JP6761462B2 - Actinic light-sensitive or radiation-sensitive resin composition, pattern forming method, and manufacturing method of electronic device - Google Patents

Description

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

In microfabrication using a resist composition, the formation of an ultrafine pattern is required as the integrated circuit becomes highly integrated. Therefore, there is a tendency for the exposure wavelength to be shortened from g-ray to i-ray, and from KrF excimer laser to ArF excimer laser. Currently, for example, the development of lithography technology using electron beams has been observed. Is progressing.

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

Japanese Unexamined Patent Publication No. 2011-170316

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

When the present inventors examined a resin containing a repeating unit having a naphthalene ring as described in Patent Document 1, it was found that having a naphthalene ring improves dry etching resistance. ..
However, as a result of further studies by the present inventors, the solubility of the resist film after exposure in a developing solution (particularly, a developing solution containing an organic solvent) is too high depending on the type of the substituent of the naphthalene ring. It was found that the formed pattern swells and causes pattern collapse (decrease in collapse resistance).

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

As a result of diligent studies on the above problems, the present inventor has made dry etching resistance and dry etching resistance by using a sensitive light-sensitive or radiation-sensitive resin composition containing a resin containing a repeating unit (a1) having a group having a specific structure. We have found that a pattern having excellent fall resistance can be formed, and have arrived at 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), and a resin (A).
Compound (B) that generates acid by irradiation with active light or radiation,
A light-sensitive or radiation-sensitive resin composition containing.
* -L _1- W- (L _2- R ₂ ) _n ... (1)
In the above 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 carbonic acid ester 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 _2s may be the same or different from each other, and the plurality of R _2s may be the same or different from each other.
* Indicates the bond position with another atom.
[2]
The actinic or radiation-sensitive resin composition according to the above [1], wherein the resin (A) further contains a repeating unit (a2) having an acid-degradable group.
[3]
[1] or [2], 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 sensitive light-sensitive or radiation-sensitive resin composition according to.
[4]
The actinic light-sensitive or radiation-sensitive resin composition according to any one of the above [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 by using the actinic cheilitis or radiation-sensitive resin composition according to any one of the above [1] to [4].
The process of irradiating the resin film with active light or radiation,
The step of developing the resin film irradiated with active light or radiation using a developing solution, and
A pattern forming method having.
[6]
The pattern forming method according to the above [5], wherein the developer contains an organic solvent.
[7]
A method for manufacturing an electronic device, including the pattern forming method according to the above [5] or [6].

As shown below, according to the present invention, a sensitive light-sensitive or radiation-sensitive resin composition capable of forming a pattern excellent in dry etching resistance and lodging 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, the numerical range represented by using "~" means a range including the numerical values before and after "~" as the lower limit value and the upper limit value.
Further, in the present invention, 1Å (Angstrom) corresponds to 0.1 nm.
In addition, when the notation of groups and atomic groups in the present invention does not specify substitution or non-substitution, 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" refers to, for example, the emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excima laser, extreme ultraviolet rays (EUV light), X-rays, electron beams, ion beams and the like. It means the particle beam of. Further, in the present invention, "light" means active light rays or radiation.
Further, unless otherwise specified, the "exposure" in the present invention includes not only exposure with far ultraviolet rays, X-rays, extreme ultraviolet rays (EUV light) represented by mercury lamps and excimer lasers, but also electron beams, ion beams and the like. Drawing with particle beams shall also be included.
Further, the "(meth) acrylate" in the present invention means "at least one of acrylate and methacrylate". Further, "(meth) acrylic acid" means "at least one of acrylic acid and methacrylic acid".

[Actinic cheilitis or radiation-sensitive resin composition]
First, the actinic 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, and a compound (B) that generates an acid by irradiation with active light or radiation. , Contain.

According to the composition of the present invention, it is possible to form a pattern having excellent dry etching resistance and tipping resistance. The details of this reason are presumed to be due to the following reasons.
The resin (A) contained in the composition of the present invention contains a repeating unit (a1) having a group represented by the general formula (1) described later. 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)), the dry pattern obtained by using the resin (A) is used. It is presumed that the etching resistance has become excellent.
Further, at the end of the group represented by the general formula (1) (“R ₂ ” of the general formula (1)), a group having a lactone structure, a group having a sulton structure, a carbonate ester group, a sulfonamide group, and an amide It has a substituent having at least one group selected from the group consisting of a group and a carboxylic acid group. As described above, since "R ₂ " of the general formula (1) is a specific polar group, the pattern obtained when the exposed resist film formed by using the resin (A) is developed with an organic solvent Swelling due to organic solvent is suppressed. As a result, it is presumed that the pattern obtained by using the resin (A) has excellent fall resistance.

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

(Repeating unit (a1) represented by the general formula (1))
The resin (A) contains 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 above 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 carbonic acid ester 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 _2s may be the same or different from each other, and the plurality of R _2s may be the same or different from each other. * Indicates the bond position with another atom.

In the above general formula (1), L ₁ represents a single bond or a divalent linking group.
When L ₁ of the general formula (1) is a divalent linking group, the divalent linking group includes, for example, -COO-, -OCO-, -CONH-, -NHCO-, -CO-, -O. -, -S-, -SO-, -SO _2- , alkylene group (preferably 1 to 6 carbon atoms), cycloalkylene group (preferably 3 to 10 carbon atoms), alkenylene group (preferably 2 to 6 carbon atoms) ) Or a group in which a plurality of these groups are combined, and the total number of carbon atoms is 12 or less. The alkylene group, the cycloalkylene group, and the alkenylene group may have a substituent, and examples of the substituent include an alkyl group (preferably having 1 to 4 carbon atoms) and the like.
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 single bond, -COO-, or -CONH- is more preferable.
In the specific example of the above-mentioned linking group, the leftmost binding hand "-" means the binding hand on the "*" side in the general formula (1), and the right binding hand "-" is in the general formula (1). Means the join hand on the "W" side of.

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, and more preferably 6 or more carbon atoms. The alicyclic hydrocarbon group preferably has 25 or less carbon atoms, and more preferably 20 or less carbon atoms.
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, there are many. It is preferably an alicyclic hydrocarbon group of the ring.
The alicyclic hydrocarbon group of a single ring preferably has 4 to 12 carbon atoms. Examples of such a monocyclic alicyclic hydrocarbon group 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. Etc., and cyclopentyl groups, cyclohexyl groups, and cyclooctyl groups are preferable.
The polycyclic alicyclic hydrocarbon group preferably has 7 to 20 carbon atoms. Examples of such a polycyclic alicyclic hydrocarbon group include a bicyclo [4.3.0] nonanyl group, a decahydronaphthalenyl group, a 1,2,3,4-tetrahydronaphthalenyl group and a 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 Examples thereof include a tricyclo [2.2.1.0 ^2,6 ] heptanyl group and a 3,7,7-trimethylbicyclo [4.1.0] heptanyl group, such as a norbornyl group, an adamantyl group, and a norl. The 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 valent, more preferably divalent.
The aromatic group may be a monocyclic group or a polycyclic (polycyclic aromatic group), but from the viewpoint of further improving the tipping resistance and the dry etching resistance, the polycyclic aromatic group may be used. It is preferably a family group.
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 and benzo. Aromatic ring heterocyclic groups containing heterocycles such as imidazole, triazole, thiadiazol and thiazole can be mentioned. Among these, aromatic hydrocarbon groups having 6 to 18 carbon atoms are preferable, and polycyclic aromatic hydrocarbon groups having 10 to 18 carbon atoms are more preferable, from the viewpoint of further improving dry etching resistance.

In the above 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 mentioned in 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 carbonic acid ester group, a sulfonamide group, an amide group and a carboxylic acid group.

In R _2, as the group having a lactone structure may be a group consisting of only a lactone structure, a group and non lactone structure and a lactone structure rings are condensed (e.g., bicyclo structure including a lactone structure and, It may be a spiro structure including a lactone structure).
The lactone structure in the group having a lactone structure is preferably a 5- to 7-membered ring lactone structure.
Further, the group having a lactone structure may have a substituent. Examples of such a substituent include an alkyl group having 1 to 8 carbon atoms, a monovalent cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, and a carboxy group. Examples thereof include a group, a halogen atom, a hydroxyl group, and a cyano group, and among these, a cyano group is preferable.
Specific examples of groups having a lactone structure are shown below. In the following specific example, "*" indicates the bonding position with L ₂ .

In R _2, as the group having a sultone structure may be a group consisting of only sultone structure, a group (for example, a ring other than sultone structure and sultone structures are condensed bicyclo structure containing 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 sultone structure having a 4- to 7-membered ring.
Further, the group having a sultone structure may have a substituent, and specific examples of the substituent are the same as those of the above-mentioned group having a lactone structure.
Specific examples of groups having a sultone structure are shown below. In the following specific example, "*" indicates the bonding position with L ₂ .

In R _2, as the group having a carbonate group (-O-CO-O-), be cyclic, may it be a non-cyclic, it is preferably annular. The group having a carbonic acid ester group may have a substituent, and specific examples of the substituent are the same as those of the above-mentioned group having a lactone structure.
Specific examples of the group having a carbonic acid ester group are shown below. In the following specific example, "*" indicates the 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 those of the above-mentioned group having a lactone structure.
Specific examples of the group having a sulfonamide group are shown below. In the following specific example, "*" indicates the bonding position with L ₂ .

In R _2, as the group having an amide group (-CO-NH-), it may be a cyclic, may be non-cyclic. The group having an amide group may have a substituent, and specific examples of the substituent are the same as those of the above-mentioned group having a lactone structure.

In the general formula (1), n represents an integer of 1 or more, preferably 1 to 3, and more preferably 1 to 2.
When n is 2 or more, the plurality of L _2s may be the same or different from each other, and the plurality of R _2s may be the same or different from each other.
* Indicates the bond 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 the general formula (a1), Ra represents a hydrogen atom or an alkyl group. Rb represents a group represented by the above-mentioned general formula (1).

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 even more preferably a methyl group. The alkyl group of Ra may be substituted. Examples of the substituent include a halogen atom (for example, a fluorine atom, a chlorine atom and a bromine atom, etc.), an alkoxy group (for example, a mercapto group, a hydroxy group, a methoxy group, an ethoxy group, an isopropoxy group, a t-butoxy group and a benzyl group. Oxy group, etc.), acetoxy group (for example, acetyl group, propionyl group, etc.) and the like. Among these, Ra is preferably a hydrogen atom and a methyl group.

Since Rb represents a group represented by the above-mentioned general formula (1), the description thereof will be omitted.

A specific example of the repeating unit (a1) having a group represented by the general formula (1) is 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%, preferably 15 to 60 mol%, based on 100 mol% of all the repeating units of the resin (A). Is more preferable, and 20 to 60 mol% is further preferable. When the content of the repeating unit (a1) is 10 mol% or more, an excellent pattern can be obtained due to the tipping resistance and the dry etching resistance. Further, when the content of the repeating unit (a1) is 60 mol% or less, high dissolution contrast can be exhibited.
The resin (A) may contain the above repeating unit (a1) alone or in combination of two or more. When two or more types of the repeating unit (a1) are contained, it is preferable that the total content of the repeating unit (a1) in the resin (A) is within the above range.

(Repeating unit having an acid degradable group (a2))
The resin (A) preferably contains a repeating unit (a2) having an acid-degradable group. An acid-degradable group is a group that is decomposed by the action of an acid to produce an alkali-soluble group.
The resin (A) contains a repeating unit (a2) having an acid-degradable group in one of the main chain and the side chain of the resin (A), or both in the main chain and the side chain.
Hereinafter, the repeating unit (a2) having an acid-degradable group may be simply referred to as an "acid-degradable repeating unit".
The resin (A) is preferably insoluble or sparingly soluble in an alkaline developer.

The acid-degradable group preferably has a structure protected by a group that decomposes and desorbs an alkali-soluble group by the action of an acid.

Examples of the alkali-soluble group include a phenolic hydroxyl group, a carboxy group, a fluorinated alcohol group, a sulfonic acid group, a sulfonamide group, a sulfonylimide group, a (alkylsulfonyl) (alkylcarbonyl) methylene group, and a (alkylsulfonyl) (alkylcarbonyl) imide. Group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, and tris (alkylsulfonyl) methylene The group etc. can be mentioned.

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

A preferred group as an acid-degradable group is a group in which the hydrogen atom of these alkali-soluble groups is replaced with a group that desorbs an acid.

Examples of the acid-eliminating groups 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 can be mentioned.
In the formula, R _{36 to} R ₃₉ each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. R ₃₆ and R ₃₇ may be combined with each other to form a ring.
R _{01 to} R ₀₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.

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

As the repeating unit having an acid-degradable group that can be contained in the resin (A), a repeating unit represented by the following general formula (AI) is preferable.

In the general formula (AI)
Xa ₁ represents a hydrogen atom, which may have a substituent methyl group 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 independently represent an alkyl group (linear or branched) or a cycloalkyl group (monocyclic or polycyclic).
At least two of Rx _{1 to} Rx ₃ may be bonded to form a cycloalkyl group (monocyclic or polycyclic).

Examples of the divalent linking group of T include an alkylene group, an -COO-Rt- group, an -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, and more preferably −CH ₂ − group and − (CH ₂ ) ₃ − group.
Alkyl groups 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.

Examples of the cycloalkyl group of Rx _{1 to} Rx ₃ include a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, and a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group. The polycyclic cycloalkyl group of is preferred.
Examples of the cycloalkyl group formed by bonding at least two of Rx _{1 to} Rx ₃ include a cyclopentyl group, a monocyclic cycloalkyl group such as a cyclohexyl group, and a norbornyl group, a tetracyclodecanyl group, and a tetracyclo. Polycyclic cycloalkyl groups such as dodecanyl groups and adamantyl groups are preferred. A monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferable.
It is preferable that Rx ₁ is a methyl group or an ethyl group, and Rx ₂ and Rx ₃ are bonded to form the above-mentioned cycloalkyl group.

Each of the above groups may have a substituent, and 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), and a carboxy group. And an alkoxycarbonyl group (2 to 6 carbon atoms) and the like, preferably 8 or less carbon atoms.

Specific examples of repeating units having a preferable acid-degradable group are shown below, but the present invention is not limited thereto.
In the specific example, Rx and Xa ₁ represent a hydrogen atom, CH ₃ , CF ₃ or CH ₂ OH. Rxa and Rxb each represent an alkyl group having 1 to 4 carbon atoms. Z represents a substituent containing a polar group, and if there are a plurality of Z, each is independent. p represents 0 or a positive integer.

The resin (A) is a resin having at least one of a repeating unit represented by the general formula (I) and a 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, R 3} each independently represent a hydrogen atom, which may have a substituent methyl group 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 represent an alkyl group or a cycloalkyl group.
R represents an atomic group required to form an alicyclic structure together with carbon atoms.
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 a linear type or a branched type, 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, more preferably those of 1 to 5 carbon atoms include, for example, methyl and ethyl.

R represents an atomic group required to form an alicyclic structure together with carbon atoms. The alicyclic structure formed by R is preferably a monocyclic alicyclic structure, and the number of carbon atoms thereof is preferably 8 or less, more preferably 3 to 7, and further preferably 5 or 6. 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 a linear type or a branched type, 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, a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, and a polycyclic cycloalkyl group 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 is synonymous with R ₁ in formula (I).
Rd _{1 to} Rd ₃ independently represent a hydrogen atom or an alkyl group.
Z represents a monocyclic structure.

Examples of the alkyl group of Rd _{1 to} Rd ₃ include an alkyl group having 1 to 4 carbon atoms. The alkyl group having 1 to 4 carbon atoms of Rd _{1 to} Rd ₃ is preferably a methyl group.

Examples of the monocyclic structure of Z include monocyclic cycloalkyl groups such as cyclopentyl group and 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.

Further, examples of the repeating unit represented by the general formula (I) include a repeating unit represented by the following general formula (1-a).

In the formula, R ₁ and R ₂ are synonymous with each in the general formula (I).
It is preferable that the repeating unit represented by the general formula (II) is the repeating unit represented by the following general formula (II-1).

In formula (II-1),
R _{3 to} R ₅ are synonymous with those in the general formula (II).
R ₁₀ represents a substituent containing a polar group. When a plurality of R _10s exist, they may be the same or different from each other. Examples of the substituent containing a polar group include a linear or branched alkyl group having a hydroxyl group, a cyano group, an amino group, an alkylamide group or a sulfonamide group, and a cycloalkyl group, preferably having a hydroxyl group. It is an alkyl group. The isopropyl group is particularly preferable as the branched alkyl group.
p represents an integer from 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). Further, in another form, it is more preferable that the resin contains at least two kinds of repeating units represented by the general formula (I).

When the resin (A) is used in combination with an acid-decomposable repeating unit, the following are preferable combinations. In the following formula, 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% and 40 to 80 mol% with respect to 100 mol% of all the repeating units of the resin (A). Is more preferable, and 40 to 70 mol% is further preferable. When the content of the repeating unit (a2) is 40 mol% or more, high dissolution contrast can be exhibited. Further, when the content of the repeating unit (a2) is 90 mol% or less, an excellent pattern can be obtained due to the tipping resistance and the dry etching resistance.
The resin (A) may contain the above repeating unit (a2) alone or in combination of two or more. When two or more types of the repeating unit (a2) are contained, it is preferable that the total content of the repeating unit (a2) in the resin (A) is within the above range.

(Other repeating units)
The resin (A) may contain a repeating unit other than the repeating unit described above. Other repeating units include repeating units (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 the sultone structure described below is a repeating unit different from the repeating unit (a1) described above. Is.

((Repeating unit (a3) including lactone structure or sultone structure))
Among 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 the preferred lactone structure is a 5 to 7-membered ring lactone structure, and the other ring structure is condensed in a form in which a bicyclo structure and a spiro structure are formed in the 5 to 7-membered ring lactone structure. Can also be preferably used.
The lactone structure is preferably a lactone structure represented by any of the following general formulas (LC1-1) to (LC1-17). Further, the lactone structure may be directly bonded to the main chain.
The lactone structure is represented by the following general formulas (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-13), (LC1-14) and (LC1-17). More preferably. By using such a lactone structure, suppression of LWR (Line Width Roughness) and development defects becomes better.

As the repeating unit having a lactone structure, a repeating unit represented by the following general formula (AII') is preferable.

In the general formula (AII'),
Rb ₀ represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. Preferred substituents that the alkyl group of Rb ₀ may have include hydroxyl groups and halogen atoms. Examples of the halogen atom of 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 preferable, and a hydrogen atom and a methyl group are more preferable.

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

Examples of the repeating unit having a particularly preferable lactone structure include the following repeating units. By selecting the optimum lactone structure, the pattern profile and sparse and dense dependence will be good.

The repeating unit having a lactone structure usually has an optical isomer, but any optical isomer may be used. Further, one kind of 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%, more preferably 20 to 50 mol%, based on 100 mol% of all the repeating units of the resin (A).
When two or more types of repeating units having a lactone structure are contained, the total content of the repeating units having a lactone structure is preferably in the above range.

Among the repeating units (a3) containing a lactone structure or a sultone structure, the repeating unit (a3) having a sultone structure (hereinafter, also simply referred to as “repeating unit having a sultone structure”) may have a sultone structure. Any of these can be used, but preferably a 5- to 7-membered sultone structure is formed, and other ring structures are condensed in a form in which a bicyclo structure or a spiro structure is formed in the 5 to 7-membered sultone structure. Is preferable.
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). Moreover, the sultone structure may be directly bonded to the main chain. Having a repeating unit having the following sultone structure improves LWR and development defects.

((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 substrate adhesion and developer affinity.
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 does not have an acid-degradable 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 the repeating unit having a preferable hydroxyl group or cyano group, a repeating unit represented by the following general formula is preferable.

When a 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 may be 5 to 40 mol% with respect to 100 mol% of all the repeating units of the resin (A). It is preferably 5 to 30 mol%, more preferably 10 to 25 mol%.
The repeating unit having a hydroxyl group or a cyano group may be used alone or in combination of two or more.

Specific examples of the repeating unit having a hydroxyl group or a cyano group include, but are not limited to, the repeating unit disclosed in paragraph 0340 of Japanese Patent Application Laid-Open No. 2012/0135348.

((Repeating unit with alkali-soluble group))
The 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 each of the repeating units described above.
Examples of the alkali-soluble group include a carboxy group, a sulfonamide group, a sulfonylimide group, a bissulfonylimide group, and an aliphatic alcohol in which the α-position is substituted with an electron-withdrawing group (for example, a hexafluoroisopropanol group). Groups are preferred. By containing a 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 made of acrylic acid or methacrylic acid, or an alkali on the main chain of the resin via a linking group. Repeat units to which soluble groups are attached can be mentioned. It is also preferable to use a polymerization initiator or a chain transfer agent having an alkali-soluble group at the time of polymerization to introduce an alkali-soluble group at the end of the resin. The linking group may have a monocyclic or polycyclic cyclic hydrocarbon structure. Particularly preferably, it is a repeating unit of acrylic acid and 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 the repeating units of the resin (A). It is more preferably 5 to 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, but are not limited to, the repeating unit disclosed in paragraph 0344 of Japanese Patent Application Laid-Open No. 2012/0135348.

((Repeating unit having an alicyclic hydrocarbon structure without polar groups and showing no acid degradability))
The resin (A) can further have an alicyclic hydrocarbon structure having no polar group (for example, the above-mentioned alkali-soluble group, hydroxyl group, cyano group, etc.) and having a repeating unit that does not exhibit acid decomposition. Examples of such a repeating unit include a repeating unit represented by the general formula (IV).

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

Ra represents a hydrogen atom, an alkyl group or _-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, and more preferably a hydrogen atom or a methyl group.

The cyclic structure of R ₅ includes a monocyclic hydrocarbon group or a polycyclic hydrocarbon group. Examples of the monocyclic hydrocarbon group include a cycloalkyl group having 3 to 12 carbon atoms such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group, and a cyclohexenyl group having 3 to 12 carbon atoms. Cycloalkenyl groups can be mentioned. Preferred monocyclic hydrocarbon groups are monocyclic hydrocarbon groups having 3 to 7 carbon atoms, and more preferably cyclopentyl groups and cyclohexyl groups.

The polycyclic hydrocarbon group includes a ring-assembled hydrocarbon group and a cross-linked ring-type hydrocarbon group, and examples of the ring-assembled hydrocarbon group include a bicyclohexyl group and a perhydronaphthalenyl group. Bicyclic hydrocarbon rings such as pinan, bornan, norpinane, norbornane and bicyclooctane (bicyclo [2.2.2] octane ring, bicyclo [3.2.1] octane ring, etc.) Tricyclic hydrocarbon rings such as hydrocarbon rings, homobredane, adamantane, 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 . 17 and ¹⁰ ] Dodecane and 4-cyclic hydrocarbon rings such as perhydro-1,4-methano-5,8-methanonaphthalene rings can be mentioned. In addition, the crosslinked cyclic hydrocarbon ring includes fused cyclic hydrocarbon rings such as perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, and the like. A fused ring in which a plurality of 5- to 8-membered cycloalkane rings such as a perhydrophenanthrene ring are condensed is also included.

As preferred crosslinked-ring hydrocarbon rings, a norbornyl group, an adamantyl group, a bicyclooctanyl group, and, like tricyclo [5,2,1,0 ^2,6] decanyl group. More preferable crosslinked cyclic hydrocarbon rings include norbonyl groups and adamantyl groups.

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

Examples of the substituent substituting 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 include alkyl groups having 1 to 4 carbon atoms, and preferred substituted methyl groups include methoxymethyl groups, methoxythiomethyl groups, benzyloxymethyl groups, t-butoxymethyl groups, and 2-methoxyethoxymethyl groups. 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 group. 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 which has an alicyclic hydrocarbon structure having no polar group and does not exhibit acid decomposition property, but when it is contained, this repetition is performed. The content of the unit is preferably 1 to 40 mol%, more preferably 2 to 20 mol%, based on 100 mol% of all the repeating units of the resin (A).
The repeating unit having an alicyclic hydrocarbon structure having no polar group and not exhibiting acid degradability 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 decomposition can be mentioned as the repeating unit disclosed in paragraph 0354 of Japanese Patent Application Laid-Open 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, resist profile, and resolution, heat resistance, and sensitivity, which are general required properties of resist. It is possible to have various repeating units for the purpose of adjusting etc.
Examples of such a repeating unit include, but are not limited to, a repeating unit corresponding to a monomer described later. This makes it possible to make fine adjustments to various performances.

As such a monomer, a compound having one addition-polymerizable unsaturated bond selected from, for example, acrylic acid esters, methacrylic acid esters, acrylamides, methacrylicamides, allyl compounds, vinyl ethers, vinyl esters and the like. Etc. can be mentioned.

In addition, any addition-polymerizable unsaturated compound that can be copolymerized with the monomers corresponding to the 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) is a repeating unit having an aromatic hydrocarbon group. It is preferably contained, and more preferably it contains a repeating unit having a phenolic hydroxyl group. As the repeating unit having a phenolic hydroxyl group, the repeating unit shown below is particularly preferable.

The resin (A) may have a repeating unit having a Si atom.
The repeating unit having a Si atom is not particularly limited as long as it has a Si atom. For example, a silane-based repeating unit (-SiR _2- : R ₂ is an organic group), a siloxane-based repeating unit (-SiR _2- O-: R ₂ is an organic group), a (meth) acrylate-based repeating unit having a Si atom, And a vinyl-based repeating unit having a Si atom and the like can be mentioned.

The repeating unit having a Si atom preferably has a silsesquioxane structure. The silsesquioxane structure may be contained in the main chain or the side chain, but it is preferably provided in the 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), and a random-type silsesquioxane structure. Of these, a cage-type silsesquioxane structure is preferable.
Here, the cage-type silsesquioxane structure is a silsesquioxane structure having a cage-like skeleton. The cage-type silsesquioxane structure may be a complete cage-type silsesquioxane structure or an incomplete cage-type silsesquioxane structure, but it may be a complete cage-type 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-type silsesquioxane structure is preferably a siloxane structure represented by the following formula (S).

In the above formula (S), R represents a monovalent organic group. The plurality of Rs may be the same or different.
The organic group is not particularly limited, and specific examples thereof include a halogen atom, a hydroxy group, a nitro group, a carboxy group, an alkoxy group, an amino group, a mercapto group, and a blocked mercapto group (for example, blocked (protected) by an acyl group). Mercapto group), acyl group, imide group, phosphino group, phosphinyl group, silyl group, vinyl group, hydrocarbon group which may have a hetero atom, (meth) acrylic group-containing group, epoxy group-containing group, etc. Can be mentioned.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Examples of the heteroatom of the hydrocarbon group which may have the heteroatom include an oxygen atom, a nitrogen atom, a sulfur atom and a phosphorus atom.
Examples of the hydrocarbon group of the hydrocarbon group which may have the hetero atom include an aliphatic hydrocarbon group, an aromatic hydrocarbon group, and 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 1 to 30 carbon atoms), a linear or branched alkenyl group (particularly 2 to 30 carbon atoms), and the like. Examples thereof include a linear or branched alkynyl group (particularly, having 2 to 30 carbon atoms).
Examples of the aromatic hydrocarbon group include an aromatic hydrocarbon group having 6 to 18 carbon atoms such as a phenyl group, a tolyl group, a xsilyl group and a naphthyl group.

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

In the above formula (I), L represents a single bond or a divalent linking group.
Examples of the divalent linking group include an alkylene group, an -COO-Rt- group, an -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 −CH ₂ − group, − (CH ₂ ) ₂ − group, and − (CH ₂ ) ₃ − group.
In the above formula (I), X represents a hydrogen atom or an organic group.
Examples of the organic group include an alkyl group which may have a substituent such as a fluorine atom and a hydroxyl group, and a hydrogen atom, a methyl group, a trifluoromethyl group and a hydroxymethyl group are preferable.
In the above formula (I), A represents a Si-containing group. Among them, the group represented by the following formula (a) or (b) is preferable.

In the above formula (a), R represents a monovalent organic group. The plurality of Rs may be the same or different. Specific examples and preferred embodiments of R are the same as 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 heteroatom are the same as R in the above formula (S).

When the resin (A) contains a repeating unit having a Si atom, one kind of repeating unit having a Si atom may be contained, or two or more kinds 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 alone or in combination of two or more.

(Method for synthesizing resin (A))
The resin (A) can be synthesized according to a conventional method (for example, radical polymerization). For example, as a general synthesis method, a batch polymerization method in which a monomer seed and an initiator are dissolved in a solvent and polymerized by heating, or a solution of the monomer seed and the initiator is added dropwise to the heating solvent over 1 to 10 hours. 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. , Solvents that dissolve the compositions of the present invention, such as propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and cyclohexanone. More preferably, it is polymerized using the same solvent as the solvent used in the composition of the present invention. As a result, the generation of particles during storage can be suppressed.

The polymerization reaction is preferably carried out in an atmosphere of an inert gas such as nitrogen and argon. As the polymerization initiator, a commercially available radical initiator (azo-based initiator, peroxide, etc.) is used. As the radical initiator, an azo-based initiator is preferable, and an azo-based 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 the reaction is completed, the reaction solution is charged with a solvent to recover the desired polymer 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., and more preferably 60 to 100 ° C.

Further, in order to suppress the aggregation of the resin after preparation of the composition, for example, as described in JP-A-2009-037108, the synthesized resin is dissolved in a solvent to prepare a solution, and the solution is prepared. 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 2,000 to 20,000 in terms of polystyrene by the GPC (Gel permeation chromatography) method. It is 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 deterioration of film forming property due to an increase in viscosity can be suppressed.

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

The resin (A) may be used alone or in combination of two or more.
The content of the resin (A) is preferably 30 to 99% by mass, more preferably 60 to 95% by mass, based on the total solid content of the composition.

Specific examples of the resin (A) are given below, but the present invention is not limited thereto. In the following specific example, "Me" represents a methyl group.

<Compound (B) that generates acid by irradiation with active light or radiation>
The composition of the present invention preferably contains a compound that generates an acid when irradiated with active light or radiation (hereinafter, also referred to as an "acid generator"). The acid generator is not particularly limited, but is preferably a compound that generates an organic acid by irradiation with active light or radiation.
As the acid generator, irradiation with active light or radiation used in a photoinitiator for photocationic polymerization, a photoinitiator for photoradical polymerization, a photochromic agent for pigments, a photodiscolorant, a microresist, or the like. A known compound that generates an acid according to the above and a mixture thereof can be appropriately selected and used. For example, the compounds described in paragraphs [0039] to [0103] of JP-A-2010-61043, the present invention. Examples thereof include the compounds described in paragraphs [0284] to [0389] of Japanese Patent Application Laid-Open No. 2013-4820, but the present invention is not limited thereto.
For example, diazonium salt, phosphonium salt, sulfonium salt, iodonium salt, imide sulfonate, oxime sulfonate, diazodisulfone, disulfone, and o-nitrobenzyl sulfonate can be mentioned.

As the acid generator contained in the composition of the present invention, for example, a compound (specific acid generator) that generates an acid by irradiation with active light or radiation represented by the following general formula (3) is preferably mentioned. Can be done.

(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 them, R ₄ and R ₅ are the same, respectively. 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 1-3. p represents an integer from 0 to 10. q represents an integer from 0 to 10.

Xf represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. The number of carbon atoms of this alkyl group is preferably 1 to 10, and more preferably 1 to 4. Further, 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. It is more preferable that Xf is a fluorine atom or CF ₃ . In particular, it is preferable that both Xfs 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 them, R ₄ and R ₅ are the same, respectively. But it can be different.
The alkyl group as R ₄ and R ₅ may have a substituent, and those having 1 to 4 carbon atoms are preferable. R ₄ and R ₅ are preferably hydrogen atoms.
Specific examples and preferred embodiments of the alkyl group substituted with at least one fluorine atom are the same as the specific examples and preferred embodiments of Xf in the general 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 −, alkylene group (preferably 1 to 6 carbon atoms), cycloalkylene group (preferably 3 to 10 carbon atoms), alkenylene group (preferably 2 to 6 carbon atoms), or a combination thereof. Examples include a divalent linking group. 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, it is preferably a cyclic organic group.
Examples of the cyclic organic group include an alicyclic group, an aryl group, and a heterocyclic group.
The alicyclic group may be a monocyclic type or a polycyclic type. Examples of the monocyclic alicyclic group include a monocyclic cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. Examples of the polycyclic alicyclic group include a polycyclic cycloalkyl group such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group. Among them, alicyclic groups 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, are subjected to a PEB (post-exposure heating) step. It is preferable from the viewpoint of suppressing the diffusivity in the membrane and improving the 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. Of these, a naphthyl group having a relatively low photoabsorbance at 193 nm is preferable.
The heterocyclic group may be monocyclic or polycyclic, but the polycyclic group can suppress the diffusion of acid more. Further, the heterocyclic group may 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 non-aromatic heterocycle include a tetrahydropyran ring, a lactone ring, a sultone ring and a decahydroisoquinoline ring. As the heterocycle in the heterocyclic group, a furan ring, a thiophene ring, a pyridine ring, or a decahydroisoquinoline ring is preferable. In addition, examples of the lactone ring and the sultone ring include the lactone structure and the sultone structure exemplified in the above-mentioned resin.

The cyclic organic group may have a substituent. The substituent may be, for example, an alkyl group (which may be linear or branched and preferably has 1 to 12 carbon atoms), a cycloalkyl group (single ring, polycyclic ring, or spiro ring). It may have 3 to 20 carbon atoms), an aryl group (preferably 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 that contributes to ring formation) may be carbonyl carbon.

o represents an integer of 1-3. p represents an integer from 0 to 10. q represents an integer from 0 to 10.
In one aspect, it is preferable that o in the general formula (3) is an integer of 1 to 3, p is an integer of 1 to 10, and q is 0. Xf is preferably a fluorine atom, R ₄ and R ₅ are both preferably hydrogen atoms, and W is preferably a polycyclic hydrocarbon group. o is more preferably 1 or 2, and even more preferably 1. p is more preferably an integer of 1-3, even more preferably 1 or 2, and particularly preferably 1. W is more preferably a polycyclic cycloalkyl group, and even more 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- it is mentioned as preferred.

(Cation)
In the general formula (3), X ⁺ represents a cation.
X ⁺ is not particularly limited as long as cation, suitable embodiments include the corresponding general formula (ZI), (ZII) or (ZIII) in cation ^- include (Z portions other than).

(Preferable aspect)
Preferable embodiments of the specific acid generator include, for example, compounds represented by the following general formulas (ZI), (ZII) or (ZIII).

In the above general formula (ZI)
R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represent 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.
Further, two of R _{201 to} R ₂₀₃ may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group. Examples of the group formed by bonding two of R _{201 to} R ₂₀₃ include an alkylene group (for example, a butylene group and a pentylene group).
And Z ^- represents an anion of the general formula (3), specifically, an anion of the following.

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, it may be a compound having a plurality of structures represented by the general formula (ZI). For example, the general formula at least one of _R 201 _{to R 203} of a compound represented by (ZI), at least one of _R 201 _{to R 203} of another compound represented by formula (ZI), a single bond or It may be a compound having a structure bonded via a linking group.

Further preferable (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 aryl sulfonium compound in which at least one of R _{201 to} R ₂₀₃ of the above general formula (ZI) is an aryl group, that is, a compound having aryl sulfonium as a cation.
In the aryl sulfonium 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 aryl sulfonium compound include a triaryl sulfonium compound, a diallyl alkyl sulfonium compound, an aryl dialkyl sulfonium compound, a diallyl cycloalkyl sulfonium compound, and an aryl dicycloalkyl sulfonium compound.

The aryl group of the aryl sulfonium compound is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The aryl group may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom or the like. Examples of the heterocyclic structure include pyrrole residues, furan residues, thiophene residues, indole residues, benzofuran residues, benzothiophene residues and the like. When the aryl sulfonium 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 contained in the arylsulfonium compound as required is preferably a linear or branched alkyl group having 1 to 15 carbon atoms and a cycloalkyl group having 3 to 15 carbon atoms, for example, a methyl group. Examples thereof include ethyl group, propyl group, n-butyl group, sec-butyl group, t-butyl group, cyclopropyl group, cyclobutyl group, cyclohexyl group and the like.

The aryl group, alkyl group, and cycloalkyl group of R _{201 to} R ₂₀₃ are an alkyl group (for example, 1 to 15 carbon atoms), a cycloalkyl group (for example, 3 to 15 carbon atoms), and an aryl group (for example, 6 to 15 carbon atoms). 14), an alkoxy group (for example, 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, or a phenylthio group may be used as a substituent.

Next, the compound (ZI-2) will be described.
The compound (ZI-2) is a compound in which R _{201 to} R ₂₀₃ in the formula (ZI) each independently represent an organic group having no aromatic ring. Here, the aromatic ring also includes an aromatic ring containing a hetero atom.
The organic group containing no aromatic ring as R _{201 to} R ₂₀₃ generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.
R _{201 to} R ₂₀₃ are independently, preferably an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group, and 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). , Cycloalkyl groups having 3 to 10 carbon atoms (cyclopentyl group, cyclohexyl group, and norbonyl group) can be mentioned.
R _{201 to} R ₂₀₃ may be further substituted with a halogen atom, an alkoxy group (for example, 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 the general formula (ZI-3),
R _{1c to} R _5c are independently hydrogen atom, alkyl group, cycloalkyl group, aryl group, alkoxy group, aryloxy group, alkoxycarbonyl group, alkylcarbonyloxy group, cycloalkylcarbonyloxy group, halogen atom, hydroxyl group. , Nitro group, alkylthio group or arylthio group.
R _6c and R _7c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an aryl group.
R _x and R _y each independently represent an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group or a vinyl group.

Even if 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 are combined to form a ring structure, respectively. Often, this ring structure may contain oxygen atoms, sulfur atoms, ketone groups, ester bonds, or amide bonds.
Examples of the ring structure include aromatic or non-aromatic hydrocarbon rings, aromatic or non-aromatic heterocycles, and polycyclic fused rings in which two or more of these rings are combined. The ring structure may include a 3 to 10-membered ring, preferably a 4- to 8-membered ring, and more preferably a 5- or 6-membered ring.

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 bonding R _5c and R _6c , and R _5c and R _x is preferably a single bond or an alkylene group, and examples of the alkylene group include a methylene group and an ethylene group. ..
Zc ⁻ represents an anion in the general formula (3), and is specifically as described above.

Examples of the cations in the compound (ZI-2) or (ZI-3) in the present invention include the cations described in paragraph [0036] and subsequent paragraphs 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 the general formula (ZI-4),
R ₁₃ represents a group having a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, or a cycloalkyl group. These groups may have substituents.
R ₁₄ is 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 independently of each other when a plurality of them exist. Represents. These groups may have substituents.
Each of R ₁₅ independently represents an alkyl group, a cycloalkyl group or a naphthyl group. These groups may have substituents. Two R ₁₅ may combine with each other to form a ring. When two R ₁₅ are combined to form a ring together, in the ring skeleton, an oxygen atom, may contain a hetero atom such as nitrogen atom. In one embodiment, two R ₁₅ is an alkylene group, it is preferable to form a ring structure.
l represents an integer from 0 to 2.
r represents an integer from 0 to 8.
Z ⁻ represents an anion in the general formula (3), and is specifically as described above.

In the general formula (ZI-4), the alkyl groups of R ₁₃ , R ₁₄ and R ₁₅ are linear or branched, preferably those having 1 to 10 carbon atoms, and are preferably a methyl group, an ethyl group and an n-. A butyl group, a t-butyl group, or the like is preferable.
Examples of the cation of the compound represented by the general formula (ZI-4) in the present invention include paragraphs [0121], [0123], and [0124] of JP-A-2010-256842, and JP-A-2011-76056. The cations described in paragraphs [0127], [0129], [0130] and the like can be mentioned.

Next, the general formulas (ZII) and (ZIII) will be described.
In the general formulas (ZII) and (ZIII), R _{204 to} R ₂₀₇ each independently represent an aryl group, an alkyl group or a cycloalkyl group.
As the aryl group of R _{204 to} R _207, a phenyl group and a naphthyl group are preferable, and a phenyl group is more preferable. 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). , Cycloalkyl groups having 3 to 10 carbon atoms (cyclopentyl group, cyclohexyl group, and norbonyl group) can be mentioned.

The aryl group, alkyl group, and cycloalkyl group of R _{204 to} R ₂₀₇ may have a substituent. Examples of the substituents that the aryl group, alkyl group, and cycloalkyl group of R _{204 to} R ₂₀₇ may have include an alkyl group (for example, 1 to 15 carbon atoms) and a cycloalkyl group (for example, 3 carbon atoms). ~ 15), aryl groups (for example, 6 to 15 carbon atoms), alkoxy groups (for example, 1 to 15 carbon atoms), halogen atoms, hydroxyl groups, phenylthio groups and the like can be mentioned.
Z ⁻ represents an anion in the general formula (3), and is specifically as described above.

The acid generator (including a specific acid generator; the same applies hereinafter) may be in the form of a low molecular weight compound or may be incorporated in a part of the polymer. Further, the form of the low molecular weight compound and the form incorporated in a part of the polymer may be used in combination.
When the acid generator is in the form of a low molecular weight 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 even more preferably 1000 or less.
When the acid generator is in the form of being incorporated in a part of the polymer, it may be incorporated in a part of the above-mentioned resin or may be incorporated in a resin different from the resin.
The acid generator can be synthesized by a known method, and for example, it can be synthesized according to the method described in JP-A-2007-161707.
The acid generator may be used alone or in combination of two or more.
The content of the acid generator in the composition (the total of a plurality of types, if present) is preferably 0.1 to 30% by mass, more preferably 0.5 to 25, based on the total solid content of the composition. It is by mass, more preferably 3 to 20% by mass, and particularly preferably 3 to 15% by mass.
When the acid generator contains a compound represented by the above general formula (ZI-3) or (ZI-4), the content of the acid generator contained in the composition (the total of multiple types, if present). 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 control agent (C)>
The composition of the present invention may contain an acid diffusion control agent (C). The acid diffusion control agent (C) acts as a quencher for trapping the acid generated from the acid generator by exposure, and plays a role of controlling the acid diffusion phenomenon in the coating film.

The acid diffusion control agent (C) may be, for example, a basic compound. The basic compound is preferably a compound having a stronger basicity than phenol. Further, this basic compound is preferably an organic basic compound, and more preferably a nitrogen-containing basic compound. The nitrogen-containing basic compound that can be used is not particularly limited, and for example, compounds classified into the following (1) to (5) can be used.

Further, in another form, the composition of the present invention may contain, for example, an ionic compound classified into the following (6) as an acid diffusion control agent.
Further, the composition of the present invention may contain, as an acid diffusion control agent, a low molecular weight compound having a nitrogen atom classified in the following (7) and having a group desorbed by the action of an acid.

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

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

The number of carbon atoms of the alkyl group as R is not particularly limited, but is usually 1 to 20, preferably 1 to 12.
The number of carbon atoms of the cycloalkyl group as R is not particularly limited, but is usually 3 to 20, preferably 5 to 15.
The number of carbon atoms of the aryl group as R is not particularly limited, but is usually 6 to 20, preferably 6 to 10. Specific examples thereof include a phenyl group and a naphthyl group.
The carbon number of the aralkyl group as R is not particularly limited, but is usually 7 to 20, preferably 7 to 11. Specific examples thereof include a benzyl group.

The alkyl group, cycloalkyl group, aryl group and aralkyl group as R may have a hydrogen atom 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, and 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, thereby resolving the mixture. It is possible to improve the properties and form a good pattern shape.

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 the basic compound having such an alkyl group include triethanolamine and N, N-dihydroxyethylaniline.

In addition, examples of the above-mentioned alkyl group having a hydrophilic group include an alkyl group having an oxygen atom, a sulfur atom or a carbonyl group in the alkyl chain. 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 the compounds exemplified in column 3 of US6040112 after the 60th line can be mentioned.

The above-mentioned alkyl group having a 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-mentioned alkyl group having a hydrophilic group may further have a substituent, and examples of such a 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 a nitrogen-containing heterocyclic structure This nitrogen-containing heterocycle may or may not have aromaticity. Further, it may have a plurality of nitrogen atoms. Further, it may contain a hetero atom other than the nitrogen atom. Specifically, for example, a compound having an imidazole structure (2-phenylbenzoimidazole, 2,4,5-triphenylimidazole, etc.), a compound having a piperidine structure [N-hydroxyethylpiperidine and bis (1,2,2) , 6,6-Pentamethyl-4-piperidyl) sebacate, etc.], compounds having a pyridine structure (4-dimethylaminopyridine, etc.), and compounds having an antipyrin structure (antipyrine, hydroxyantipyrine, etc.).

Further, a compound having two or more ring structures is also preferably used. Specific examples thereof include 1,5-diazabicyclo [4.3.0] nona-5-ene and 1,8-diazabicyclo [5.4.0] -undeca-7-ene.

(3) Amine Compound Having a Phenoxy Group The 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 asyloxy group and an aryloxy group. May have.

The 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 to 9, and more preferably 4 to 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. ], Examples of the compounds (C1-1) to (C3-3) are mentioned.

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. An amine compound having a phenoxy group can be obtained by adding it to the reaction solution and extracting it with an organic solvent such as ethyl acetate and chloroform. Further, the amine compound having a phenoxy group is prepared by heating a primary or secondary amine with a haloalkyl ether having a phenoxy group at the terminal 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 appropriately used.
Ammonium salt anions include, for example, halides, sulfonates, borates and phosphates. Of these, halide and sulfonate are preferred.

Chlorides, bromides and iodides are preferred as halides.

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 this 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 sulphonate include methane sulphonate, ethane sulphonate, butane sulphonate, hexane sulphonate, octane sulphonate, benzyl sulphonate, trifluoromethane sulphonate, pentafluoroethane sulphonate and nonafluorobutane sulphonate.

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 the substituent, for example, a linear or branched alkyl group having 1 to 6 carbon atoms and a cycloalkyl group having 3 to 6 carbon atoms are preferable. 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.

This ammonium salt may be hydroxyd or carboxylate. In this case, the ammonium salt is preferably 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, aminomorpholin and aminoalkylmorpholin. .. These may have additional substituents. Preferred substituents include, for example, an amino group, an aminoalkyl group, an alkylamino group, an aminoaryl group, an arylamino group, an alkyl group, an alkoxy group, an acyl group, an acyloxy group, an aryl group, an aryloxy group, a nitro group and a hydroxyl group. And a cyano group.

(5) A compound having a proton-accepting functional group and decomposing by irradiation with active light or radiation to generate a compound whose proton-accepting property is reduced or eliminated, or whose proton-accepting property is changed to acidic ( PA)
The composition according to the present invention has a proton-accepting functional group as a basic compound, and is decomposed by irradiation with active light or radiation to reduce, eliminate, or have proton-accepting properties. It may further contain a compound (hereinafter, also referred to as compound (PA)) that generates a compound that has changed to acidic.

The proton-accepting functional group is a functional group having a group or an electron that can electrostatically interact with a proton, and is, for example, a functional group having a macrocyclic structure such as a cyclic polyether, or π-conjugated. It means a functional group having a nitrogen atom having 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 shown in the following general formula.

Preferred partial structures of the proton acceptor functional group include, for example, crown ethers, azacrown ethers, 1-3-order amines, pyridines, imidazoles, and pyrazine structures.

The compound (PA) is decomposed by irradiation with active light or radiation to generate a compound whose proton acceptor property is reduced or eliminated, or whose proton acceptor property is changed to acidic. Here, the decrease or disappearance of the proton acceptor property, or the change from the proton acceptor property to the acidity is a change in the proton acceptor property due to the addition of a proton to the proton acceptor property functional group. Specifically, it means that when a proton adduct is formed from a compound (PA) having a proton-accepting functional group and a proton, the equilibrium constant in its chemical equilibrium decreases.

Proton acceptability 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) by irradiation with active light or radiation preferably satisfies pKa <-1, and 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) (Revised 4th Edition, 1993, edited by Japan Chemical Society, Maruzen Co., Ltd.). The lower this value is, the higher the acid strength is. Specifically, the acid dissociation constant pKa in an aqueous solution can be measured by measuring the acid dissociation constant at 25 ° C. using an infinitely diluted aqueous solution. In addition, the following software package 1 can be used to calculate Hammett's substituent constants and values based on a database of publicly known literature values. All of the pKa values described herein indicate values calculated using this software package.

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

The compound (PA) generates, for example, a compound represented by the following general formula (PA-1) as the proton adduct generated by decomposition by irradiation with active light or radiation. Since the compound represented by the general formula (PA-1) has an acidic group together with a proton-accepting functional group, the proton accepting property is lowered, eliminated, or the proton accepting property is higher than that of the compound (PA). It is a compound that has changed to acidic.

In the 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 independently represent −SO _2- or −CO −, respectively.
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 be combined with Ry to form a ring, or may be combined with R to form a ring.
R represents a monovalent organic group having a proton acceptor functional group.

Further, in the present invention, a compound (PA) other than the compound that generates the compound represented by the general formula (PA-1) can be appropriately selected. For example, an ionic compound having a proton acceptor site in the cation portion may be used. More specifically, a compound represented by the following general formula (7) can be mentioned.

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

(6) Ionic Compound The composition of the present invention can contain an ionic compound that has a relatively weak acidity with respect to the acid generator. The onium salt is preferable as the ionic compound. When the acid generated from the acid generator by irradiation with active light or radiation collides with an onium salt having an unreacted weak acid anion, the weak acid is released by salt exchange to produce an onium salt having a strong acid anion. In this process, the strong acid is exchanged for the weak acid having a lower catalytic ability, so that the acid is apparently inactivated and the acid diffusion can be controlled.

The onium salt, which has a relatively weak acidity with respect 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 the fluorine atom is not 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 represent a single bond or a divalent linking group. However, this does not apply when both Z ₁ and Z ₂ are −SO _2- .

The general formula (4) will be described below.
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.
X ₄ ⁺ cations, for example, sulfonium or iodonium cation. Preferred examples of the sulfonium cation or an iodonium cation represented as X ₄ ^+, can be cited illustrated sulfonium cation by formula (ZI).

Examples of the cyclic group of Rz ₄ include an aryl group and a cycloalkyl group. The cyclic group of Rz ₄ may be monocyclic or polycyclic. Substituents that the cyclic group of Rz ₄ may have include, for example, halogen atoms such as hydroxyl groups, alkyl groups, alkoxy groups and fluorine atoms, alkyl halide groups, carbonyl groups, ether bonds, ester bonds, and Examples include a nitro group.

The alkyl group of Rz ₄ preferably has, for example, 1 to 30 carbon atoms, and more preferably 3 to 10 carbon atoms. Substituents that the alkyl group of Rz ₄ may have include, for example, halogen atoms such as hydroxyl groups, alkyl groups and fluorine atoms, alkyl halide groups, carbonyl groups, ether bonds, ester bonds, nitro groups and the like. Can be mentioned.

Examples of the alkenyl group of Rz ₄ include an alkenyl group having 2 to 10 carbon atoms, which may be linear or branched. The alkenyl group of 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. Substituents that the alkenyl group of Rz ₄ may have include, for example, halogen atoms such as hydroxyl groups, alkyl groups and fluorine atoms, alkyl halide groups, carbonyl groups, ether bonds, ester bonds, nitro groups and the like. Can be mentioned.

As a preferable example of the anion portion of the compound represented by the general formula (4), the structure exemplified in paragraph [0198] of JP2012-242799A can be mentioned.

Specific examples of the anion portion of the compound represented by the general formula (4) are shown below, but the present invention is not limited thereto.

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 the fluorine atom is not bonded to the carbon atom adjacent to the S atom.

X ₅ ⁺ cations, for example, sulfonium or iodonium cation. Preferred examples of the sulfonium cation or an iodonium cation represented as X ₅ ^+, can be mentioned exemplified iodonium cations exemplified sulfonium cation and the general formula in formula (ZI) (ZII).

Examples of the cyclic group of Rz ₅ include an aryl group and a cycloalkyl group. The cyclic group of Rz ₅ may be monocyclic or polycyclic. Substituents that the cyclic group of Rz ₅ may have include, for example, halogen atoms such as hydroxyl groups, alkyl groups and fluorine atoms, alkyl halide groups, carbonyl groups, ether bonds, ester bonds, nitro groups and the like. Can be mentioned.

The alkyl group of Rz ₅ preferably has, for example, 1 to 30 carbon atoms, and more preferably 3 to 10 carbon atoms. Substituents that the alkyl group of Rz ₅ may have include, for example, halogen atoms such as hydroxyl groups, alkyl groups and fluorine atoms, alkyl halide groups, carbonyl groups, ether bonds, ester bonds, nitro groups and the like. Can be mentioned.

Examples of the alkenyl group of Rz ₅ include an alkenyl group having 2 to 10 carbon atoms, which may be linear or branched. The alkenyl group of 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. Substituents that the alkenyl group of Rz ₅ may have include, for example, halogen atoms such as hydroxyl groups, alkyl groups and fluorine atoms, alkyl halide groups, carbonyl groups, ether bonds, ester bonds, nitro groups and the like. Can be mentioned.

As a preferable example of the anion portion of the compound represented by the general formula (5), the structure exemplified in paragraph [0201] of JP2012-242799A can be mentioned.

Specific examples of the anion portion of the compound represented by the general formula (5) are shown below, but the present invention is not limited thereto.

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 represent a single bond or a divalent linking group. However, this does not apply when both Z ₁ and Z ₂ are −SO _2- .

Preferred examples of the sulfonium cation or an iodonium cation represented as X ₆ ^+, can be mentioned exemplified iodonium cations exemplified sulfonium cation and the general formula in formula (ZI) (ZII).

Cyclic groups of Rz _6a and Rz _6b include, for example, aryl groups and cycloalkyl groups. 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 It is more preferably 3 to 10.

Examples of the alkenyl groups of Rz _6a and Rz _6b include alkenyl groups having 2 to 10 carbon atoms, which may be linear or branched. The alkenyl group of 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.

Substituents that the cyclic group, alkyl group and alkenyl group of Rz _6a and Rz _6b may each have are, for example, halogen atoms such as hydroxyl groups, alkyl groups and fluorine atoms, alkyl halide groups, carbonyl groups and ethers. Examples thereof include a bond, an ester bond, and a nitro group.

The divalent linking groups of Z ₁ and Z ₂ include, for example, a divalent hydrocarbon group (aliphatic hydrocarbon group, aromatic hydrocarbon group) which may have a substituent and a hetero atom. Examples include divalent linking groups. Examples of the substituent include a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms substituted with a fluorine atom, a carbonyl group and the like. 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 more preferably a linear or branched alkylene group, and even more preferably a methylene group or an ethylene group.

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

Specific examples of the anion portion of the compound represented by the general formula (6) are shown below, but the present invention is not limited thereto.

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

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

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

In the general formulas (C-1) to (C-3),
R ₁ , R ₂ , and R ₃ represent substituents having 1 or more carbon atoms.
L ₁ represents a divalent linking group or a single bond that links the cation moiety and the anion moiety.
-X ^{- _{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 linking site with the adjacent N atom. Represents a monovalent substituent having.
R ₁ , R ₂ , R ₃ , R ₄ , and L ₁ may be combined with each other to form a ring structure. Further, in (C-3), two of R _{1 to} R ₃ may be combined to form a double bond with an N atom.

Substituents 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. Preferred are alkyl groups, cycloalkyl groups, and aryl groups.

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

Preferred examples of the compound represented by the general formula (C-1) are paragraphs [0037] to [0039] of JP2013-6827A and paragraphs [0027] to [0029] of JP2013-8020A. ], Examples of the compounds can be mentioned.

Preferred 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 JP2012-252124A.

(7) Low-molecular-weight compound having a nitrogen atom and having a group desorbed by the action of an acid The composition of the present invention is a low-molecular-weight compound having a nitrogen atom and having a group desorbed by the action of an acid (hereinafter, It may also contain (also referred to as "compound (C)").
The group desorbed by the action of an acid is not particularly limited, but an acetal group, a carbonate group, a carbamate group, a tertiary ester group, a tertiary hydroxyl group and a hemiaminol ether group are preferable, and a carbamate group and a hemiaminol ether group are used. It is particularly preferable to have.
The molecular weight of compound (C) is preferably 100 to 1000, more preferably 100 to 700, and particularly preferably 100 to 500.
As the compound (C), an amine derivative having a group eliminated by the action of an acid on a 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 the general formula (d-1)
Rb is independently 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), and an aralkyl group (preferably 3 to 30 carbon atoms). It preferably represents 1 to 10 carbon atoms) or an alkoxyalkyl group (preferably 1 to 10 carbon atoms). Rb may be connected to each other to form a ring.
The alkyl group, cycloalkyl group, aryl group and aralkyl group represented by Rb are substituted with functional groups such as hydroxyl group, cyano group, amino group, pyrrolidino group, piperidino group, morpholino group and oxo group, alkoxy group and halogen atom. You may be. The same applies to the alkoxyalkyl group indicated by Rb.
The alkyl group, cycloalkyl group, aryl group, and aralkyl group of Rb (these alkyl group, cycloalkyl group, aryl group, and aralkyl group may be substituted with the functional group, alkoxy group, halogen atom. ) Examples include groups derived from linear and branched alkanes such as methane, ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, undecane, and dodecane, and derived from these alcans. A group in which the group is substituted with one or more or one or more cycloalkyl groups such as a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclobutane, a cyclopentane, a cyclohexane, a cycloheptane, a cyclooctane, a norbornan, an adamantan, a noradamantan. Groups derived from cycloalkanes such as, and groups derived from these cycloalcans, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, 2-methylpropyl group, 1- A group substituted with one or more or one or more linear or branched alkyl groups such as a methylpropyl group and a t-butyl group, a group derived from an aromatic compound such as benzene, naphthalene and anthracene, and fragrances thereof. Groups derived from group compounds are, for example, direct groups such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group and the like. Group substituted with one or more or one or more chain or branched alkyl groups, heterocycles such as pyrrolidine, piperidine, morpholin, tetrahydrofuran, tetrahydropyran, indol, indolin, quinoline, perhydroquinolin, indazole, benzimidazole and the like. Groups derived from compounds, groups in which groups derived from these heterocyclic compounds are substituted with one or more or one or more linear or branched alkyl groups or groups derived from aromatic compounds, linear, linear, A group obtained by substituting one or more or one or more groups derived from an aromatic compound such as a phenyl group, a naphthyl group, an anthracenyl group, or the like or the above-mentioned substitution of a group derived from a branched alkane or a group derived from a cycloalcan. Examples thereof include a group in which the group 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 or an oxo group.
The 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 the two Rbs to each other include an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic hydrocarbon group or a derivative thereof.
Specific structures of the group represented by the general formula (d-1) include, but are limited to, the structures disclosed in paragraph [0466] of U.S. Patent Application Publication 2012/0135348. 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, the two Ras may be the same or different, and the two Ras may be interconnected to form a heterocycle with the nitrogen atom in the equation. The heterocycle may contain a heteroatom other than the nitrogen atom in the formula.
Rb has the same meaning as Rb in the above general formula (d-1), and the same applies to preferred examples.
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 alkyl group, cycloalkyl group, aryl group, and aralkyl group of Ra (these alkyl group, cycloalkyl group, aryl group, and aralkyl group may be substituted with the above group) include. Examples of Rb include the same groups as the specific examples described above.
The heterocycle formed by linking the Ra to each other preferably has 20 or less carbon atoms, and is, for example, pyrrolidine, piperidine, morpholin, 1,4,5,6-tetrahydropyrimidine, 1,2,3. , 4-Tetrahydroquinoline, 1,2,3,6-tetrahydropyridine, Homopiperazin, 4-azabenzimidazole, benzotriazole, 5-azabenzotriazole, 1H-1,2,3-triazole, 1,4,7 -Triazacyclononane, tetrazole, 7-azaindole, indazole, benzimidazole, imidazole [1,2-a] pyridine, (1S, 4S)-(+)-2,5-diazabicyclo [2.2.1] Heptane, 1,5,7-Triazabicyclo [4.4.0] Deck-5-ene, Indol, Indolin, 1,2,3,4-Tetrahydroquinoxalin, Perhydroquinolin, 1,5,9-Tria Groups derived from heterocyclic compounds such as the cyclododecane, groups derived from these heterocyclic compounds derived from linear and branched alkanes, groups derived from cycloalcans, aromatic compounds Groups, groups derived from heterocyclic compounds, hydroxyl groups, cyano groups, amino groups, pyrrolidino groups, piperidino groups, morpholino groups, oxo groups and other functional groups substituted with one or more or one or more functional groups. Be done.

Specific examples of the particularly preferable compound (C) in the present invention include, but are not limited to, the compound disclosed in paragraph [0475] of US Patent Application Publication 2012/0135348.
The compound represented by the general formula (6) can be synthesized based on JP-A-2007-298569, JP-A-2009-199021 and the like.
In the present invention, the compound (C) can be used alone or in combination of two or more.
When the sensitive light-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 more preferably 0.001 to 10% by mass, and even more preferably 0.01 to 5% by mass.

In addition, as the acid diffusion control agent (C) that can be used in the composition according to the present invention, the compound synthesized in the examples of JP-A-2002-363146 and paragraph 0108 of JP-A-2007-298569 Examples of the compounds described in.

A photosensitive basic compound may be used as the acid diffusion control agent (C). Examples of the photosensitive basic compound include JP-A-2003-524799 and J. Mol. Photopolym. Sci & Tech. Vol. 8, P. The compounds described in 543-553 (1995) and the like can be used.

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

One of these acid diffusion control agents (C) may be used alone, or two or more of them may be used in combination.

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

The molar ratio of the acid diffusion control agent (C) to the acid generator (B) is preferably 0.01 to 10, more preferably 0.05 to 5, and even more preferably 0.1 to 3. Excessively increasing this molar ratio may reduce sensitivity and / or resolution. Excessively reducing this molar ratio can result in pattern thinning between exposure and heating (post-baking).

<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, but unlike a surfactant, it does not necessarily have to have a hydrophilic group in the molecule, and polar / non-polar substances are uniformly mixed. It does not have to contribute to doing so.
The effects of adding the hydrophobic resin include control of the static / dynamic contact angle of the resist film surface with water, improvement of immersion liquid followability, suppression of outgas, and the like.

Hydrophobic resin (D), from the viewpoint of uneven distribution in the film surface layer, "fluorine atom", "silicon atom", and, any one of "CH ₃ partial structure contained in the side chain portion of the resin" It is preferable to have the above, and it is more preferable to have two or more kinds.
When the hydrophobic resin (D) contains a fluorine atom and / or a silicon atom, the fluorine atom and / or the silicon atom in the hydrophobic resin (D) may be contained in the main chain of the resin, and the side chain may be contained. 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. It is preferable to have.
The alkyl group having a fluorine atom (preferably 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.
The cycloalkyl group having a fluorine atom and the 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 have a substituent other than the fluorine atom. You may have.

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

In the general formulas (F2) to (F4),
R _{57 to} R ₆₈ each independently represent a hydrogen atom, a fluorine atom or an alkyl group (linear or branched). However, 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 being a fluorine atom. It represents a substituted alkyl group (preferably 1 to 4 carbon atoms).
It is preferable that all of R _{57 to} R ₆₁ and R _{65 to} R ₆₇ are fluorine atoms. R ₆₂ , R ₆₃ and R ₆₈ are preferably an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom (preferably having 1 to 4 carbon atoms), and preferably a perfluoroalkyl group having 1 to 4 carbon atoms. More preferred. R ₆₂ and R ₆₃ may be connected to each other to form a ring.

The hydrophobic resin (D) may contain silicon atoms. As the partial structure having a silicon atom, a resin having an alkylsilyl structure (preferably a trialkylsilyl group) or a cyclic siloxane structure is preferable.
Examples of repeating units 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 It includes.
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 a repeating unit having a methacrylic acid structure) is on the surface of the hydrophobic resin (D) due to the influence of the main chain. for contribution to uneven distribution is small, and shall not be included in the CH ₃ partial structures 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, for example, a repeating unit represented by the following general formula (M). When R _{11 to} R ₁₄ are CH ₃ “itself”, the CH ₃ is not included in the CH ₃ partial structure of the side chain portion 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 to have "one" CH ₃ partial structure in the present invention.

In the above general formula (M),
R _{11 to} R ₁₄ each independently represent a side chain portion.
Examples of R _{11 to} R ₁₄ of the side chain portion include a hydrogen atom and a monovalent organic group.
The monovalent organic groups 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. Examples thereof include a 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- part structure in the side chain portion, and as such a repeating unit, a repeating unit represented by the following general formula (II) and a repeating unit. , It is more preferable to have at least one repeating unit (x) among the repeating units represented by the following general formula (III).

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

In the above general formula (II), X _b1 represents a hydrogen atom, an alkyl group, a cyano group or a halogen atom, and R ₂ represents an organic group stable to an acid having one or more CH ₃ partial structures. Here, the organic group stable to an acid is, more specifically, an organic group having no acid-degradable group (a group that decomposes by the action of an acid to generate a polar group such as a carboxy group). Is preferable.

The alkyl group of X _b1 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, but a methyl group is preferable.
X _b1 is preferably a hydrogen atom or a methyl group.
The R _2, has one or more CH ₃ moiety, alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, aryl group, and, aralkyl groups. The cycloalkyl group, alkenyl group, cycloalkenyl group, aryl group, and aralkyl group described above may further have an alkyl group as a substituent.
R ₂ has one or more CH ₃ moiety, the alkyl group or alkyl-substituted cycloalkyl groups are preferred.
Acid stable organic group having one or more CH ₃ partial structure as R ₂ preferably has a CH ₃ partial structure more than 10 or less, and more preferably has 8 or less 2 or more.
Preferred specific examples of the repeating unit represented by the general formula (II) are given below. The present invention is not limited to this.

The repeating unit represented by the general formula (II) is preferably an acid-stable (non-acidic) repeating unit, and specifically, a group that is decomposed by the action of an acid to generate a polar group. It is preferably a repeating unit that does not have.
Hereinafter, the repeating unit represented by the general formula (III) will be described in detail.

In the above general formula (III), X _b2 represents a hydrogen atom, an alkyl group, a cyano group or a halogen atom, and R ₃ represents an acid-stable organic group having one or more CH ₃ partial structures. n represents an integer from 1 to 5.
The alkyl group of X _b2 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, but a hydrogen atom is preferable.
X _b2 is preferably a hydrogen atom.
Since R ₃ is an organic group stable to an acid, more specifically, it is preferably an organic group having no acid-degradable group.

Examples of R ₃ include alkyl groups 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, and more preferably 1 or more and 8 or less. It is more preferable to have 1 or more and 4 or less.
n represents an integer from 1 to 5, more preferably an integer from 1 to 3, and even more preferably 1 or 2.

A preferable specific example of the repeating unit represented by the general formula (III) is given below. The present invention is not limited to this.

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

When the hydrophobic resin (D) contains a CH _3- part structure in the side chain portion, and further does not have a fluorine atom and a silicon atom, the repeating unit represented by the general formula (II) and the repeating unit 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 with respect to all the repeating units of the hydrophobic resin (D). More preferably, it is 95 mol% or more. The content is usually 100 mol% or less with respect to all the repeating units of the hydrophobic resin (D).

The hydrophobic resin (D) uses at least one of the repeating unit represented by the general formula (II) and the repeating unit represented by the general formula (III) (x) as the hydrophobic resin (D). The surface free energy of the hydrophobic resin (D) is increased by containing 90 mol% or more with respect to all the repeating units of). As a result, the hydrophobic resin (D) is less likely to be unevenly distributed on the surface of the resist membrane, the static / dynamic contact angle of the resist membrane with respect to water is surely improved, and the immersion liquid followability is improved. it can.

Further, the hydrophobic resin (D) contains the following (x) to (z) regardless of whether the hydrophobic resin (D) contains (i) a fluorine atom and / or a silicon atom, or (ii) contains a CH _3- part structure in the side chain portion. ) May have at least one group selected from the group.
(X) Acid group,
(Y) A group that decomposes due to the action of an alkaline developer and increases its solubility in an alkaline developer (hereinafter, also referred to as a polarity converting group).
(Z) Group decomposed by the action of 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 sulfonyl group, a sulfonylimide group, a (alkylsulfonyl) (alkylcarbonyl) methylene group, and (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) Examples include a methylene group.
Preferred acid groups include fluorinated alcohol groups (preferably hexafluoroisopropanol), sulfonimide groups, and bis (alkylcarbonyl) methylene groups.

The repeating unit having an acid group (x) is a repeating unit in which an acid group is directly bonded to the main chain of a resin such as a repeating unit made of acrylic acid or methacrylic acid, or a repeating unit of a resin via a linking group. A repeating unit in which an acid group is bonded to the main chain can be mentioned, and a polymerization initiator or a chain transfer agent having an acid group can be used at the time of polymerization to be introduced into the end of the polymer chain. In either case. preferable. The repeating unit having an acid group (x) may have at least one of a fluorine atom and a silicon atom.
The content of the repeating unit having an acid group (x) is preferably 1 to 50 mol%, more preferably 3 to 35 mol%, still more preferably 5 to 5 mol% with respect to all the repeating units in the hydrophobic resin (D). It is 20 mol%.
Specific examples of the repeating unit having an acid group (x) are shown below, but the present invention is not limited thereto. In the formula, Rx represents a hydrogen atom, CH ₃ , CF ₃ , or CH ₂ OH.

As the group (y) which is decomposed by the action of the alkaline developing solution and whose solubility in the alkaline developing solution is increased, a group having a lactone structure, an acid anhydride group, or an acidimide group is preferable, and a group having a lactone structure is particularly preferable. ..
The repeating unit containing these groups is a repeating unit in which this group is directly bonded to the main chain of the resin, for example, a repeating unit made of an acrylic acid ester and a methacrylic acid ester. Alternatively, the repeating unit may be a repeating unit in which the group is bonded to the main chain of the resin via a linking group. Alternatively, the repeating unit may be introduced into the end of the resin by using a polymerization initiator or chain transfer agent having this group at the time of polymerization.
Examples of the repeating unit having a group having a lactone structure include the same repeating units having a lactone structure described above in the section of resin (A).

The content of the repeating unit having a group (y) that decomposes by the action of the alkaline developer and increases the solubility in the alkaline developer is 1 to 100 mol% based on all the repeating units in the hydrophobic resin (D). It is preferably 3 to 98 mol%, more preferably 5 to 95 mol%.

The repeating unit having a group (z) that decomposes by the action of an acid in the hydrophobic resin (D) is the same as the repeating unit having an acid-degradable group mentioned in the resin (A). The repeating unit having a group (z) decomposed by the action of an acid may have at least one of a fluorine atom and a silicon atom. The content of the repeating unit having a group (z) decomposed by the action of an acid in the hydrophobic resin (D) is preferably 1 to 80 mol%, more preferably 1 to 80 mol%, based on all the repeating units in the resin (D). It is 10 to 80 mol%, more preferably 20 to 60 mol%.
The hydrophobic resin (D) may further have a repeating unit different from the repeating unit described above.

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

On the other hand, especially if the hydrophobic resin (D) comprises a CH ₃ partial structure side chain moiety, a hydrophobic resin (D) is a form that does not contain a fluorine atom and a silicon atom substantially also preferred. Further, it is preferable that the hydrophobic resin (D) is substantially composed of only repeating units composed of only atoms selected from carbon atoms, oxygen atoms, hydrogen atoms, nitrogen atoms and sulfur atoms.

The weight average molecular weight of the hydrophobic resin (D) in terms of standard polystyrene is preferably 1,000 to 100,000, more preferably 1,000 to 50,000.
Further, the hydrophobic resin (D) may be used alone or in combination of two or more.
The content of the hydrophobic resin (D) in the composition is preferably 0.01 to 10% by mass, more preferably 0.05 to 8% by mass, based on the total solid content in the composition of the present invention.

The hydrophobic resin (D) preferably contains 0.01 to 5% by mass of residual monomers and oligomer components, 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, and more preferably in the range of 1 to 3.

As the hydrophobic resin (D), various commercially available products can be used, or 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.
As the solvent, an organic solvent is typically used. As the organic solvent, for example, alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, lactate alkyl ester, alkyl alkoxypropionate, cyclic lactone (preferably having 4 to 10 carbon atoms), and a ring may be contained. Examples include good monoketone compounds (preferably 4-10 carbon atoms), alkylene carbonates, alkyl alkoxyacetates, and alkyl pyruvates.

Examples of the alkylene glycol monoalkyl ether carboxylate include propylene glycol monomethyl ether acetate (PGMEA; also known as 1-methoxy-2-acetoxypropane), propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate. , 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 are preferable.

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, and ethylene. Glycol monomethyl ether and ethylene glycol monoethyl ether can be mentioned.

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. Examples include iclactone and α-hydroxy-γ-butyrolactone.

Examples of the monoketone compound that may contain a ring include 2-butanone, 3-methylbutanone, pinacol, 2-pentanone, 3-pentanone, 3-methyl-2-pentanone, 4-methyl-2-pentanone, and the like. 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-Nanonone, 5-Nanonanone, 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, Included are 2,2-dimethylcyclohexanone, 2,6-dimethylcyclohexanone, 2,2,6-trimethylcyclohexanone, cycloheptanone, 2-methylcycloheptanone and 3-methylcycloheptanone.

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

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

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 can be mentioned.

One type of these solvents may be used alone, or two or more types may be mixed and used. 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 preferable.

Examples of the hydroxyl group-free solvent include PGMEA, ethylethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, perfluorobutyltetrahydrofuran, butyl acetate, N-methylpyrrolidone, N, N-dimethylacetamide, and dimethyl. Sulfoxide and the like can be mentioned, and among these, propylene glycol monomethyl ether acetate, ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, perfluorobutyl tetrahydrofuran and butyl acetate are preferably mentioned. Of these, PGMEA, ethylethoxypropionate and 2-heptanone are more preferred.

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

In addition, when a mixed solvent containing 50% by mass or more of a solvent containing no hydroxyl group is used, particularly excellent coating uniformity can be achieved. Further, 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 in general, the total solid content concentration of the composition is 0.5 to 30% by mass, preferably 0.5 to 30% by mass. It is adjusted to be 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. When a surfactant is contained, any one of fluorine-based and / or silicon-based surfactants (fluorine-based surfactant, silicon-based surfactant, surfactant having both fluorine atom and silicon atom), or 2 It preferably contains more than a seed.

By containing the above-mentioned surfactant in the composition of the present invention, it is possible to provide a resist pattern with good sensitivity and resolution, adhesion and few development defects 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 the surfactants described in [0276] of US Patent Application Publication No. 2008/0248425, for example, Ftop EF301, EF303, (Shin-Akita Kasei Co., Ltd.). ), Florard FC430, 431, 4430 (manufactured by Sumitomo 3M Co., Ltd.), Megafuck F171, F173, F176, F189, F113, F110, F177, F120, R08 (manufactured by Dainippon Ink and Chemicals Co., Ltd.), Surfron S-382, SC101, 102, 103, 104, 105, 106 (manufactured by Asahi Glass Co., Ltd.), Troysol S-366 (manufactured by Troy Chemical Co., Ltd.), GF-300, GF-150 (Toa Synthetic Chemical Co., Ltd.) ), Surfron S-393 (manufactured by Seimi Chemical Co., Ltd.), Ftop EF121, EF122A, EF122B, RF122C, EF125M, EF135M, EF351, EF352, EF801, EF802, EF601 (manufactured by Gemco Co., Ltd.), PF636, PF656, PF6320, PF6520 (manufactured by OMNOVA), FTX-204G, 208G, 218G, 230G, 204D, 208D, 212D, 218D, 222D (manufactured by Neos Co., Ltd.) and the like. Further, the 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 as shown above, the surfactant is derived from a fluoroaliphatic compound produced by a telomerization method (also called a telomer method) or an oligomerization method (also called an oligomer method). A surfactant using a polymer having a obtained fluoroaliphatic group can be used. The fluoroaliphatic compound can be synthesized by the method described in JP-A-2002-090991.

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

For example, as commercially available surfactants, Megafuck F178, F-470, F-473, F-475, F-476, F-472 (manufactured by Dainippon Ink and Chemicals Co., Ltd.), C ₆ F ₁₃ units are used. acrylates having (or methacrylate) and (poly (oxyalkylene)) acrylate (or methacrylate), and acrylate having a C ₃ F ₇ group (or methacrylate) (poly (oxyethylene)) acrylate (or methacrylate) And (poly (oxypropylene)) acrylate (or methacrylate) copolymers and the like can be mentioned.

Further, in the present invention, surfactants other than the 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 combination of several.
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 cheilitis or radiation-sensitive resin composition. %, More preferably 0 to 1% by mass.

<Carboxylic acid onium salt>
The composition of the present invention may contain an onium carboxylic acid salt. As the onium carboxylic acid salt, an iodonium salt and a sulfonium salt are preferable. As the anion portion, 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 fluorinated is preferable. An oxygen atom may be contained in the alkyl chain. As a result, transparency to light of 220 nm or less is ensured, sensitivity and resolution are improved, and sparse and dense dependence and exposure margin are improved.

Fluorosubstituted 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 onium carboxylic acid salt in the composition is generally 0.1 to 20% by mass, preferably 0.5 to 10% by mass, and more preferably 1 to 7 with respect to the total solid content of the composition. It is mass%.
The onium carboxylic acid salt may be used alone or in combination of two or more.

<Dissolution-inhibiting compound with a molecular weight of 3000 or less, which decomposes due to the action of acid and increases its 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"), which is decomposed by the action of an acid to increase the solubility in an alkaline developer. .. The dissolution-inhibiting compound contains an acid-degradable group such as a coleic acid derivative containing an acid-degradable group described in Proceeding of SPIE, 2724,355 (1996) so as not to reduce the permeability of 220 nm or less. Alicyclic or aliphatic compounds are preferred. Examples of the acid-decomposable group and the alicyclic structure include those similar to 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 replaced with an acid-decomposing group. preferable. As the phenol compound, those containing 1 to 9 phenol skeletons are preferable, and those containing 2 to 6 phenol skeletons are more preferable.

The amount of the dissolution-inhibiting compound added is preferably 3 to 50% by mass, more preferably 5 to 40% by mass, based on the total solid content of the actinic cheilitis or radiation-sensitive resin composition.
The dissolution-inhibiting compound may be used alone or in combination of two or more.
Specific examples of the dissolution-inhibiting compound are shown below, but the present invention is not limited thereto.

<Other additives>
If necessary, the composition of the present invention further contains a dye, a plasticizer, a photosensitizer, a light absorber, and a compound that promotes solubility in a developing solution (for example, a phenol compound having a molecular weight of 1000 or less, a carboxy group). It can contain an alicyclic compound or an aliphatic compound).

Such phenolic compounds having a molecular weight of 1000 or less are described, for example, in JP-A-4-122938, JP-A-2-28531, US Pat. No. 4,916,210, and European Patent No. 2192994. It can be easily synthesized by a person skilled in the art with reference to the method described in the above.

Specific examples of the alicyclic group having a carboxy group or the aliphatic compound include carboxylic acid derivatives having a steroid structure such as cholic acid, deoxycholic acid and lithocholic acid, adamantanecarboxylic acid derivatives, adamantanedicarboxylic acids, cyclohexanecarboxylic acids, and , Cyclohexanedicarboxylic acid and the like, but are not limited thereto.

[Pattern formation method]
The pattern forming method of the present invention is carried out using the above-mentioned sensitive light-sensitive or radiation-sensitive resin composition.
Specifically, the pattern forming method of the present invention is a step of adhering the above-mentioned actinic cheilitis or radiation-sensitive resin composition onto a substrate to form a resin film (hereinafter, "step (1)" or "step (1)"). (Also referred to as “coating step”), a step of irradiating the resin film with active light or radiation (hereinafter, also referred to as “step (2)” or “exposure step”), and active light or using a developing solution. It has a step of developing the resin film irradiated with radiation (hereinafter, also referred to as “step (3)” or “exposure step”).
Each step will be described in detail below.

<Step (1): Coating step>
The procedure of step (1) is not particularly limited, but a method of applying the composition of the present invention on a substrate (coating method) and performing a curing treatment as necessary, and forming a resin film on a temporary support. Then, a method of transferring the resin film onto the substrate can be mentioned. Of these, the coating method is preferable because it is excellent in 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 ICs, liquid crystals, thermal heads and the like. Substrates commonly used in the circuit board manufacturing process and other photolithography 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, for example, a two-layer resist process as disclosed in Japanese Patent Application Laid-Open No. 2008-083384, and exposure and exposure as disclosed in International Publication No. 2011/122336 pamphlet. It may be combined with a process that has multiple developments. When the present invention is combined with the process disclosed in International Publication No. 2011/122336, the pattern forming method of the present invention is used as the second negative pattern forming method in claim 1 of International Publication No. 2011/122336. 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, preferably 1 to 500 nm, for the reason that a finer pattern with higher accuracy can be formed. It is more preferably 100 nm. By setting the solid content concentration in the composition to an appropriate range to give an appropriate viscosity and improving the coatability or the film-forming property, it becomes easy to obtain such a film thickness.

<Step (2): Exposure step>
The step (2) is an exposure step of irradiating the resin film formed in the step (1) with active light 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, polar ultraviolet light, X-rays, and electron beams. Far-ultraviolet light having a wavelength of 250 nm or less, more preferably 220 nm or less, still more preferably 1 to 200 nm can be mentioned.

More specifically, the light used for exposure includes KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ₂ excimer laser (157 nm), X-ray, EUV (13 nm), electron beam and the like. Among them, KrF excimer laser, ArF excimer laser, EUV or electron beam is preferable, and ArF excimer laser is more preferable.

Immersion exposure processing can be applied in the exposure step. 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 treatment can be performed, for example, according to the method described in paragraphs [0594] to [0601] of JP2013-242397A.

If the receding contact angle of the resin film formed by using the composition of the present invention is too small, it cannot be suitably used when exposed through an immersion medium, and water residue (watermark) defects. It may not be possible to fully exert the effect of reduction.
In order to realize a preferable receding contact angle, it is preferable to include the above-mentioned hydrophobic resin (D) in the composition. Alternatively, an immersion liquid poorly soluble film (hereinafter, also referred to as “top coat”) formed of the above-mentioned 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 required for the top coat are proper application to the upper part of the resin film and poor immersion liquid solubility. It is preferable that the top coat is not mixed with the resin film and can be uniformly applied to the upper part of the resin film.

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

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

The solvent that can be used is not particularly limited as long as the compound described later is not dissolved and the resist film is not dissolved. For example, an alcohol solvent, an ether solvent, an ester solvent, a fluorine solvent, a hydrocarbon solvent, etc. Is preferably mentioned, and it is more preferable to use a non-fluorine-based alcohol solvent. As a result, the insolubility in the resist film is further improved, and when the top coat composition is applied onto the resist film, the top coat can be formed more uniformly without dissolving the resist film. The viscosity of the solvent is preferably 5 cP (centipores) or less, more preferably 3 cP or less, further preferably 2 cP or less, and particularly preferably 1 cP or less. From centipores to pascal seconds, it can be converted by the following formula.
1000cP = 1Pa · s

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

The topcoat composition preferably further contains at least one compound selected from the group consisting of the following (A1) to (A3).
(A1) Acid diffusion control agent (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 control agent)
The topcoat composition preferably further contains an acid diffusion control agent. The acid diffusion control agent that can be contained in the topcoat composition is the same as that listed as the acid diffusion control agent that can be contained in the actinic light-sensitive or radiation-sensitive resin composition.

(Content of acid diffusion control agent)
The content of the acid diffusion control agent in the topcoat 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 topcoat composition. % Is more preferable.

((A2) A compound containing a bond or group 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)
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 the interaction with the acid diffused from the sensitive photosensitive or radiation-sensitive membrane.

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

The molecular weight of the compound (A2) is preferably 3000 or less, more preferably 2500 or less, further 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 further preferably 10 or more.
The number of carbon atoms contained in the compound (A2) is preferably 30 or less, more preferably 20 or less, and even more 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.

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

During the ceremony
R ₁₁ represents an alkylene group which may have a substituent and represents
n represents an integer of 2 or more
* Represents a bond.

The carbon number 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 preferably 2 or 3. More preferably, it is particularly preferably 2. When this alkylene group has a substituent, the substituent is not particularly limited, but is preferably an alkyl group (preferably 1 to 10 carbon atoms).
n is preferably an integer of 2 to 20, and more preferably 10 or less because of the larger DOF.
The average value of n is preferably 20 or less, more preferably 2 to 10, further preferably 2 to 8, and particularly preferably 4 to 6 because the DOF becomes larger. preferable. Here, the "average value of n" means a value of n determined by measuring the weight average molecular weight of the compound (A2) by GPC and making the obtained weight average molecular weight consistent with the general formula. If n is not an integer, it shall be rounded off.
The plurality of R _11s may be the same or different.

Further, the compound having a partial structure represented by the general formula (1) is preferably a compound represented by the following general formula (1-1) because the DOF becomes larger.

During the ceremony
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 represent a hydrogen atom or an alkyl group. The number of carbon atoms of the alkyl group is not particularly limited, but is preferably 1 to 15. R ₁₂ and R ₁₃ may be combined 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 more preferably 10 or less because of the larger DOF.
The average value of m is preferably 20 or less, more preferably 1 to 10, further 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 above-mentioned "average value of n".
When m is 2 or more, a plurality of R _11s may be the same or different.

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

The compound (A2) may be a commercially available product or may be synthesized by a known method.

Specific examples of the compound (A2) will be given below, but the present invention is not limited thereto.

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

((A3) Compound having radical trap group)
(A3) A compound having a radical trap group is also referred to as a compound (A3).
A radical trap group is a group that captures active radicals and terminates the radical reaction. Examples of such a radical trap group include a group that reacts with an active radical and is converted into a stable free radical, and a group having a stable free radical.
Examples of the compound having such a radical trap group include hydroquinone, catechol, benzoquinone, nitroxyl radical compound, aromatic nitro compound, N-nitroso compound, benzothiazole, dimethylaniline, phenothiazine, vinylpyrene, and derivatives thereof. And so on.
Further, as the non-basic radical trap group, specifically, at least selected from the group consisting of, for example, a hindered phenol group, a hydroquinone group, an N-oxyl-free radical group, a nitroso group, and a nitrone group. One type of group is preferably mentioned.

The number of radical trap groups contained in the compound (A3) is not particularly limited, but when the compound (A3) is a compound other than a polymer compound, the number of radical trap groups is preferably 1 to 10 in one molecule, and 1 to 1 5 is more preferable, and 1 to 3 is even 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 preferably has 1 to 3 radical trap groups. Is more preferable. 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%, 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 of the following general formulas (1) to (3) is more preferable.

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

In the general formulas (1) to (3), R _{1 to} R ₆ independently represent an alkyl group, a cycloalkyl group, or an aryl group, respectively. In the formula (1), R ₁ and R ₂ may be combined to form a ring, and in the formula (3), at least two of R _{4 to} R ₆ may be combined to form a ring.
An alkyl group represented by R _{1 to} R ₆ , a cycloalkyl group, a ring which may be formed by bonding an aryl group, R ₁ and R _2, and at least two of R _{4 to} R ₆ are bonded. The ring that 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 and the like, among which methyl group , Ethyl group, n-butyl group, t-butyl group are preferable.

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. Preferred examples include a group, a cyclooctyl group, a norbornyl group, an adamantyl group and the like.

Examples of the aryl group represented by R _{1 to} R ₆ include an aryl group having 6 to 14 carbon atoms, and specific examples thereof preferably include a phenyl group, a tolyl group, a naphthyl group and the like.

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

An alkyl group represented by R _{1 to} R ₆ , a cycloalkyl group, a ring which may be formed by bonding an aryl group, R ₁ and R _2, and at least two of R _{4 to} R ₆ are bonded. Examples of the substituent that the ring that may be formed may have include 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. , Alkoxyalkyl group, alkoxycarbonyl group, alkoxycarbonyloxy group, acylamide group (RCONH-: R is a substituted or unsubstituted alkyl group or phenyl group), -SO ₂ Na, -P (= O) (OC ₂ H) ₅ ) _2nd grade can be mentioned.
Further, examples of the cycloalkyl group represented by R _{1 to} R ₆ and the substituent which the aryl group may have include an alkyl group.

The compound represented by any of the general formulas (1) to (3) may be in the form of a resin, and 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, its molecular weight is not particularly limited, and the molecular weight is preferably 100 to 5000, more preferably 100 to 2000, and 100 to 1000. Is even more preferable.
When the compound (A3) having a radical trap group is a polymer compound having a repeating unit, the weight average molecular weight thereof is preferably 5000 to 20000, more preferably 5000 to 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. The compound (A3) is a reaction between a commercially available low molecular weight compound having a radical trap group and a high molecular weight compound having a reactive group such as an epoxy group, an alkyl halide group, an acid halide group, a carboxyl group and an isocyanate group. May be synthesized by.

The content of the compound (A3) having a radical trap group is usually 0.001 to 10% by mass, preferably 0.01 to 5% by mass, based on the total solid content of the topcoat composition.

The topcoat composition may contain a plurality of one compound selected from the group consisting of (A1) to (A3). For example, it may contain two or more compounds (A1) that are distinguished from each other.
Moreover, the top coat composition may contain two or more compounds selected from the group consisting of (A1) to (A3). For example, it may contain both compound (A1) and 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. It is .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.

A top coat may be formed on the resin film even when the exposure is performed by a method other than the immersion exposure treatment.

After the step (2) and before the step (3) described later, the resin film irradiated with the active light beam or the radiation in the step (2) may be subjected to a heat treatment (PEB: Post Exposure Bake). This step promotes the reaction of the exposed portion of the resin film. The heat treatment (PEB) may be performed a plurality of times.

The temperature of the heat treatment is preferably 70 to 130 ° C, more preferably 80 to 120 ° C.
The heat treatment time is preferably 30 to 300 seconds, more preferably 30 to 180 seconds, and even more 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.

<Process (3): Development process>
The pattern forming step of the present invention includes a developing step. The developing solution is not particularly limited, and examples thereof include a developing solution containing an alkaline developing solution and an organic solvent.

The step (3) may be a step of developing the film irradiated with the active light beam or the radiation in the step (2) using an alkaline developer.

As the alkaline developer, it is preferable to use an alkaline aqueous solution containing an alkali. The type of alkaline aqueous solution is not particularly limited, and 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, a cyclic amine, or the like can be used. Examples thereof include an alkaline aqueous solution containing the mixture. Of these, an aqueous solution of a quaternary ammonium salt typified by tetramethylammonium hydroxide (TMAH) is preferable. An appropriate amount of alcohols, surfactants and the like may be added to the alkaline developer. The alkali concentration of the alkaline developer is usually 0.1 to 20% by mass. The pH of the alkaline developer is usually 10.0 to 15.0.

Further, the step (3) is a step of developing the film irradiated with the active light or the radiation in the step (2) using a developing solution containing an organic solvent (hereinafter, also referred to as "organic solvent developing solution"). Is preferable. Development using a developing solution containing an organic solvent has an advantage that the top coat can be peeled off and developed at the same time.
Further, since the resin film (exposed portion) after exposure obtained by using the composition of the present invention is unlikely to swell due to an organic solvent, the effect of the present invention can be obtained by developing with an organic solvent developer. It is more prominently expressed.

As the organic solvent developing solution, a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent, a polar solvent such as an ether solvent, and a hydrocarbon solvent can be used.

Examples of the ketone solvent include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methylamyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, and diisobutyl ketone. Cyclohexanone, methylcyclohexanone, phenylacetone, methylethylketone, methylisobutylketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methylnaphthylketone, isophorone, propylene carbonate and the like can be mentioned.

Examples of the ester solvent include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isopentyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and 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, isoamyl acetate and the like 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, and n-heptyl alcohol. N-octyl alcohol, 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, and propylene glycol. Examples thereof include monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and glycol ether-based solvents such as methoxymethylbutanol.

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

Examples of the amide solvent 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. Further, a mixed solvent in which the above solvent and a solvent other than the above and / or water are mixed may be used. However, in order to fully exert the effect of the present invention, it is preferable that the water content of the developing solution as a whole is less than 10% by mass, and it does not substantially contain water (specifically, the developing solution). The water content in the medium is 1% by mass or less) is more preferable.

The content of the organic solvent in the organic solvent developer is preferably 90 to 100% by mass, more preferably 95 to 100% by mass, based on the total mass of the organic solvent developer.

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

The vapor pressure of the organic solvent developer is preferably 5 kPa or less, more preferably 3 kPa or less, and even more preferably 2 kPa or less at 20 ° C. By reducing the vapor pressure of the organic solvent developer to 5 kPa or less, evaporation of the developer on the substrate or in the developing cup can be suppressed, the temperature uniformity in the wafer surface is improved, and as a result, the dimensions in the wafer surface are improved. The uniformity is improved.

An appropriate amount of surfactant can be added to the organic solvent developer, if necessary.

The surfactant is not particularly limited, and for example, an ionic or nonionic fluorine-based and / or silicon-based surfactant can be used. Examples of these fluorine and / or silicon-based surfactants include Japanese Patent Application Laid-Open No. 62-36663, Japanese Patent Application Laid-Open No. 61-226746, Japanese Patent Application Laid-Open No. 61-226745, and Japanese Patent Application Laid-Open No. 62-170950. Japanese Patent Application Laid-Open No. 63-34540, Japanese Patent Application Laid-Open No. 7-230165, Japanese Patent Application Laid-Open No. 8-62834, Japanese Patent Application Laid-Open No. 9-54432, Japanese Patent Application Laid-Open No. 9-5988, US Pat. No. 5,405720, the same. The surfactants described in 5360692, 5529881, 5296330, 5436098, 5576143, 5294511, and 5824451 are mentioned. And preferably a non-ionic surfactant. The nonionic surfactant is not particularly limited, but it is preferable to use a fluorine-based surfactant or a silicon-based 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 0.01 to 0.5% by mass.

The organic solvent developer may contain a basic compound. Specific examples and preferable examples of the basic compound that can be contained in the organic solvent developer are the same as those of the basic compound in the above-mentioned acid diffusion control agent section.

Examples of the developing method include a method of immersing the substrate in a tank filled with a developing solution for a certain period of time (dip method), and a method of developing by raising the developing solution on the surface of the substrate by surface tension and allowing it to stand still for a certain period of time (paddle). Method), a method of spraying the developer on the surface of the substrate (spray method), and a method of continuing to discharge the developer while scanning the developer discharge nozzle at a constant speed on the substrate rotating at a constant speed (dynamic discharge). Law) and so on. The preferable range of the discharge pressure of the developer to be discharged, the method of adjusting the discharge pressure of the developer, and the like are not particularly limited, but for example, paragraphs [0631] to [0631] of JP2013-242397A. 0636] can be used in the range and method described.

In one aspect of the pattern forming method of the present invention, a step of developing with an organic solvent developer (organic solvent developing step) and a step of developing with an alkaline aqueous solution (alkali developing step) are used in combination. You may. As a result, a finer pattern can be formed.

Pure water may be used as the rinsing solution in the rinsing treatment performed after the alkaline development, and an appropriate amount of a surfactant may be added and used.

In the present invention, the portion having a weak exposure intensity is removed by the organic solvent developing step, but the portion having a strong exposure intensity is also removed by further performing the alkali developing step. By the multiple development process in which the development is performed a plurality of times in this way, the pattern can be formed without dissolving only the region of the intermediate exposure intensity, so that a finer pattern than usual can be formed (Japanese Patent Laid-Open No. 2008-292975 [0077]. ] Same mechanism).

In one aspect of the pattern forming method of the present invention, the order of the alkaline development step and the organic solvent development step is not particularly limited, but it is more preferable that the alkali development is performed before the organic solvent development step.

After the step of developing with a developing solution containing an organic solvent, it is preferable to include a step of washing with a rinsing solution.

The rinse solution used in the rinse 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 solution, use a rinsing solution 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. Is preferable.

Specific examples of the hydrocarbon solvent, the ketone solvent, the ester solvent, the alcohol solvent, the amide solvent and the ether solvent include the same as those described for the developing solution containing the organic solvent.

After the step of developing with a developing solution containing an organic solvent, more preferably at least one selected from the group consisting of a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent, and a hydrocarbon solvent. A step of cleaning with a rinsing solution containing various kinds of organic solvents is performed, and more preferably, a step of cleaning with a rinsing solution containing an alcohol solvent or an ester solvent is performed, and particularly preferably a monohydric alcohol. The step of cleaning with a rinsing solution containing the above is performed, and most preferably, the step of cleaning with a rinsing solution containing a monohydric alcohol having 5 or more carbon atoms is performed.

As the rinsing solution containing a hydrocarbon solvent, a hydrocarbon compound having 6 to 30 carbon atoms is preferable, a hydrocarbon compound having 8 to 30 carbon atoms is more preferable, and a hydrocarbon compound having 10 to 30 carbon atoms is further preferable. Above all, by using a rinse solution containing decane and / or undecane, pattern collapse is further suppressed.

When an ester solvent is used as the organic solvent, a glycol ether solvent may be used in addition to the ester solvent (1 type or 2 or more types). As a specific example in this case, an ester solvent (preferably butyl acetate) is used as a main component, and a glycol ether solvent (preferably propylene glycol monomethyl ether (PGME)) is used as a sub component. As a result, residual defects are further suppressed.

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. , Turt-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 and 4-methyl-. 2-Pentanol (methylisobutylcarbinol: MIBC), 1-pentanol, 3-methyl-1-butanol and the like can be used.

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

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

The vapor pressure of the rinse solution used after the step of developing with a developer containing an organic solvent is preferably 0.05 kPa or more and 5 kPa or less, more preferably 0.1 kPa or more and 5 kPa or less, and 0.12 kPa at 20 ° C. As mentioned above, 3 kPa or less is more preferable. 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 the swelling of the pattern due to the permeation of the rinsing liquid is further suppressed, and the swelling of the pattern in the wafer surface is further suppressed. Dimensional uniformity is improved.

An appropriate amount of a surfactant may be added to the rinse solution before use.

In the rinsing step, the wafer developed using the developer containing an organic solvent is washed with the above-mentioned rinse solution containing an organic solvent. The cleaning treatment method is not particularly limited, but for example, a method of continuously discharging the rinse liquid onto the substrate rotating at a constant speed (rotary coating method), or immersing the substrate in a tank filled with the rinse liquid for a certain period of time. A method (dip method) and a method of spraying a rinse solution on the surface of the substrate (spray method) can be applied. Among them, the cleaning treatment is performed by the rotary coating method, and the substrate is rotated at 2000 rpm to 4000 rpm after cleaning. It is preferable to rotate the number of times to remove the rinse liquid from the substrate. It is also preferable to include a heating step (Post Bake) after the rinsing step. Baking removes the developer and rinse solution remaining between and inside the patterns. The heating step after the rinsing step is usually 40 to 160 ° C., preferably 70 to 95 ° C., usually 10 seconds to 3 minutes, preferably 30 seconds to 90 seconds.

The sensitive light-sensitive or radiation-sensitive resin composition of the present invention, and various materials used in the pattern forming method of the present invention (for example, resist solvent, developing solution, rinsing solution, antireflection film forming composition, top The coat-forming composition, etc.) 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 pppb 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 and the like can be mentioned.

As a method for removing impurities such as metals from the various materials, for example, filtration using a filter can be mentioned. The filter pore size is preferably 10 nm or less, more preferably 5 nm or less, and even more 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 in which these materials and an ion exchange medium are combined. The filter may be one that has been pre-cleaned with an organic solvent. Filter In the 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. Further, various materials may be filtered a plurality of times, and the step of filtering the various materials a plurality of times may be a circulation filtration step.
In the production of an actinic light-sensitive or radiation-sensitive resin composition, after each component such as a resin and a photoacid generator is dissolved in a resist solvent, circulation filtration may be performed using a plurality of filters made of different materials. preferable. For example, it is preferable to connect 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 in a permutation, and perform circulation filtration 10 times or more. The smaller the pressure difference between the filters, the more preferable it is, and generally 0.1 MPa or less, preferably 0.05 MPa or less, and even more preferably 0.01 MPa or less. The smaller the pressure difference between the filter and the filling nozzle, the more preferable, and generally, it is 0.5 MPa or less, preferably 0.2 MPa or less, and further preferably 0.1 MPa or less.
It is preferable to replace the inside of the apparatus for producing the actinic light-sensitive or radiation-sensitive resin composition with an inert gas such as nitrogen. Thereby, it is possible to suppress the dissolution of the active gas such as oxygen in the composition.
The sensitive light-sensitive or radiation-sensitive resin composition is filtered by a filter and then filled in a clean container. The composition filled in the container is preferably stored refrigerated. As a result, performance deterioration over time is suppressed. The shorter the time from the completion of filling the composition into the container to the start of refrigerated storage is preferably, generally within 24 hours, preferably within 16 hours, more preferably within 12 hours, and 10 Within hours is even more preferred. The storage temperature is preferably 0 to 15 ° C, more preferably 0 to 10 ° C, and even more preferably 0 to 5 ° C.

Further, 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 such as lining the inside of the apparatus with Teflon (registered trademark) to perform distillation under conditions in which contamination is suppressed as much as possible can be mentioned. The preferred conditions for filter filtration performed on the raw materials constituting the various materials are the same as those described above.

In addition to filter filtration, impurities may be removed by an adsorbent, or filter filtration and an adsorbent may be used in combination. As the adsorbent, a known adsorbent can be used. For example, an inorganic adsorbent such as silica gel and zeolite, and an organic adsorbent 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 the mixing of metal impurities 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 trillion) or less, further preferably 10 ppt or less, and particularly preferably 1 ppt or less.

Organic treatment solutions such as developer and rinse solution are made of conductive compounds in order to prevent the chemical liquid piping and various parts (filters, O-rings, tubes, etc.) from being damaged due to static electricity charging and subsequent electrostatic discharge. It may be added. The conductive compound is not particularly limited, and examples thereof include methanol. The amount to be added is not particularly limited, but is preferably 10% by mass or less, more preferably 5% by mass or less, from the viewpoint of maintaining preferable development characteristics and rinsing characteristics. As for the members of the chemical solution piping, it is possible to use various piping coated with SUS (stainless steel) or antistatic polyethylene, polypropylene or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.). it can. Similarly, for the filter and the O-ring, antistatic treated polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene, perflooloalkoxy resin, etc.) can be used.
The inner wall surface of the container for storing the various materials is preferably treated so that impurities such as metals do not elute. As the inner wall surface of the container, a surface made of electropolished stainless steel, a glass-lined surface, and a surface coated with a fluororesin are more preferable.

A method for improving the surface roughness of the pattern may be applied to the pattern formed by the method of the present invention. Examples of the method for improving the surface roughness of the pattern include a method of treating the resist pattern with a plasma of a hydrogen-containing gas disclosed in International Publication No. 2014/002808. In addition, JP-A-2004-235468, US Patent Application Publication No. 2010/0020297, JP-A-2008-83384, and Proc. of SPIE Vol. A known method as described in 832883280N-1 "EUV Rest Curing Technology for LWR Redox Selection and Etch Sensitivity Enhancement" may be applied.

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

Further, the resist pattern formed by the above method can be used as, for example, the core material (core) of the spacer process disclosed in JP-A-3-270227 and JP2013-164509.

[Electronic device]
The present invention also relates to a method for manufacturing an electronic device 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 an electric electronic device (home appliance, OA (Office Automation), media-related device, optical device, communication device, etc.).

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, 34.1 g and 40.74 g of the polymerization initiator V-601 (3.4 g manufactured by Wako Pure Chemical Industries, Ltd.) and the monomers corresponding to each repeating unit of the resin A-1 described below are added in order from the left to 195 g of cyclohexanone. The solution dissolved in the mixture was added dropwise to a three-necked flask over 4 hours. After completion of the dropping, the reaction was further carried out at 85 ° C. for 3 hours to obtain a reaction solution. After allowing the obtained reaction solution to cool, the obtained reaction solution is added dropwise to a mixed solution of methanol and water over 20 minutes, and the precipitated powder is collected by filtration and dried to obtain the following resin A, which is an acid-degradable resin. -1 (76 g) was obtained.
The composition of the repeating unit of the resin A-1 determined by the NMR (Nuclear Magnetic Resonance) method is 40 mol% and 60 mol in order from the left in each repeating unit in the structure of the resin A-1 described later. %Met. The weight average molecular weight of the obtained resin A-1 is 10000 in terms of standard polystyrene under the above-mentioned conditions, and the dispersity (Mw / Mn = weight average molecular weight / number average molecular weight) of the resin A-1 is 1.7. there were.

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

[Preparation of resist composition]
The components shown in Table 1 below were dissolved in the solvent shown in the table so as to have the content shown in the table (content in total solid content (mass%)), and the solid content concentration of each was 4.9% by mass. Solution was prepared. Then, the obtained solution was filtered through a polyethylene filter having a pore size of 0.1 μm to prepare an actinic light-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 unit 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: perfluorobutyl tetrahydrofuran SL-8: ethyl lactate

[Evaluation]
<Formation of resist pattern>
The composition for forming an organic antireflection film ARC29SR (manufactured by Nissan Chemical Industries, Ltd.) was applied onto a silicon wafer, and the obtained silicon wafer was baked at 205 ° C. for 60 seconds to form an antireflection film having a film thickness of 95 nm. The above resist composition was applied onto the obtained antireflection film, and baking (PB: Prebake) was performed at 100 ° C. for 60 seconds to form a resist film (resin film) having a film thickness of 100 nm.
A silicon wafer on which an antireflection film and a resist film are formed is subjected to an ArF excimer laser immersion scanner (manufactured by ASML; XT1700i, NA1.20, C-Quad, outer sigma 0.900, inner sigma 0.812, XY deflection). It was 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. Ultrapure water was used as the immersion liquid.
Then, the obtained silicon wafer was heated at 105 ° C. for 60 seconds (PEB: Post Exposure Bake). Then, it was developed by paddling with an organic solvent developer (butyl acetate) for 30 seconds, and then padded with a rinsing solution [Methyl isobutyl carbinol (MIBC)] for 30 seconds for rinsing. Subsequently, the silicon wafer was rotated at a rotation 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 optimum exposure amount is the exposure amount that reproduces the mask pattern with a pitch of 90 nm and a space width of 35 nm under the exposure and development conditions for forming the resist pattern, and the line width of the line pattern formed by further reducing the exposure amount from the optimum exposure amount. The maximum space width at which the pattern resolves without collapsing when the pattern is thinned is defined as a value (nm) indicating the collapse resistance. The results are shown in Table 1.
The larger the value indicating the collapse resistance, the more fine the pattern is resolved without being collapsed, and the more the pattern is less likely to collapse and the higher the resolving power is. More specifically, the tilt 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 / _minute, N 2 500ml / _min, O 2 10ml / min). In consideration of plasma stabilization, the dry etching rate was as follows: the film thickness was dry-etched 10 seconds after the start of dry etching, and the dry etching rate was 5 seconds after the start of dry etching. It was obtained from the difference from the film thickness. The dry etching resistance was evaluated based on the dry etching rate (Å / sec) obtained in this way. The results are shown in Table 1.
In practical use, the dry etching rate is preferably 8.0 Å / sec (seconds) or less, more preferably 5.5 Å / sec or less, and further preferably 2.5 Å / sec or less. ..
(Dry etching rate) = {(Dry-etched film thickness in 10 seconds)-(Dry-etched film thickness in 5 seconds)} / 5

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

As shown in Table 1, a resin (A) containing a repeating unit (a1) having a group represented by the above-mentioned general formula (1) and a compound (B) that generates an acid by irradiation with active light or radiation. It was shown that a pattern having excellent tipping resistance and dry etching resistance can be formed by using a resist composition containing the above (Examples 1 to 24).
Further, from the comparison of Examples 1 to 24, the resin (A) in which W in the general formula (1) is a divalent polycyclic aromatic group is used, and the repeating unit in the 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 having better tipping resistance and dry etching resistance is formed. It has been shown that it can be done (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 the resin (A). It was shown that a more excellent pattern can be formed due to the tipping resistance and the dry etching resistance by satisfying both of 10 to 60 mol% with respect to 100 mol% of all the repeating units of (Example 1). ~ 3, 7, 11, 14, 16 ~ 20, 22 ~ 24).

On the other hand, it was shown that when a resin having no group represented by the above-mentioned general formula (1) was used, at least one of the collapse resistance and the dry etching resistance of the obtained pattern was 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) and a repeating unit (a2) having an acid-degradable group.
Compound (B) that generates acid by irradiation with active light or radiation,
Contains,
A light-sensitive or radiation-sensitive resin composition in which the compound (B) is not incorporated in the resin (A).
* -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 polycyclic aromatic group.
L ₂ represents a divalent linking group.
R ₂ represents a substituent having a group having a lactone structure, carbonate group, at least one group selected from the group consisting of sulfonamide Moto及beauty carboxylic acid groups.
n represents an integer of 1 or more.
When n is 2 or more, the plurality of L _2s may be the same or different from each other, and the plurality of R _2s may be the same or different from each other.
* Indicates the bond position with another atom.
However, the group having the lactone structure is a group represented by any of the following, and * in the following groups represents the bonding position with L ₂ of the general formula (1) .
The actinic or radiation-sensitive resin composition according to claim 1, wherein the group having the lactone structure is a group represented by any of the following.
However, * in the following group is L in the general formula (1). ₂ Represents the connection position with.
A resin (A) containing a repeating unit (a1) having a group represented by the general formula (1) and a repeating unit (a2) having an acid-degradable group.
Compound (B) that generates acid by irradiation with active light or radiation,
A light-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 polycyclic aromatic group.
L ₂ represents a divalent linking group.
R ₂ represents a substituent having at least one group carbonic acid ester group is selected from the group consisting of sulfonamide Moto及beauty carboxylic acid groups.
n represents an integer of 1 or more.
When n is 2 or more, the plurality of L _2s may be the same or different from each other, and the plurality of R _2s may be the same or different from each other.
* Indicates the bond position with another atom. Any of claims 1 to 3 , 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 according to item 1. A step of forming a resin film on a substrate by using the actinic light-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 4 .
The step of irradiating the resin film with active light or radiation,
The step of developing the resin film irradiated with active light or radiation using a developing solution, and
A pattern forming method having. The pattern forming method according to claim 5 , wherein the developer contains an organic solvent. A method for manufacturing an electronic device, which comprises the pattern forming method according to claim 5 or 6 .