JP2002351063A - Positive type photosensitive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a positive type photosensitive composition having high sensitivity and improved edge roughness of a pattern. SOLUTION: The positive type photosensitive composition contains (A) a specified acid generator which generates an acid when irradiated with active light or radiation, (B) a resin which has a mono- or polycyclic alicyclic hydrocarbon structure and is decomposed by the action of the acid to increase its solubility in an alkali developing solution, (C) a specified basic compound and (D) a fluorine- and/or silicon-containing surfactant.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive photosensitive composition used in a semiconductor manufacturing process such as an IC, a circuit board such as a liquid crystal and a thermal head, and other photofabrication processes. . More specifically, the present invention relates to a positive photosensitive composition suitable for use as a light source for exposure to far ultraviolet rays of 250 nm or less.

[0002]

2. Description of the Related Art A chemically amplified positive resist composition generates an acid in an exposed portion by irradiation with radiation such as far ultraviolet light.
This acid-catalyzed reaction changes the solubility of the irradiated portion and the non-irradiated portion of the active radiation in a developing solution, and is a pattern forming material for forming a pattern on a substrate.

[0003] When a KrF excimer laser is used as an exposure light source, absorption having a small absorption mainly in a 248 nm region is obtained.
High sensitivity, high resolution and good pattern are formed by using resin having poly (hydroxystyrene) as the main skeleton as a main component, making it a better system than conventional naphthoquinonediazide / novolak resin system. ing.

However, when a light source having an even shorter wavelength, for example, an ArF excimer laser (193 nm) is used as an exposure light source, the compound having an aromatic group essentially exhibits a large absorption in the 193 nm region. The system was not enough. Further, as a polymer having a small absorption in a wavelength region of 193 nm, the use of poly (meth) acrylate is described in J. Am. Vac. Sci. Technol. ,
B9, 3357 (1991). However, this polymer has a problem that its resistance to dry etching generally performed in a semiconductor manufacturing process is lower than that of a conventional phenol resin having an aromatic group.

As the acid generator for the chemically amplified positive resist composition, a triarylsulfonium salt-based acid generator and a phenacylsulfonium salt-based acid generator are known. Agent is 19
All of the phenacylsulfonium salt-based acid generators had low sensitivity because of their high absorption at 3 nm and low acid generating ability.

In recent years, with the demand for miniaturization of semiconductor chips, the design pattern of the fine semiconductor has been reduced to 0.13.
It reaches a fine region of about 0.35 μm. However, the conventional resist composition has a problem that the resolution of the pattern is hindered by factors such as the edge roughness of the line pattern. Here, the edge roughness means that the top and bottom edges of the line pattern of the resist fluctuate irregularly in the direction perpendicular to the line direction due to the characteristics of the resist. Sometimes the edge looks uneven.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a positive photosensitive composition having high sensitivity and improved pattern edge roughness.

[0008]

Means for Solving the Problems The present invention is a positive photosensitive composition having the following constitution, thereby achieving the above object of the present invention.

(1) (A) an acid generator represented by the following formula (I) which generates an acid upon irradiation with actinic rays or radiation;
(B) a resin having a monocyclic or polycyclic alicyclic hydrocarbon structure, which is decomposed by the action of an acid to increase the solubility in an alkali developer, (C) a primary aliphatic amine, a secondary Aliphatic amines, tertiary aliphatic amines, primary oxygen-containing aliphatic amines, secondary oxygen-containing aliphatic amines, tertiary oxygen-containing aliphatic amines, alcoholic nitrogen-containing compounds and substituted anilines A positive photosensitive composition comprising at least one selected basic compound and (D) a fluorine and / or silicon-based surfactant.

[0010]

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[0011] In formula (I), R ₁ ~R ₅ represent a hydrogen atom, an alkyl group, an alkoxy group, a nitro group, a halogen atom, an alkyl oxycarbonyl group or an aryl group, R ₁ ~
At least two or more of R ₅ may combine to form a ring structure. R ₆ and R ₇ represent a hydrogen atom, an alkyl group, a cyano group or an aryl group. Y ₁ and Y ₂ represent an alkyl group, an aryl group, an aralkyl group or an aromatic group containing a hetero atom, and Y ₁ and Y ₂ may combine to form a ring. Y ₃ represents a single bond or a divalent linking group. X ^- is,
Represents a non-nucleophilic anion. Provided that at least one of R ₁ to R ₅ and at least one of Y ₁ or Y ₂ are combined to form a ring, or at least one of R ₁ to R ₅ and R _1
At least one of ₆ or R ₇ is bonded to form a ring.
It should be noted that any _one of R ₁ to R ₇ , or any one of Y _{1 and} Y ₂ may be bonded via a linking group to have two or more structures of the formula (I).

(2) The acid generator (A) is a compound represented by the following formula (IA) or (IB) (1)
4. The positive photosensitive composition according to item 1.

[0013]

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In the formula (IA), R _{1 to} R ₄ , R ₇ , Y ₁ and Y ₂
And X ^- are the same as those in the above formula (I);
Represents a single bond or a divalent linking group. In the formula (IB), R
_{1 to} R ₄ , R ₆ , R ₇ , Y ₁ and X ⁻ are the same as those in the above formula (I), and Y represents a single bond or a divalent linking group.

(3) Further, (F) having a group which is decomposed by the action of an acid to increase the solubility in an alkaline developer,
The positive photosensitive composition according to (1) or (2), comprising a dissolution-inhibiting low-molecular compound having a molecular weight of 3000 or less. (4) (E) It contains a mixed solvent obtained by mixing a solvent containing a hydroxyl group and a solvent not containing a hydroxyl group (1) to (1).
The positive photosensitive composition according to any one of (3).

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION (A) Acid Generator The acid generator used in the present invention is a compound represented by the above formula (I) which generates an acid upon irradiation with actinic rays or radiation, and is represented by the formula (I)
Compounds represented by A) or Formula (IB) are more preferred.
In the formula (I), R _{1 to} R ₅ represent a hydrogen atom, an alkyl group, an alkoxy group, a nitro group, a halogen atom, an alkyloxycarbonyl group or an aryl group, and at least two or more of R _{1 to} R ₅ They may combine to form a ring structure. R
₆ and R ₇ represent a hydrogen atom, an alkyl group, a cyano group or an aryl group. Y ₁ and Y ₂ is an alkyl group, an aryl group, an aromatic group containing an aralkyl group or a hetero atom, Y ₁ and Y ₂ and bonded to good Y ₃ to form a ring is,
Represents a single bond or a divalent linking group. X ^- represents a non-nucleophilic anion. However, at least one of R ₁ to R ₅ and Y
_At least one of ₁ or Y ₂ is bonded to form a ring,
Alternatively, at least one of R ₁ to R ₅ and at least one of R ₆ or R ₇ combine to form a ring. It should be noted that any _one of R ₁ to R ₇ , or any one of Y _{1 and} Y ₂ may be bonded via a linking group to have two or more structures of the formula (I).

The alkyl group of R _{1 to} R ₇ is a substituted or unsubstituted alkyl group, preferably an alkyl group having 1 to 5 carbon atoms. Examples of the unsubstituted alkyl group include a methyl group and an ethyl group. Group, propyl group, n-butyl group,
Examples thereof include a sec-butyl group and a t-butyl group. The alkoxy group in R _{1 to} R _{5 and} the alkoxy group in the alkyloxycarbonyl group are a substituted or unsubstituted alkoxy group, preferably an alkoxy group having 1 to 5 carbon atoms. Examples of the unsubstituted alkoxy group include Methoxy group, ethoxy group, propoxy group, butoxy group and the like. The aryl group of R _{1 to} R ₇ , Y ₁ and Y ₂ is a substituted or unsubstituted aryl group, preferably an aryl group having 6 to 14 carbon atoms. Examples of the unsubstituted aryl group include phenyl Group, tolyl group,
Examples include a naphthyl group. Examples of the halogen atom for R _{1 to} R ₅ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The alkyl group for Y ₁ and Y ₂ is a substituted or unsubstituted alkyl group, preferably having 1 to 30 carbon atoms.
Is an alkyl group. Examples of the unsubstituted alkyl group include a linear or branched alkyl group such as a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, and a cyclopropyl group. Examples include cyclic alkyl groups such as a cyclopentyl group, a cyclohexyl group, an adamantyl group, a norbornyl group, and a boronyl group.

The aralkyl group of Y ₁ and Y ₂ is a substituted or unsubstituted aralkyl group, preferably having 7 to 7 carbon atoms.
Twelve aralkyl groups, and examples of the unsubstituted aralkyl group include a benzyl group, a phenethyl group, and a cumyl group.

The aromatic group containing a hetero atom means a group having a hetero atom, for example, a nitrogen atom, an oxygen atom, a sulfur atom, etc. in an aromatic group such as an aryl group having 6 to 14 carbon atoms. The aromatic group containing a hetero atom of Y ₁ and Y ₂ is a substituted or unsubstituted aromatic group containing a hetero atom, and examples of the unsubstituted group include furan, thiophene, pyrrole, pyridine, indole and the like. Is a heterocyclic aromatic hydrocarbon group.

Y ₁ and Y ₂ are combined to form S ⁺ in the formula (I).
Together, they may form a ring. In this case, the group formed by combining Y ₁ and Y ₂ is, for example, a group having 4 to 1 carbon atoms.
An alkylene group of 0, preferably a butylene group, a pentylene group, and a hexylene group, particularly preferably a butylene group and a pentylene group can be exemplified. Further, a hetero atom may be contained in the ring formed by bonding with Y ₁ and Y ₂ together with S ⁺ in the formula (I).

Each of the above alkyl groups, alkoxy groups, alkoxycarbonyl groups, aryl groups and aralkyl groups is, for example, a nitro group, a halogen atom, a carboxyl group, a hydroxyl group, an amino group, a cyano group, an alkoxy group (preferably having 1-5) and the like. Further, the aryl group and the aralkyl group may be substituted with an alkyl group (preferably having 1 to 5 carbon atoms). Further, a halogen atom is preferable as a substituent of the alkyl group.

Y ₃ represents a single bond or a divalent linking group. Examples of the divalent linking group include an optionally substituted alkylene group, alkenylene group, —O—, —S—, —CO—,
-CONR- (R is hydrogen, an alkyl group, or an acyl group), and a linking group that may contain two or more of these are preferable.

[0024] X ^- include the non-nucleophilic anion, for example, may be mentioned sulfonic acid anion, a carboxylic acid anion. The non-nucleophilic anion is an anion having an extremely low ability to cause a nucleophilic reaction, and an anion capable of suppressing the decomposition with time due to an intramolecular nucleophilic reaction. This improves the temporal stability of the resist. Examples of the sulfonic acid anion include an alkylsulfonic acid anion, an arylsulfonic acid anion, and a camphorsulfonic acid anion. Examples of the carboxylate anion include an alkyl carboxylate anion, an aryl carboxylate anion, and an aralkyl carboxylate anion.

The alkyl group in the alkylsulfonic acid anion is preferably an alkyl group having 1 to 30 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group. , Pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl Group, cyclopropyl group, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, boronyl group and the like. The aryl group in the arylsulfonic acid anion preferably includes an aryl group having 6 to 14 carbon atoms, such as a phenyl group, a tolyl group, and a naphthyl group.

The alkyl group and the aryl group in the above alkylsulfonic acid anion and arylsulfonic acid anion may have a substituent. As the substituent,
For example, a halogen atom, an alkyl group, an alkoxy group, an alkylthio group and the like can be mentioned.

Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom and an iodine atom. As the alkyl group, for example, preferably an alkyl group having 1 to 15 carbon atoms, for example, a methyl group, an ethyl group,
Propyl, isopropyl, n-butyl, isobutyl, sec-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl,
Decyl group, undecyl group, dodecyl group, tridecyl group,
Examples thereof include a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group and an eicosyl group. As the alkoxy group, for example, an alkoxy group preferably having 1 to 5 carbon atoms,
For example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group and the like can be mentioned. As the alkylthio group, for example, preferably an alkylthio group having 1 to 15 carbon atoms, for example, a methylthio group, an ethylthio group, a propylthio group, an isopropylthio group, an n-butylthio group, an isobutylthio group, a sec-butylthio group, a pentylthio group,
Neopentylthio, hexylthio, heptylthio, octylthio, nonylthio, decylthio, undecylthio, dodecylthio, tridecylthio,
Tetradecylthio, pentadecylthio, hexadecylthio, heptadecylthio, octadecylthio,
Examples include a nonadecylthio group and an eicosylthio group. Incidentally, the alkyl group, the alkoxy group and the alkylthio group may be further substituted with a halogen atom (preferably a fluorine atom).

Examples of the alkyl group in the alkyl carboxylate anion include the same alkyl groups as those in the alkyl sulfonic acid anion. Examples of the aryl group in the aryl carboxylate anion include the same as the aryl group in the aryl sulfonate anion. The aralkyl group in the aralkyl carboxylate anion preferably includes an aralkyl group having 6 to 12 carbon atoms, such as a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group, and a naphthylmethyl group.

The alkyl group, aryl group and aralkyl group in the above-mentioned alkyl carboxylate anion, aryl carboxylate anion and aralkyl carboxylate anion may have a substituent.
Examples include the same halogen atoms, alkyl groups, alkoxy groups, and alkylthio groups as in the arylsulfonate anion.

Examples of other non-nucleophilic anions include fluorinated phosphorus, fluorinated boron and fluorinated antimony.

[0031] Incidentally, in the formula (I) of the present invention, the R ₁ or at least one of the at least one Y ₁ or Y ₂ in R ₅ is ring bond is formed, or, of R ₁ to R ₅ At least one and at least one of R _{6 and} R ₇ are bonded to form a ring. The compound represented by the formula (I) forms a ring, thereby fixing the three-dimensional structure and improving optical resolution. In addition, any _one of R ₁ to R ₇ or Y ₁
Or at any position of Y ₂ , linked via a linking group,
It may have two or more structures of the formula (I).

The compound of the formula (I) of the present invention is preferably represented by the above-mentioned general formula (IA) or (IB).
In the formula (IA), R _{1 to} R ₄ , R ₇ , Y ₁ , Y ₂ and X ⁻ are the same as those in the formula (I), and Y represents a single bond or a divalent linking group. . In the formula (IB), R _{1 to} R ₄ , R ₆ , R ₇ , Y
₁ and X ^- are the same as those in the formula (I), and Y represents a single bond or a divalent linking group.

Y represents a single bond or a divalent linking group,
Examples of the valent linking group include an optionally substituted alkylene group, alkenylene group, -O-, -S-, -CO-, -C
ONR- (R is hydrogen, an alkyl group, or an acyl group), and a linking group that may contain two or more of these are preferred. In compounds represented by formula (IA), the alkylene group as the Y containing alkylene group or an oxygen atom, an alkylene group containing a sulfur atom are preferred, specifically a methylene group, an ethylene group, a propylene group, -CH ₂ -O -, - CH ₂ -S- are preferred, and most preferably an ethylene group, -CH ₂ -O-,
Is a linking group forming a 6-membered ring as -CH ₂ -S-. By forming a 6-membered ring, the carbonyl plane and C-
The S + sigma coupling becomes more vertical, and the orbital interaction improves the photolysis efficiency.

The following are specific examples of the compound represented by the above formula (I) of the present invention, but the present invention is not limited to these.

[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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Among the above acid generators, (IA-1) to (IA-1)
A-30) and (IB-1) to (IB-12) are more preferred.

The compounds of the above formula (I) can be used alone or in combination of two or more.

The compound of formula (IA) has the corresponding α-
A method of reacting a halocyclic ketone with a sulfide compound,
Alternatively, it can be obtained by converting the corresponding cyclic ketone into silyl enol ether, and then reacting it with sulfoxide. The compound represented by the formula (IB) can be obtained by reacting an allyl alkyl sulfide with an α- or β-halogenated halide.

The content of the compound (A) in the positive photosensitive composition of the present invention is based on the solid content of the composition.
0.1-20% by weight is preferred, more preferably 0.5%
10 to 10% by weight, more preferably 1 to 7% by weight.

Acid-generating compounds other than component (A) which can be used in combination In the present invention, compounds which decompose upon irradiation with actinic rays or radiation to generate an acid may be used in addition to component (A). The amount of the photoacid generator that can be used in combination with the component (A) of the present invention is usually 100/0 to 20/80, preferably 10 / molar ratio (component (A) / other photoacid generator).
0/0 to 40/60, more preferably 100/0 to 50
/ 50. Such photoacid generators that can be used together are used in photoinitiators for photocationic polymerization, photoinitiators for photoradical polymerization, photodecolorants for dyes, photochromic agents, or microresists. Known compounds that generate an acid upon irradiation with actinic rays or radiation and mixtures thereof can be appropriately selected and used.

For example, onium salts such as diazonium salts, ammonium salts, phosphonium salts, iodonium salts, sulfonium salts, selenonium salts and arsonium salts;
Organic halogen compound, organic metal / organic halide, o
-Photoacid generators having a nitrobenzyl-type protecting group, compounds that generate sulfonic acid upon photolysis, such as iminosulfonate, and disulfone compounds.

Further, compounds in which a group or a compound capable of generating an acid upon irradiation with an actinic ray or radiation is introduced into a main chain or a side chain of a polymer, for example, US Pat.
No. 849,137, German Patent No. 3914407, JP-A-63-26653,
JP-A-55-164824, JP-A-62-69263, JP-A-63-1460
Compounds described in JP-A-38-163452, JP-A-63-163452, JP-A-62-153853, JP-A-63-146029 and the like can be used.

Further, compounds capable of generating an acid by light described in US Pat. No. 3,779,778 and European Patent 126,712 can also be used.

Among the compounds which can be used together and decompose upon irradiation with actinic rays or radiation to generate an acid, those which are particularly effectively used are described below. (1) The following general formula (PAG) substituted with a trihalomethyl group
The oxazole derivative represented by 1) or the general formula (PAG)
An S-triazine derivative represented by 2).

[0053]

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In the formula, R ²⁰¹ is a substituted or unsubstituted aryl group or alkenyl group, and R ²⁰² is a substituted or unsubstituted aryl group, alkenyl group, alkyl group, —C (Y) ₃
Show Y represents a chlorine atom or a bromine atom. Specific examples include the following compounds, but the present invention is not limited thereto.

[0055]

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[0056]

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(2) An iodonium salt represented by the following formula (PAG3) or a sulfonium salt represented by the following formula (PAG4).

[0058]

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Here, the formulas Ar ¹ and Ar ² each independently represent a substituted or unsubstituted aryl group. Preferred substituents include an alkyl group, a haloalkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a nitro group, a carboxyl group, an alkoxycarbonyl group, a hydroxy group, a mercapto group, and a halogen atom.

R ²⁰³ , R ²⁰⁴ and R ²⁰⁵ each independently represent a substituted or unsubstituted alkyl group or aryl group. Preferably, it is an aryl group having 6 to 14 carbon atoms, an alkyl group having 1 to 8 carbon atoms, or a substituted derivative thereof. Preferred substituents are an alkoxy group having 1 to 8 carbon atoms, an alkyl group having 1 to 8 carbon atoms, a nitro group, a carboxyl group, a hydroxy group and a halogen atom with respect to the aryl group,
Examples of the alkyl group include an alkoxy group having 1 to 8 carbon atoms, a carboxyl group, and an alkoxycarbonyl group.

[0061] Z ^- represents a counter anion, for example BF ₄ ^{-,
_{AsF 6 -, PF 6 -,}} SbF 6 -, SiF 6 2-, ClO 4 -,
CF ₃ SO ₃ ^-, etc. perfluoroalkane sulfonate anion, pentafluorobenzenesulfonic acid anion, condensed polynuclear aromatic sulfonic acid anion such as naphthalene-1-sulfonic acid anion, anthraquinone sulfonic acid anion, a sulfonic acid group-containing dyes Examples include, but are not limited to:

Further, two of R ²⁰³ , R ²⁰⁴ and R ²⁰⁵ and Ar ¹ and Ar ² may be bonded through a single bond or a substituent.

Specific examples include the following compounds, but are not limited thereto.

[0064]

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[0065]

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[0066]

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[0067]

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[0068]

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[0069]

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[0070]

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[0071]

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[0072]

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[0073]

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[0074]

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The above onium salts represented by the general formulas (PAG3) and (PAG4) are known, and are described, for example, in US Pat.
It can be synthesized by the methods described in 807,648 and 4,247,473, JP-A-53-101,331 and the like.

(3) Disulfone derivatives represented by the following formula (PAG5) or iminosulfonate derivatives represented by the following formula (PAG6).

[0077]

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In the formula, Ar ³ and Ar ⁴ each independently represent a substituted or unsubstituted aryl group. R ²⁰⁶ represents a substituted or unsubstituted alkyl group or aryl group. A represents a substituted or unsubstituted alkylene group, alkenylene group, or arylene group. Specific examples include the following compounds, but are not limited thereto.

[0079]

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[0080]

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[0081]

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[0082]

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[0083]

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(4) A diazodisulfone derivative represented by the following general formula (PAG7).

[0085]

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Here, R represents a linear, branched or cyclic alkyl group or an optionally substituted aryl group. Specific examples include the following compounds,
It is not limited to these.

[0087]

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Among the compounds which may be used in combination and which decompose upon irradiation with actinic rays or radiation to generate an acid, particularly preferred examples are shown below.

[0089]

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[0090]

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[0091]

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[0092]

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{(B) Resin whose dissolution rate in an alkaline developer is increased by the action of an acid (also referred to as "acid-decomposable resin")}

As the acid-decomposable resin (B) of the present invention, any resin can be used as long as it has a monocyclic or polycyclic alicyclic hydrocarbon structure and the dissolution rate in an alkali developing solution is increased by the action of an acid. Or any of the general formulas (pI) to (pVI)
It is preferable that the resin contains at least one selected from the group consisting of a repeating unit having a partial structure containing an alicyclic hydrocarbon represented by and a repeating unit represented by the general formula (II-AB).

[0095]

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(Wherein R ₁₁ is a methyl group, an ethyl group, n
-Represents a propyl group, isopropyl group, n-butyl group, isobutyl group or sec-butyl group, and Z represents an atomic group necessary for forming an alicyclic hydrocarbon group together with a carbon atom. R _{12 to} R ₁₆ each independently represent a group having 1 to 4 carbon atoms;
It represents a linear or branched alkyl group or an alicyclic hydrocarbon group, provided that at least one of R _{12 to} R ₁₄ , or any of R ₁₅ and R ₁₆ represents an alicyclic hydrocarbon group. R
_{17 to} R ₂₁ each independently represent a hydrogen atom, a linear or branched alkyl group or an alicyclic hydrocarbon group having 1 to 4 carbon atoms, provided that at least one of R _{17 to} R ₂₁ Represents an alicyclic hydrocarbon group. Further, either R ₁₉ or R ₂₁ represents a linear or branched alkyl group or an alicyclic hydrocarbon group having 1 to 4 carbon atoms. R _{22 to} R ₂₅ are each independently
It represents a linear or branched alkyl group or an alicyclic hydrocarbon group having 1 to 4 carbon atoms, provided that at least one of R _{22 to} R ₂₅ represents an alicyclic hydrocarbon group. Also, R ₂₃ and R
₂₄ may combine with each other to form a ring. )

[0097]

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In the formula (II-AB), R ₁₁ ′ and R ₁₂ ′ each independently represent a hydrogen atom, a cyano group, a halogen atom, or an alkyl group which may have a substituent. Z ′ represents an atomic group for forming an alicyclic structure which may have a substituent and includes two bonded carbon atoms (C—C).

The above formula (II-AB) is more preferably the following formula (II-A) or (II-B).

[0100]

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In the formulas (II-A) and (II-B): R ₁₃ ′ to R
₁₆ ′ is each independently a hydrogen atom, a halogen atom, a cyano group, —COOH, —COOR ₅ , a group decomposed by the action of an acid, —C (＝ O) —XA′-R ₁₇ ′, or substituted Represents an alkyl group or a cyclic hydrocarbon group which may have a group. Wherein, R ₅ may have a substituent, an alkyl group, cyclic hydrocarbon group, or -Y group shown below. X
It represents an oxygen atom, a sulfur atom, -NH -, - NHSO ₂ - or an -NHSO ₂ NH-. A ′ represents a single bond or a divalent linking group. Further, at least two of R ₁₃ ′ to R ₁₆ ′ may combine to form a ring. n represents 0 or 1.
R ₁₇ ′ represents —COOH, —COOR ₅ , —CN, a hydroxyl group,
An alkoxy group which may have a substituent, -CO-NH
—R ₆ , —CO—NH—SO ₂ —R ₆ or the following —Y group. R ₆ represents an alkyl group or a cyclic hydrocarbon group which may have a substituent. A —Y group;

[0102]

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(In the —Y group, R ₂₁ ′ to R ₃₀ ′ each independently represent a hydrogen atom or an alkyl group which may have a substituent. A and b each represent 1 or 2.)

In the general formulas (pI) to (pVI), R
The alkyl group for _{12 to} R ₂₅ represents a linear or branched alkyl group having 1 to 4 carbon atoms, which may be substituted or unsubstituted. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group,
Examples include a sec-butyl group and a t-butyl group. Further, as a further substituent of the above alkyl group, one having 1 carbon atom
And 4 to 4 alkoxy groups, halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine atom), acyl group, acyloxy group, cyano group, hydroxyl group, carboxy group, alkoxycarbonyl group, nitro group and the like.

The alicyclic hydrocarbon group for R _{11 to} R _{25 or} the alicyclic hydrocarbon group formed by Z and a carbon atom may be monocyclic or polycyclic. Specific examples include groups having a monocyclo, bicyclo, tricyclo, tetracyclo structure or the like having 5 or more carbon atoms. The number of carbon atoms is preferably from 6 to 30, particularly preferably from 7 to 25. These alicyclic hydrocarbon groups may have a substituent. Below, the structural example of an alicyclic part among alicyclic hydrocarbon groups is shown.

[0106]

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[0107]

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[0108]

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In the present invention, preferred examples of the alicyclic moiety include an adamantyl group, a noradamantyl group, a decalin residue, a tricyclodecanyl group, a tetracyclododecanyl group, a norbornyl group, a cedrol group, and a cyclohexyl group. , Cycloheptyl group, cyclooctyl group,
Examples thereof include a cyclodecanyl group and a cyclododecanyl group. More preferred are an adamantyl group, a decalin residue, a norbornyl group, a cedrol group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecanyl group, and a cyclododecanyl group.

Examples of the substituent of these alicyclic hydrocarbon groups include an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group, an alkoxy group, a carboxyl group and an alkoxycarbonyl group. The alkyl group is preferably a lower alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group, and more preferably a methyl group, an ethyl group, a propyl group, and a substituent selected from the group consisting of an isopropyl group. Represent. Examples of the substituent of the substituted alkyl group include a hydroxyl group, a halogen atom and an alkoxy group. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group.

The above resins represented by the general formulas (pI) to (pV)
The structure represented by I) can be used for protecting an alkali-soluble group. Examples of the alkali-soluble group include various groups known in this technical field. Specific examples include a carboxylic acid group, a sulfonic acid group, a phenol group, and a thiol group, and a carboxylic acid group and a sulfonic acid group are preferable. General formula (pI) to above resin
The alkali-soluble group protected by the structure represented by (pVI) is preferably the following general formulas (pVII) to (pVII).
XI).

[0112]

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Here, R _{11 to} R ₂₅ and Z are the same as defined above. In the above resin, as the repeating unit having an alkali-soluble group protected by the structure represented by any of formulas (pI) to (pVI), a repeating unit represented by the following formula (pA) is preferable.

[0114]

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Here, R represents a hydrogen atom, a halogen atom, or a substituted or unsubstituted linear or branched alkyl group having 1 to 4 carbon atoms. A plurality of Rs may be the same or different. A is singly or two or more selected from the group consisting of a single bond, an alkylene group, a substituted alkylene group, an ether group, a thioether group, a carbonyl group, an ester group, an amide group, a sulfonamide group, a urethane group, and a urea group. Represents a combination of groups. Ra represents any one of the above formulas (pI) to (pVI).

Hereinafter, specific examples of the monomer corresponding to the repeating unit represented by formula (pA) will be shown.

[0117]

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[0118]

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[0119]

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[0120]

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[0121]

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[0122]

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In the above formula (II-AB), R ₁₁ ′, R _11
12 ′ each independently represents a hydrogen atom, a cyano group, a halogen atom, or an alkyl group which may have a substituent.
Z ′ represents an atomic group for forming an alicyclic structure which may have a substituent and includes two bonded carbon atoms (C—C).

Examples of the halogen atom for R ₁₁ ′ and R ₁₂ ′ include a chlorine atom, a bromine atom, a fluorine atom and an iodine atom. R ₁₁ ′, R ₁₂ ′, R ₂₁ ′ to R
The alkyl group at ₃₀ ′ is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, more preferably a linear or branched alkyl group having 1 to 6 carbon atoms, and still more preferably Methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group,
They are a sec-butyl group and a t-butyl group.

Further substituents in the above alkyl group include a hydroxyl group, a halogen atom, a carboxyl group, an alkoxy group, an acyl group, a cyano group, an acyloxy group and the like. Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, an iodine atom,
Examples of the alkoxy group include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group. Examples of the acyl group include a formyl group and an acetyl group. Is an acetoxy group.

The atomic group for forming the alicyclic structure of Z ′ is an atomic group for forming a repeating unit of an alicyclic hydrocarbon which may have a substituent on the resin, An atomic group for forming a bridged alicyclic structure forming a repeating unit of the alicyclic hydrocarbon of the formula is preferred. Examples of the skeleton of the formed alicyclic hydrocarbon include those represented by the following structures.

[0127]

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[0128]

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Preferred skeletons of the bridged alicyclic hydrocarbon include (5), (6), (7) and
(9), (10), (13), (14), (15),
(23), (28), (36), (37), (42),
(47).

The skeleton of the alicyclic hydrocarbon may have a substituent. Examples of such a substituent include R ₁₃ ′ to R ₁₆ ′ in the above formula (II-A) or (II-B). Among the repeating units having a bridged alicyclic hydrocarbon, a repeating unit represented by the above general formula (II-A) or (II-B) is more preferable.

Formula (II-A) or (II-B)
In the formula, R ₁₃ ′ to R ₁₆ ′ each independently represent a hydrogen atom, a halogen atom, a cyano group, —COOH, —COOR ₅ , a group decomposed by the action of an acid, —C (＝ O) —XA ′. -R
₁₇ ′ represents an alkyl group or a cyclic hydrocarbon group which may have a substituent. R ₅ represents an optionally substituted alkyl group, cyclic hydrocarbon group or the above-mentioned —Y group. X is an oxygen atom, a sulfur atom, -NH-, -NH
Represents SO ₂ — or —NHSO ₂ NH—. A ′ represents a single bond or a divalent linking group. Further, at least two of R ₁₃ ′ to R ₁₆ ′ may combine to form a ring. n is 0
Or represents 1. R ₁₇ ′ represents —COOH, —COOR ₅ ,
—CN, a hydroxyl group, an optionally substituted alkoxy group, —CO—NH—R ₆ , —CO—NH—SO ₂ —R ₆
Or represents the following -Y group. R ₆ represents an alkyl group or a cyclic hydrocarbon group which may have a substituent. The-
In the Y group, R ₂₁ ′ to R ₃₀ ′ each independently represent a hydrogen atom or an alkyl group which may have a substituent;
b represents 1 or 2.

In the resin according to the present invention, the acid-decomposable group may be included in the above-mentioned —C (＝ O) -XA′-R ₁₇ ′, or Z ′ in the general formula (II-AB) May be included as a substituent. The structure of the acid-decomposable group is -C (= O) -X ₁
-R ₀ . In the formula, R ₀ represents a tertiary alkyl group such as a t-butyl group, a t-amyl group, an isobornyl group, a 1-ethoxyethyl group, a 1-butoxyethyl group,
1-alkoxyethyl groups such as isobutoxyethyl group and 1-cyclohexyloxyethyl group, alkoxymethyl groups such as 1-methoxymethyl group and 1-ethoxymethyl group, 3
-Oxoalkyl group, tetrahydropyranyl group, tetrahydrofuranyl group, trialkylsilyl ester group, 3
-Oxocyclohexyl ester group, 2-methyl-2-
An adamantyl group, a mevalonic lactone residue and the like can be mentioned. X ₁ has the same meaning as X described above.

Examples of the halogen atom in R ₁₃ ′ to R ₁₆ ′ include a chlorine atom, a bromine atom, a fluorine atom, an iodine atom and the like.

The alkyl group for R ₅ , R ₆ and R ₁₃ ′ to R ₁₆ ′ is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, more preferably 1 to 10 carbon atoms.
It is six linear or branched alkyl groups, more preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a t-butyl group.

Examples of the cyclic hydrocarbon group for R ₅ , R ₆ and R ₁₃ ′ to R ₁₆ ′ include a cyclic alkyl group and a bridged hydrocarbon group, such as a cyclopropyl group, a cyclopentyl group,
Cyclohexyl group, adamantyl group, 2-methyl-2-
An adamantyl group, a norbornyl group, a boronyl group, an isobornyl group, a tricyclodecanyl group, a dicyclopentenyl group, a nobornane epoxy group, a menthyl group, an isomenthyl group, a neomenthyl group, a tetracyclododecanyl group, and the like can be given. As the ring formed by bonding at least two of R ₁₃ ′ to R ₁₆ ′, cyclopentene,
Rings having 5 to 12 carbon atoms such as cyclohexene, cycloheptane, cyclooctane and the like can be mentioned.

Examples of the alkoxy group for R ₁₇ ′ include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group.

Further substituents in the above alkyl group, cyclic hydrocarbon group and alkoxy group include a hydroxyl group, a halogen atom, a carboxyl group, an alkoxy group, an acyl group, a cyano group, an acyloxy group, an alkyl group, a cyclic hydrocarbon group and the like. Can be mentioned. Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Examples of the acyl group include a formyl group and an acetyl group. Examples thereof include an acetoxy group. Also,
Examples of the alkyl group and the cyclic hydrocarbon group include those described above.

The divalent linking group represented by A ′ is selected from the group consisting of an alkylene group, a substituted alkylene group, an ether group, a thioether group, a carbonyl group, an ester group, an amide group, a sulfonamide group, a urethane group and a urea group. The selected one or a combination of two or more groups can be mentioned. Examples of the alkylene group and substituted alkylene group in A ′ include groups represented by the following formula. -[C (R _a ) (R _b )] _r-wherein R _a and R _b represent a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group, an alkoxy group,
Both may be the same or different. The alkyl group is preferably a lower alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group and a butyl group, and more preferably selected from a methyl group, an ethyl group, a propyl group and an isopropyl group. As the substituent of the substituted alkyl group,
Examples include a hydroxyl group, a halogen atom and an alkoxy group. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group. Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom. r represents an integer of 1 to 10.

In the resin according to the present invention, the groups decomposed by the action of an acid are represented by the general formulas (pI) to (pV).
A repeating unit having a partial structure containing an alicyclic hydrocarbon represented by I), a repeating unit represented by the general formula (II-AB), and at least one kind of a repeating unit of a copolymer component described below. Can be contained.

The formula (II-A) or (II
The various substituents of R ₁₃ ′ to R ₁₆ ′ in —B) are an atomic group for forming an alicyclic structure or a bridged alicyclic structure for forming an alicyclic structure in the general formula (II-AB). It is also a substituent of the atomic group Z.

The formula (II-A) or the formula (II
-B) As specific examples of the repeating unit represented by the following [II]
-1] to [II-175], but the present invention is not limited to these specific examples.

[0142]

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[0143]

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[0144]

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[0145]

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[0146]

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[0147]

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[0148]

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[0149]

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[0150]

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[0151]

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[0152]

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[0153]

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[0154]

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[0155]

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[0156]

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[0157]

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[0158]

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[0159]

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[0160]

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The acid-decomposable resin of the present invention may further contain a repeating unit having a lactone structure represented by the following general formula (IV).

[0162]

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[0163] In the general formula (IV), R ₁ a represents a hydrogen atom or a methyl group. W ₁ represents a single bond, an alkylene group, an ether group, a thioether group, a carbonyl group, or a combination of two or more groups selected from the group consisting of an ester group. _{Ra 1, Rb 1, Rc 1} , Rd 1, Re 1 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. m and n each independently represent an integer of 0 to 3;
Is 2 or more and 6 or less.

Examples of the alkyl group having 1 to 4 carbon atoms of Ra _{1 to} Re ₁ include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group and a t-butyl group. Can be mentioned.

In formula (IV), examples of the alkylene group represented by W ₁ include groups represented by the following formula. — [C (Rf) (Rg)] r ₁ — In the above formula, Rf and Rg represent a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group, or an alkoxy group, and they may be the same or different. Good. The alkyl group is preferably a lower alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group and a butyl group, and more preferably selected from a methyl group, an ethyl group, a propyl group and an isopropyl group. Examples of the substituent of the substituted alkyl group include a hydroxyl group, a halogen atom and an alkoxy group. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group. Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom. r ₁ is an integer of ₁ to 10.

Further substituents on the above alkyl group include carboxyl group, acyloxy group, cyano group, alkyl group, substituted alkyl group, halogen atom, hydroxyl group, alkoxy group, substituted alkoxy group, acetylamide group, alkoxycarbonyl group, An acyl group is exemplified. Here, examples of the alkyl group include lower alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a cyclopropyl group, a cyclobutyl group, and a cyclopentyl group. Examples of the substituent of the substituted alkyl group include a hydroxyl group, a halogen atom and an alkoxy group. Examples of the substituent of the substituted alkoxy group include an alkoxy group. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group. Examples of the acyloxy group include an acetoxy group. Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom.

Specific examples of the monomer corresponding to the repeating structural unit represented by the general formula (IV) are shown below, but it should not be construed that the invention is limited thereto.

[0168]

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[0169]

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[0170]

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In the specific example of the above general formula (IV), (IV-17) to (IV-17)
(IV-36) is preferred. Further, as the structure of the general formula (IV), those having an acrylate structure are preferable from the viewpoint that edge roughness is improved.

Further, the following general formulas (V-1) to (V-4)
And a repeating unit having a group represented by any of the above.

[0173]

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In the general formulas (V-1) to (V-4),
R _{1b to} R _5b each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group or an alkenyl group which may have a substituent. Two of R _{1b to} R _5b may combine to form a ring.

In the general formulas (V-1) to (V-4),
Examples of the alkyl group for R _{1b to} R _5b include a linear or branched alkyl group, and may have a substituent. The linear or branched alkyl group has 1 to 1 carbon atoms.
Twelve linear or branched alkyl groups are preferred,
More preferably, it is a linear or branched alkyl group having 1 to 10 carbon atoms, and still more preferably, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, -Butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group,
Decyl group. The cycloalkyl group in R _{1b to} R _5b is preferably a cycloalkyl group having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group and the like. The alkenyl group in R _{1b to} R _5b is preferably an alkenyl group having 2 to 6 carbon atoms such as a vinyl group, a propenyl group, a butenyl group, and a hexenyl group. Examples of the ring formed by combining two members out of R _{1b to} R _5b include a 3- to 8-membered ring such as a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, and a cyclooctane ring. The general formula (V-1)
R _{1b to} R _5b in (V-4) may be connected to any of the carbon atoms constituting the cyclic skeleton.

Preferred examples of the substituent which the alkyl group, cycloalkyl group and alkenyl group may have include an alkoxy group having 1 to 4 carbon atoms, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom and an iodine atom). Atom), an acyl group having 2 to 5 carbon atoms, an acyloxy group having 2 to 5 carbon atoms, a cyano group, a hydroxyl group, a carboxy group, an alkoxycarbonyl group having 2 to 5 carbon atoms, and a nitro group.

The repeating units having groups represented by formulas (V-1) to (V-4) include those represented by formula (II-
A) or (II-B) wherein at least one of R ₁₃ ′ to R ₁₆ ′ has a group represented by the above general formulas (V-1) to (V-4) (for example, -COOR ₅ R ₅ is a group represented by the general formula (V-
1) to (V-4)), or a repeating unit represented by the following general formula (AI).

[0178]

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In formula (AI), R _b0 represents a hydrogen atom, a halogen atom, or a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms. Preferred substituents which the alkyl group of _Rb0 may have are those represented by the general formulas (V-1) to (V-1).
Preferred examples of the substituent which may be possessed by the alkyl group as R _1b in (V-4) include those exemplified above. Examples of the halogen atom for R _b0 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. R
_b0 is preferably a hydrogen atom. A ′ represents a single bond, an ether group, an ester group, a carbonyl group, an alkylene group, or a divalent group obtained by combining these. B ₂ represents a group represented by any one of formulas (V-1) to (V-4). In A ′, examples of the combined divalent group include those represented by the following formulas.

[0180]

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In the above formula, Rab and Rbb represent a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group, or an alkoxy group, and they may be the same or different. The alkyl group is preferably a lower alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group and a butyl group, and more preferably selected from a methyl group, an ethyl group, a propyl group and an isopropyl group. Examples of the substituent of the substituted alkyl group include a hydroxyl group, a halogen atom, and an alkoxy group having 1 to 4 carbon atoms. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group. Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom. r
1 represents an integer of 1 to 10, preferably an integer of 1 to 4.
m represents an integer of 1 to 3, preferably 1 or 2.

Specific examples of the repeating unit represented by formula (AI) are shown below, but the invention is not limited thereto.

[0183]

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[0184]

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[0185]

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[0186]

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[0187]

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[0188]

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[0189]

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The acid-decomposable resin of the present invention may further contain a repeating unit represented by the following general formula (VI).

[0191]

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In the general formula (VI), A ₆ is a single bond, an alkylene group, a cycloalkylene group, an ether group, a thioether group, a carbonyl group, an ester group, or a combination of two or more groups. Represents R _6a represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cyano group, or a halogen atom.

In the general formula (VI), examples of the alkylene group represented by A ₆ include groups represented by the following formula. -[C (Rnf) (Rng)] r-wherein Rn
f and Rng represent a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group, or an alkoxy group, and they may be the same or different. As the alkyl group,
A lower alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group is preferred, and more preferably a methyl group, an ethyl group, a propyl group, and an isopropyl group. Examples of the substituent of the substituted alkyl group include a hydroxyl group, a halogen atom and an alkoxy group. As the alkoxy group, a methoxy group, an ethoxy group,
Those having 1 to 4 carbon atoms such as a propoxy group and a butoxy group can be exemplified. As the halogen atom, a chlorine atom,
Examples thereof include a bromine atom, a fluorine atom, and an iodine atom. r is an integer of 1 to 10. In the general formula (VI), examples of the cycloalkylene group represented by A ₆ include those having 3 to 10 carbon atoms, such as a cyclopentylene group, a cyclohexylene group, and a cyclooctylene group.

The bridged alicyclic ring containing Z ₆ may have a substituent. Examples of the substituent include a halogen atom, an alkoxy group (preferably having 1 to 4 carbon atoms), an alkoxycarbonyl group (preferably having 1 to 5 carbon atoms), an acyl group (eg, a formyl group and a benzoyl group), and an acyloxy group ( For example, a propylcarbonyloxy group, a benzoyloxy group), an alkyl group (preferably having 1 to 4 carbon atoms), a carboxyl group, a hydroxyl group, an alkylsulfonylsulfamoyl group (such as —CONHSO ₂ CH ₃ ) are exemplified. still,
The alkyl group as a substituent may be further substituted with a hydroxyl group, a halogen atom, an alkoxy group (preferably having 1 to 4 carbon atoms), or the like.

In the general formula (VI), the oxygen atom of the ester group bonded to A ₆ may be bonded at any position of the carbon atom constituting the bridged alicyclic ring structure including Z _6. Good.

Specific examples of the repeating unit represented by formula (VI) are shown below, but it should not be construed that the invention is limited thereto.

[0197]

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[0198]

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Further, it may contain a repeating unit having a group represented by the following formula (VII).

[0200]

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[0202] In the general formula _{(VII), R 2 c~R 4} c represents a hydrogen atom or a hydroxyl group independently. Provided that at least one of R ₂ c to R ₄ c represents a hydroxyl group.

The group represented by formula (VII) is preferably a dihydroxy form or a monohydroxy form, more preferably a dihydroxy form.

The repeating unit having a group represented by the general formula (VII) includes the above-mentioned general formula (II-A) or (II-
B) wherein at least one of R ₁₃ ′ to R ₁₆ ′ has a group represented by the general formula (VII) (for example, —COO
R ₅ of R ₅ represents a group represented by formulas (V-1) to (V-4)), or a repeating unit represented by the following formula (AII).

[0204]

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[0205] In formula (AII), R ₁ c represents a hydrogen atom or a methyl group. R ₂ c~R ₄ c represents a hydrogen atom or a hydroxyl group independently. Provided that at least one of R ₂ c to R ₄ c represents a hydroxyl group.

Specific examples of the repeating unit having the structure represented by formula (AII) are shown below, but it should not be construed that the invention is limited thereto.

[0207]

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Further, it may contain a repeating unit having a group represented by the following formula (VIII).

[0209]

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In the general formula (VIII): Z ₂ represents —O— or —
N (R ₄₁ )-. Here, R ₄₁ is a hydrogen atom, a hydroxyl group, an alkyl group, a haloalkyl group, or —OSO ₂ —R
Represents ₄₂ . R ₄₂ represents an alkyl group, a haloalkyl group, a cycloalkyl group or a camphor residue.

In the above formula (VIII), Z ₂ represents-
Represents O- or -N ( _R41 )-. Here, R ₄₁ represents a hydrogen atom, a hydroxyl group, an alkyl group, a haloalkyl group, or —OS
Represents O ₂ -R ₄₂ . R ₄₂ represents an alkyl group, a haloalkyl group, a cycloalkyl group or a camphor residue.

The alkyl group for R ₄₁ and R ₄₂ is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, more preferably a linear or branched alkyl group having 1 to 6 carbon atoms. And more preferably methyl, ethyl, propyl, isopropyl, n-
A butyl group, an isobutyl group, a sec-butyl group and a t-butyl group. Examples of the haloalkyl group for R ₄₁ and R ₄₂ include a trifluoromethyl group, a nanofluorobutyl group, a pentadecafluorooctyl group, and a trichloromethyl group. Examples of the cycloalkyl group for R ₄₂ include a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.

The alkyl group and haloalkyl group as R ₄₁ and R ₄₂ , the cycloalkyl group or camphor residue as R ₄₂ may have a substituent. Examples of such a substituent include a hydroxyl group, a carboxyl group, a cyano group, a halogen atom (for example, a chlorine atom, a bromine atom, a fluorine atom and an iodine atom), and an alkoxy group (preferably having 1 to 1 carbon atoms).
4, for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, etc., an acyl group (preferably having 2 to 5 carbon atoms, for example, a formyl group, an acetyl group, etc.), an acyloxy group (preferably having 2 to 5 carbon atoms, for example, An acetoxy group) and an aryl group (preferably having 6 to 14 carbon atoms, for example, a phenyl group).

Specific examples of the repeating unit represented by the general formula (VIII) include the following [I'-1] to [I'-7], but the present invention is limited to these specific examples. Not something.

[0215]

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[0216]

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The acid-decomposable resin as the component (B) is, in addition to the above-mentioned repeating structural units, dry etching resistance, suitability for a standard developer, substrate adhesion, resist profile, and general necessary properties of a resist. Various repeating structural units can be contained for the purpose of adjusting resolution, heat resistance, sensitivity and the like.

Examples of such a repeating structural unit include repeating structural units corresponding to the following monomers, but are not limited thereto. Thereby, the performance required for the acid-decomposable resin, in particular, (1) solubility in a coating solvent, (2) film-forming property (glass transition point),
Fine adjustment of (3) alkali developability, (4) film loss (hydrophobicity, selection of alkali-soluble group), (5) adhesion of unexposed portion to substrate, (6) dry etching resistance, etc. becomes possible. . As such monomers, for example, acrylates, methacrylates, acrylamides,
Examples thereof include compounds having one addition-polymerizable unsaturated bond selected from methacrylamides, allyl compounds, vinyl ethers, vinyl esters, and the like.

Specifically, the following monomers can be mentioned. Acrylic esters (preferably alkyl acrylates having 1 to 10 carbon atoms in the alkyl group): methyl acrylate, ethyl acrylate, propyl acrylate,
Amyl acrylate, cyclohexyl acrylate, ethyl hexyl acrylate, octyl acrylate, tert-octyl acrylate, chloroethyl acrylate, 2-hydroxyethyl acrylate 2,2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimethylolpropane Monoacrylate, pentaerythritol monoacrylate, benzyl acrylate, methoxybenzyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate and the like.

Methacrylic esters (preferably alkyl methacrylate having an alkyl group having 1 to 10 carbon atoms): methyl methacrylate, ethyl methacrylate,
Propyl methacrylate, isopropyl methacrylate, amyl methacrylate, hexyl methacrylate,
Cyclohexyl methacrylate, benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, 2,2-dimethyl-3-hydroxypropyl methacrylate, trimethylolpropane monomethacrylate, penta Erythritol monomethacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate and the like.

Acrylamides: acrylamide, N-
Alkyl acrylamide (the alkyl group has 1 carbon atom
And 10 such as methyl, ethyl, propyl, butyl, t-butyl, heptyl, octyl, cyclohexyl, and hydroxyethyl. ), N, N-dialkylacrylamide (alkyl group having 1 to 10 carbon atoms, for example, methyl group, ethyl group, butyl group, isobutyl group, ethylhexyl group,
A cyclohexyl group, etc.), N-hydroxyethyl-
N-methylacrylamide, N-2-acetamidoethyl-N-acetylacrylamide and the like.

Methacrylamides: methacrylamide,
N-alkyl methacrylamide (an alkyl group having 1 to 10 carbon atoms, such as a methyl group, an ethyl group,
Butyl group, ethylhexyl group, hydroxyethyl group, cyclohexyl group, etc.), N, N-dialkylmethacrylamide (alkyl group includes ethyl group, propyl group, butyl group, etc.), N-hydroxyethyl-N-
Methyl methacrylamide and the like.

Allyl compounds: allyl esters (for example, allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate, etc.), allyloxyethanol etc.

Vinyl ethers: alkyl vinyl ethers (eg, hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1
-Methyl-2,2-dimethylpropyl vinyl ether,
2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether,
Dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether and the like.

Vinyl esters: vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxy acetate, vinyl butoxy acetate, vinyl Acetoacetate, vinyl lactate, vinyl-β-phenylbutyrate, vinylcyclohexylcarboxylate and the like.

Dialkyl itaconates: dimethyl itaconate, diethyl itaconate, dibutyl itaconate and the like. Dialkyl esters or monoalkyl esters of fumaric acid; dibutyl fumarate;

Others crotonic acid, itaconic acid, maleic anhydride, maleimide, acrylonitrile, methacrylonitrile, maleilenitrile and the like.

In addition, any addition-polymerizable unsaturated compound copolymerizable with the monomer corresponding to the above-mentioned various repeating structural units may be copolymerized.

In the acid-decomposable resin, the molar ratio of each repeating structural unit depends on the dry etching resistance of the resist, the suitability for a standard developing solution, the substrate adhesion, the resist profile, and the resolving power, heat resistance, which is a general required performance of the resist. It is set as appropriate to adjust properties, sensitivity, and the like.

Preferred embodiments of the acid-decomposable resin of the present invention include the following. (1) Those containing a repeating unit having a partial structure containing an alicyclic hydrocarbon represented by the above general formulas (pI) to (pVI) (side chain type) (2) In the general formula (II-AB) Those containing a repeating unit represented (main chain type). However, in (2), for example,
Further, the following may be mentioned. (3) Having a repeating unit represented by the general formula (II-AB), a maleic anhydride derivative and a (meth) acrylate structure (hybrid type)

In the acid-decomposable resin, the compounds represented by formulas (pI) to (pV)
The content of the repeating unit having a partial structure containing an alicyclic hydrocarbon represented by I) is 30 to
It is preferably 70 mol%, more preferably 35 to 65 mol%, and still more preferably 40 to 60 mol%. In the acid-decomposable resin, the content of the repeating unit represented by the general formula (II-AB) is preferably from 10 to 60 mol%, more preferably from 15 to 55 mol%, even more preferably from 20 to 70 mol% of all the repeating structural units. ５０50 mol%.

The content of the repeating structural unit based on the monomer of the further copolymer component in the resin can be appropriately set according to the desired performance of the resist. Based on the total number of moles of the repeating structural unit having a partial structure containing an alicyclic hydrocarbon represented by any one of the formulas (pI) to (pVI) and the repeating unit represented by the general formula (II-AB) It is preferably at most 99 mol%, more preferably at most 90 mol%, even more preferably at most 80 mol%. When the composition of the present invention is for ArF exposure,
From the viewpoint of transparency to ArF light, the resin preferably has no aromatic group.

The acid-decomposable resin used in the present invention can be synthesized according to a conventional method (for example, radical polymerization). For example, as a general synthesis method, monomer species are charged into a reaction vessel at once or in the middle of a reaction, and this is reacted with a reaction solvent as necessary, for example, ethers such as tetrahydrofuran, 1,4-dioxane, diisopropyl ether, methyl ethyl ketone, Ketones such as methyl isobutyl ketone, ester solvents such as ethyl acetate, and further dissolved in a solvent that dissolves the composition of the present invention such as propylene glycol monomethyl ether acetate described below, and then homogenized. Under an inert gas atmosphere, if necessary, heating is performed, and polymerization is started using a commercially available radical initiator (such as an azo initiator or a peroxide).
If desired, an initiator is added or added in portions, and after completion of the reaction, the mixture is poured into a solvent and a desired polymer is recovered by a method such as powder or solid recovery. Reaction concentration is 20% by weight
It is preferably at least 30% by weight, more preferably at least 40% by weight. Reaction temperature is 10 ° C. to 150
° C, preferably from 30 ° C to 120 ° C, more preferably from 50 to 100 ° C.

The weight average molecular weight of the resin according to the present invention is G
It is preferably from 1,000 to 200,000 in terms of polystyrene according to the PC method. When the weight average molecular weight is less than 1,000, heat resistance and dry etching resistance are deteriorated, so that it is not preferable. When the weight average molecular weight exceeds 200,000, the developability is deteriorated and the viscosity becomes extremely high, so that the film forming property is deteriorated. And so on, which produces very unfavorable results.

In the positive photosensitive composition of the present invention, the compounding amount of all resins according to the present invention in the whole composition is preferably 40 to 99.99% by weight based on the total solid content of the resist.
More preferably, it is 50 to 99.97% by weight.

{(C) Basic compound} The positive photosensitive composition of the present invention comprises (C) a primary aliphatic amine and a secondary aliphatic amine in order to reduce a change in performance over time from exposure to heating. Aliphatic amines, tertiary aliphatic amines, primary oxygen-containing aliphatic amines, secondary oxygen-containing aliphatic amines, tertiary oxygen-containing aliphatic amines, alcoholic nitrogen-containing compounds and substituted anilines Contains at least one selected basic compound.

Examples of the primary aliphatic amine include methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine,
Pentylamine, tert-amylamine, cyclopentylamine, hexylamine, cyclohexylamine,
Examples include heptylamine, octylamine, nonylamine, decylamine, dodecylamine, cetylamine, methylenediamine, ethylenediamine, tetraethylenepentamine and the like.

Examples of the secondary aliphatic amine include dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-sec-butylamine, dipentylamine and dicyclopentylamine. , Dihexylamine, dicyclohexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, didodecylamine, dicetylamine, N, N'-dimethylmethylenediamine, N, N'-dimethylethylenediamine, N, N'-dimethyltetraethylenepentane Min and the like can be mentioned.

Examples of the tertiary aliphatic amine include trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-sec-butylamine, tripentylamine, and the like. Tricyclopentylamine, trihexylamine, tricyclohexylamine,
Triheptylamine, trioctylamine, trinonylamine, tridecylamine, tridodecylamine, tricetylamine, N, N, N ', N'-tetramethylmethylenediamine, N, N, N', N ',- Examples include tetramethylethylenediamine, N, N, N ', N'-tetramethyltetraethylenepentamine.

The primary, secondary and tertiary oxygen-containing aliphatic amines include, for example, methoxyethoxyethylamine, bis (methoxyethoxyethyl) amine, tris
{2- (methoxymethoxy) ethyl} amine, tris {2
-(Methoxyethoxy) ethyl} amine, tris [2-
{(2-methoxyethoxy) methoxy} ethyl] amine,
Tris {2- (2-methoxyethoxy) ethyl} amine,
Tris {2- (1-methoxyethoxy) ethyl} amine,
Tris {2- (1-ethoxyethoxy) ethyl} amine,
Tris {2- (1-ethoxypropoxy) ethyl} amine, tris [2- {2- (2-hydroxyethoxy) ethoxy} ethyl] amine, 4,7,13,16,21,
24-hexaoxa-1,10-diazabicyclo [8.
8.8] hexacosan, 4,7,13,18-tetraoxa-1,10-diazabicyclo [8.5.5] eicosan, 1,4,10,13-tetraoxa-7,16-
Examples include diazabicyclooctadecane.

Examples of the alcoholic nitrogen-containing compound include monoethanolamine, diethanolamine, triethanolamine, N-ethyldiethanolamine,
N, N-diethylethanolamine, triisopropanolamine, 3-amino-1-propanol, 4-amino-1-butanol, 4- (2-hydroxyethyl) morpholine, 2- (2-hydroxyethyl) pyridine,
-(2-hydroxyethyl) piperazine, 1- [2-
(2-Hydroxyethoxy) ethyl] piperazine, piperidineethanol, 1- (2-hydroxyethyl) pyrrolidine, 1- (2-hydroxyethyl) -2-pyrrolidinone, 3-piperidino-1,2-propanediol, 3
-Pyrrolidino-1,2-propanediol, 8-hydroxyurolidine, 3-quinuclidinol, 3-tropanol, 1-methyl-2-pyrrolidineethanol, 1-aziridineethanol, N- (2-hydroxyethyl) Examples include phthalimide and N- (2-hydroxyethyl) isonicotinamide.

As the substituted aniline, for example, N, N-
Dimethylaniline, N-methylaniline, 2-methylaniline, 2-methyl-N, N-dimethylaniline, 2,
6-dimethylaniline, 2,6-dimethyl-N, N-dimethylaniline, 2,6-diethylaniline, 2,6-
Diisopropylaniline, 2,6-dipropylaniline, 2,6-dibutylamiline, 2,6-diisobutylaniline, 2,6-di-t-butylaniline, 2,4
Examples thereof include 6-triisopropylaniline, 2,4,6-tripropylaniline, and 2,4,6-tributylaniline, but are not limited thereto as long as they are substituted anilines.

The basic compound (C) used in the present invention includes tributylamine, trihexylamine, trioctylamine, triethanolamine, trismethoxymethoxyethylamine, trismethoxyethoxyethylamine, trismethoxyethoxymethoxyethylamine, And 6-diisopropylaniline are more preferred.

These (C) basic compounds may be used alone or in combination of two or more. (C) The amount of the basic compound used is usually 0.001 to 10% by weight, preferably 0.01 to 5% by weight, based on the solid content of the positive photosensitive composition.
% By weight. If the amount is less than 0.001% by weight, the effect of the addition of the basic compound cannot be obtained. On the other hand, if it exceeds 10% by weight, the sensitivity tends to decrease and the developability of the unexposed portion tends to deteriorate.

{(D) Fluorine and / or Silicon Surfactant >> The positive photosensitive composition of the present invention comprises a fluorine and / or silicon surfactant (a fluorine surfactant and a silicon surfactant). Or a surfactant containing both a fluorine atom and a silicon atom), or two or more kinds. When the positive photosensitive composition of the present invention contains the surfactant (D) described above, 2
When using an exposure light source of 50 nm or less, particularly 220 nm or less, it becomes possible to provide a resist pattern with good sensitivity and resolution, and with little adhesion and development defects. As these surfactants (D), for example, JP-A-62-36663
No., JP-A-61-226746, JP-A-61-226745, JP-A-61-226745
No. 62-170950, JP-A-63-34540, JP-A-7-230165,
JP-A-8-62834, JP-A-9-54432, JP-A-9-5988,
U.S. Pat.Nos. 5,405,720, 5,306,692, 5,529,881, and 529
6330, 5436098, 5576143, 5294511,
No. 5,824,451, and the following commercially available surfactants can be used as they are. As a commercially available surfactant that can be used, for example, F-top EF30
1, EF303, (Shin-Akita Chemical Co., Ltd.), Florard FC430, 431
(Manufactured by Sumitomo 3M Limited), Mega Fuck F171, F173, F1
76, F189, R08 (Dai Nippon Ink Co., Ltd.), Surflon S
-382, SC101, 102, 103, 104, 105, 106 (manufactured by Asahi Glass Co., Ltd.) and fluorinated surfactants such as Troysol S-366 (manufactured by Troy Chemical Co., Ltd.) or silicon-based surfactants. Can be. Also, polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can be used as a silicon-based surfactant.

The amount of the surfactant used is preferably 0.000 to the total amount of the positive photosensitive composition (excluding the solvent).
The content is 1 to 2% by weight, more preferably 0.001 to 1% by weight.

{(E) Organic Solvent} The positive photosensitive composition of the present invention is used by dissolving the above components in a predetermined organic solvent. Examples of the organic solvent that can be used include, for example, ethylene dichloride, cyclohexanone, cyclopentanone,
-Heptanone, γ-butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, toluene, ethyl acetate, lactic acid Methyl, ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate,
Examples thereof include methyl pyruvate, ethyl pyruvate, propyl pyruvate, N, N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, tetrahydrofuran and the like.

In the present invention, it is preferable to use, as the organic solvent, a mixed solvent obtained by mixing a solvent containing a hydroxyl group in the structure and a solvent not containing a hydroxyl group. This can reduce generation of particles during storage of the resist solution. As the solvent containing a hydroxyl group, for example,
Ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethyl lactate and the like, among which propylene glycol monomethyl ether and ethyl lactate are particularly preferred preferable. Examples of the solvent containing no hydroxyl group include propylene glycol monomethyl ether acetate, ethylethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, butyl acetate, N-methylpyrrolidone, N, N-dimethylacetamide, dimethylsulfoxide and the like. Among these, propylene glycol monomethyl ether acetate, ethyl ethoxypropionate, 2-heptanone,
γ-butyrolactone, cyclohexanone and butyl acetate are particularly preferred, and propylene glycol monomethyl ether acetate, ethyl ethoxypropionate and 2-heptanone are most preferred. The mixing ratio (weight) of the solvent containing a hydroxyl group to the solvent not containing a hydroxyl group is from 1/99 to
The ratio is 99/1, preferably 10/90 to 90/10, and more preferably 20/80 to 60/40. A mixed solvent containing 50% by weight or more of a solvent containing no hydroxyl group is particularly preferred in view of coating uniformity.

{(F) Acid Decomposable Dissolution Inhibiting Compound} The positive photosensitive composition of the present invention has a group which is decomposed by the action of (F) acid to increase the solubility in an alkaline developer. ,
Dissolution inhibiting low molecular weight compounds having a molecular weight of 3000 or less (hereinafter, referred to as
"(F) acid-decomposable dissolution inhibiting compound"). Proceeding of SPIE, 2724,355 (1996)
An alicyclic or aliphatic compound containing an acid-decomposable group, such as the cholic acid derivative containing an acid-decomposable group described in (1), is preferred as the acid-decomposable dissolution inhibiting compound (F). Examples of the acid-decomposable group and the alicyclic structure include the same as those described for the acid-decomposable resin. (F) The amount of the acid-decomposable dissolution-inhibiting compound to be added is preferably 3 to 50% by weight, more preferably 5 to 40% by weight, based on the solid content of the whole positive photosensitive composition. . Specific examples of (F) the acid-decomposable dissolution inhibiting compound are shown below, but the invention is not limited thereto.

[0250]

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{(G) Alkali-soluble resin} The positive photosensitive composition of the present invention does not contain an acid-decomposable group.
(D) A resin that is insoluble in water and soluble in an alkaline developer can be contained, thereby improving sensitivity. In the present invention, a novolak resin having a molecular weight of about 1,000 to 20,000 and a polyhydroxystyrene derivative having a molecular weight of about 3,000 to 50,000 can be used as such a resin. However, these resins have large absorption for light having a wavelength of 250 nm or less. It is preferable to use a partially hydrogenated product or to use it in an amount of 30% by weight or less of the total resin amount. Further, a resin containing a carboxyl group as an alkali-soluble group can also be used. The resin containing a carboxyl group preferably has a monocyclic or polycyclic alicyclic hydrocarbon group for improving dry etching resistance.
Specifically, a copolymer of a methacrylic acid ester having an alicyclic hydrocarbon structure and a non-acid-decomposable structure and a (meth) acrylic acid or a (meth) acrylic acid ester of an alicyclic hydrocarbon group having a terminal carboxyl group And the like.

{Other Additives} In the positive photosensitive composition of the present invention, if necessary, a dye, a plasticizer, a surfactant other than the above-mentioned component (D), a photosensitizer, and a developer And the like which promote the solubility of the compound. The compound capable of accelerating dissolution in a developer that can be used in the present invention is a low molecular compound having a molecular weight of 1,000 or less and having two or more phenolic OH groups or one or more carboxy groups. When it has a carboxy group, an alicyclic or aliphatic compound is preferable for the same reason as described above. The preferred addition amount of these dissolution promoting compounds is 2 to 50% by weight, more preferably 5 to 50% by weight, based on the resin which is decomposed by the action of the acid (B) and has increased solubility in an alkali developer.
30% by weight. An addition amount exceeding 50% by weight is not preferable because new development defects such as development residue deterioration and pattern deformation during development occur.

A phenol compound having a molecular weight of 1,000 or less can be prepared by those skilled in the art by referring to the methods described in, for example, JP-A-4-122938, JP-A-2-28531, US Pat. No. 4,916,210, and EP 219294. It can be easily synthesized. Specific examples of the alicyclic group having a carboxyl group or an aliphatic compound include carboxylic acid derivatives having a steroid structure such as cholic acid, deoxycholic acid, and lithocholic acid, adamantanecarboxylic acid derivatives, adamantanedicarboxylic acid, cyclohexanecarboxylic acid, and cyclohexane. Examples include, but are not limited to, dicarboxylic acids.

In the present invention, a surfactant other than the (D) fluorine-based and / or silicon-based surfactant may be added. Specifically, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether, polyoxyethylene octyl phenol ether, polyoxyethylene nonyl phenol ether and the like Polyoxyethylene alkyl allyl ethers, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate,
Sorbitan fatty acid esters such as sorbitan tristearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate,
Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate, and the like. These surfactants may be added alone or in some combination.

<Method of Use> The positive photosensitive composition of the present invention is used by dissolving the above-mentioned components in a predetermined organic solvent, preferably in the above-mentioned mixed solvent, and coating it on a predetermined support as follows. . That is, the above-mentioned positive photosensitive composition is applied to a substrate (for example, silicon / silicon) used for manufacturing a precision integrated circuit device.
(A silicon dioxide coating) by a suitable coating method such as a spinner or a coater. After the application, the film is exposed through a predetermined mask, baked and developed. By doing so, a good resist pattern can be obtained. Here, the exposure light is preferably far ultraviolet light having a wavelength of 250 nm or less, more preferably 220 nm or less. Specifically, a KrF excimer laser (248 nm), Ar
Examples include an F excimer laser (193 nm), an F ₂ excimer laser (157 nm), X-rays, and an electron beam.

In the developing step, a developing solution is used as follows. Examples of the developer for the positive photosensitive composition include inorganic hydroxides such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia; primary amines such as ethylamine and n-propylamine. , Secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcoholamines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide And alkaline aqueous solutions of cyclic amines such as pyrrole and pyrhelidine. Further, an appropriate amount of an alcohol or a surfactant may be added to the above alkaline aqueous solution for use.

[0257]

EXAMPLES The present invention will now be described in detail with reference to examples, but the scope of the present invention is not at all limited by the examples.

<Synthesis example of resin> Synthesis example (1) Synthesis of resin (1) (side chain type) 2-ethyl-2-adamantyl methacrylate and butyrolactone methacrylate were charged at a ratio of 55/45, and methyl ethyl ketone / tetrahydrofuran = 5 / 5 to prepare 100 mL of a 20% solids solution. To this solution, 2 mol% of V-65 manufactured by Wako Pure Chemical Industries, Ltd. was added, and this was added dropwise to 10 mL of methyl ethyl ketone heated to 60 ° C. over 4 hours under a nitrogen atmosphere. After the addition was completed, the reaction solution was heated for 4 hours, 1 mol% of V-65 was added again, and the mixture was stirred for 4 hours. After completion of the reaction, the reaction solution was cooled to room temperature, and 3 L of a mixed solvent of distilled water / ISO propyl alcohol = 1/1 was used.
The resin (1) as a white powder crystallized and precipitated was recovered. The polymer composition ratio determined from C ¹³ NMR was 46/54.
Met. The weight average molecular weight in terms of standard polystyrene determined by GPC measurement was 10,700.

Resins (2) to (15) were synthesized by the same operation as in Synthesis Example (1). The following resin (2) to
The composition ratio and molecular weight of (15) are shown. (Repeat unit 1,
2, 3, and 4 are the order from the left of the structural formula. )

[0260]

[Table 1]

The structures of the resins (1) to (15) are shown below.

[0262]

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[0263]

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[0264]

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[0265]

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Synthesis Example (2) Synthesis of Resin (16) (Main Chain Type) Norbornene carboxylic acid t-butyl ester, norbornene carboxylic acid butyrolactone ester and maleic anhydride (molar ratio 40/10/50) and THF (reaction temperature 6)
0% by weight) was placed in a separable flask and heated at 60 ° C. under a nitrogen stream. When the reaction temperature was stabilized, 2 mol% of a radical initiator V-601 manufactured by Wako Pure Chemical Industries, Ltd. was added to start the reaction. Heat for 12 hours. After diluting the obtained reaction mixture twice with tetrahydrofuran, hexane /
It was poured into a mixed solution of isopropyl alcohol = 1/1 to precipitate a white powder. Filter out the precipitated powder,
Drying yielded the desired resin (16). When the molecular weight analysis of the obtained resin (16) by GPC was attempted, it was 8300 (weight average) in terms of polystyrene. From the NMR spectrum, it was confirmed that the molar ratio of norbornene carboxylic acid t-butyl ester / norbornene carboxylic acid butyrolactone ester / maleic anhydride repeating unit of the resin (1) was 42/8/50.

Resins (17) to (27) were synthesized in the same manner as in Synthesis Example (2). The following resin (1)
The composition ratios and molecular weights of 7) to (27) are shown. (Alicyclic olefin units 1, 2, and 3 are in order from the left in the structural formula.)

[0268]

[Table 2]

The following resins (16) to (27)
The structure of is shown.

[0270]

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[0271]

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Synthesis Example (3) Synthesis of Resin (28) (Hybrid Type) Norbornene, maleic anhydride, tbutyl acrylate, and 2-methylcyclohexyl-2-propyl acrylate were reacted at a molar ratio of 35/35/20/10. The solution was charged in a container and dissolved in tetrahydrofuran to prepare a solution having a solid content of 60%. This was heated at 65 ° C. under a stream of nitrogen. When the reaction temperature was stabilized, 1 mol% of a radical initiator V-601 manufactured by Wako Pure Chemical Industries, Ltd. was added to start the reaction. After heating for 8 hours, the reaction mixture was diluted twice with tetrahydrofuran, and then poured into 5 times the volume of hexane of the reaction mixture to precipitate a white powder. The precipitated powder was taken out by filtration, dissolved in methyl ethyl ketone, reprecipitated in a 5-fold volume hexane / t-butyl methyl ether = 1/1 mixed solvent, and the precipitated white powder was collected by filtration, dried, and dried. As a result, a resin (28) was obtained. When the molecular weight analysis of the obtained resin (28) by GPC was tried, it was 1 in terms of polystyrene.
2,100 (weight average). From the NMR spectrum, the composition of the resin (1) was as follows: norbornene / maleic anhydride / t-butyl acrylate / 2-methylcyclohexyl-2-propyl acrylate of the present invention in a molar ratio of 32 /
39/19/10.

In the same manner as in Synthesis Example (3), Resins (29) to (41) were synthesized. The following resin (2)
The composition ratios and molecular weights of 9) to (41) are shown.

[0274]

[Table 3]

The following resins (28) to (41)
The structure of is shown.

[0276]

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[0277]

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[0278]

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[0279]

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Synthesis Example (4) Synthesis of Resin (42) (Hybrid Type) Norbornene carboxylic acid t-butyl ester, maleic anhydride, 2-methyl-2-adamantyl acrylate, norbornene lactone acrylate in a molar ratio of 20/20.
/ 35/25, and dissolved in a solvent of methyl ethyl ketone / tetrahydrofuran = 1/1 to obtain a solid content of 6
A 0% solution was prepared. This was heated at 65 ° C. under a stream of nitrogen. When the reaction temperature was stabilized, 3 mol% of a radical initiator V-601 manufactured by Wako Pure Chemical Industries, Ltd. was added to start the reaction. After heating for 12 hours, the reaction mixture was poured into 5 times the amount of hexane to precipitate a white powder. The precipitated powder was dissolved again in a solvent of methyl ethyl ketone / tetrahydrofuran = 1/1 and poured into a 5-fold amount of hexane / methyl tBu ether to precipitate a white powder, which was filtered and taken out. This operation was repeated again to obtain the desired resin (42) by drying. When the molecular weight analysis (RI analysis) of the obtained resin (42) by GPC was attempted, polystyrene conversion was 11%.
600 (weight average), the amount of residual monomer was 0.4%. From the NMR spectrum, the composition of the resin (1) was found to be the norbornene / maleic anhydride / 2-methyl-
The molar ratio of 2-adamantyl acrylate / norbornene lactone acrylate was 18/23/34/25.

Resins (43) to (66) were synthesized in the same manner as in Synthesis Example (4). The following resin (4)
The composition ratios and molecular weights of 3) to (66) are shown.

[0282]

[Table 4]

The following resins (42) to (66)
The structure of is shown.

[0284]

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[0285]

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[0286]

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[0287]

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[0288]

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<Preparation of Resist> [Examples 1 to 66 and Comparative Examples 1 to 4] The materials shown in Tables 5 to 7 were dissolved to prepare a solution having a solid concentration of 12% by weight, and this was then dissolved in 0.1 μm Teflon ( (Trademark) filter to prepare a positive photosensitive composition. The prepared compositions were evaluated by the following methods, and the results are shown in Tables 8 to 10.

[0290]

[Table 5]

[0291]

[Table 6]

[0292]

[Table 7]

The abbreviations in Tables 5 to 7 are as follows. OA; octylamine DOA; dioctylamine TBA; tributylamine THA; trihexylamine TOA; trioctylamine TETA; triethanolamine MEEA; methoxyethoxyethylamine BMEEA; bis (methoxyethoxyethyl) amine TMMEA; trismethoxymethoxyethylamine TMEAA; Methoxyethoxyethylamine TMMEA; Trismethoxyethoxymethoxyethylamine DIA; 2,6-diisopropylaniline LCB; t-butyl lithocholic acid

W-1: Megafac F176 (Dai Nippon Ink Co., Ltd.) (fluorine) W-2: Megafac R08 (Dai Nippon Ink Co., Ltd.)
(Fluorine and silicon type) W-3; Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) (silicon type) W-4; Troysol S-366 (Troy Chemical Co., Ltd.)
Made)

The abbreviations for the solvents are as follows. In addition, the ratio in the case of multiple use in Tables 5-7 is a weight ratio. A1; propylene glycol methyl ether acetate A2; 2-heptanone A3; ethyl ethoxypropionate A4; γ-butyrolactone A5; cyclohexanone B1; propylene glycol methyl ether B2; ethyl lactate

<Image Evaluation Method> (1) Sensitivity Evaluation An antireflection film DUV-42 manufactured by Brewer Science Co. was uniformly applied on a silicon substrate which had been subjected to hexamethyldisilazane treatment by a spin coater at 600 Å, and the coating was performed at 100 ° C. After drying on a hot plate for 90 seconds, heat drying was performed at 190 ° C. for 240 seconds. afterwards,
Each photosensitive resin composition is applied by a spin coater and is applied at 120 ° C.
For 90 seconds to form a 0.30 μm resist film. An ArF excimer laser stepper (ISI NA = 0.
Exposure was performed in 6), and immediately after the exposure, heating was performed on a hot plate at 120 ° C. for 90 seconds. Further, the resist was developed with a 2.38% aqueous solution of tetramethylammonium hydroxide at 23 ° C. for 60 seconds, rinsed with pure water for 30 seconds, and dried to obtain a resist line pattern. The sensitivity indicates an exposure amount for reproducing a 0.15 μm line and space (1/1) pattern.

(2) Evaluation of Edge Roughness The edge roughness was measured using a length-measuring scanning electron microscope (SE).
M) using the edge roughness of the isolated pattern,
In the range of 5 μm in the longitudinal direction edge of the line pattern, the distance from the reference line where the edge should be located is measured by the SEM.
(S-8840 manufactured by Hitachi, Ltd.) was used to measure 50 points, the standard deviation was determined, and 3σ was calculated. The smaller the value, the better the performance.

[0298]

[Table 8]

[0299]

[Table 9]

[0300]

[Table 10]

The following are clear from the results shown in Tables 8 to 10. The compositions of Examples 1 to 66 have high sensitivity and excellent edge roughness. On the other hand, Comparative Examples 1 to 4
The composition of Example 1 is inferior in sensitivity and edge roughness as compared with the compositions of Examples.

[0302]

The positive photosensitive composition according to the present invention comprises:
High sensitivity and excellent edge roughness.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Kenichiro Sato 4000F, Kawajiri, Yoshida-cho, Haibara-gun, Shizuoka Prefecture F-term in Fujisha Shin Film Co., Ltd. AR11P BA02P BA03P BA04P BA05P BA06P BA11P BA12P BA15P BA16P BA20P BA34P BA40P BA55P BB01P BB03P BB05P BB07P BC02P BC03P BC04P BC07P BC08P BC09P BC12P BC15P BC53P CA01 JA38

Claims (4)

[Claims] (A) an acid generator represented by the following formula (I) that generates an acid upon irradiation with actinic rays or radiation; (B) an acid generator having a monocyclic or polycyclic alicyclic hydrocarbon structure, A resin that decomposes by action to increase its solubility in an alkaline developer,
(C) primary aliphatic amine, secondary aliphatic amine, tertiary aliphatic amine, primary oxygen-containing aliphatic amine, secondary oxygen-containing aliphatic amine, tertiary oxygen-containing aliphatic amine ,
At least one basic compound selected from the group consisting of alcoholic nitrogen-containing compounds and substituted anilines, and (D)
A positive photosensitive composition containing fluorine and / or a silicon-based surfactant. Embedded image In the formula (I), R _{1 to} R ₅ represent a hydrogen atom, an alkyl group, an alkoxy group, a nitro group, a halogen atom, an alkyloxycarbonyl group or an aryl group, and at least two or more of R _{1 to} R ₅ They may combine to form a ring structure. R
₆ and R ₇ represent a hydrogen atom, an alkyl group, a cyano group or an aryl group. Y ₁ and Y ₂ represent an alkyl group, an aryl group, an aralkyl group or an aromatic group containing a hetero atom, and Y ₁ and Y ₂ may combine to form a ring. Y
₃ represents a single bond or a divalent linking group. X ^- represents a non-nucleophilic anion. Provided that at least one of R ₁ to R ₅ and at least one of Y ₁ or Y ₂ are bonded to form a ring, or at least one of R ₁ to R ₅ is bonded to at least one of R ₆ or R ₇ To form a ring. Note that R ₁
To R ₇ , or at any position of Y ₁ or Y ₂ , via a linking group to form the structure of formula (I) 2
You may have more than one. 2. The method according to claim 1, wherein the acid generator (A) has the following general formula (I):
The positive photosensitive composition according to claim 1, which is a compound represented by A) or (IB). Embedded image In the formula (IA), R _{1 to} R ₄ , R ₇ , Y ₁ , Y ₂ and X ⁻ are the same as those in the above formula (I), and Y is a single bond or 2
Represents a valent linking group. In the formula (IB), R _{1 to} R ₄ , R ₆ ,
R ₇ , Y ₁ and X ⁻ are the same as those in the above formula (I), and Y represents a single bond or a divalent linking group. 3. The method according to claim 1, further comprising (F) a dissolution inhibiting low molecular compound having a group capable of increasing the solubility in an alkaline developer by being decomposed by the action of an acid and having a molecular weight of 3000 or less. The positive photosensitive composition as described in the above. 4. The positive photosensitive composition according to claim 1, further comprising (E) a mixed solvent obtained by mixing a solvent containing a hydroxyl group and a solvent not containing a hydroxyl group.