure, a group having a sultone structure, a carbonate group, a sulfonamide group, an amide group, and a carboxylic acid group.
n represents an integer of 1 or more.
When n is 2 or more, the plurality of L ₂ may be the same as or different from each other, and the plurality of R ₂ may be the same as or different from each other.
* Indicates a bonding position with another atom.
[2]
Furthermore, the actinic ray-sensitive or radiation-sensitive resin composition according to the above [1], wherein the resin (A) comprises a repeating unit (a2) having an acid-decomposable group.
[3]
[1] or [2] above, wherein the content of the repeating unit (a1) in the resin (A) is 10 to 60 mol% with respect to 100 mol% of all the repeating units of the resin (A). The actinic ray-sensitive or radiation-sensitive resin composition described in 1.
[4]
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [3], wherein W in the general formula (1) is an n + 1 valent polycyclic aromatic group.
[5]
A step of forming a resin film on a substrate using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of the above [1] to [4];
Irradiating the resin film with actinic rays or radiation;
Developing the resin film irradiated with actinic rays or radiation using a developer; and
A pattern forming method.
[6]
The pattern forming method according to [5], wherein the developer contains an organic solvent.
[7]
The manufacturing method of an electronic device containing the pattern formation method as described in said [5] or [6].

  As shown below, according to the present invention, an actinic ray-sensitive or radiation-sensitive resin composition capable of forming a pattern excellent in dry etching resistance and collapse resistance, and a pattern forming method using the same And a method of manufacturing an electronic device can be provided.

The present invention will be described below.
In the present invention, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
In the present invention, 1 Å (angstrom) corresponds to 0.1 nm.
Moreover, in the description of the group and atomic group in the present invention, when substitution or non-substitution is not clearly shown, 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). I will do it.
Further, in the present invention, “active light” or “radiation” means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams, ion beams, etc. Means particle beam. In the present invention, “light” means actinic rays or radiation.
In addition, the “exposure” in the present invention is not limited to exposure by far ultraviolet rays such as mercury lamps and excimer lasers, X-rays, extreme ultraviolet rays (EUV light), etc. It also includes drawing by particle beams.
Further, “(meth) acrylate” in the present invention means “at least one of acrylate and methacrylate”. “(Meth) acrylic acid” means “at least one of acrylic acid and methacrylic acid”.

[Actinic ray-sensitive or radiation-sensitive resin composition]
First, the actinic ray-sensitive or radiation-sensitive resin composition (hereinafter also referred to as “composition” or “resist composition”) according to the present invention will be described.
The composition of the present invention comprises a resin (A) containing a repeating unit (a1) having a group represented by the general formula (1) described later, a compound (B) that generates an acid upon irradiation with actinic rays or radiation, and , Containing.

According to the composition of the present invention, a pattern having excellent dry etching resistance and collapse resistance can be formed. The details of this reason are presumed to be as follows.
The resin (A) contained in the composition of the present invention includes a repeating unit (a1) having a group represented by the following general formula (1). Since the repeating unit (a1) has an n + 1 valent alicyclic hydrocarbon group or an n + 1 valent aromatic group (“W” in the general formula (1)), a dry pattern having a pattern obtained using the resin (A) is used. It is presumed that the etching resistance is excellent.
Furthermore, at the terminal of the group represented by the general formula (1) (“R ₂ ” in the general formula (1)), a group having a lactone structure, a group having a sultone structure, a carbonate group, a sulfonamide group, an amide And a substituent having at least one group selected from the group consisting of a group and a carboxylic acid group. Thus, since “R ₂ ” in the general formula (1) is a specific polar group, when the resist film after exposure formed using the resin (A) is developed with an organic solvent, Swelling by an organic solvent is suppressed. Thereby, it is estimated that the fall resistance of the pattern obtained using resin (A) became excellent.

<Resin (A)>
The composition of the present invention contains a resin (A).

(Repeating unit (a1) represented by general formula (1))
The resin (A) includes a repeating unit (a1) having a group represented by the following general formula (1).
* -L ₁ -W- (L ₂ -R ₂ ) _n (1)
In the general formula (1), L ₁ represents a single bond or a divalent linking group. W represents an n + 1 valent alicyclic hydrocarbon group or an n + 1 valent aromatic group. L ₂ represents a divalent linking group. R ₂ represents a substituent having at least one group selected from the group consisting of a group having a lactone structure, a group having a sultone structure, a carbonate group, a sulfonamide group, an amide group, and a carboxylic acid group. n represents an integer of 1 or more. When n is 2 or more, the plurality of L ₂ may be the same as or different from each other, and the plurality of R ₂ may be the same as or different from each other. * Indicates a bonding position with another atom.

In the general formula (1), L ₁ represents a single bond or a divalent linking group.
When L _{1 in the} general formula (1) is a divalent linking group, examples of the divalent linking group include -COO-, -OCO-, -CONH-, -NHCO-, -CO-, -O. -, - S -, - SO -, - SO 2 -, an alkylene group (preferably having 1 to 6 carbon atoms), a cycloalkylene group (preferably having from 3 to 10 carbon atoms), an alkenylene group (preferably having 2 to 6 carbon atoms ), Or a group obtained by combining a plurality of these groups. The total number of carbon atoms is preferably 12 or less. The alkylene group, cycloalkylene group, and alkenylene group may have a substituent, and examples of the substituent include an alkyl group (preferably having 1 to 4 carbon atoms).
L ₁ is a single bond, -COO-, -OCO-, -CONH-, -NHCO-, -alkylene group -COO-, -alkylene group -OCO-, -alkylene group -CONH-, -alkylene group -NHCO- , —CO—, —O—, —SO ₂ —, or —alkylene group —O— is preferable, and a single bond, —COO—, or —CONH— is more preferable.
In the specific examples of the linking group, the leftmost bond “−” means a bond on the “*” side in the general formula (1), and the right bond “−” in the general formula (1). Means a bond on the “W” side.

In the general formula (1), W represents an n + 1 valent alicyclic hydrocarbon group or an n + 1 valent aromatic group.
The alicyclic hydrocarbon group is n + 1 valent. The preferred range of n will be described in detail later, but the alicyclic hydrocarbon group is preferably 2-3 valent, more preferably divalent.
The alicyclic hydrocarbon group preferably has 4 or more carbon atoms, more preferably 6 or more. The alicyclic hydrocarbon group preferably has 25 or less carbon atoms, more preferably 20 or less.
The alicyclic hydrocarbon group may be a monocyclic alicyclic hydrocarbon group or a polycyclic alicyclic hydrocarbon group, but from the viewpoint of further improving dry etching resistance, A ring alicyclic hydrocarbon group is preferred.
The carbon number of the monocyclic alicyclic hydrocarbon group is preferably 4-12. Examples of such monocyclic alicyclic hydrocarbon groups include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclododecanyl group, a cyclopentenyl group, a cyclohexenyl group, and a cyclooctadienyl group. And a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group are preferable.
It is preferable that carbon number of a polycyclic alicyclic hydrocarbon group is 7-20. Examples of such polycyclic alicyclic hydrocarbon groups include bicyclo [4.3.0] nonanyl group, decahydronaphthalenyl group, 1,2,3,4-tetrahydronaphthalenyl group, and tricyclo [5]. .2.1.0 (2,6)] decanyl group, tetracyclodecanyl group, tetracyclododecanyl group, bornyl group, isobornyl group, norbornyl group, adamantyl group, noradamantyl group, 1,7,7-trimethyl And tricyclo [2.2.1.0 ^2,6 ] heptanyl group, 3,7,7-trimethylbicyclo [4.1.0] heptanyl group, and the like. Norbornyl group, adamantyl group, and nor An adamantyl group is preferred.

The aromatic group in W of the general formula (1) is n + 1 valent. The preferred range of n will be described in detail later, but the aromatic group is preferably 2-3, more preferably divalent.
The aromatic group may be monocyclic or polycyclic (polycyclic aromatic group), but from the viewpoint of further improving the fall resistance and dry etching resistance, A group is preferable.
Aromatic groups include aromatic hydrocarbon groups having 6 to 18 carbon atoms such as benzene, naphthalene, anthracene, fluorene and phenanthrene, and thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzo Mention may be made of aromatic heterocyclic groups containing a heterocyclic ring such as imidazole, triazole, thiadiazole and thiazole. Among these, from the viewpoint that dry etching resistance is further improved, an aromatic hydrocarbon group having 6 to 18 carbon atoms is preferable, and a polycyclic aromatic hydrocarbon group having 10 to 18 carbon atoms is more preferable.

In the general formula (1), L ₂ represents a divalent linking group.
Specific examples of the divalent linking group representing L ₂ are the same as those described for L ₁ described above.

R ₂ represents a substituent having at least one group selected from the group consisting of a group having a lactone structure, a group having a sultone structure, a carbonate group, a sulfonamide group, an amide group, and a carboxylic acid group.

In R ₂ , the group having a lactone structure may be a group consisting only of a lactone structure, or a group in which a lactone structure and a ring other than the lactone structure are condensed (for example, a bicyclo structure including a lactone structure, and It may be a spiro structure containing a lactone structure.
The lactone structure in the group having a lactone structure is preferably a 5- to 7-membered lactone structure.
Further, the group having a lactone structure may have a substituent. Examples of such substituents include alkyl groups having 1 to 8 carbon atoms, monovalent 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 carboxy. Group, a halogen atom, a hydroxyl group, a cyano group, etc. are mentioned, Among these, a cyano group is preferable.
Specific examples of the group having a lactone structure are shown below. In the following specific examples, “*” indicates a bonding position with L ₂ .

In R ₂ , the group having a sultone structure may be a group consisting of only a sultone structure, or a group in which a sultone structure and a ring other than the sultone structure are condensed (for example, a bicyclo structure including a sultone structure, and It may be a spiro structure including a sultone structure.
The sultone structure in the group having a sultone structure is preferably a 4- to 7-membered sultone structure.
Further, the group having a sultone structure may have a substituent, and specific examples of the substituent are the same as the substituent that the group having the lactone structure may have.
Specific examples of the group having a sultone structure are shown below. In the following specific examples, “*” indicates a bonding position with L ₂ .

In R ₂ , the group having a carbonate group (—O—CO—O—) may be cyclic or acyclic, but is preferably cyclic. The group having a carbonate group may have a substituent, and specific examples of the substituent are the same as the substituent that the group having the lactone structure may have.
Specific examples of the group having a carbonate group are shown below. In the following specific examples, “*” indicates a bonding position with L ₂ .

In R ₂ , the group having a sulfonamide group (—SO ₂ —NH—) may be cyclic or acyclic. The group having a sulfonamide group may have a substituent, and specific examples of the substituent are the same as the substituent that the group having the lactone structure may have.
Specific examples of the group having a sulfonamide group are shown below. In the following specific examples, “*” indicates a bonding position with L ₂ .

In R ₂ , the group having an amide group (—CO—NH—) may be cyclic or acyclic. The group having an amide group may have a substituent, and specific examples of the substituent are the same as the substituent that the group having the lactone structure may have.

In general formula (1), n represents an integer of 1 or more, preferably 1 to 3, and more preferably 1 or 2.
When n is 2 or more, the plurality of L ₂ may be the same as or different from each other, and the plurality of R ₂ may be the same as or different from each other.
* Indicates a bonding position with another atom.

  The repeating unit (a1) having a group represented by the general formula (1) is preferably a repeating unit represented by the following general formula (a1).

  In general formula (a1), Ra represents a hydrogen atom or an alkyl group. Rb represents a group represented by the general formula (1) described above.

  The alkyl group of Ra is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and further preferably a methyl group. The alkyl group of Ra may be substituted. Examples of the substituent include a halogen atom (for example, fluorine atom, chlorine atom and bromine atom), an alkoxy group (for example, mercapto group, hydroxy group, methoxy group, ethoxy group, isopropoxy group, t-butoxy group and benzyl). Oxy group etc.) and acetoxy group (for example, acetyl group, propionyl group etc.) etc. are mentioned. Among these, Ra is preferably a hydrogen atom or a methyl group.

  Since Rb represents the group represented by the general formula (1) described above, description thereof is omitted.

  Specific examples of the repeating unit (a1) having a group represented by the general formula (1) are shown below. In the specific examples below, “Me” represents a methyl group.

The content of the repeating unit (a1) in the resin (A) is preferably 10 to 60 mol% with respect to 100 mol% of all the repeating units of the resin (A), and preferably 15 to 60 mol%. Is more preferable, and it is still more preferable that it is 20-60 mol%. When the content of the repeating unit (a1) is 10 mol% or more, a pattern superior in fall resistance and dry etching resistance can be obtained. Moreover, when the content of the repeating unit (a1) is 60 mol% or less, a high dissolution contrast can be expressed.
Resin (A) may contain the said repeating unit (a1) individually by 1 type, and may contain 2 or more types. When two or more kinds of the above repeating units (a1) are included, the total content of the repeating units (a1) in the resin (A) is preferably within the above range.

(Repeating unit having acid-decomposable group (a2))
The resin (A) preferably contains a repeating unit (a2) having an acid-decomposable group. An acid-decomposable group is a group that decomposes by the action of an acid to produce an alkali-soluble group.
Resin (A) contains the repeating unit (a2) which has an acid-decomposable group in one of the main chain or side chain of resin (A), or both of the main chain and side chain.
Hereinafter, the repeating unit (a2) having an acid-decomposable group may be simply referred to as “acid-decomposable repeating unit”.
The resin (A) is preferably insoluble or hardly soluble in an alkali developer.

  The acid-decomposable group preferably has a structure protected with a group capable of decomposing and leaving an alkali-soluble group by the action of an acid.

  Alkali-soluble groups include phenolic hydroxyl groups, carboxy groups, fluorinated alcohol groups, sulfonic acid groups, sulfonamido groups, sulfonylimide groups, (alkylsulfonyl) (alkylcarbonyl) methylene groups, (alkylsulfonyl) (alkylcarbonyl) imides. Group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, and tris (alkylsulfonyl) methylene Groups and the like.

  Preferred alkali-soluble groups include carboxy groups, fluorinated alcohol groups (preferably hexafluoroisopropanol), and sulfonic acid groups.

  A preferable group as the acid-decomposable group is a group obtained by substituting the hydrogen atom of these alkali-soluble groups with a group capable of leaving with an acid.

Examples of the group capable of leaving with an acid include —C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), —C (R ₃₆ ) (R ₃₇ ) (OR ₃₉ ), and —C (R ₀₁ ) ( R ₀₂ ) (OR ₃₉ ) and the like.
In the formula, R _{36 to} R ₃₉ each independently 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 acid-decomposable group is preferably a cumyl ester group, an enol ester group, an acetal ester group, or a tertiary alkyl ester group. More preferably, it is a tertiary alkyl ester group.

  The repeating unit having an acid-decomposable group that can be contained in the resin (A) is preferably a repeating unit represented by the following general formula (AI).

In general formula (AI):
Xa ₁ represents a hydrogen atom, a methyl group which may have a substituent, or a group represented by —CH ₂ —R ₉ . R ₉ represents a hydroxy group or a monovalent organic group, and examples thereof include an alkyl group having 5 or less carbon atoms and an acyl group, preferably an alkyl group having 3 or less carbon atoms, and more preferably a methyl group. . Xa ₁ preferably represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.

T represents a single bond or a divalent linking group.
Rx _{1 to} Rx ₃ each independently represents an alkyl group (straight or branched) or a cycloalkyl group (monocyclic or polycyclic).
At least two of Rx _{1 to} Rx ₃ may combine to form a cycloalkyl group (monocyclic or polycyclic).

Examples of the divalent linking group for T include an alkylene group, a —COO—Rt— group, a —O—Rt— 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 or a — (CH ₂ ) ₃ — group.
Examples of the alkyl group of Rx _{1 to} Rx ₃ include alkyl groups having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, and t-butyl group. preferable.

As the cycloalkyl group of Rx _{1 to} Rx ₃ , a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, an adamantyl group, and the like The polycyclic cycloalkyl group is preferable.
Examples of the cycloalkyl group formed by combining at least two of Rx _{1 to} Rx ₃ include a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, a tetracyclo group. A polycyclic cycloalkyl group such as a dodecanyl group and an adamantyl group is preferred. A monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferable.
An embodiment in which Rx ₁ is a methyl group or an ethyl group, and Rx ₂ and Rx ₃ are bonded to form the above-described cycloalkyl group is preferable.

  Each of the above groups may have a substituent. Examples of the substituent include an alkyl group (1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (1 to 4 carbon atoms), a carboxy group, And an alkoxycarbonyl group (having 2 to 6 carbon atoms), and the like, preferably having 8 or less carbon atoms.

Although the specific example of the repeating unit which has a preferable acid-decomposable group is shown below, this invention is not limited to this.
In specific examples, Rx and Xa ₁ represent a hydrogen atom, CH ₃ , CF ₃ , or CH ₂ OH. Rxa and Rxb each represents an alkyl group having 1 to 4 carbon atoms. Z represents a substituent containing a polar group, and when there are a plurality of them, each is independent. p represents 0 or a positive integer.

  The resin (A) is a resin having at least one of the repeating unit represented by the general formula (I) and the repeating unit represented by the general formula (II) as the repeating unit represented by the general formula (AI). More preferably.

In formulas (I) and (II),
R ₁ and R ₃ each independently represent a hydrogen atom, a methyl group which may have a substituent, or a group represented by —CH ₂ —R ₉ . R ₉ represents a monovalent organic group.
R ₂ , R ₄ , R ₅ and R ₆ each independently represents an alkyl group or a cycloalkyl group.
R represents an atomic group necessary for forming an alicyclic structure together with a carbon atom.
R ₁ preferably represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.

The alkyl group in R ₂ may be linear or branched, and may have a substituent.
The cycloalkyl group in R ₂ may be monocyclic or polycyclic and may have a substituent.
R ₂ is preferably an alkyl group, more preferably 1 to 10 carbon atoms, still more preferably 1 to 5 carbon atoms, and examples thereof include a methyl group and an ethyl group.

  R represents an atomic group necessary for forming an alicyclic structure together with a carbon atom. The alicyclic structure formed by R is preferably a monocyclic alicyclic structure, and the carbon number thereof is preferably 8 or less, more preferably 3 to 7, and still more preferably 5 or 6 It is.

R ₃ is preferably a hydrogen atom or a methyl group, and more preferably a methyl group.

The alkyl group in R ₄ , R ₅ , and R ₆ may be linear or branched and may have a substituent. As the alkyl group, an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a t-butyl group is preferable.

The cycloalkyl group in R ₄ , R ₅ and R ₆ may be monocyclic or polycyclic and may have a substituent. As the cycloalkyl group, monocyclic cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group, and polycyclic cycloalkyl groups such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group are preferable.

  Examples of the repeating unit represented by the general formula (I) include a repeating unit represented by the following general formula (3).

In general formula (3),
R ₁ has the same meaning as _{R 1} of formula (I).
Rd _{1 to} Rd ₃ each independently represents a hydrogen atom or an alkyl group.
Z represents a monocyclic structure.

Alkyl group Rd ₁ ~ Rd _3, for example, include an alkyl group having 1 to 4 carbon atoms. Alkyl group having 1 to 4 carbon atoms Rd ₁ ~ Rd ₃ is preferably a methyl group.

  Examples of the monocyclic structure of Z include monocyclic cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group. The monocyclic cycloalkyl group preferably has 8 or less carbon atoms. The monocyclic cycloalkyl group having 8 or less carbon atoms of Z is preferably a cyclopentyl group or a cyclohexyl group.

  Moreover, as a repeating unit represented by general formula (I), the repeating unit represented by the following general formula (1-a) is mentioned, for example.

In the formula, _{R 1} and _{R 2} have the same meanings as those in formula (I).
The repeating unit represented by the general formula (II) is preferably a repeating unit represented by the following general formula (II-1).

In formula (II-1),
R _{3 to} R ₅ have the same meaning as in general formula (II).
R ₁₀ represents a substituent containing a polar group. When a plurality of R ₁₀ are present, they may be the same as or different from each other. Examples of the substituent containing a polar group include a linear or branched alkyl group or cycloalkyl group having a hydroxyl group, a cyano group, an amino group, an alkylamide group or a sulfonamide group, and preferably a hydroxyl group. It is an alkyl group. As the branched alkyl group, an isopropyl group is particularly preferable.
p represents an integer of 0 to 15. p is preferably 0 to 2, more preferably 0 or 1.

  The resin (A) is more preferably a resin containing at least one of the repeating unit represented by the general formula (I) and the repeating unit represented by the general formula (II). In another embodiment, a resin containing at least two repeating units represented by the general formula (I) is more preferable.

  Preferred combinations when the resin (A) uses an acid-decomposable repeating unit are listed below. In the following formula, each R independently represents a hydrogen atom or a methyl group.

The content of the repeating unit (a2) in the resin (A) is preferably 40 to 90 mol%, preferably 40 to 80 mol%, based on 100 mol% of all the repeating units of the resin (A). Is more preferable, and it is further more preferable that it is 40-70 mol%. When the content of the repeating unit (a2) is 40 mol% or more, a high dissolution contrast can be expressed. In addition, when the content of the repeating unit (a2) is 90 mol% or less, a pattern that is more excellent in collapse resistance and dry etching resistance can be obtained.
Resin (A) may contain the said repeating unit (a2) individually by 1 type, and may contain 2 or more types. When two or more types of the repeating unit (a2) are included, the total content of the repeating unit (a2) in the resin (A) is preferably within the above range.

(Other repeat units)
Resin (A) may contain other repeating units other than the repeating units described above. Examples of the other repeating unit include a repeating unit (a3) containing a lactone structure or a sultone structure.
Here, when the repeating unit (a1) described above has a lactone structure or a sultone structure, the repeating unit (a3) containing the lactone structure or sultone structure described below is different from the repeating unit (a1) described above. It is.

((Repeating unit containing lactone structure or sultone structure (a3)))
Of the repeating units (a3) containing a lactone structure or a sultone structure, the repeating unit (a3) having a lactone structure (hereinafter also simply referred to as “repeating unit having a lactone structure”) may have a lactone structure. Any of these can be used, but a preferred lactone structure is a 5- to 7-membered ring lactone structure, and other ring structures are condensed to form a bicyclo structure or a spiro structure on the 5- to 7-membered ring lactone structure. What is present can also be preferably used.
The lactone structure is preferably a lactone structure represented by any one of the following general formulas (LC1-1) to (LC1-17). The lactone structure may be directly bonded to the main chain.
As the lactone structure, the following general formulas (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-13), (LC1-14) and (LC1-17) are used. More preferably. By using such a lactone structure, suppression of LWR (Line Width Roughness) and development defects becomes better.

  The repeating unit having a lactone structure is preferably a repeating unit represented by the following general formula (AII ′).

In general formula (AII ′),
Rb ₀ represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms. Preferable substituents that the alkyl group of Rb ₀ may have include a hydroxyl group and a halogen atom. Examples of the halogen atom for Rb ₀ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. A hydrogen atom, a methyl group, a hydroxymethyl group and a trifluoromethyl group are preferred, and a hydrogen atom and a methyl group are more preferred.

V represents a group having a structure represented by any one of the general formulas (LC1-1) to (LC1-17).
Specific examples of the repeating unit having a lactone structure are given below, but the present invention is not limited thereto.

  Particularly preferred repeating units having a lactone structure include the following repeating units. By selecting an optimal lactone structure, the pattern profile and the density dependency are improved.

The repeating unit having a lactone 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 content of the repeating unit having a lactone structure is preferably 15 to 60 mol% and more preferably 20 to 50 mol% with respect to 100 mol% of all repeating units of the resin (A).
When two or more types of repeating units having a lactone structure are contained, the total content of repeating units having a lactone structure is preferably within the above range.

Of the repeating units (a3) containing a lactone structure or a sultone structure, the repeating unit (a3) having a sultone structure (hereinafter also referred to simply as “a repeating unit having a sultone structure”) has a sultone structure. Any of these can be used, but a 5- to 7-membered sultone structure is preferable, and a 5-cyclomembered sultone structure forms a bicyclo structure or a spiro structure, and other ring structures are condensed. Is preferred.
Specifically, it is more preferable to have a repeating unit having a sultone structure represented by any of the following general formulas (SL1-1) and (SL1-2). Further, the sultone structure may be directly bonded to the main chain. By having a repeating unit having the following sultone structure, LWR and development defects are improved.

((Repeating unit having a hydroxyl group or a cyano group))
The resin (A) may have a repeating unit having a hydroxyl group or a cyano group other than the repeating units (a1) to (a3) described above. This improves the substrate adhesion and developer compatibility.
The repeating unit having a hydroxyl group or a cyano group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group, and preferably has no acid-decomposable group.
The alicyclic hydrocarbon structure in the alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group is preferably an adamantyl group, a diamantyl group, or a norbornane group. As a preferred repeating unit having a hydroxyl group or a cyano group, a repeating unit represented by the following general formula is preferred.

When the repeating unit having a hydroxyl group or a cyano group is contained, the content of the repeating unit having a hydroxyl group or a cyano group is 5 to 40 mol% with respect to 100 mol% of all repeating units of the resin (A). Preferably, it is 5-30 mol%, More preferably, it is 10-25 mol%.
One type of repeating unit having a hydroxyl group or a cyano group may be used alone, or two or more types may be used in combination.

  Specific examples of the repeating unit having a hydroxyl group or a cyano group include the repeating unit disclosed in paragraph 0340 of US Patent Publication No. 2012/0135348, but the present invention is not limited thereto.

((Repeating unit having an alkali-soluble group))
Resin (A) may have a repeating unit having an alkali-soluble group. The repeating unit having an alkali-soluble group is a repeating unit different from the above-described repeating units.
Examples of the alkali-soluble group include a carboxy 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. Groups are preferred. By containing the repeating unit having an alkali-soluble group, the resolution in contact hole applications is increased. The repeating unit having an alkali-soluble group includes a repeating unit in which an alkali-soluble group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid or methacrylic acid, or an alkali in the main chain of the resin through a linking group. Examples include a repeating unit to which a soluble group is bonded. Moreover, it is also preferable to introduce | transduce an alkali-soluble group into the terminal of resin using the polymerization initiator or chain transfer agent which has an alkali-soluble group at the time of superposition | polymerization. The linking group may have a monocyclic or polycyclic hydrocarbon structure. Particularly preferred are repeating units of acrylic acid or methacrylic acid.

The content of the repeating unit having an alkali-soluble group is preferably 0 to 20 mol%, more preferably 3 to 15 mol%, based on 100 mol% of all repeating units of the resin (A). More preferably, it is 5-10 mol%.
The repeating unit having an alkali-soluble group may be used alone or in combination of two or more.

  Specific examples of the repeating unit having an alkali-soluble group include the repeating unit disclosed in paragraph 0344 of US Patent Publication No. 2012/0135348, but the present invention is not limited thereto.

((Repeating unit having an alicyclic hydrocarbon structure having no polar group and not exhibiting acid decomposability))
The resin (A) can further have a repeating unit that has an alicyclic hydrocarbon structure having no polar group (for example, the above alkali-soluble group, hydroxyl group, cyano group, etc.) and does not exhibit acid decomposability. Examples of such a repeating unit include a repeating unit represented by the general formula (IV).

In the general formula (IV), R ₅ represents a hydrocarbon group having at least one cyclic structure and having no polar group.

Ra represents a hydrogen atom, an alkyl group, or a —CH ₂ —O—Ra ₂ group. In the formula, Ra ₂ represents a hydrogen atom, an alkyl group, or an acyl group. Ra is preferably a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group, more preferably a hydrogen atom or a methyl group.

The cyclic structure possessed by R ₅ includes a monocyclic hydrocarbon group or a polycyclic hydrocarbon group. Examples of the monocyclic hydrocarbon group include cycloalkyl groups having 3 to 12 carbon atoms such as cyclopentyl group, cyclohexyl group, cycloheptyl group, and cyclooctyl group, and those having 3 to 12 carbon atoms such as cyclohexenyl group. A cycloalkenyl group is mentioned. Preferable monocyclic hydrocarbon group is a monocyclic hydrocarbon group having 3 to 7 carbon atoms, and more preferable examples include a cyclopentyl group and a cyclohexyl group.

The polycyclic hydrocarbon group includes a ring assembly hydrocarbon group and a bridged cyclic hydrocarbon group, and examples of the ring assembly hydrocarbon group include a bicyclohexyl group and a perhydronaphthalenyl group. As the bridged cyclic hydrocarbon ring, for example, bicyclic such as pinane, bornane, norpinane, norbornane and bicyclooctane ring (bicyclo [2.2.2] octane ring, bicyclo [3.2.1] octane ring, etc.) Hydrocarbon rings, homobredans, adamantanes, tricyclic hydrocarbon rings such as tricyclo [5.2.1.0 ^2,6 ] decane and tricyclo [4.3.1.1 ^2,5 ] undecane rings, and tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecane and tetracyclic hydrocarbon rings such as perhydro-1,4-methano-5,8-methanonaphthalene ring. The bridged cyclic hydrocarbon ring includes a condensed cyclic hydrocarbon ring, such as perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, and A condensed ring in which a plurality of 5- to 8-membered cycloalkane rings such as a perhydrophenalene ring are condensed is also included.

Preferred examples of the bridged cyclic hydrocarbon ring include a norbornyl group, an adamantyl group, a bicyclooctanyl group, and a tricyclo [5,2,1,0 ^2,6 ] decanyl group. More preferable examples of the bridged cyclic hydrocarbon ring include a norbornyl group and an adamantyl group.

  These alicyclic hydrocarbon groups may have a substituent, and preferred substituents include a halogen atom, an alkyl group, a group in which a hydrogen atom of a hydroxy group is substituted by a substituent, or a hydrogen atom substituted An amino group etc. are mentioned. Preferred halogen atoms include bromine, chlorine and fluorine atoms, and preferred alkyl groups include methyl, ethyl, butyl and t-butyl groups. The alkyl group may further have a substituent, and examples of the substituent that may further have a halogen atom, an alkyl group, a group in which a hydrogen atom of a hydroxy group is substituted with a substituent, and An amino group in which a hydrogen atom is substituted can be mentioned.

  Examples of the substituent that substitutes the hydrogen atom of the hydroxy group include an alkyl group, a cycloalkyl group, an aralkyl group, a substituted methyl group, a substituted ethyl group, an acyl group, an alkoxycarbonyl group, and an aralkyloxycarbonyl group. Preferred alkyl groups are alkyl groups having 1 to 4 carbon atoms, preferred substituted methyl groups are methoxymethyl group, methoxythiomethyl group, benzyloxymethyl group, t-butoxymethyl group, and 2-methoxyethoxymethyl group, Preferred substituted ethyl groups are 1-ethoxyethyl group and 1-methyl-1-methoxyethyl group, and preferred acyl groups are formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, and pivaloyl. Examples of the aliphatic acyl group having 1 to 6 carbon atoms such as a group and the alkoxycarbonyl group include an alkoxycarbonyl group having 1 to 4 carbon atoms.

The resin (A) may or may not contain a repeating unit that has an alicyclic hydrocarbon structure that does not have a polar group and does not exhibit acid decomposability. The content of units is preferably 1 to 40 mol%, more preferably 2 to 20 mol%, based on 100 mol% of all repeating units of the resin (A).
The repeating unit which has an alicyclic hydrocarbon structure having no polar group and does not exhibit acid decomposability may be used alone or in combination of two or more.

  Specific examples of the repeating unit having an alicyclic hydrocarbon structure having no polar group and not exhibiting acid decomposability include the repeating unit disclosed in paragraph 0354 of US Published Patent Application No. 2012/0135348. However, the present invention is not limited to these.

((Repeating unit corresponding to monomer))
In addition to the above repeating units, the resin (A) has dry etching resistance, standard developer suitability, substrate adhesion, and resist profile, as well as resolution, heat resistance, and sensitivity, which are general required characteristics of the resist. It can have various repeating units for the purpose of adjusting the etc.
Examples of such a repeating unit include, but are not limited to, repeating units corresponding to the monomers described below. As a result, various performances can be finely adjusted.

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

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

  When the resist film is irradiated with KrF excimer laser light, electron beam, X-ray, or high-energy light beam (EUV, etc.) having a wavelength of 50 nm or less, the resin (A) contains a repeating unit having an aromatic hydrocarbon group. It is preferable to include, and it is more preferable to include a repeating unit having a phenolic hydroxyl group. As the repeating unit having a phenolic hydroxyl group, the repeating units shown below are particularly preferred.

The resin (A) may have a repeating unit having Si atoms.
The repeating unit having Si atoms is not particularly limited as long as it has Si atoms. For example, a silane repeating unit (—SiR ₂ —: R ₂ is an organic group), a siloxane repeating unit (—SiR ₂ —O—: R ₂ is an organic group), a (meth) acrylate repeating unit having a Si atom, And vinyl-based repeating units having Si atoms.

The repeating unit having a Si atom preferably has a silsesquioxane structure. In addition, although it may have a silsesquioxane structure in a main chain or in a side chain, it is preferable to have in a side chain. By having the silsesquioxane structure in the side chain, the storage stability of the resin (A) is improved.
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 organic group. A plurality of R may be the same or different.
The organic group is not particularly limited, and specific examples 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.
As said halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned, for example.
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 of the hydrocarbon group that may have a hetero atom include an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group in which these are combined.
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 having 1 to 30 carbon atoms), a linear or branched alkenyl group (particularly having 2 to 30 carbon atoms), Examples thereof include a linear or branched alkynyl group (particularly having 2 to 30 carbon atoms).
As said aromatic hydrocarbon group, C6-C18 aromatic hydrocarbon groups, such as a phenyl group, a tolyl group, a xylyl group, a naphthyl group, etc. are mentioned, for example.

  The repeating unit having an 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.
As an organic group, the alkyl group which may have substituents, such as a fluorine atom and a hydroxyl group, is mentioned, for example, 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 organic group. 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). When A in the above formula (I) is a group represented by the above formula (a), the above formula (I) is represented by the following formula (Ia).

In the above formula (b), R _b represents a hydrocarbon group which 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).

  When resin (A) contains the repeating unit which has Si atom, 1 type of repeating unit which has Si atom may be contained, and 2 or more types may be contained.

In the resin (A), the molar ratio of each repeating unit is appropriately set according to the desired performance.
Each repeating unit may be used individually by 1 type, and may be used together 2 or more types.

(Method for synthesizing resin (A))
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 heating is performed, 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, and amide solvents such as dimethylformamide and dimethylacetamide. , Propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and solvents that dissolve the composition of the present invention, such as cyclohexanone. More preferably, the polymerization is performed using the same solvent as the solvent used in the composition of the present invention. Thereby, the generation of particles during storage can be suppressed.

  The polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen and argon. Commercially available radical initiators (azo initiators, peroxides, etc.) are used as the polymerization initiator. As the radical initiator, an azo initiator is preferable, and an azo initiator having an ester group, a cyano group, or a carboxy 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, the reaction solution is poured 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 60-100 ° C.

  In order to prevent the resin from aggregating after the preparation of the composition, for example, as described in JP2009-037108A, the synthesized resin is dissolved in a solvent to form a solution. A step of heating at about 30 ° C. to 90 ° C. for about 30 minutes to 4 hours may be added.

  The weight average molecular weight of the resin (A) is preferably 1,000 to 200,000, more preferably 2,000 to 20,000, and even more preferably, as a polystyrene conversion value by GPC (Gel permeation chromatography) method. 3,000 to 15,000, particularly preferably 3,000 to 10,000. By setting the weight average molecular weight to 1,000 to 200,000, heat resistance and dry etching resistance can be further improved, developability can be improved, and a decrease in film forming property due to an increase in viscosity can be suppressed.

  The degree of dispersion (molecular weight distribution) of the resin (A) is usually 1 to 3, preferably 1 to 2.6, more preferably 1 to 2, and still more preferably 1.4 to 2.0. The smaller the molecular weight distribution, the better the resolution and the resist shape, the smoother the sidewall of the resist pattern, and the better the roughness.

Resin (A) may be used individually by 1 type, and may use 2 or more types together.
30-99 mass% is preferable with respect to the total solid of a composition, and, as for content of resin (A), More preferably, it is 60-95 mass%.

  Although the specific example of resin (A) is given to the following, this invention is not limited to these. In the specific examples below, “Me” represents a methyl group.

<Compound (B) that generates acid upon irradiation with actinic ray or radiation>
The composition of the present invention preferably contains a compound that generates an acid upon irradiation with actinic rays or radiation (hereinafter also referred to as “acid generator”). 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.
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 include compounds described in paragraphs [0284] to [0389] of JP 2013-4820 A, 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.

  Preferable examples of the acid generator contained in the composition of the present invention include a compound (specific acid generator) that generates an acid upon irradiation with actinic rays or radiation represented by the following general formula (3). Can do.

(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.

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.
The alkyl group as R ₄ and R ₅ may have a substituent, and preferably has 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 formula (3).

L represents a divalent linking group, and when there are a plurality of L, L may be the same or different.
Examples of the divalent linking group include —COO — (— C (═O) —O—), —OCO—, —CONH—, —NHCO—, —CO—, —O—, —S—, — SO—, —SO ₂ —, 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 them, -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 them, an alicyclic group having a bulky structure having 7 or more carbon atoms, such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group, is a PEB (post-exposure heating) step. From the viewpoints of suppressing diffusibility in the film and improving 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, but the polycyclic group 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 preferable. Examples of the lactone ring and sultone ring include the lactone structure and sultone structure exemplified in the above resin.

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

o represents an integer of 1 to 3. p represents an integer of 0 to 10. q represents an integer of 0 to 10.
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 further preferably 1. p is more preferably an integer of 1 to 3, further 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.

In the general formula (3), as a combination of partial structures other than ^{_{W, SO 3 - -CF 2 -CH}} 2 -OCO-, SO 3 - -CF 2 -CHF-CH 2 -OCO-, SO 3 - -CF ^{_{2 -COO-, SO 3 - -CF 2}} -CF 2 -CH 2 -, SO 3 - -CF 2 -CH (CF 3) -OCO- are mentioned as preferred.

(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 carbon number of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is generally 1 to 30, preferably 1 to 20.
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 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 another 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 triarylsulfonium compounds, diarylalkylsulfonium compounds, aryldialkylsulfonium compounds, diarylcycloalkylsulfonium compounds, and aryldicycloalkylsulfonium compounds.

The aryl group of the arylsulfonium compound is preferably a phenyl group or a naphthyl group, 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, or a sulfur atom. 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 that the arylsulfonium compound has as necessary 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 thereof 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 (eg, having 1 to 15 carbon atoms), a cycloalkyl group (eg, having 3 to 15 carbon atoms), an aryl group (eg, having 6 to 6 carbon atoms). 14), an alkoxy group (for example, having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, or 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 not containing an aromatic ring as R _{201 to} R ₂₀₃ generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.
R _{201 to} R ₂₀₃ are each independently preferably an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group, more preferably a linear or branched 2-oxoalkyl group or 2-oxocycloalkyl group. Or an alkoxycarbonylmethyl group, more preferably a linear or branched 2-oxoalkyl group.

The alkyl group and cycloalkyl group of R _{201 to} R ₂₀₃ are preferably a linear or branched alkyl group having 1 to 10 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group). And cycloalkyl groups having 3 to 10 carbon atoms (cyclopentyl group, cyclohexyl group, and 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, the 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 heterocycle, 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, and 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 of the general formula (3), specifically, as described above.

  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 of 0 to 8.
Z ⁻ represents an anion in the general formula (3), specifically, as described above.

In the general formula (ZI-4), the alkyl group of R ₁₃ , R ₁₄ and R ₁₅ is linear or branched, and preferably has 1 to 10 carbon atoms, and is preferably a methyl group, an ethyl group, n- A butyl group or a t-butyl group is preferred.
Examples of the cation of the compound represented by the general formula (ZI-4) in the present invention include paragraphs [0121], [0123], [0124] of JP2010-256842A, and JP2011-76056A. The cations described in paragraphs [0127], [0129], and [0130] of

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.
Phenyl group and a naphthyl group are preferred as the aryl group of R ₂₀₄ to R _207, and 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, a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group). And cycloalkyl groups having 3 to 10 carbon atoms (cyclopentyl group, cyclohexyl group, and 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 (for example, 1 to 15 carbon atoms) and a cycloalkyl group (for example, 3 carbon atoms). To 15), an aryl group (for example, having 6 to 15 carbon atoms), an alkoxy group (for example, having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, and a phenylthio group.
Z ⁻ represents an anion in the general formula (3), specifically, as described above.

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. . The upper limit is not particularly limited, but is preferably 3000 or less, more preferably 2000 or less, and still more preferably 1000 or less.
When the acid generator is in a form incorporated in a part of the polymer, it may be incorporated in a part of the resin described above or may be incorporated in a resin different from the resin.
The acid generator can be synthesized by a known method, for example, according to the method described in JP-A No. 2007-161707.
An acid generator can be used individually by 1 type or in combination of 2 or more types.
The content of the acid generator in the composition (when there are a plurality of types) 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, further preferably 9 to 30% by mass, and particularly preferably 9 to 25% by mass based on the total solid content of the composition.

<Acid diffusion controller (C)>
The composition of the present invention may contain an acid diffusion controller (C). The acid diffusion controller (C) acts as a quencher that traps the acid generated from the acid generator by exposure, and plays a role in controlling the acid diffusion phenomenon in the coating.

  The acid diffusion controller (C) may be a basic compound, for example. The basic compound is preferably a compound having a stronger basicity than phenol. Moreover, this basic compound is preferably an organic basic compound, more preferably a nitrogen-containing basic compound. Although the nitrogen-containing basic compound which can be used is not specifically limited, For example, the compound classified into the following (1)-(5) can be used.

Moreover, the composition of this invention may also contain the ionic compound classified into the following (6) as an acid diffusion control agent in another form.
Moreover, the composition of this invention may contain the low molecular weight compound which has a nitrogen atom classified into the following (7) as an acid diffusion control agent, and has a group which remove | eliminates by the effect | action of an acid.

(1) Basic compound (C1) having a hydrophilic functional group
The basic compound (C1) having a hydrophilic functional group is preferably a compound represented by the following general formula (BS-1).

In general formula (BS-1),
Each R independently represents a hydrogen atom or an organic group. However, at least one of the three Rs is an organic group. This organic group is a linear or branched alkyl group, a monocyclic or polycyclic cycloalkyl group, an aryl group, or an aralkyl group.

Although carbon number of the alkyl group as R is not specifically limited, Usually, it is 1-20, Preferably it is 1-12.
Although carbon number of the cycloalkyl group as R is not specifically limited, Usually, it is 3-20, Preferably it is 5-15.
Although carbon number of the aryl group as R is not specifically limited, Usually, it is 6-20, Preferably it is 6-10. Specific examples include a phenyl group and a naphthyl group.
Although carbon number of the aralkyl group as R is not specifically limited, Usually, it is 7-20, Preferably it is 7-11. Specific examples include a benzyl group.

In the alkyl group, cycloalkyl group, aryl group and aralkyl group as R, a hydrogen atom may be substituted with a substituent. Examples of the substituent include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, a hydroxy group, a carboxy group, an alkoxy group, an aryloxy group, an alkylcarbonyloxy group, and an alkyloxycarbonyl group.
In the compound represented by the general formula (BS-1), it is preferable that at least two of R are organic groups.

  Specific examples of the compound represented by the general formula (BS-1) include tri-n-butylamine, tri-n-pentylamine, tri-n-octylamine, tri-n-decylamine, triisodecylamine, dicyclohexyl. Methylamine, tetradecylamine, pentadecylamine, hexadecylamine, octadecylamine, didecylamine, methyloctadecylamine, dimethylundecylamine, N, N-dimethyldodecylamine, methyldioctadecylamine, N, N-dibutylaniline, N , N-dihexylaniline, 2,6-diisopropylaniline, and 2,4,6-tri (t-butyl) aniline.

  Further, the basic compound represented by the general formula (BS-1) is preferably a basic compound in which at least one of the three Rs is an alkyl group having a hydrophilic group. And a good pattern shape can be formed.

  The alkyl group having a hydrophilic group preferably has 1 to 8 carbon atoms, and more preferably 1 to 6 carbon atoms.

  Examples of the alkyl group having a hydrophilic group include an alkyl group having a hydroxy group or a mercapto group. Specific examples of such a basic compound having an alkyl group include triethanolamine and N, N-dihydroxyethylaniline.

Moreover, as an alkyl group which has said hydrophilic group, the alkyl group which has an oxygen atom, a sulfur atom, or a carbonyl group in an alkyl chain is also mentioned. That is, the alkyl group as R may contain an oxyalkylene group, a thioalkylene group or a ketoalkylene group as its partial structure. As the oxyalkylene chain, —CH ₂ CH ₂ O— is preferable. Specifically, for example, tris (methoxyethoxyethyl) amine and compounds exemplified in the 60th and subsequent lines of column 3 of US6040112 can be mentioned.

  The alkyl group having the above hydrophilic group may be an alkyl group having a hydroxy group or a mercapto group as a substituent and having an oxygen atom, a sulfur atom or a carbonyl group in the alkyl chain.

  The above alkyl group having a hydrophilic group may further have a substituent, and examples of such further substituent include a substituted or unsubstituted aryl group. When this aryl group is a substituted aryl group, examples of the substituent in the substituted aryl group include an alkyl group, an alkoxy group, and an aryl group.

(2) Compound having nitrogen-containing heterocyclic structure This nitrogen-containing heterocyclic ring may have aromaticity or may not have aromaticity. Moreover, you may have two or more nitrogen atoms. Furthermore, you may contain hetero atoms other than a nitrogen atom. Specifically, for example, compounds having an imidazole structure (2-phenylbenzimidazole, 2,4,5-triphenylimidazole, etc.), compounds having a piperidine structure [N-hydroxyethylpiperidine and bis (1,2,2) , 6,6-pentamethyl-4-piperidyl) sebacate], compounds having a pyridine structure (such as 4-dimethylaminopyridine), and compounds having an antipyrine structure (such as antipyrine and hydroxyantipyrine).

  A compound having two or more ring structures is also preferably used. Specific examples include 1,5-diazabicyclo [4.3.0] non-5-ene and 1,8-diazabicyclo [5.4.0] -undec-7-ene.

(3) Amine compound having a phenoxy group An amine compound having a phenoxy group is a compound having a phenoxy group at the terminal opposite to the N atom of the alkyl group contained in the amine compound. The phenoxy group is, for example, a substituent such as an alkyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, a carboxy group, a carboxylic acid ester group, a sulfonic acid ester group, an aryl group, an aralkyl group, an acyloxy group, and an aryloxy group. You may have.

This compound more preferably has at least one oxyalkylene chain between the phenoxy group and the nitrogen atom. The number of oxyalkylene chains in one molecule is preferably 3-9, more preferably 4-6. Among the oxyalkylene chains, —CH ₂ CH ₂ O— is particularly preferable.

  Specific examples include 2- [2- {2- (2,2-dimethoxy-phenoxyethoxy) ethyl} -bis- (2-methoxyethyl)]-amine, and paragraph [0066] of US2007 / 0224539A1. ] Compounds (C1-1) to (C3-3) exemplified in the above.

  The amine compound having a phenoxy group can be obtained, for example, by the following method. Specifically, a primary or secondary amine having a phenoxy group and a haloalkyl ether are heated and reacted to obtain a reaction solution, and then an aqueous solution of a strong base such as sodium hydroxide, potassium hydroxide and tetraalkylammonium is added. By adding to the reaction solution and extracting with an organic solvent such as ethyl acetate and chloroform, an amine compound having a phenoxy group is obtained. The amine compound having a phenoxy group is obtained by reacting a primary or secondary amine with a haloalkyl ether having a phenoxy group at the end to obtain a reaction solution, and then sodium hydroxide, potassium hydroxide and tetraalkyl. It can also be obtained by adding an aqueous solution of a strong base such as ammonium to the reaction solution and extracting with an organic solvent such as ethyl acetate and chloroform.

(4) Ammonium salt As the basic compound, an ammonium salt can also be used as appropriate.
Examples of the anion of the ammonium salt include halides, sulfonates, borates, and phosphates. Of these, halides and sulfonates are preferred.

  As the halide, chloride, bromide and iodide are preferable.

  As the sulfonate, an organic sulfonate having 1 to 20 carbon atoms is preferable. Examples of the organic sulfonate include alkyl sulfonates having 1 to 20 carbon atoms and aryl sulfonates.

  The alkyl group contained in the alkyl sulfonate may have a substituent. Examples of the substituent include a fluorine atom, a chlorine atom, a bromine atom, an alkoxy group, an acyl group, and an aryl group. Specific examples of the alkyl sulfonate include methane sulfonate, ethane sulfonate, butane sulfonate, hexane sulfonate, octane sulfonate, benzyl sulfonate, trifluoromethane sulfonate, pentafluoroethane sulfonate, and nonafluorobutane sulfonate.

  Examples of the aryl group contained in the aryl sulfonate include a phenyl group, a naphthyl group, and an anthryl group. These aryl groups may have a substituent. As this substituent, a C1-C6 linear or branched alkyl group and a C3-C6 cycloalkyl group are preferable, for example. Specifically, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an i-butyl group, a t-butyl group, an n-hexyl group, and a cyclohexyl group are preferable. Examples of other substituents include an alkoxy group having 1 to 6 carbon atoms, a halogen atom, a cyano group, a nitro group, an acyl group, and an acyloxy group.

  The ammonium salt may be hydroxide or carboxylate. In this case, the ammonium salt is preferably a tetraalkylammonium hydroxide having 1 to 8 carbon atoms such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetra- (n-butyl) ammonium hydroxide.

  Preferred basic compounds include, for example, guanidine, aminopyridine, aminoalkylpyridine, aminopyrrolidine, indazole, imidazole, pyrazole, pyrazine, pyrimidine, purine, imidazoline, pyrazoline, piperazine, aminomorpholine and aminoalkylmorpholine. . These may further have a substituent. Preferred substituents include, for example, amino group, aminoalkyl group, alkylamino group, aminoaryl group, arylamino group, alkyl group, alkoxy group, acyl group, acyloxy group, aryl group, aryloxy group, nitro group, hydroxyl group And a cyano group.

(5) A compound having a proton acceptor functional group and generating a compound which is decomposed by irradiation with actinic rays or radiation to decrease or disappear the proton acceptor property or change from proton acceptor property to acidity ( PA)
The composition according to the present invention has a proton acceptor functional group as a basic compound, and is decomposed by irradiation with actinic rays or radiation, resulting in a decrease, disappearance, or a proton acceptor property. A compound that generates an acidic compound (hereinafter also referred to as compound (PA)) may be further included.

  The proton acceptor functional group is a group capable of electrostatically interacting 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 conjugate. It means a functional group having a nitrogen atom with an unshared electron pair that does not contribute to. 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 general 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 an actinic ray or radiation to generate a compound in which the 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. Specifically, when a proton adduct is produced from a compound having a proton acceptor functional group (PA) and a proton, it means that the equilibrium constant in the chemical equilibrium is reduced.

  Proton acceptor property 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. And more preferably −13 <pKa <−3.

  In the present invention, the acid dissociation constant pKa represents the acid dissociation constant pKa in an aqueous solution, and is described in, for example, Chemical Handbook (II) (4th revised edition, 1993, edited by the Chemical Society of Japan, Maruzen Co., Ltd.). The lower the value, the higher the acid strength. Specifically, the acid dissociation constant pKa in the aqueous solution can be actually measured by measuring the acid dissociation constant at 25 ° C. using an infinitely diluted aqueous solution. Further, by using the following software package 1, a value based on a Hammett substituent constant and a database of known literature values can 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. The compound represented by the general formula (PA-1) has an acidic group as well as a proton acceptor functional group, so that the proton acceptor property is reduced or disappeared compared to the compound (PA), or from the proton acceptor property. It is a compound that has changed to acidic.

In general formula (PA-1),
Q _represents -SO 3 H, _-CO 2 H, or _-X 1 _NHX 2 _{R f.} Here, R _f represents an alkyl group, a cycloalkyl group, or an aryl group, and X ₁ and X ₂ each independently represent —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 (Rx) Ry-. Rx represents a hydrogen atom or a monovalent organic group, and Ry represents a single bond or a divalent organic group. Rx may combine with Ry to form a ring, or Rx may combine with R to form a ring.
R represents a monovalent organic group having a proton acceptor functional group.

  Moreover, in this invention, compounds (PA) other than the compound which generate | occur | produces the compound represented by general formula (PA-1) can also be selected suitably. 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.

X ^- include specific examples of, X in formula (ZI) ^- it includes the same as.

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 above formula (PA-1).

  When the compound (PA) is contained, the content of the compound (PA) is preferably 0.1 to 10% by mass and more preferably 1 to 8% by mass with respect to the total solid content of the composition.

(6) Ionic compound The composition of this invention can contain the ionic compound used as a weak acid relatively with respect to an acid generator. An onium salt is preferred as the ionic compound. When an acid generated from an acid generator upon irradiation with actinic rays or radiation collides with an onium salt having an unreacted weak acid anion, an onium salt having a strong acid anion is generated by releasing a weak acid by salt exchange. 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 (4), (5), and (6).

In general formula (4),
X ₄ ⁺ represents a cation.
Rz ₄ represents a cyclic group, an alkyl group or an alkenyl group.

In general formula (5),
X ₅ ⁺ represents a cation.
Rz ₅ represents a cyclic group, an alkyl group or an alkenyl group. However, it is assumed that no fluorine atom is bonded to the carbon atom adjacent to the S atom.

In general formula (6),
X ₆ ⁺ represents a cation.
Rz _6a and Rz _6b each independently represent a cyclic group, an alkyl group or an alkenyl group.
Z ₁ and Z ₂ each independently represents a single bond or a divalent linking group. However, the case where Z ₁ and Z ₂ are both —SO ₂ — is excluded.

Hereinafter, the general formula (4) will be described.
X ₄ ⁺ represents a cation.
Rz ₄ represents a cyclic group, an alkyl group or an alkenyl group. The cyclic group, alkyl group, and alkenyl group of Rz ₄ may each have a substituent.
Examples of the cation of X ₄ ⁺ include a sulfonium or iodonium cation. Preferable examples of the sulfonium cation or iodonium cation represented by X ₄ ⁺ include the sulfonium cation exemplified in General Formula (ZI).

Cyclic group Rz _4, for example, an aryl group and a cycloalkyl group. The cyclic group for Rz ₄ may be monocyclic or polycyclic. Examples of the substituent that the cyclic group of Rz ₄ may have include a hydroxyl group, an alkyl group, an alkoxy group, a halogen atom such as a fluorine atom, a halogenated alkyl group, a carbonyl group, an ether bond, an ester bond, and A nitro group etc. are mentioned.

The alkyl group for Rz ₄ preferably has, for example, 1 to 30 carbon atoms, and more preferably 3 to 10 carbon atoms. Examples of the substituent that the alkyl group of Rz ₄ may have include a hydroxyl group, an alkyl group, a halogen atom such as a fluorine atom, a halogenated alkyl group, a carbonyl group, an ether bond, an ester bond, and a nitro group. Can be mentioned.

Examples of the alkenyl group for Rz ₄ include alkenyl groups having 2 to 10 carbon atoms, which may be linear or branched. The alkenyl group for Rz ₄ is preferably a linear alkenyl group having 2 to 4 carbon atoms. The linear alkenyl group having 2 to 4 carbon atoms is preferably a vinyl group or a propenyl group. Examples of the substituent that the alkenyl group of Rz ₄ may have include a hydroxyl atom, an alkyl group, a halogen atom such as a fluorine atom, a halogenated alkyl group, a carbonyl group, an ether bond, an ester bond, and a nitro group. Can be mentioned.

  Preferable examples of the anion moiety of the compound represented by the general formula (4) include the structures exemplified in paragraph [0198] of JP2012-242799A.

  Although the specific example of the anion part of the compound represented by General formula (4) below is shown, it is not limited to these.

The general formula (5) will be described below.
X ₅ ⁺ represents a cation.
Rz ₅ represents a cyclic group, an alkyl group or an alkenyl group. The cyclic group, alkyl group, and alkenyl group of Rz ₅ may each have a substituent. However, it is assumed that no fluorine atom is bonded to the carbon atom adjacent to the S atom.

Examples of the cation of X ₅ ⁺ include a sulfonium or iodonium cation. Preferable examples of the sulfonium cation or iodonium cation represented by X ₅ ⁺ include the sulfonium cation exemplified in general formula (ZI) and the iodonium cation exemplified in general formula (ZII).

Cyclic group Rz _5, for example, an aryl group and a cycloalkyl group. The cyclic group for Rz ₅ may be monocyclic or polycyclic. Examples of the substituent that the cyclic group of Rz ₅ may have include, for example, a hydroxyl atom, an alkyl group, a halogen atom such as a fluorine atom, a halogenated alkyl group, a carbonyl group, an ether bond, an ester bond, and a nitro group. Is mentioned.

Alkyl group Rz _5, for example, preferably from 1 to 30 carbon atoms, and more preferably 3 to 10 carbon atoms. Examples of the substituent that the alkyl group of Rz ₅ may have include a hydroxyl group, an alkyl group, a halogen atom such as a fluorine atom, a halogenated alkyl group, a carbonyl group, an ether bond, an ester bond, and a nitro group. Can be mentioned.

Examples of the alkenyl group for Rz ₅ include an alkenyl group having 2 to 10 carbon atoms, which may be linear or branched. The alkenyl group for Rz ₄ is preferably a linear alkenyl group having 2 to 4 carbon atoms. The linear alkenyl group having 2 to 4 carbon atoms is preferably a vinyl group or a propenyl group. Examples of the substituent that the alkenyl group of Rz ₅ may have include a hydroxyl group, an alkyl group, a halogen atom such as a fluorine atom, a halogenated alkyl group, a carbonyl group, an ether bond, an ester bond, and a nitro group. Can be mentioned.

  Preferable examples of the anion moiety of the compound represented by the general formula (5) include the structures exemplified in paragraph [0201] of JP2012-242799A.

  Although the specific example of the anion part of the compound represented by General formula (5) below is shown, it is not limited to these.

The general formula (6) will be described below.
X ₆ ⁺ represents a cation.
Rz _6a and Rz _6b each independently represent a cyclic group, an alkyl group or an alkenyl group. The cyclic group, alkyl group, and alkenyl group of Rz _6a and Rz _6b may each have a substituent.
Z ₁ and Z ₂ each independently represents a single bond or a divalent linking group. However, the case where Z ₁ and Z ₂ are both —SO ₂ — is excluded.

Preferable examples of the sulfonium cation or iodonium cation represented by X ₆ ⁺ include a sulfonium cation exemplified by the general formula (ZI) and an iodonium cation exemplified by the general formula (ZII).

Examples of the cyclic group of Rz _6a and Rz _6b include an aryl group and a cycloalkyl group. Cyclic groups Rz _6a and _{Rz 6b} can be a single ring, alkyl group of polycyclic, which may be a Rz _6a and _{Rz 6b,} for example, preferably from 1 to 30 carbon atoms, carbon atoms More preferably, it is 3-10.

Examples of the alkenyl group of Rz _6a and Rz _6b include an alkenyl group having 2 to 10 carbon atoms, and may be linear or branched. The alkenyl group for Rz ₄ is preferably a linear alkenyl group having 2 to 4 carbon atoms. The linear alkenyl group having 2 to 4 carbon atoms is preferably a vinyl group or a propenyl group.

The substituents that each of the cyclic group, alkyl group, and alkenyl group of Rz _6a and Rz _6b may have include, for example, a halogen atom such as a hydroxyl group, an alkyl group, and a fluorine atom, a halogenated alkyl group, a carbonyl group, and an ether. Examples include a bond, an ester bond, and a nitro group.

The divalent linking group of Z ₁ and Z ₂ includes, for example, a divalent hydrocarbon group (aliphatic hydrocarbon group or aromatic hydrocarbon group) which may have a substituent, and a hetero atom. A bivalent coupling group etc. are mentioned. Examples of the substituent include a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms substituted with a fluorine atom, and a carbonyl group. The divalent linking group of Z ₁ and Z ₂ is preferably a carbonyl group, an ester bond, an amide bond, an alkylene group, or a combination thereof. The alkylene group is preferably a linear or branched alkylene group, and more preferably a methylene group or an ethylene group.

  Preferable examples of the anion moiety of the compound represented by the general formula (6) include the structures exemplified in paragraphs [0209] and [0210] of JP2012-242799A.

  Although the specific example of the anion part of the compound represented by General formula (6) below is shown, it is not limited to these.

  Specific examples of the compounds represented by the general formulas (4) to (6) are shown below, but are not limited thereto.

  The onium salt that is a weak acid relative to the acid generator is a compound (C) 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 -,}} -SO 2 -, and, ^-N - represents an anion portion selected from -R _4. R ₄ has a carbonyl group: —C (═O) —, a sulfonyl group: —S (═O) ₂ —, or a sulfinyl group: —S (═O) — at the site of connection with the adjacent N atom. The monovalent substituent which has.
R ₁ , R ₂ , R ₃ , R ₄ , and L ₁ may be bonded to each other to form a ring structure. In (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 an alkyl group, a cycloalkyl group, an aryl group, an alkyloxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, an alkylaminocarbonyl group, and a cycloalkylamino. Examples thereof include a carbonyl group and an arylaminocarbonyl group. 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. The compounds exemplified in the above can be mentioned.

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

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

(7) Low molecular weight compound having a nitrogen atom and having a group capable of leaving by the action of an acid The composition of the present invention comprises a low molecular weight compound having a nitrogen atom and having a group capable of leaving by the action of an acid (hereinafter referred to as “low molecular compound” (Also referred to as “compound (C)”).
The group capable of leaving by the action of an acid is not particularly limited, but is preferably an acetal group, a carbonate group, a carbamate group, a tertiary ester group, a tertiary hydroxyl group, or a hemiaminal ether group, and a carbamate group or a hemiaminal ether group. It is particularly preferred.
100-1000 are preferable, as for the molecular weight of a compound (C), 100-700 are more preferable, and 100-500 are especially preferable.
As the compound (C), an amine derivative having a group capable of leaving by the action of an acid on the nitrogen atom is preferable.
Compound (C) 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 C1-C10) or an alkoxyalkyl group (preferably C1-C10). 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 alkyl group, cycloalkyl group, aryl group, and aralkyl group (These alkyl group, cycloalkyl group, aryl group, and aralkyl group may be substituted with the functional group, alkoxy group, or halogen atom. ), For example, groups derived from linear or branched alkanes such as methane, ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, etc., derived from these alkanes Groups substituted with one or more cycloalkyl groups such as cyclobutyl group, cyclopentyl group, cyclohexyl group, etc., cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, norbornane, adamantane, noradamantane Derived from cycloalkanes Groups derived from these cycloalkanes are, for example, methyl, ethyl, n-propyl, i-propyl, n-butyl, 2-methylpropyl, 1-methylpropyl, t- Groups derived from aromatic compounds such as benzene, naphthalene and anthracene, groups derived from these aromatic compounds, groups substituted with one or more linear or branched alkyl groups such as butyl groups For example, a linear or branched group such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a 2-methylpropyl group, a 1-methylpropyl group, or a t-butyl group. Groups substituted with one or more alkyl groups, pyrrolidine, piperidine, morpholine, tetrahydrofuran, tetrahydropyran, indole, indoline, quinoline, perhydroquino A group derived from a heterocyclic compound such as benzene, indazole, benzimidazole, etc., or a group derived from these heterocyclic compounds, one or more or one group derived from a linear, branched alkyl group or aromatic compound One or more groups derived from aromatic compounds such as phenyl group, naphthyl group, anthracenyl group, etc., or a group derived from the above group, a group derived from a linear or branched alkane or a group derived from cycloalkane Examples include groups substituted by the above, or groups in which the above substituent is substituted with a functional group such as a hydroxyl group, a cyano group, an amino group, a pyrrolidino group, a piperidino group, a morpholino group, and an oxo group.
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 paragraph [0466] of US Patent Application Publication 2012/0135348, but are not limited thereto. is not.

  It is particularly preferable that the compound (C) 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. The heterocycle may contain a heteroatom other than the nitrogen atom in the formula.
Rb is synonymous with Rb in the general 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 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.
In addition, the heterocyclic ring formed by connecting the Ra to each other preferably has 20 or less carbon atoms. For example, pyrrolidine, piperidine, morpholine, 1,4,5,6-tetrahydropyrimidine, 1,2,3 , 4-tetrahydroquinoline, 1,2,3,6-tetrahydropyridine, homopiperazine, 4-azabenzimidazole, benzotriazole, 5-azabenzotriazole, 1H-1,2,3-triazole, 1,4,7 -Triazacyclononane, tetrazole, 7-azaindole, indazole, benzimidazole, imidazo [1,2-a] pyridine, (1S, 4S)-(+)-2,5-diazabicyclo [2.2.1] Heptane, 1,5,7-triazabicyclo [4.4.0] dec-5-ene, indole, indoline, 1,2, , 4-tetrahydroquinoxaline, perhydroquinoline, groups derived from heterocyclic compounds such as 1,5,9-triazacyclododecane, and groups derived from these heterocyclic compounds are linear or branched alkanes Groups derived from the above, groups derived from cycloalkanes, groups derived from aromatic compounds, groups derived from heterocyclic compounds, hydroxyl groups, cyano groups, amino groups, pyrrolidino groups, piperidino groups, morpholino groups, oxo groups, etc. Examples include groups substituted with one or more functional groups or one or more functional groups.

Specific examples of the particularly preferred compound (C) in the present invention include, but are not limited to, compounds disclosed in paragraph [0475] of US Patent Application Publication 2012/0135348.
The compound represented by the general formula (6) can be synthesized based on JP2007-298869A, JP2009-199021A, and the like.
In the present invention, the compound (C) can be used alone or in combination of two or more.
When the actinic ray-sensitive or radiation-sensitive resin composition of the present invention contains the compound (C), the content of the compound (C) is 0.001 to 20% by mass based on the total solid content of the composition. It is preferable that it is 0.001-10 mass%, More preferably, it is 0.01-5 mass%.

  In addition, examples of the acid diffusion controller (C) that can be used in the composition according to the present invention include compounds synthesized in Examples of JP-A No. 2002-363146, and paragraph 0108 of JP-A No. 2007-29869. And the like.

  As the acid diffusion controller (C), a photosensitive basic compound may be used. As the photosensitive basic compound, for example, JP-T-2003-524799 and J. Org. Photopolym. Sci & Tech. Vol. 8, P.I. 543-553 (1995) etc. can be used.

  The molecular weight of the acid diffusion controller (C) (excluding the above compound (C)) is usually from 100 to 1500, preferably from 150 to 1300, more preferably from 200 to 1000.

  These acid diffusion control agents (C) may be used alone or in combination of two or more.

  When the composition according to the present invention contains the acid diffusion controller (C), the content thereof is preferably 0.001 to 20% by mass based on the total solid content of the composition. More preferably, it is 001-10 mass%, It is further more preferable that it is 0.01-8.0 mass%, It is especially preferable that it is 0.1-5.0 mass%, 0.2-4. Most preferably, it is 0 mass%.

  The molar ratio of the acid diffusion controller (C) to the acid generator (B) is preferably 0.01 to 10, more preferably 0.05 to 5, and still more preferably 0.1 to 3. If this molar ratio is excessively increased, sensitivity and / or resolution may be reduced. If this molar ratio is excessively small, there is a possibility that pattern thinning occurs between exposure and heating (post-bake).

<Hydrophobic resin (D)>
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 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 it is 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. It may be contained in the 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, and further 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 represent 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).
R _{57 to} R ₆₁ and R _{65 to} R ₆₇ are preferably all 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 US2012 / 0251948A1 [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, the methyl group directly bonded to the main chain of the hydrophobic resin (D) (for example, the α-methyl group of the 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, and those falling under CH ₃ partial structures in the present invention. For example, when R ₁₁ is an ethyl group (CH ₂ CH ₃ ), it is assumed that it has “one” CH ₃ partial structure in the present invention.

In the general formula (M),
R < ₁₁ > -R < ₁₄ > represents a side chain part each independently.
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 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 an acid is more specifically an organic group that does not have an acid-decomposable group (a group that decomposes by the action of an acid to generate a polar group such as a carboxy group). Is preferred.

The alkyl group of _Xb1 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 _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-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 shown below. Note that 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, 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 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 of _Xb2 preferably has 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, and a trifluoromethyl group, and a hydrogen atom is preferable.
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 having no acid-decomposable group.

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 shown below. Note that 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) even when (i) contains a fluorine atom and / or a silicon atom, and (ii) contains a CH ₃ partial structure in the side chain portion. ) May have at least one group selected from the group of
(X) an acid group,
(Y) a group that is decomposed by the action of an alkali developer to increase the solubility in the alkali developer (hereinafter also referred to as a polar conversion group);
(Z) a group decomposable by the action of an acid

Examples of the acid group (x) include a phenolic hydroxyl group, a carboxylic acid group, a fluorinated alcohol group, a sulfonic acid group, a sulfonamide group, a sulfonylimide group, an (alkylsulfonyl) (alkylcarbonyl) methylene group, and an (alkylsulfonyl) (alkyl Carbonyl) imide group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, tris (alkylsulfonyl) A methylene group etc. are mentioned.
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.
As for content of the repeating unit which has an acid group (x), 1-50 mol% is preferable with respect to all the repeating units in hydrophobic resin (D), More preferably, it is 3-35 mol%, More preferably, it is 5- 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.

The group (y) that decomposes by the action of an alkali developer and increases the solubility in the alkali developer is preferably a group having a lactone structure, an acid anhydride group, or an acid imide group, and particularly preferably a group having a lactone structure. .
The repeating unit containing these groups is a repeating unit in which this group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid ester and methacrylic acid 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 (y) that is decomposed by the action of the alkali developer and increases the solubility in the alkali developer is 1 to 100 mol% based on all repeating units in the hydrophobic resin (D). It is preferable that it is 3-98 mol%, and it is still more preferable that it is 5-95 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 described 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 decomposes by the action of an acid is preferably 1 to 80 mol%, more preferably, based on all repeating units in the resin (D). It is 10-80 mol%, More preferably, it is 20-60 mol%.
The hydrophobic resin (D) may further have a repeating unit different from the above-described repeating unit.

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

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.
In addition, the hydrophobic resin (D) may be used alone or in combination.
0.01-10 mass% is preferable with respect to the total solid in the composition of this invention, and, as for content in the composition of hydrophobic resin (D), 0.05-8 mass% is more preferable.

  In the hydrophobic resin (D), the residual monomer or oligomer component is preferably 0.01 to 5% by mass, and 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).

<Solvent>
The composition according to the present invention may contain a solvent.
Typically, an organic solvent is used as this solvent. Examples of the organic solvent include alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, alkyl lactate ester, alkyl alkoxypropionate, cyclic lactone (preferably having 4 to 10 carbon atoms), and a ring. Good monoketone compounds (preferably having 4 to 10 carbon atoms), alkylene carbonate, alkyl alkoxyacetate, and alkyl pyruvate are mentioned.

  Examples of alkylene glycol monoalkyl ether carboxylates include propylene glycol monomethyl ether acetate (PGMEA; also known as 1-methoxy-2-acetoxypropane), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate. And propylene glycol monobutyl ether acetate, propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether acetate.

  Examples of the alkylene glycol monoalkyl ether include propylene glycol monomethyl ether (PGME; also known as 1-methoxy-2-propanol), propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethylene Examples include glycol monomethyl ether and ethylene glycol monoethyl ether.

  Examples of the lactate alkyl ester include methyl lactate, ethyl lactate, propyl lactate and butyl lactate.

  Examples of the alkyl alkoxypropionate include ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate and ethyl 3-methoxypropionate.

  Examples of the cyclic lactone include β-propiolactone, β-butyrolactone, γ-butyrolactone, α-methyl-γ-butyrolactone, β-methyl-γ-butyrolactone, γ-valerolactone, γ-caprolactone, and γ-octano. And iclactone and α-hydroxy-γ-butyrolactone.

  Examples of the monoketone compound which may contain a ring include 2-butanone, 3-methylbutanone, pinacolone, 2-pentanone, 3-pentanone, 3-methyl-2-pentanone, 4-methyl-2-pentanone, 2-methyl-3-pentanone, 4,4-dimethyl-2-pentanone, 2,4-dimethyl-3-pentanone, 2,2,4,4-tetramethyl-3-pentanone, 2-hexanone, 3-hexanone 5-methyl-3-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-methyl-3-heptanone, 5-methyl-3-heptanone, 2,6-dimethyl-4-heptanone, 2-octanone , 3-octanone, 2-nonanone, 3-nonanone, 5-nonanone, 2-decanone, 3-decanone, 4-decanone, 5-hexen-2-one 3-penten-2-one, cyclopentanone, 2-methylcyclopentanone, 3-methylcyclopentanone, 2,2-dimethylcyclopentanone, 2,4,4-trimethylcyclopentanone, cyclohexanone, 3 -Methylcyclohexanone, 4-methylcyclohexanone, 4-ethylcyclohexanone, 2,2-dimethylcyclohexanone, 2,6-dimethylcyclohexanone, 2,2,6-trimethylcyclohexanone, cycloheptanone, 2-methylcycloheptanone and 3- And methylcycloheptanone.

  Examples of the alkylene carbonate include propylene carbonate, vinylene carbonate, ethylene carbonate, and butylene carbonate.

  Examples of the alkyl alkoxyacetate include 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2- (2-ethoxyethoxy) ethyl acetate, 3-methoxy-3-methylbutyl acetate, and 1-methoxy acetate. -2-propyl.

  Examples of the alkyl pyruvate include methyl pyruvate, ethyl pyruvate, and propyl pyruvate.

  As the solvent, it is preferable to use a solvent having a boiling point of 130 ° C. or higher under normal temperature and pressure. Specifically, for example, cyclopentanone, γ-butyrolactone, cyclohexanone, ethyl lactate, ethylene glycol monoethyl ether acetate, PGMEA, ethyl 3-ethoxypropionate, ethyl pyruvate, 2-ethoxyethyl acetate, acetic acid-2 -(2-Ethoxyethoxy) ethyl and propylene carbonate are mentioned.

  These solvents may be used alone or in combination of two or more. In the latter case, it is preferable to use a mixed solvent of a solvent containing a hydroxyl group and a solvent not containing a hydroxyl group.

  Examples of the solvent containing a hydroxyl group include 2-ethylbutanol, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol, PGME, propylene glycol monoethyl ether, and ethyl lactate. Of these, PGME and ethyl lactate are preferred.

  Examples of the solvent not containing a hydroxyl group include PGMEA, ethylethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, perfluorobutyltetrahydrofuran, butyl acetate, N-methylpyrrolidone, N, N-dimethylacetamide, dimethyl Sulphoxide etc. can be mentioned, Among these, propylene glycol monomethyl ether acetate, ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, perfluorobutyltetrahydrofuran and butyl acetate are preferred. Of these, PGMEA, ethylethoxypropionate and 2-heptanone are more preferred.

  When using a mixed solvent of a solvent containing a hydroxyl group and a solvent not containing a hydroxyl group, these mass ratios are preferably 1/99 to 99/1, more preferably 10/90 to 90/10, More preferably, it is 20/80 to 60/40.

  When a mixed solvent containing 50% by mass or more of a solvent not containing a hydroxyl group is used, particularly excellent coating uniformity can be achieved. The solvent is particularly preferably a mixed solvent of PGMEA and one or more other solvents.

  The content of the solvent in the composition of the present invention can be appropriately adjusted according to the desired film thickness and the like, but generally the total solid content concentration of the composition is 0.5 to 30% by mass, preferably It is adjusted to 1.0 to 20% by mass, more preferably 1.5 to 10% by mass.

<Surfactant>
The composition of the present invention may contain a surfactant. In the case of containing a surfactant, either fluorine-based and / or silicon-based surfactant (fluorine-based surfactant, silicon-based surfactant, surfactant having both fluorine atom and silicon atom), or 2 It is preferable to contain seeds or more.

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

  Examples of the fluorine-based and / or silicon-based surfactant include surfactants described in [0276] of US Patent Application Publication No. 2008/0248425. For example, Ftop EF301, EF303, (Shin-Akita Kasei Corporation ), Florard FC430, 431, 4430 (manufactured by Sumitomo 3M Co., Ltd.), Megafac F171, F173, F176, F189, F113, F110, F177, F120, R08 (manufactured by Dainippon Ink & Chemicals, Inc.), Surflon S-382, SC101, 102, 103, 104, 105, 106 (manufactured by Asahi Glass Co., Ltd.), Troisol S-366 (manufactured by Troy Chemical Co., Ltd.), GF-300, GF-150 (Toagosei Chemical Co., Ltd.) ), Surflon S-393 (manufactured by Seimi Chemical Co., Ltd.), F-top EF121, EF122A EF122B, RF122C, EF125M, EF135M, EF351, EF352, EF801, EF802, EF601 (manufactured by Gemco), PF636, PF656, PF6320, PF6520 (manufactured by OMNOVA), FTX-204G, 208G, 218G230G 208D, 212D, 218D, 222D (manufactured by Neos Co., Ltd.) and the like. Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon-based surfactant.

  In addition to the known surfactants described above, surfactants are derived from fluoroaliphatic compounds produced by the telomerization method (also referred to as the telomer method) or the oligomerization method (also referred to as the oligomer method). A surfactant using a polymer having a fluoroaliphatic group can be used. The fluoroaliphatic compound can be synthesized by the method described in JP-A-2002-90991.

  As the polymer having a fluoroaliphatic group, a copolymer of a monomer having a fluoroaliphatic group and (poly (oxyalkylene)) acrylate and / or (poly (oxyalkylene)) methacrylate is preferable and distributed irregularly. Or may be block copolymerized. Examples of the poly (oxyalkylene) group include a poly (oxyethylene) group, a poly (oxypropylene) group, a poly (oxybutylene) group, and the like, and a poly (oxyethylene, oxypropylene, and oxyethylene group). A unit having different chain lengths in the same chain length, such as a block link) or poly (block link of oxyethylene and oxypropylene) may be used. Furthermore, a copolymer of a monomer having a fluoroaliphatic group and (poly (oxyalkylene)) acrylate (or methacrylate) is not only a binary copolymer but also a monomer having two or more different fluoroaliphatic groups, Further, it may be a ternary or higher copolymer obtained by simultaneously copolymerizing two or more different (poly (oxyalkylene)) acrylates (or methacrylates).

For example, as a commercially available surfactant, Megafac F178, F-470, F-473, F-475, F-476, F-472 (manufactured by Dainippon Ink & Chemicals, Inc.), C ₆ F ₁₃ group Copolymer of acrylate (or methacrylate) and (poly (oxyalkylene)) acrylate (or methacrylate), acrylate (or methacrylate) and (poly (oxyethylene)) acrylate (or methacrylate) having C ₃ F ₇ groups And a copolymer of (poly (oxypropylene)) acrylate (or methacrylate).

In the present invention, surfactants other than fluorine-based and / or silicon-based surfactants described in [0280] of US Patent Application Publication No. 2008/0248425 can also be used.
These surfactants may be used alone or in any combination.
The content of the surfactant is preferably 0 to 2% by mass, more preferably 0 to 1.5% by mass, based on the total solid content (total amount excluding the solvent) of the actinic ray-sensitive or radiation-sensitive resin composition. %, More preferably 0 to 1% by mass.

<Carboxylic acid onium salt>
The composition of the present invention may contain a carboxylic acid onium salt. As the carboxylic acid onium salt, an iodonium salt and a sulfonium salt are preferable. As the anion moiety, a linear, branched, monocyclic or polycyclic alkylcarboxylic acid anion having 1 to 30 carbon atoms is preferable. More preferably, an anion of a carboxylic acid in which some or all of these alkyl groups are fluorine-substituted is preferable. The alkyl chain may contain an oxygen atom. This ensures transparency with respect to light of 220 nm or less, improves sensitivity and resolution, and improves density dependency and exposure margin.

  Fluorine-substituted carboxylic acid anions include fluoroacetic acid, difluoroacetic acid, trifluoroacetic acid, pentafluoropropionic acid, heptafluorobutyric acid, nonafluoropentanoic acid, perfluorododecanoic acid, perfluorotridecanoic acid, perfluorocyclohexanecarboxylic acid, and 2,2-bistrifluoromethylpropionic acid anion and the like.

The content of the carboxylic acid onium salt in the composition is generally 0.1 to 20% by mass, preferably 0.5 to 10% by mass, more preferably 1 to 7%, based on the total solid content of the composition. % By mass.
Carboxylic acid onium salt may be used individually by 1 type, and may use 2 or more types together.

<Dissolution-inhibiting compound having a molecular weight of 3000 or less, which is decomposed by the action of an acid to increase the solubility in an alkaline developer>
The composition of the present invention may contain a dissolution-inhibiting compound having a molecular weight of 3000 or less (hereinafter also referred to as “dissolution-inhibiting compound”) that is decomposed by the action of an acid to increase the solubility in an alkaline developer. . The dissolution inhibiting compound contains an acid-decomposable group, such as a cholic acid derivative containing an acid-decomposable group described in Proceeding of SPIE, 2724,355 (1996), in order not to lower the permeability of 220 nm or less. Preferred are alicyclic or aliphatic compounds. Examples of the acid-decomposable group and the alicyclic structure are the same as those described for the resin (A).

  When the composition of the present invention is exposed with a KrF excimer laser or irradiated with an electron beam, the dissolution inhibiting compound contains a structure in which the phenolic hydroxyl group of the phenol compound is substituted with an acid-decomposable group. preferable. As a phenol compound, what contains 1-9 phenol frame | skeleton is preferable, More preferably, it contains 2-6 pieces.

The addition amount of the dissolution inhibiting compound is preferably 3 to 50% by mass, more preferably 5 to 40% by mass, based on the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition.
A dissolution inhibiting compound may be used individually by 1 type, and may use 2 or more types together.
Specific examples of the dissolution inhibiting compound are shown below, but the present invention is not limited thereto.

<Other additives>
In the composition of the present invention, if necessary, a dye, a plasticizer, a photosensitizer, a light absorber, and a compound that promotes solubility in a developer (for example, a phenol compound having a molecular weight of 1000 or less, a carboxy group) Alicyclic or aliphatic compound) or the like.

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

  Specific examples of alicyclic or aliphatic compounds having a carboxy 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, and And cyclohexanedicarboxylic acid, but are not limited thereto.

[Pattern formation method]
The pattern formation method of this invention is implemented using the actinic-ray-sensitive or radiation-sensitive resin composition mentioned above.
Specifically, in the pattern forming method of the present invention, the above-described actinic ray-sensitive or radiation-sensitive resin composition is attached on a substrate to form a resin film (hereinafter referred to as “step (1)” or (Also referred to as “coating step”), a step of irradiating the resin film with actinic rays or radiation (hereinafter also referred to as “step (2)” or “exposure step”), and actinic rays or radiation using a developer. A step of developing the resin film irradiated with radiation (hereinafter also referred to as “step (3)” or “exposure step”).
Below, each process is demonstrated in detail.

<Process (1): Application process>
The procedure of step (1) is not particularly limited, but the composition of the present invention is coated on a substrate (coating method), a curing treatment is performed as necessary, and a resin film is formed on a temporary support. For example, a method of transferring a resin film onto a substrate may be used. Of these, the coating method is preferable in terms of excellent productivity.

The substrate is not particularly limited, and includes inorganic substrates such as silicon, SiN, SiO ₂ and TiN, coated inorganic substrates such as SOG (Spin on Glass), semiconductor manufacturing processes such as IC, liquid crystal and thermal heads, etc. A substrate generally used in a circuit board manufacturing process and other photofabrication lithography processes can be used.
Further, if necessary, an antireflection film may be formed between the resin 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 the exposure and exposure as disclosed in WO 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.

(Resin film)
The thickness of the resin film (also referred to as “resist film” in the present invention) is not particularly limited, but is preferably 1 to 500 nm because a highly precise fine pattern can be formed. More preferably, it is 100 nm. By setting the solid content concentration in the composition to an appropriate range to give an appropriate viscosity and improving the coating property or film forming property, it becomes easy to obtain such a film thickness.

<Process (2): Exposure process>
Step (2) is an exposure step of irradiating the resin film formed in step (1) with actinic rays or radiation.

  The light used for exposure (irradiation) 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, examples of light used for exposure include KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ₂ excimer laser (157 nm), X-ray, EUV (13 nm), and electron beam. Among them, KrF excimer laser, ArF excimer laser, EUV or electron beam is preferable, and ArF excimer laser is more preferable.

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

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

The topcoat is not particularly limited, and a conventionally known topcoat can be formed by a conventionally known method. For example, the topcoat is formed based on the description in paragraphs [0072] to [0082] of JP-A-2014-059543. Can be formed.
Moreover, it is preferable to form on the resist film the topcoat containing the basic compound described in JP2013-61648A.

(Topcoat composition)
The top coat can be formed using, for example, a top coat composition. The topcoat composition generally includes a solvent and the hydrophobic resin described above.

The solvent that can be used is not particularly limited as long as it dissolves the compound described below and does not dissolve the resist film. For example, alcohol solvents, ether solvents, ester solvents, fluorine solvents, hydrocarbon solvents, etc. It is more preferable to use a non-fluorinated alcohol solvent. Thereby, the insolubility with respect to a resist film improves further, and when a topcoat composition is apply | coated on a resist film, a topcoat can be formed more uniformly, without melt | dissolving a resist film. The viscosity of the solvent is preferably 5 cP (centipoise) or less, more preferably 3 cP or less, still more preferably 2 cP or less, and particularly preferably 1 cP or less. Note that centipoise to Pascal second can be converted by the following formula.
1000 cP = 1 Pa · s

  These solvents may be used alone or in combination.

The top coat composition preferably further contains at least one compound selected from the group consisting of the following (A1) to (A3).
(A1) Acid diffusion controller (A2) Compound containing a bond or group selected from the group consisting of ether bond, thioether bond, hydroxyl group, thiol group, carbonyl bond and ester bond (A3) Compound having radical trap group

((A1) acid diffusion controller)
The top coat composition preferably further contains an acid diffusion controller. The acid diffusion control agent that can be contained in the top coat composition is the same as that mentioned as the acid diffusion control agent that can be contained in the actinic ray-sensitive or radiation-sensitive resin composition.

(Content of acid diffusion control agent)
The content of the acid diffusion controller in the top coat composition is preferably 0.01 to 20% by mass, more preferably 0.1 to 10% by mass, and 1 to 5% by mass based on the solid content of the top coat composition. % Is more preferable.

((A2) Compound containing a bond or group selected from the group consisting of ether bond, thioether bond, hydroxyl group, thiol group, carbonyl bond and ester bond)
A compound containing at least one group or bond selected from the group consisting of an ether bond, a thioether bond, a hydroxyl group, a thiol group, a carbonyl bond and an ester bond (hereinafter also referred to as compound (A2)) will be described below.

  As described above, the compound (A2) is a compound containing at least one group or bond selected from the group consisting of an ether bond, a thioether bond, a hydroxyl group, a thiol group, a carbonyl bond and an ester bond. Since the oxygen atom or sulfur atom contained in these groups or bonds has an unshared electron pair, the acid can be trapped by interaction with the acid diffused from the actinic ray-sensitive or radiation-sensitive film.

  In one form of the topcoat composition, the compound (A2) preferably has two or more groups or bonds selected from the above group, more preferably three or more, and still more preferably four or more. . In this case, groups or bonds selected from an ether bond, a thioether bond, a hydroxyl group, a thiol group, a carbonyl bond and an ester bond contained in a plurality of compounds (A2) may be the same or different. Good.

  The compound (A2) has a molecular weight of preferably 3000 or less, more preferably 2500 or less, still more preferably 2000 or less, and particularly preferably 1500 or less.

Further, the number of carbon atoms contained in the compound (A2) is preferably 8 or more, more preferably 9 or more, and still more preferably 10 or more.
Further, the number of carbon atoms contained in the compound (A2) is preferably 30 or less, more preferably 20 or less, and further preferably 15 or less.

  Further, the compound (A2) is preferably a compound having a boiling point of 200 ° C. or higher, more preferably a compound having a boiling point of 220 ° C. or higher, and further preferably a compound having a boiling point of 240 ° C. or higher.

In addition, the compound (A2) is preferably a compound having an ether bond, preferably two or more ether bonds, more preferably three or more, and still more preferably four or more.
In the topcoat composition, the compound (A2) further preferably contains a repeating unit containing an oxyalkylene structure represented by the following general formula (1).

Where
R ₁₁ represents an alkylene group which may have a substituent,
n represents an integer of 2 or more,
* Represents a bond.

The number of carbon atoms of the alkylene group represented by R ₁₁ in the general formula (1) is not particularly limited, but is preferably 1 to 15, more preferably 1 to 5, and 2 or 3. More preferably, 2 is particularly preferable. When this alkylene group has a substituent, the substituent is not particularly limited, but is preferably an alkyl group (preferably having 1 to 10 carbon atoms), for example.
n is preferably an integer of 2 to 20, and among them, it is more preferably 10 or less because DOF becomes larger.
The average value of n is preferably 20 or less, more preferably 2 to 10, more preferably 2 to 8, and particularly preferably 4 to 6 because the DOF becomes larger. preferable. Here, the “average value of n” means the value of n determined so that the weight average molecular weight of the compound (A2) is measured by GPC and the obtained weight average molecular weight matches the general formula. If n is not an integer, round it off.
A plurality of R ₁₁ may be the same or different.

  Moreover, it is preferable that the compound which has the partial structure represented by the said General formula (1) is a compound represented by the following general formula (1-1) from the reason for DOF becoming larger.

Where
Definition of R _11, specific examples and preferred embodiments are the same as R ₁₁ in general formula (1).
R ₁₂ and R ₁₃ each independently represents a hydrogen atom or an alkyl group. The number of carbon atoms of the alkyl group is not particularly limited, but is preferably 1-15. R ₁₂ and R ₁₃ may combine with each other to form a ring.
m represents an integer of 1 or more. m is preferably an integer of 1 to 20, and among them, it is more preferably 10 or less for the reason that DOF becomes larger.
The average value of m is preferably 20 or less, more preferably 1 to 10, more preferably 1 to 8, and particularly preferably 4 to 6 because the DOF becomes larger. preferable. Here, the “average value of m” is synonymous with the “average value of n” described above.
When m is 2 or more, a plurality of R ₁₁ may be the same or different.

  In the topcoat composition, the compound having a partial structure represented by the general formula (1) is preferably an alkylene glycol containing at least two ether bonds.

  Compound (A2) may be a commercially available product, or may be synthesized by a known method.

  Although the specific example of a compound (A2) is given to the following, this invention is not limited to these.

  The content of the compound (A2) is preferably 0.1 to 30% by mass, more preferably 1 to 25% by mass, and further preferably 2 to 20% by mass based on the total solid content in the upper layer film (top coat). 3 to 18% by mass is preferable.

((A3) Compound having radical trap group)
(A3) A compound having a radical trap group is also referred to as a compound (A3).
The radical trap group is a group that traps an active radical and stops a radical reaction. Examples of such radical trap groups include groups that react with active radicals to be converted into stable free radicals, and groups that have stable free radicals.
Examples of such a compound having a radical trap group include hydroquinone, catechol, benzoquinone, nitroxyl radical compound, aromatic nitro compound, N-nitroso compound, benzothiazole, dimethylaniline, phenothiazine, vinylpyrene, and derivatives thereof. Etc.
Further, the radical trap group having no basicity is specifically at least selected from the group consisting of a hindered phenol group, a hydroquinone group, an N-oxyl free radical group, a nitroso group, and a nitrone group. One group is preferably exemplified.

  The number of radical trap groups possessed by the compound (A3) is not particularly limited, but when the compound (A3) is a compound other than a polymer compound, 1 to 10 radical trap groups per molecule are preferred. 5 is more preferable, and 1 to 3 is more preferable.

  On the other hand, when the compound (A3) is a polymer compound having a repeating unit, the repeating unit having a radical trap group preferably has 1 to 5 radical trap groups, and has 1 to 3 radical trap groups. It is more preferable. In addition, the composition ratio of the repeating unit having a radical trap group in the polymer compound is preferably 1 to 100 mol%, more preferably 10 to 100 mol%, and still more preferably 30 to 100 mol%.

  As the compound (A3) having a radical trap group, a compound having a nitrogen-oxygen bond is preferable, and a compound represented by any one of the following general formulas (1) to (3) is more preferable.

  In addition, the compound represented by the following general formula (1) corresponds to a compound having an N-oxyl free radical group, the compound represented by the following general formula (2) corresponds to a compound having a nitroso group, A compound represented by the following general formula (3) corresponds to a compound having a nitrone group.

In general formulas (1) to (3), R _{1 to} R ₆ each independently represents an alkyl group, a cycloalkyl group, or an aryl group. In Formula (1), R ₁ and R ₂ may be bonded to form a ring, and in Formula (3), at least two of R _{4 to} R ₆ may be bonded to form a ring.
The alkyl group, cycloalkyl group, and aryl group represented by R _{1 to} R ₆ , the ring that R ₁ and R ₂ may be bonded to each other, and at least two of R _{4 to} R ₆ are bonded to each other; The ring which may be formed may have a substituent.

Examples of the alkyl group represented by R _{1 to} R ₆ include a linear or branched alkyl group having 1 to 10 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, and an n-propyl group. I-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group, n-pentyl group, neopentyl group, n-hexyl group, etc., among them, methyl group , Ethyl group, n-butyl group and t-butyl group are preferred.

Examples of the cycloalkyl group represented by R _{1 to} R ₆ include a cycloalkyl group having 3 to 15 carbon atoms, and specific examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group. Preferred examples include a group, a cyclooctyl group, a norbornyl group, an adamantyl group and the like.

The aryl group represented by R ₁ to R _6, for example, include an aryl group having 6 to 14 carbon atoms, and specific examples thereof include a phenyl group, a tolyl group, a naphthyl group are preferably exemplified.

The ring that R ₁ and R ₂ may form and the ring that R _{4 to} R ₆ may form are preferably 5 to 10-membered rings, more preferably 5 or 6-membered rings. It is.

The alkyl group, cycloalkyl group, and aryl group represented by R _{1 to} R ₆ , the ring that R ₁ and R ₂ may be bonded to each other, and at least two of R _{4 to} R ₆ are bonded to each other; Examples of the substituent that the ring that may be formed may have include, for example, a halogen atom (for example, a fluorine atom), a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an amino group, an oxy group, and an alkoxy group. , an alkoxyalkyl group, an alkoxycarbonyl group, an alkoxycarbonyloxy group, an acylamido group (RCONH-: R is a substituted or unsubstituted alkyl group or a phenyl _{group), - SO 2 Na, -P} (= O) (OC 2 H ₅ ) ₂ etc. can be mentioned.
Examples of the cycloalkyl group represented by R _{1 to} R ₆ and the substituent that the aryl group may have include an alkyl group.

The compound represented by any one of the general formulas (1) to (3) may be in the form of a resin. In this case, at least one of R _{1 to} R ₆ is a main chain or a side chain of the resin. It may be bound to.

  Specific examples of the compound (A3) having a radical trap group are shown below, but the present invention is not limited thereto.

When the compound (A3) having a radical trap group is a low molecular weight compound, the molecular weight thereof is not particularly limited, the molecular weight is preferably 100 to 5000, more preferably 100 to 2000, and more preferably 100 to 1000. More preferably.
Moreover, when the compound (A3) which has a radical trap group is a high molecular compound which has a repeating unit, 5000-20000 are preferable and the weight average molecular weights have more preferable 5000-10000.

  As the compound (A3) having a radical trap group, a commercially available compound may be used, or a compound synthesized by a known method may be used. Compound (A3) is a reaction between a commercially available low molecular compound having a radical trap group and a high molecular compound having a reactive group such as an epoxy group, a halogenated alkyl group, an acid halide group, a carboxyl group, or an isocyanate group. May be synthesized.

  Content of the compound (A3) which has a radical trap group is 0.001-10 mass% normally on the basis of the total solid of a topcoat composition, Preferably it is 0.01-5 mass%.

The topcoat composition may contain a plurality of one type of compound selected from the group consisting of (A1) to (A3). For example, two or more compounds (A1) distinguished from each other may be included.
The topcoat composition may contain two or more compounds selected from the group consisting of (A1) to (A3). For example, you may contain both a compound (A1) and a compound (A2).
When the topcoat composition contains a plurality of compounds selected from the group consisting of (A1) to (A3), the total content of these compounds is usually 0 based on the total solid content of the topcoat composition. 0.001 to 20% by mass, preferably 0.01 to 10% by mass, and more preferably 1 to 8% by mass.
The compound (A3) having a radical trap group can be used alone or in combination of two or more.

  Even when the exposure is performed by a method other than the immersion exposure process, a top coat may be formed on the resin film.

  A heat treatment (PEB: Post Exposure Bake) may be applied to the resin film irradiated with the actinic ray or the radiation in the step (2) after the step (2) and before the step (3) described later. By this step, the reaction of the exposed portion of the resin film 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, and more preferably 80 to 120 ° C.
The heat treatment time 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.

  Step (3) may be a step of developing the film irradiated with actinic rays or radiation in step (2) using an alkali developer.

  As the alkali developer, an alkali aqueous solution containing an alkali is preferably used. The type of the aqueous alkali solution is not particularly limited. For example, a quaternary ammonium salt typified by tetramethylammonium hydroxide, an inorganic alkali, a primary amine, a secondary amine, a tertiary amine, an alcohol amine, or a cyclic amine can be used. Examples include alkaline aqueous solutions. 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”). It is preferable. Development using a developer containing an organic solvent has the advantage that the topcoat can be peeled off and developed simultaneously.
In addition, since the exposed resin film (exposed portion) obtained using the composition of the present invention hardly swells with an organic solvent, the effect of the present invention can be obtained by performing development using an organic solvent developer. More prominently expressed.

  As the organic solvent developer, polar solvents such as ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents, and hydrocarbon solvents can be used.

  Examples of ketone solvents include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methyl amyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, Examples include cyclohexanone, methylcyclohexanone, phenylacetone, methylethylketone, methylisobutylketone, acetylacetone, acetonylacetone, ionone, diacetylalcohol, acetylcarbinol, acetophenone, methylnaphthylketone, isophorone and propylene carbonate.

  Examples of ester solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isopentyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl. Ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, 2 -Methyl hydroxyisobutyrate, isobutyl isobutyrate, butyl propionate, butyl butanoate and isoamyl acetate can be mentioned.

  Examples of the alcohol solvent include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, n-heptyl alcohol, n-octyl alcohol and alcohols such as n-decanol, glycol solvents such as ethylene glycol, diethylene glycol and triethylene glycol, and ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol Monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and , And glycol ether-based solvents such as methoxymethyl butanol.

  Examples of the ether solvent include dioxane and tetrahydrofuran in addition to the above glycol ether solvent.

  Examples of amide solvents include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric triamide and 1,3-dimethyl-2-imidazolidinone. Can be mentioned.

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

  A plurality of the above solvents may be mixed or used. Moreover, you may use the mixed solvent which mixed the said solvent and solvent other than the above, and / or water. However, in order to fully achieve the effects of the present invention, the water content of the developer as a whole is preferably less than 10% by mass, and substantially contains no water (specifically, the developer It is more preferable that the water content is 1% by mass or less.

  The content of the organic solvent in the organic solvent developer is preferably 90 to 100% by mass and more preferably 95 to 100% by mass with respect to the total mass of the organic solvent developer.

  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 further preferably 2 kPa or less at 20 ° C. By setting the vapor pressure of the organic solvent developer to 5 kPa or less, the developer can be prevented from evaporating on the substrate or in the developing cup, and the temperature uniformity within the wafer surface is improved. As a result, the dimensions within the wafer surface are improved. Uniformity improves.

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

  Although it does not specifically limit as surfactant, For example, an ionic or nonionic fluorine type and / or silicon type surfactant etc. 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, etc. The surfactants described in the specifications of US Pat. Nos. 5,360,692, 5,298,881, 5,296,330, 5,346,098, 5,576,143, 5,294,511, and 5,824,451 are listed. Preferably, it is a nonionic surfactant. Although it does not specifically limit as a nonionic surfactant, It is preferable to use a fluorochemical surfactant or a silicon-type surfactant.

  When the organic solvent developer contains a surfactant, the content of the surfactant is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, based on the total mass of the organic solvent developer. More preferably, it is 0.01-0.5 mass%.

  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 are the same as the basic compound in the above-mentioned section of the acid diffusion controller.

  As a development 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 a developer on the substrate surface (spray method), and a method of continuously discharging the developer while scanning the developer discharge nozzle at a constant speed on a substrate rotating at a constant speed (dynamic dispensing). Law). 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 [0631] to [ 0636] can be used.

  In one aspect of the pattern forming 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) are used in combination. May be. Thereby, a finer pattern can be formed.

  As a rinsing solution 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]. ] And the same mechanism).

  In one aspect of 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 to include the process of wash | cleaning using a rinse liquid after the process developed using the developing solution 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 pattern (resist pattern) is not dissolved, and a solution containing a general organic solvent is used. be able to. 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, the ketone solvent, the ester solvent, the alcohol solvent, the amide solvent, and the 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 various organic solvents 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. The washing step is performed using a rinse solution containing, 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 further preferably a hydrocarbon compound having 10 to 30 carbon atoms. Especially, pattern collapse is suppressed more 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, and specifically, 1-butanol, 2-butanol, 3-methyl-1-butanol. Tert-butyl alcohol, 1-pentanol, 2-pentanol, 1-hexanol, 4-methyl-2-pentanol, 1-heptanol, 1-octanol, 2-hexanol, cyclopentanol, 2-heptanol, 2 -Octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol and the like can be used, and particularly preferable monohydric alcohols having 5 or more carbon atoms include 1-hexanol, 2-hexanol, 4-methyl- 2-pentanol (methyl isobutyl carbinol: MIBC), 1-pentanol And, 3-methyl-1-butanol.

  A plurality of each component may be mixed or 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 in the rinse liquid 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 using 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, and 0.12 kPa at 20 ° C. More preferably, it is 3 kPa or less. By setting the vapor pressure of the rinsing 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 of the pattern due to the penetration of the rinsing liquid is further suppressed. Dimensional uniformity is improved.

  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 method of the cleaning process 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), and immersing the substrate in a bath filled with the rinse liquid for a certain period of time. A method (dip method) and a method of spraying a rinsing liquid on the substrate surface (spray method) can be applied. Among them, a cleaning process is performed by a spin coating method, and the substrate is rotated at 2000 rpm to 4000 rpm after cleaning. It is preferable to remove the rinse liquid from the substrate by rotating the film by a number. 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 40 to 160 ° C., preferably 70 to 95 ° C., and 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, further preferably 100 ppt or less, particularly preferably 10 ppt or less, and most preferably 1 ppt or less. Here, as metal impurities, Na, K, Ca, Fe, Cu, Mg, Al, Li, Cr, Ni, Sn, Ag, As, Au, Ba, Cd, Co, Pb, Ti, V, W, Zn etc. can be mentioned.

Examples of a method for removing impurities such as metals from the various materials include filtration using a filter. The filter pore diameter is preferably 10 nm or less, more preferably 5 nm or less, and further preferably 3 nm or less. As the 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.
In the production of an actinic ray-sensitive or radiation-sensitive resin composition, each component such as a resin and a photoacid generator is dissolved in a resist solvent, and then circulation filtration is performed using a plurality of filters made of different materials. preferable. For example, it is preferable that a polyethylene filter having a pore diameter of 50 nm, a nylon filter having a pore diameter of 10 nm, and a polyethylene filter having a pore diameter of 3 nm are connected in series and subjected to circulation filtration 10 times or more. The smaller the pressure difference between the filters, the better. Generally, it is 0.1 MPa or less, preferably 0.05 MPa or less, and more preferably 0.01 MPa or less. The pressure difference between the filter and the filling nozzle is preferably as small as possible, generally 0.5 MPa or less, preferably 0.2 MPa or less, and more preferably 0.1 MPa or less.
The inside of the production apparatus for the actinic ray-sensitive or radiation-sensitive resin composition is preferably gas-substituted with an inert gas such as nitrogen. Thereby, it can suppress that active gas, such as oxygen, melt | dissolves in a composition.
The actinic ray-sensitive or radiation-sensitive resin composition is filtered through a filter and then filled into a clean container. The composition filled in the container is preferably stored refrigerated. Thereby, the performance deterioration with time is suppressed. The shorter the time from the completion of filling of the composition into the container to the start of refrigerated storage is preferred, it is generally within 24 hours, preferably within 16 hours, more preferably within 12 hours. Within hours are more preferred. The storage temperature is preferably 0 to 15 ° C, more preferably 0 to 10 ° C, and still more preferably 0 to 5 ° C.

  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. In addition, a method of performing distillation under a condition in which contamination is suppressed as much as possible by lining the inside of the apparatus with Teflon (registered trademark) can be exemplified. 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 a combination of filter filtration and adsorbent may be used. As the adsorbent, known adsorbents can be used. For example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be used. In order to reduce impurities such as metals contained in the various materials, it is necessary to prevent metal impurities from being mixed in the manufacturing process. Whether or not the metal impurities have been sufficiently removed from the manufacturing apparatus can be confirmed by measuring the content of the metal component contained in the cleaning liquid used for cleaning the manufacturing apparatus. The content of the metal component contained in the cleaning liquid after use is more preferably 100 ppt (parts per trigger) or less, further preferably 10 ppt or less, and particularly preferably 1 ppt or less.

Organic processing liquids such as developers 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, and more preferably 5% by mass or less from the viewpoint of maintaining preferable development characteristics and rinse characteristics. For chemical solution piping members, SUS (stainless steel) or various piping coated with antistatic treated polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.) should be used. it can. Similarly, polyethylene, polypropylene, or fluororesin (such as polytetrafluoroethylene and perfluoroalkoxy resin) subjected to antistatic treatment can be used for the filter and the O-ring.
The inner wall surface of the container for storing the various materials is preferably treated so that impurities such as metals do not elute. The inner wall surface of the container is more preferably an electropolished stainless steel surface, a glass-lined surface, or a surface coated with a fluorine-containing resin.

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

  The pattern forming 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, JP-A-3-270227 and JP-A-2013-164509.

[Electronic device]
The present invention also relates to an electronic device manufacturing method including the pattern forming method of the present invention described above, 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, and the like).

  Hereinafter, the present invention will be described in detail with reference to examples. However, the present invention is not limited to this.

[Synthesis Example 1: Synthesis of Resin A-1]
Under a nitrogen stream, 105 g of cyclohexanone was placed in a three-necked flask and heated to 85 ° C. Then, the polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries, 3.4 g), and monomers corresponding to the respective repeating units of the resin A-1 described later, 34.1 g and 40.74 g of cyclohexanone 195 g in order from the left. The solution dissolved in was dropped into a three-necked flask over 4 hours. After completion of the dropping, the reaction was further performed at 85 ° C. for 3 hours to obtain a reaction solution. The resulting reaction solution is allowed to cool, and then the obtained reaction solution is added dropwise to a mixed solution of methanol and water over 20 minutes. The precipitated powder is collected by filtration and dried to give the following resin A, which is an acid-decomposable resin. -1 (76 g) was obtained.
The composition of the repeating unit of Resin A-1 obtained from NMR (Nuclear Magnetic Resonance) method was 40 mol%, 60 mol in order from the left in each repeating unit in the structure of Resin A-1 described later. %Met. The obtained resin A-1 has a weight average molecular weight of 10,000 in terms of standard polystyrene under the above-mentioned conditions, and the resin A-1 has a dispersity (Mw / Mn = weight average molecular weight / number average molecular weight) of 1.7. there were.

  The same operations as in Synthesis Example 1 were performed to synthesize resins A-2 to A-23 described later. In Resins A-2 to A-23, the composition (mol%), weight average molecular weight (Mw) and dispersity (Mw / Mn) of each repeating unit are determined by the same method as that for Resin A-1. It was.

[Preparation of resist composition]
The components shown in Table 1 below are dissolved in the solvents shown in the table so as to have the contents shown in the same table (content (% by mass) in the total solid content), and the solid content concentration is 4.9% by mass for each. A solution of was prepared. 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).

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

  In Table 1, the structure of the acid diffusion control agent is as follows.

  In Table 1, the structure of the hydrophobic resin is as follows. Here, the composition ratio of the repeating units is a molar ratio (mol%).

In Table 1, the solvents are as follows.
SL-1: Propylene glycol monomethyl ether acetate (PGMEA)
SL-2: cyclohexanone SL-3: propylene glycol monomethyl ether (PGME)
SL-4: γ-butyrolactone SL-5: propylene carbonate SL-6: 2-ethylbutanol SL-7: perfluorobutyltetrahydrofuran SL-8: ethyl lactate

[Evaluation]
<Formation of resist pattern>
An organic antireflection film-forming composition ARC29SR (manufactured by Nissan Chemical Industries, Ltd.) was applied onto a silicon wafer, and the resulting silicon wafer was baked at 205 ° C. for 60 seconds to form an antireflection film having a thickness of 95 nm. The resist composition was applied on the obtained antireflection film, and baked (PB: Prebake) at 100 ° C. for 60 seconds to form a resist film (resin film) having a thickness of 100 nm.
ArF excimer laser immersion scanner (manufactured by ASML; XT1700i, NA1.20, C-Quad, outer sigma 0.900, inner sigma 0.812, XY deflection) Used and exposed through a 6% halftone mask with a line and space pattern with a pitch of 90 nm and a space width of 35 nm. Ultra pure water was used as the immersion liquid.
Thereafter, the obtained silicon wafer was heated at 105 ° C. for 60 seconds (PEB: Post Exposure Bake). Subsequently, the film was developed by paddle with an organic solvent developer (butyl acetate) for 30 seconds, and rinsed with paddle for 30 seconds with a rinse solution [Methyl isobutyl carbinol (MIBC)]. Subsequently, the silicon 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 fall resistance>
The exposure amount for reproducing a mask pattern having a pitch of 90 nm and a space width of 35 nm under the exposure and development conditions for forming the resist pattern is the optimum exposure amount, and the line width of the line pattern formed by further reducing the exposure amount from the optimum exposure amount The width of the maximum space that can be resolved without falling down when the pattern is thinned is defined as a value (nm) indicating the fall resistance. The results are shown in Table 1.
The larger the value indicating the fall resistance, the finer pattern is resolved without falling, and the pattern collapse is less likely to occur and the resolution is higher. More specifically, the collapse resistance is preferably 45 nm or more, more preferably 50 nm or more, and further preferably 55 nm or more.

<Evaluation of dry etching resistance>
The obtained line and space pattern having a pitch of 90 nm and a space width of 35 nm was dry-etched using a plasma etching apparatus (Hitachi ECR plasma etching apparatus U-621), and the dry etching rate was determined (plasma condition: Ar 500 ml / Min., N ₂ 500 ml / min, O ₂ 10 ml / min). The dry etching rate is as follows. In view of the stabilization of the plasma, the dry etching is performed in 10 seconds after starting dry etching and the dry etching is performed in 5 seconds after starting dry etching. It calculated | required from the difference with a film thickness. The dry etching resistance was evaluated based on the dry etching rate (Å / sec) thus determined. The results are shown in Table 1.
In practice, the dry etching rate is preferably 8.0 Å / sec or less, more preferably 5.5 Å / sec or less, and further preferably 2.5 Å / sec or less. .
(Dry etching rate) = {(Film thickness dry etched in 10 seconds) − (Film thickness dry etched in 5 seconds)} / 5

<Evaluation results>
The results of the above evaluation tests are shown in Table 1 below.

As shown in Table 1, the resin (A) containing the repeating unit (a1) having the group represented by the general formula (1) described above, and the compound (B) that generates an acid upon irradiation with actinic rays or radiation It was shown that a pattern excellent in collapse resistance and dry etching resistance can be formed by using a resist composition containing (Examples 1 to 24).
Moreover, from the comparison with Examples 1-24, W in the said General formula (1) uses resin (A) whose bivalent polycyclic aromatic group is used, and the repeating unit (in resin (A) ( By satisfying at least one of the content of a1) being 10 to 60 mol% with respect to 100 mol% of all repeating units of the resin (A), a pattern excellent in fall resistance and dry etching resistance is formed. It was shown that it was possible (Examples 1-3, 5-24).
Further, the resin (A) in which W in the general formula (1) is a divalent polycyclic aromatic group is used, and the content of the repeating unit (a1) in the resin (A) is a resin (A It was shown that by satisfying both of 10 to 60 mol% with respect to 100 mol% of all repeating units of), a more excellent pattern can be formed due to collapse resistance and dry etching resistance (Example 1). -3, 7, 11, 14, 16-20, 22-24).

  On the other hand, when the resin not having the group represented by the general formula (1) is used, it was shown that at least one of the fall resistance and the dry etching resistance of the obtained pattern is inferior (Comparative Examples 1 to 1). 4).

Claims (7)

A resin (A) containing a repeating unit (a1) having a group represented by the general formula (1);
A compound (B) that generates an acid upon irradiation with actinic rays or radiation; and
An actinic ray-sensitive or radiation-sensitive resin composition containing
* -L ₁ -W- (L ₂ -R ₂ ) _n (1)
In the general formula (1), L ₁ represents a single bond or a divalent linking group.
W represents an n + 1 valent alicyclic hydrocarbon group or an n + 1 valent aromatic group.
L ₂ represents a divalent linking group.
R ₂ represents a substituent having at least one group selected from the group consisting of a group having a lactone structure, a group having a sultone structure, a carbonate group, a sulfonamide group, an amide group, and a carboxylic acid group.
n represents an integer of 1 or more.
When n is 2 or more, the plurality of L ₂ may be the same as or different from each other, and the plurality of R ₂ may be the same as or different from each other.
* Indicates a bonding position with another atom.   Furthermore, the actinic-ray sensitive or radiation sensitive resin composition of Claim 1 in which the said resin (A) contains the repeating unit (a2) which has an acid-decomposable group.   The content of the repeating unit (a1) in the resin (A) is 10 to 60 mol% with respect to 100 mol% of all the repeating units of the resin (A). An actinic ray-sensitive or radiation-sensitive resin composition.   The actinic-ray sensitive or radiation sensitive resin composition of any one of Claims 1-3 whose W in the said General formula (1) is a n + 1 valent polycyclic aromatic group. A step of forming a resin film on a substrate using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 4,
Irradiating the resin film with actinic rays or radiation; and
Developing the resin film irradiated with actinic rays or radiation using a developer; and
A pattern forming method.   The pattern forming method according to claim 5, wherein the developer contains an organic solvent.   The manufacturing method of an electronic device containing the pattern formation method of Claim 5 or 6.