JP2008287283A - Positive photosensitive composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a positive photosensitive composition which has high sensitivity and is improved in edge roughness of a pattern. <P>SOLUTION: The positive photosensitive composition comprises: (A) a compound capable of generating an acid upon irradiation with actinic rays or radiation; (B) a resin which has a monocyclic or polycyclic alicyclic hydrocarbon structure and decomposes by an action of an acid to increase its solubility in an alkali developer; (C) a basic compound containing a ≥8C substituted or unsubstituted aliphatic hydrocarbon group within a molecule; and a nitrogen-containing basic compound other than the basic compound (C). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  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 or a thermal head, and other photofabrication processes. More specifically, the present invention relates to a positive photosensitive composition suitable for using far ultraviolet rays of 250 nm or less as an exposure light source.

  The chemically amplified positive resist composition generates an acid in the exposed area by irradiation with radiation such as far ultraviolet light, and dissolves in the developing solution of the active radiation irradiated area and the non-irradiated area by a reaction using this acid as a catalyst. It is a pattern forming material that changes the properties and forms the pattern on the substrate.

  When a KrF excimer laser is used as an exposure light source, a resin having a basic skeleton of poly (hydroxystyrene) having a small absorption mainly in the 248 nm region is used as a main component. A pattern is formed, which is a better system than the conventional naphthoquinone diazide / novolak resin system.

However, when a further short wavelength light source, for example, an ArF excimer laser (193 nm) is used as an exposure light source, the compound having an aromatic group exhibits a large absorption in the 193 nm region. It wasn't.
In addition, the use of poly (meth) acrylate as a polymer having a small absorption in the 193 nm wavelength region is described in Non-Patent Document 1, but this polymer is generally resistant to dry etching performed in a semiconductor manufacturing process. There was the problem that it was low compared with the conventional phenol resin which has this.

  Triarylsulfonium salt acid generators and phenacylsulfonium salt acid generators are known as acid generators for chemically amplified positive resist compositions, but triarylsulfonium salt acid generators are 193 nm. The phenacylsulfonium salt-based acid generator has low sensitivity because of its low acid-generating ability.

In recent years, with the demand for miniaturization of semiconductor chips, the design pattern of the fine semiconductor has reached a fine region of 0.13 to 0.35 μm. However, the conventional techniques have not been able to satisfy various characteristics such as suitability for halftone exposure.
Here, the suitability for halftone exposure means that side lobes (a phenomenon in which the surface of an unexposed part becomes weak and holes begin to be perforated) that occur when exposure using a halftone phase shift mask is performed, Or it shows that it is hard to generate | occur | produce and is also called sidelobe tolerance.

J. et al. Vac. Sci. Technol. B9, 3357 (1991).

  Accordingly, an object of the present invention is to provide a positive photosensitive composition having excellent halftone exposure suitability (side lobe resistance).

  The present invention is a positive photosensitive composition having the following constitution, whereby the above-mentioned object of the present invention is achieved.

(1) (A) a compound that generates an acid upon irradiation with actinic rays or radiation,
(B) a resin having a monocyclic or polycyclic alicyclic hydrocarbon structure, decomposed by the action of an acid, and increased in solubility in an alkali developer,
(C) A basic compound containing a substituted or unsubstituted aliphatic hydrocarbon group having at least 8 carbon atoms in the molecule and a nitrogen-containing basic compound other than the basic compound of component (C) A positive photosensitive composition.

  (2) The positive photosensitive material as described in (1), wherein the basic compound of component (C) contains a substituted or unsubstituted aliphatic hydrocarbon group having at least 10 carbon atoms in the molecule. Composition.

  (3) The positive photosensitive composition as described in (1) or (2), further comprising (E) a mixed solvent obtained by mixing a solvent containing a hydroxyl group and a solvent not containing a hydroxyl group.

  (4) The resin of the component (B) is represented by the repeating unit having a partial structure containing an alicyclic hydrocarbon represented by the following general formula (pI) to general formula (pVI) and the general formula (II-AB). The positive photosensitive composition as described in any one of (1) to (3), which is a resin containing at least one selected from the group of repeating units.

In the formula, R ₁₁ represents a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group or a sec-butyl group, and Z forms an alicyclic hydrocarbon group together with a carbon atom. Represents the atomic group necessary to do.
R _{12 to} R ₁₆ each independently represents a linear or branched alkyl group or alicyclic hydrocarbon group having 1 to 4 carbon atoms, provided that at least one of R _{12 to} R ₁₄ , or Either R ₁₅ or R ₁₆ represents an alicyclic hydrocarbon group.
R _{17 to} R ₂₁ each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or an alicyclic hydrocarbon group, 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 alicyclic hydrocarbon group having 1 to 4 carbon atoms.
R _{22 to} R ₂₅ each independently represents a linear or branched alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group, provided that at least one of R _{22 to} R ₂₅ is a fat Represents a cyclic hydrocarbon group. R ₂₃ and R ₂₄ may be bonded to each other to form a ring.

In 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 contains two bonded carbon atoms (C—C) and may have a substituent.

  (5) The positive photosensitive composition according to any one of (1) to (4), further comprising (D) fluorine and / or a silicon-based surfactant.

  (6) Further, (F) a dissolution inhibiting low molecular weight compound having a group that decomposes by the action of an acid to increase the solubility in an alkali developer and has a molecular weight of 3000 or less (1) to (5) The positive photosensitive composition according to any one of the above.

  (7) A pattern forming method comprising forming a film from the positive photosensitive composition according to any one of (1) to (6), and exposing and developing the film.

  The present invention can provide a positive photosensitive composition excellent in halftone exposure suitability.

Hereinafter, the compounds used in the present invention will be described in detail.
<< (A) Compound that generates acid upon irradiation with actinic ray or radiation >>

The composition of the present invention contains a compound (photoacid generator) that generates an acid upon irradiation with actinic rays or radiation as the component (A).
Examples of such photoacid generators include photoinitiators for photocationic polymerization, photoinitiators for photoradical polymerization, photodecolorants for dyes, photochromic agents, actinic rays used in microresists, etc. Known compounds that generate an acid upon irradiation with radiation and mixtures thereof can be appropriately selected and used.

  For example, diazonium salts, ammonium salts, phosphonium salts, iodonium salts, sulfonium salts, selenonium salts, onium salts such as arsonium salts, organic halogen compounds, organic metal / organic halides, photoacid generators having o-nitrobenzyl type protecting groups Examples thereof include disulfone compounds and compounds that generate photosulfonic acid by photolysis, such as agents and iminosulfonates.

  Further, a group which generates an acid upon irradiation with these actinic rays or radiation, or a compound in which a compound is introduced into the main chain or side chain of the polymer, for example, US Pat. No. 3,849,137, German Patent No. 3914407, JP 63-26653, JP 55-164824, JP 62-69263, JP 63-146038, JP 63-163452, JP 62-153853, JP 63- The compounds described in No. 146029 and the like can be used.

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

  Of the compounds that decompose upon irradiation with actinic rays or radiation to generate an acid, those that are particularly effective are described below.

(1) An iodonium salt represented by the following general formula (PAG1) or a sulfonium salt represented by the general formula (PAG2).

Here, the formulas Ar ¹ and Ar ² each independently represent a substituted or unsubstituted aryl group.
Preferable 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 represents a substituted or unsubstituted alkyl group or aryl group. Preferred are aryl groups having 6 to 14 carbon atoms, alkyl groups having 1 to 8 carbon atoms, and substituted derivatives thereof.
Preferred substituents are an aryl 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. An alkoxy group having 1 to 8 carbon atoms, a carboxyl group, and an alkoxycarbonyl group;

Z ⁻ represents a counter anion, for example, a perfluoroalkanesulfonic acid anion such as BF ₄ ⁻ , AsF ₆ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ , Si F ₆ ²⁻ , ClO ₄ ⁻ , CF ₃ SO ₃ ⁻ , penta Examples include, but are not limited to, condensed polynuclear aromatic sulfonate anions such as fluorobenzene sulfonate anion and naphthalene-1-sulfonate anion, anthraquinone sulfonate anion, and sulfonate group-containing dyes.

Two of R ²⁰³ , R ²⁰⁴ and R ²⁰⁵ and Ar ¹ and Ar ² may be bonded via a single bond or a substituent.

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

  The above onium salts represented by the general formulas (PAG1) and (PAG2) are known and can be synthesized by, for example, the methods described in US Pat. Nos. 2,807,648 and 4,247,473, and JP-A-53-101,331.

(2) A disulfone derivative represented by the following general formula (PAG3) or an iminosulfonate derivative represented by the general formula (PAG4).

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.

(3) A diazodisulfone derivative represented by the following general formula (PAG5).

Here, R represents a linear, branched or cyclic alkyl group, or an aryl group which may be substituted.
Specific examples include the following compounds, but are not limited thereto.

  In addition to the above compounds, compounds represented by the following general formula (I) are also effectively used as the acid generator of the component (A) of the present invention.

In 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 of R _{1 to} R ₅ are bonded to form a ring structure. It may be formed.
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 be bonded 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 and at least one of R ₆ or R ₇ are bonded. To form a ring.
In addition, it may be bonded via a linking group at any position of R ₁ to R ₇ or at any position of Y ₁ or Y ₂ and may have two or more structures of the formula (I).

The alkyl group represented by 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, an ethyl group, and a propyl group. Group, n-butyl group, sec-butyl group, t-butyl group and the like.
The alkoxy group in R _{1 to} R ₅ and the alkyloxycarbonyl group is a substituted or unsubstituted alkoxy group, preferably an alkoxy group having 1 to 5 carbon atoms. 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. As the unsubstituted aryl group, for example, phenyl Group, tolyl group, naphthyl group and the like.
Examples of the halogen atom represented by R _{1 to} R ₅ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The alkyl group of Y ₁ and Y ₂ is a substituted or unsubstituted alkyl group, preferably an alkyl group having 1 to 30 carbon atoms. Examples of the unsubstituted alkyl group include linear or branched alkyl groups such as a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, and a t-butyl group, and a cyclopropyl group, Examples thereof 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 an aralkyl group having 7 to 12 carbon atoms. Examples of the unsubstituted aralkyl group include benzyl group, phenethyl group, cumyl group Groups and the like.

The aromatic group containing a hetero atom represents 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 an aromatic group containing a substituted or unsubstituted hetero atom. Examples of the unsubstituted group include furan, thiophene, pyrrole, pyridine, and indole. And the heterocyclic aromatic hydrocarbon group.

Y ₁ and Y ₂ may combine to form a ring together with S ⁺ in formula (I).
In this case, examples of the group formed by combining Y ₁ and Y ₂ include an alkylene group having 4 to 10 carbon atoms, preferably a butylene group, a pentylene group, and a hexylene group, and particularly preferably a butylene group and a pentylene group. Can be mentioned.
In addition, the ring formed by combining Y ₁ and Y ₂ together with S ⁺ in formula (I) may contain a hetero atom.

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

Y ₃ represents a single bond or a divalent linking group, and 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 include two or more of these are preferable.

Examples of the non-nucleophilic anion X ⁻ include a sulfonate anion and a carboxylate anion.
A non-nucleophilic anion is an anion that has an extremely low ability to cause a nucleophilic reaction, and is an anion that can suppress degradation over time due to an intramolecular nucleophilic reaction. This improves the temporal stability of the resist.
Examples of the sulfonate anion include an alkyl sulfonate anion, an aryl sulfonate anion, and a camphor sulfonate anion.
Examples of the carboxylate anion include an alkylcarboxylate anion, an arylcarboxylate anion, and an aralkylcarboxylate anion.

The alkyl group in the alkylsulfonate anion is preferably an alkyl group having 1 to 30 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, or a pentyl group. , Neopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, cyclo Examples thereof include a propyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, a norbornyl group, and a boronyl group.
The aryl group in the aryl sulfonate anion is preferably 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 aryl group in the alkyl sulfonate anion and aryl sulfonate anion may have a substituent.
Examples of the substituent include a halogen atom, an alkyl group, an alkoxy group, and an alkylthio group.

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, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, pentyl group, neopentyl group Hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group, etc. it can.
As an alkoxy group, Preferably a C1-C5 alkoxy group, for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group etc. can be mentioned, for example.
As the alkylthio group, for example, preferably an alkylthio group having 1 to 15 carbon atoms, for example, methylthio group, ethylthio group, propylthio group, isopropylthio group, n-butylthio group, isobutylthio group, sec-butylthio group, pentylthio group, Neopentylthio group, hexylthio group, heptylthio group, octylthio group, nonylthio group, decylthio group, undecylthio group, dodecylthio group, tridecylthio group, tetradecylthio group, pentadecylthio group, hexadecylthio group, heptadecylthio group, octadecylthio group, nonadecylthio group Group, eicosylthio group and the like. The alkyl group, alkoxy group, and alkylthio group may be further substituted with a halogen atom (preferably a fluorine atom).

Examples of the alkyl group in the alkylcarboxylate anion include the same alkyl groups as in the alkylsulfonate anion.
Examples of the aryl group in the arylcarboxylate anion include the same aryl groups as in the arylsulfonate anion.
The aralkyl group in the aralkyl carboxylate anion is preferably 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 alkylcarboxylate anion, arylcarboxylate anion and aralkylcarboxylate anion may have a substituent. Examples of the substituent are the same as those in the arylsulfonate anion. A halogen atom, an alkyl group, an alkoxy group, an alkylthio group, etc. can be mentioned.

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

In the formula (I) of the present invention, 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 At least one of R _{6 and} R ₇ is bonded to form a ring. In the compound represented by the formula (I), by forming a ring, the three-dimensional structure is fixed and the optical resolution is improved.
Further, it may be bonded via a linking group at any position of R ₁ to R ₇ , or any position of Y ₁ or Y ₂ , and may have two or more structures of the formula (I).

  Furthermore, the compound of the formula (I) is preferably the following 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 above formula (I), and Y represents a single bond or a divalent linking group. To express.
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. To express.

Y 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 include two or more of these is preferable.
In formula (IA), Y is preferably an alkylene group, an alkylene group containing an oxygen atom, or an alkylene group containing a sulfur atom. Specifically, a methylene group, an ethylene group, a propylene group, —CH ₂ —O—, —CH ₂ -S- are preferred, most preferably an ethylene group, -CH ₂ -O -, - it is a CH ₂ -S- linking group forming a 6-membered ring as. By forming a 6-membered ring, the carbonyl plane and the C—S + sigma bond become closer to vertical, and the photolysis efficiency is improved by orbital interaction.

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

  Specific examples of the compound represented by the above formula (I) are shown below, but the present invention is not limited thereto.

  In the specific example of the acid generator represented by the general formula (I), (IA-1) to (IA-30) and (IB-1) to (IB-12) are more preferable.

  The compound of the said formula (I) can be used individually by 1 type or in combination of 2 or more types.

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

  Of the compounds that generate an acid upon irradiation with actinic rays or radiation used in the present invention, examples of particularly preferred ones are listed below.

≪ (B) Resin whose dissolution rate in an alkaline developer is increased by the action of acid (also referred to as “acid-decomposable resin”) ≫

  The acid-decomposable resin (B) of the present invention may be any resin as long as it has a monocyclic or polycyclic alicyclic hydrocarbon structure and the dissolution rate in an alkali developer increases by the action of an acid. , At least one selected from the group consisting of repeating units having a partial structure containing an alicyclic hydrocarbon represented by general formula (pI) to general formula (pVI) and repeating units represented by general formula (II-AB) It is preferable that it is resin containing.

(Wherein R ₁₁ represents a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group or a sec-butyl group, and Z represents an alicyclic hydrocarbon group together with a carbon atom. Represents the atomic group necessary to form.
R _{12 to} R ₁₆ each independently represents a linear or branched alkyl group or alicyclic hydrocarbon group having 1 to 4 carbon atoms, provided that at least one of R _{12 to} R ₁₄ , or Either R ₁₅ or R ₁₆ represents an alicyclic hydrocarbon group.
R _{17 to} R ₂₁ each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or an alicyclic hydrocarbon group, 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 alicyclic hydrocarbon group having 1 to 4 carbon atoms.
R _{22 to} R ₂₅ each independently represents a linear or branched alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group, provided that at least one of R _{22 to} R ₂₅ is a fat Represents a cyclic hydrocarbon group. R ₂₃ and R ₂₄ may be bonded to each other to form a ring. )

In 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 contains two bonded carbon atoms (C—C) and may have a substituent.

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

In formulas (II-A) and (II-B):
R ₁₃ ′ to R ₁₆ ′ each independently represents a hydrogen atom, a halogen atom, a cyano group, —COOH, —C
OOR _{5 represents} a group capable of decomposing by the action of an acid, —C (═O) —XA′—R ₁₇ ′, or an optionally substituted alkyl group or cyclic hydrocarbon group.
Here, R ₅ represents an alkyl group, a cyclic hydrocarbon group, or the following —Y group, which may have a substituent.
X 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 be bonded to form a ring. n represents 0 or 1.
R ₁₇ ′ is —COOH, —COOR ₅ , —CN, a hydroxyl group, an optionally substituted alkoxy group, —CO—NH—R ₆ , —CO—NH—SO ₂ —R ₆ or -Y group is represented.
R ₆ represents an alkyl group or a cyclic hydrocarbon group which may have a substituent.
The -Y group;

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

In the general formulas (pI) to (pVI), the alkyl group in R _{12 to} R ₂₅ may be substituted or unsubstituted, and is a linear or branched alkyl group having 1 to 4 carbon atoms. Represents. 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, a sec-butyl group, and a t-butyl group.
Further, the further substituent of the alkyl group includes an alkoxy group having 1 to 4 carbon atoms, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an acyl group, an acyloxy group, a cyano group, a hydroxyl group, A carboxy group, an alkoxycarbonyl group, a nitro group, etc. can be mentioned.

The alicyclic hydrocarbon group in 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 carbon number is preferably 6-30, and particularly preferably 7-25. These alicyclic hydrocarbon groups may have a substituent.
Below, the structural example of an alicyclic part is shown among alicyclic hydrocarbon groups.

  In the present invention, preferred examples of the alicyclic moiety include adamantyl group, noradamantyl group, decalin residue, tricyclodecanyl group, tetracyclododecanyl group, norbornyl group, cedrol group, cyclohexyl group, cycloheptyl. Group, cyclooctyl group, cyclodecanyl group and 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 for 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, or a butyl group, and more preferably a substituent selected from the group consisting of a methyl group, an ethyl group, a propyl group, and an isopropyl group. To express. 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 structures represented by the general formulas (pI) to (pVI) in the resin can be used for protecting alkali-soluble groups. 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.
Preferred examples of the alkali-soluble group protected by the structure represented by the general formulas (pI) to (pVI) in the resin include groups represented by the following general formulas (pVII) to (pXI).

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

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 R may be the same or different.
A is 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, or a urea group. Represents a combination of groups.
Ra represents any group of the above formulas (pI) to (pVI).

  Specific examples of the monomer corresponding to the repeating unit represented by the general formula (pA) are shown below.

In the general 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 contains two bonded carbon atoms (C—C) and may have a substituent.

Examples of the halogen atom in R ₁₁ ′ and R ₁₂ ′ include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom.
The alkyl group in R ₁₁ ′, R ₁₂ ′, and R ₂₁ ′ to R ₃₀ ′ is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms. It is a linear or branched alkyl group, 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, or a t-butyl group.

Examples of the further substituent in the above alkyl group include a hydroxyl group, a halogen atom, a carboxyl group, an alkoxy group, an acyl group, a cyano group, and an acyloxy group. 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, and examples of the acyloxy group include an acetoxy group.

The atomic group for forming the alicyclic structure of Z ′ is an atomic group that forms a repeating unit of an alicyclic hydrocarbon which may have a substituent in a resin, and among them, a bridged type alicyclic group. An atomic group for forming a bridged alicyclic structure forming a cyclic hydrocarbon repeating unit is preferred.
Examples of the skeleton of the alicyclic hydrocarbon formed include those represented by the following structures.

  Among the above structures, preferred bridged alicyclic hydrocarbon skeletons include (5), (6), (7), (9), (10), (13), (14), (15 ), (23), (28), (36), (37), (42), (47).

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

In the general formula (II-A) or (II-B), R ₁₃ ′ to R ₁₆ ′ are each independently decomposed by the action of a hydrogen atom, a halogen atom, a cyano group, —COOH, —COOR ₅ , or an acid. Group, —C (═O) —XA′—R ₁₇ ′, or an optionally substituted alkyl group or cyclic hydrocarbon group.
R ₅ represents an alkyl group, a cyclic hydrocarbon group, or the aforementioned —Y group, which may have a substituent.
X 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 be bonded to form a ring. n represents 0 or 1.
R ₁₇ ′ is —COOH, —COOR ₅ , —CN, a hydroxyl group, an optionally substituted alkoxy group, —CO—NH—R ₆ , —CO—NH—SO ₂ —R ₆ or -Y group is represented.
R ₆ represents an alkyl group or a cyclic hydrocarbon group which may have a substituent.
In the —Y group, R ₂₁ ′ to R ₃₀ ′ each independently represents a hydrogen atom or an optionally substituted alkyl group, and a and b represent 1 or 2.

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

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

The alkyl group in 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 a linear chain having 1 to 6 carbon atoms. Or a branched alkyl group, 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, or a t-butyl group.

Examples of the cyclic hydrocarbon group in 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, a cyclohexyl group, an adamantyl group, 2- List methyl-2-adamantyl group, norbornyl group, boronyl group, isobornyl group, tricyclodecanyl group, dicyclopentenyl group, nobornane epoxy group, menthyl group, isomenthyl group, neomenthyl group, tetracyclododecanyl group, etc. Can do.
Examples of the ring formed by combining at least two of R ₁₃ ′ to R ₁₆ ′ include rings having 5 to 12 carbon atoms such as cyclopentene, cyclohexene, cycloheptane, and cyclooctane.

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.

Examples of further substituents in the 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, and a cyclic hydrocarbon group. Can do. 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.
Examples of the alkyl group and cyclic hydrocarbon group include those listed above.

The divalent linking group of 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. Single or a combination of two or more groups may be mentioned.
Examples of the alkylene group and substituted alkylene group in A ′ include groups represented by the following formulas.
− [C (R _a ) (R _b )] _r −
In the formula, R _a and R _b represent a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group, or an alkoxy group, and 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, or 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 represents an integer of 1 to 10.

  In the resin according to the present invention, the group decomposed by the action of an acid is a repeating unit having a partial structure containing an alicyclic hydrocarbon represented by the general formula (pI) to the general formula (pVI), a general formula (II -AB) and at least one repeating unit among the repeating units of the copolymerization component described below.

Various substituents of R ₁₃ ′ to R ₁₆ ′ in the general formula (II-A) or the general formula (II-B) are atomic groups for forming an alicyclic structure in the general formula (II-AB). Or it becomes a substituent of atomic group Z for forming a bridged alicyclic structure.

  Specific examples of the repeating unit represented by the general formula (II-A) or the general formula (II-B) include the following [II-1] to [II-175]. It is not limited to examples.

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

In 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 ester groups.
Ra ₁ , Rb ₁ , Rc ₁ , Rd ₁ and Re ₁ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. m and n each independently represents an integer of 0 to 3, and m + n 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 do.

In the general formula (IV), examples of the alkylene group for W ₁ include groups represented by the following formulae.
− [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 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, or 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.

Examples of further substituents in the alkyl group include a carboxyl group, an acyloxy group, a cyano group, an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group, an alkoxy group, a substituted alkoxy group, an acetylamide group, an alkoxycarbonyl group, and an acyl group. Can be mentioned.
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 unit represented by the general formula (IV) are shown below, but are not limited thereto.

In the specific example of the general formula (IV), (IV-17) to (IV-36) are preferable because the exposure margin becomes better.
Further, as the structure of the general formula (IV), those having an acrylate structure are preferable from the viewpoint that the edge roughness becomes good.

  Moreover, you may contain the repeating unit which has group represented by either of the following general formula (V-1)-(V-4).

In General Formulas (V-1) to (V-4), R _{1b to} R _5b each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an alkenyl group that 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 in R _{1b to} R _5b include linear and branched alkyl groups, which may have a substituent.
The linear or branched alkyl group is preferably a linear or branched alkyl group having 1 to 12 carbon atoms, more preferably a linear or branched alkyl group having 1 to 10 carbon atoms. More preferably, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl It is a group.
As a cycloalkyl group in R _<1b > -R < _5b >, C3-C8 things, such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, are preferable.
As an alkenyl group in R _<1b > -R < _5b >, C2-C6 things, such as a vinyl group, a propenyl group, a butenyl group, a hexenyl group, are preferable.
Examples of the ring formed by combining two of R _{1b to} R _5b include 3- to 8-membered rings such as a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, and a cyclooctane ring.
In the general formulas (V-1) to (V-4), R _{1b to} R _5b may be connected to any carbon atom constituting the cyclic skeleton.

  Moreover, as a preferable substituent which the said alkyl group, a cycloalkyl group, and an alkenyl group may have, a C1-C4 alkoxy group, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), Examples thereof include 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.

Among the repeating units having groups represented by general formulas (V-1) to (V-4), among R ₁₃ ′ to R ₁₆ ′ in general formula (II-A) or (II-B) above At least one having a group represented by the above general formulas (V-1) to (V-4) (for example, R _{5 of} —COOR ₅ is represented by the general formulas (V-1) to (V-4)). And a repeating unit represented by the following general formula (AI).

In general formula (AI), R _b0 represents a hydrogen atom, a halogen atom, or a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms. As a preferable substituent which the alkyl group of R _b0 may have, as a preferable substituent which the alkyl group as R _1b in the general formulas (V-1) to (V-4) may have. What was illustrated previously is mentioned.
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 the general formulas (V-1) to (V-4). In A ′, examples of the combined divalent group include those represented by the following formulae.

In the above formula, R _ab and R _bb represent a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group, and an alkoxy group, and 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, or 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. r1 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.

  Although the specific example of the repeating unit represented by general formula (AI) is given to the following, the content of this invention is not limited to these.

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

In the general formula (VI), A ₆ represents a single bond, an alkylene group, a cycloalkylene group, an ether group, a thioether group, a carbonyl group, or a group of two or more groups selected from the group consisting of ester groups.
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 formulae.
-[C (Rnf) (Rng)] r-
In the above formula, Rnf and Rng represent a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group, and an alkoxy group, and 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, or 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 is an integer of 1-10.
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 (for example, a formyl group and a benzoyl group), an acyloxy group ( For example, propyl carbonyloxy group, benzoyloxy group), an alkyl group (preferably having from 1 to 4 carbon atoms), a carboxyl group, a hydroxyl group and an alkylsulfonylsulfamoyl group (-CONHSO ₂ CH _3, etc.). In addition, 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 containing Z ₆ .

  Although the specific example of the repeating unit represented by general formula (VI) below is given, it is not limited to these.

  Furthermore, you may contain the repeating unit which has group represented by the following general formula (VII).

In general formula (VII), R _{2c to} R _4c each independently represents a hydrogen atom or a hydroxyl group. However, at least one of R _{2c to} R _4c represents a hydroxyl group.

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

As the repeating unit having a group represented by the general formula (VII), at least one of R ₁₃ ′ to R ₁₆ ′ in the general formula (II-A) or (II-B) is the above general formula (VII ) (For example, R _{5 in} —COOR ₅ represents a group represented by general formulas (V-1) to (V-4)), or represented by the following general formula (AII) And the like.

In general formula (AII), R _1c represents a hydrogen atom or a methyl group.
R _{2c to} R _4c each independently represents a hydrogen atom or a hydroxyl group. However, at least one of R _{2c to} R _4c represents a hydroxyl group.

  Although the specific example of the repeating unit which has a structure represented by general formula (AII) below is given, it is not limited to these.

  Furthermore, you may contain the repeating unit which has group represented by the following general formula (VIII).

In general formula (VIII):
Z ₂ represents —O— or —N (R ₄₁ ) —. Here, R ₄₁ represents a hydrogen atom, a hydroxyl group, an alkyl group, a haloalkyl group, or —OSO ₂ —R ₄₂ . _R42 represents an alkyl group, a haloalkyl group, a cycloalkyl group or a camphor residue.

In the general formula (VIII), Z ₂ represents —O— or —N (R ₄₁ ) —. Here, R ₄₁ represents a hydrogen atom, a hydroxyl group, an alkyl group, a haloalkyl group, or —OSO ₂ —R ₄₂ . _R42 represents an alkyl group, a haloalkyl group, a cycloalkyl group or a camphor residue.

The alkyl group in 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. More preferred are methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group and t-butyl group.
Examples of the haloalkyl group in 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 as R ₄₂ , or the camphor residue 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), an alkoxy group (preferably having 1 to 4 carbon atoms, for example, methoxy Group, ethoxy group, propoxy group, butoxy group, etc.), acyl group (preferably having 2 to 5 carbon atoms, such as formyl group, acetyl group, etc.), acyloxy group (preferably having 2 to 5 carbon atoms, such as acetoxy group), An aryl group (preferably having 6 to 14 carbon atoms, for example, a phenyl group) and the like can be mentioned.

  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 not limited to these specific examples. .

  In addition to the above repeating units, the acid-decomposable resin as component (B) includes dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and general required properties of resist, resolving power and heat resistance. Various repeating units can be contained for the purpose of adjusting sensitivity and the like.

Examples of such a repeating unit include, but are not limited to, repeating units corresponding to the following monomers.
Thereby, the performance required for the acid-decomposable resin, in particular,
(1) Solubility in coating solvent,
(2) Film formability (glass transition point),
(3) Alkali developability,
(4) Membrane slip (hydrophobic, alkali-soluble group selection),
(5) Adhesion of unexposed part to substrate,
(6) Dry etching resistance,
Etc. can be finely adjusted.
As such a monomer, for example, a compound having one addition polymerizable unsaturated bond selected from acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, etc. Etc.

Specifically, the following monomers can be mentioned.
Acrylic acid esters (preferably alkyl acrylates having an alkyl group with 1 to 10 carbon atoms):
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-dimethylhydroxy Propyl acrylate, 5-hydroxypentyl acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, benzyl acrylate, methoxybenzyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, and the like.

Methacrylic acid esters (preferably alkyl methacrylate having 1 to 10 carbon atoms in the alkyl group):
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, pentaerythritol monomethacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate and the like.

Acrylamides:
Acrylamide, N-alkylacrylamide (alkyl group having 1 to 10 carbon atoms, such as methyl group, ethyl group, propyl group, butyl group, t-butyl group, heptyl group, octyl group, cyclohexyl group, hydroxyethyl group, etc. N, N-dialkylacrylamide (alkyl groups having 1 to 10 carbon atoms, such as methyl, ethyl, butyl, isobutyl, ethylhexyl, cyclohexyl, etc.), N-hydroxy Ethyl-N-methylacrylamide, N-2-acetamidoethyl-N-acetylacrylamide and the like.

Methacrylamide:
Methacrylamide, N-alkylmethacrylamide (alkyl groups having 1 to 10 carbon atoms, such as methyl, ethyl, t-butyl, ethylhexyl, hydroxyethyl, cyclohexyl, etc.), N, N -Dialkylmethacrylamide (there are alkyl groups such as ethyl group, propyl group, butyl group), N-hydroxyethyl-N-methylmethacrylamide 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 and the like.

Vinyl ethers:
Alkyl vinyl ethers (eg hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethyl hexyl 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 valerate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, vinyl acetoacetate, vinyl lactate, vinyl -Β-phenylbutyrate, vinylcyclohexylcarboxylate and the like.

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

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

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

  In acid-decomposable resins, the molar ratio of each repeating unit is the resist dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and general resist performance required for resolution, heat resistance, sensitivity, etc. It is set appropriately to adjust.

The following are mentioned as a preferable aspect of the acid-decomposable resin of the present invention.
(1) Containing a repeating unit having a partial structure containing an alicyclic hydrocarbon represented by the general formulas (pI) to (pVI) (side chain type)
(2) Containing repeating units represented by general formula (II-AB) (main chain type)
However, in (2), for example, the following can be further mentioned.
(3) 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 content of the repeating unit having a partial structure containing the alicyclic hydrocarbon represented by the general formulas (pI) to (pVI) is preferably 30 to 70 mol% in all repeating units. Preferably it is 35-65 mol%, More preferably, it is 40-60 mol%.
In the acid-decomposable resin, the content of the repeating unit represented by the general formula (II-AB) is preferably 10 to 60 mol%, more preferably 15 to 55 mol%, still more preferably 20 to 20 in all repeating units. 50 mol%.

Further, the content of the repeating unit based on the monomer of the further copolymer component in the resin can be appropriately set according to the performance of the desired resist. Generally, the general formula (pI) 99 mol% or less with respect to the total number of moles of the repeating unit having a partial structure containing an alicyclic hydrocarbon represented by (pVI) and the repeating unit represented by the general formula (II-AB) More preferably, it is 90 mol% or less, More preferably, it is 80 mol% or less.
When the composition of the present invention is for ArF exposure, the resin preferably has no aromatic group from the viewpoint of transparency to ArF light.

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 in a batch or in the course of reaction, and if necessary, a reaction solvent such as ethers such as tetrahydrofuran, 1,4-dioxane, diisopropyl ether, methyl ethyl ketone, A ketone such as methyl isobutyl ketone, an ester solvent such as ethyl acetate, and the composition of the present invention such as propylene glycol monomethyl ether acetate described below are dissolved in a solvent that dissolves uniformly and then nitrogen, argon, etc. Polymerization is started using a commercially available radical initiator (azo initiator, peroxide, etc.) as necessary under an inert gas atmosphere. If desired, an initiator is added or added in portions, and after completion of the reaction, it is put into a solvent and a desired polymer is recovered by a method such as powder or solid recovery. The concentration of the reaction is 20% by weight or more, preferably 30% by weight or more, more preferably 40% by weight or more.
The reaction temperature is 10 ° C to 150 ° C, preferably 30 ° C to 120 ° C, more preferably 50-100 ° C.

  The weight average molecular weight of the resin according to the present invention is preferably 1,000 to 200,000 as a polystyrene conversion value by the GPC method. When the weight average molecular weight is less than 1,000, heat resistance and dry etching resistance are deteriorated, which is not preferable. When the weight average molecular weight exceeds 200,000, developability is deteriorated, and the viscosity is extremely high, so that the film forming property is deteriorated. Produces less favorable results.

  In the positive photosensitive composition of the present invention, the blending amount of all the resins according to the present invention in the entire composition is preferably 40 to 99.99% by weight, more preferably 50 to 99.99% by weight based on the total resist solid content. 97% by weight.

≪ (C) Basic compound≫
The positive photosensitive composition of the present invention contains (C) a basic compound containing a substituted or unsubstituted aliphatic hydrocarbon group having at least 8 carbon atoms, preferably 8 to 19 carbon atoms in the molecule.

These basic compounds may contain at least one substituted or unsubstituted aliphatic hydrocarbon group having at least 8 carbon atoms in the molecule, and may of course have two or more.
Examples of the substituted or unsubstituted aliphatic hydrocarbon group having at least 8 carbon atoms include n-octyl group, i-octyl group, t-octyl group, n-nonyl group, i-nonyl group, t-nonyl group, n -Decanyl group, i-decanyl group, t-decanyl group, n-undecanyl group, i-undecanyl group, t-undecanyl group, n-dodecanyl group, i-dodecanyl group, t-dodecanyl group, n-tridecanyl group, i -Tridecanyl group, t-tridecanyl group, n-tetradecanyl group, i-tetradecanyl group, t-tetradecanyl group, n-pentadecanyl group, i-pentadecanyl group, t-pentadecanyl group, n-hexadecanyl group, i-hexadecanyl group, t -Hexadecanyl group, n-heptadecanyl group, i-heptadecanyl group, t-heptadecanyl group, n-octadecanyl group, i Octadecanyl group, t-octadecanyl group, n- nonadecanyl group, i- nonadecanyl group, t-nonadecanyl group and the like, these groups may be further substituted by other substituents. Examples of the substituent include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group and other alkyl groups, benzyl group and other aralkyl groups, phenyl group, An aryl group such as a tolyl group, an allyl group, a halogen atom and the like can be mentioned.
These aliphatic hydrocarbon groups preferably have 10 or more carbon atoms.

Examples of the basic compound having an aliphatic hydrocarbon group include those described below, but are not limited thereto.
Octylamine, dioctylamine, trioctylamine, dioctylmethylamine, nonylamine, dinonylamine, trinonylamine, dinonylmethylamine, decylamine, didecylamine, tridecylamine, didecylmethylamine, undecylamine, diundecylamine, triun Decylamine, diundecylmethylamine, dodecylamine, didodecylamine, tridodecylamine, didodecylmethylamine, tridecylamine, ditridecylamine, tritridecylamine, ditridecylmethylamine, tetradecylamine, ditetradecylamine, Tritetradecylamine, ditetradecylmethylamine, pentadecylamine, dipentadecylamine, tripentadecylamine, dipentadecylmethylamine, hexadecyl Amine, dihexadecylamine, trihexadecylamine, dihexadecylmethylamine, heptadecylamine, diheptadecylamine, triheptadecylamine, diheptadecylmethylamine, octadecylamine, dioctadecylamine, trioctadecylamine, di Octadecylmethylamine, nonadecylamine, dinonadecylamine, trinonadecylamine, dinonadecylmethylamine, i-octylamine, di-i-octylamine, tri-i-octylamine, di-i-octylmethylamine, i -Nonylamine, di-i-nonylamine, tri-i-nonylamine, di-i-nonylmethylamine, i-decylamine, di-i-decylamine, tri-i-decylamine, di-i-decylmethylamine, i-un Decylamine, di i-undecylamine, tri-i-undecylamine, di-i-undecylmethylamine, i-dodecylamine, di-i-dodecylamine, tri-i-dodecylamine, di-i-dodecylmethylamine, Tri-i-decylamine, di-i-tridecylamine, tri-i-tridecylamine, di-i-tridecylmethylamine, i-tetradecylamine, di-i-tetradecylamine, tri-i-tetra Decylamine, di-i-tetradecylmethylamine, i-pentadecylamine, di-i-pentadecylamine, tri-i-pentadecylamine, di-i-pentadecylmethylamine, i-hexadecylamine, di -I-hexadecylamine, tri-i-hexadecylamine, di-i-hexadecylmethylamine, i-heptadecylamine, di -I-heptadecylamine, tri-i-heptadecylamine, di-i-heptadecylmethylamine, i-octadecylamine, di-i-octadecylamine, tri-i-octadecylamine, di-i-octadecylmethylamine I-nonadecylamine, di-i-nonadecylamine, tri-i-nonadecylamine, di-i-nonadecylmethylamine and the like.
Of these, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, octadecylamine, didecylamine, methyloctadecylamine, triisodecylamine, N, N-dimethylundecylamine, N, N-dimethyldodecylamine , Tridodecylamine, methyldioctadecylamine, and trioctylamine are more preferable.
In addition to these basic compounds, conventionally known basic compounds are used in combination. Examples of basic compounds that can be used in combination include nitrogen-containing basic compounds.

As the nitrogen-containing basic compound, an organic amine, a basic ammonium salt, a basic sulfonium salt, or the like is used, as long as it does not deteriorate sublimation or resist performance.
Among these nitrogen-containing basic compounds, organic amines are preferable in terms of excellent image performance. For example, JP-A-63-149640, JP-A-5-249662, JP-A-5-127369, JP-A-5-289322, JP-A-5-249683, JP-A-5-289340, JP-A-5-232706 JP-A-5-257282, JP-A-62-242605, JP-A-6-242606, JP-A-6-266100, JP-A-6-266110, JP-A-6-317902, JP-A-7-120929, JP-A-7-65558, JP-A-7-319163, JP-A-7-508840, JP-A-7-333844, JP-A-7-219217, JP-A-7-92678, JP-A-7-28247, Special Kaihei 8-22120, JP-A-8110638, JP-A8-123030, JP-A-9-274312, JP-A-9-66871, JP-A-9-292708, JP-A-9-325496, Special table Basic compounds described in JP-A-7-508840, USP5525453, USP5629134, USP5667938 and the like can be used.

As the nitrogen-containing basic compound, 1,5-diazabicyclo [4.3.0] -5-nonene, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,4-diazabicyclo is preferable. [2.2.2] Octane, 4-dimethylaminopyridine, 1-naphthylamine, piperidine, hexamethylenetetramine, imidazoles, hydroxypyridines, pyridines, 4,4′-diaminodiphenyl ether, pyridinium p-toluenesulfonate, Examples include 2,4,6-trimethylpyridinium p-toluenesulfonate, tetramethylammonium p-toluenesulfonate, tetrabutylammonium lactate, triethylamine, and tributylamine.
Among these, 1,5-diazabicyclo [4.3.0] -5-nonene, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,4-diazabicyclo [2.2.2] Organic amines such as octane, 4-dimethylaminopyridine, 1-naphthylamine, piperidine, hexamethylenetetramine, imidazoles, hydroxypyridines, pyridines, 4,4′-diaminodiphenyl ether, triethylamine, and tributylamine are preferred.

These basic compounds are used alone or in combination of two or more. (C) The amount of the basic compound used is a base containing a substituted or unsubstituted aliphatic hydrocarbon group having at least 8 carbon atoms in the molecule of the present invention based on the solid content of the positive photosensitive composition. The total amount including the basic compound that can be used in combination with the functional compound is usually 0.001 to 10% by weight, preferably 0.01 to 5% by weight. If it is less than 0.001% by weight, the effect of adding the basic compound cannot be obtained. On the other hand, when it exceeds 10% by weight, there is a tendency for the sensitivity to deteriorate and the developability of the non-exposed area to deteriorate.
The mixing ratio of the basic compound containing at least a substituted or unsubstituted aliphatic hydrocarbon group having 8 or more carbon atoms in the molecule of the present invention and the basic compound that can be used in combination is usually 10 by weight. / 90 to 90/10, preferably 15/85 to 85/15, more preferably 20/80 to 80/20.

<< (D) Fluorine-based and / or silicon-based surfactant >>
The positive photosensitive composition of the present invention contains at least the above components (A) to (C), but is further (D) a fluorine-based and / or silicon-based surfactant (fluorine-based surfactant and silicon-based interface). It is preferable to contain any one or two or more of an activator and a surfactant containing both a fluorine atom and a silicon atom.
When the positive photosensitive composition of the present invention contains the surfactant (D), adhesion and development defects can be obtained with good sensitivity and resolution when using an exposure light source of 250 nm or less, particularly 220 nm or less. A small resist pattern can be provided.
As these (D) surfactants, for example, JP-A-62-36663, JP-A-61-226746, JP-A-61-226745, JP-A-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. 5405720, 5360692, 5529881, 5296330, 5436098, Surfactants described in JP-A-5576143, JP-A-5294511 and JP-A-5842451 can be exemplified, and the following commercially available surfactants can also be used as they are.
Examples of commercially available surfactants that can be used include F-top EF301 and EF303 (made by Shin-Akita Kasei Co., Ltd.), Florard FC430 and 431 (made by Sumitomo 3M Co., Ltd.), MegaFuck F171, F173, F176, F189, and R08. (Dainippon Ink Co., Ltd.), Surflon S-382, SC101, 102, 103, 104, 105, 106 (Asahi Glass Co., Ltd.), Troisol S-366 (Troy Chemical Co., Ltd.) A surfactant or a silicon-based surfactant can be mentioned. Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon surfactant.

  The amount of the surfactant used is preferably 0.0001 to 2% by weight, more preferably 0.001 to 1% by weight, based on the total amount of the positive photosensitive composition (excluding the solvent).

≪ (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 ethylene dichloride, cyclohexanone, cyclopentanone, 2-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, methyl lactate, ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, N, N -Dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, tetrahydrofuran, etc.

In the present invention, it is preferable to use a mixed solvent in which a solvent containing a hydroxyl group in the structure and a solvent not containing a hydroxyl group are mixed as the organic solvent. Thereby, the generation of particles during storage of the resist solution can be reduced.
Examples of the solvent containing a hydroxyl group include 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. Particularly preferred are propylene glycol monomethyl ether and ethyl lactate.
Examples of the solvent not containing a hydroxyl group include propylene glycol monomethyl ether acetate, ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, butyl acetate, N-methylpyrrolidone, N, N-dimethylacetamide, dimethyl sulfoxide 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. 2-heptanone is most preferred.
The mixing ratio (weight) of the solvent containing a hydroxyl group and the solvent not containing a hydroxyl group is 1/99 to 99/1, preferably 10/90 to 90/10, more preferably 20/80 to 60/40. . A mixed solvent containing 50% by weight or more of a solvent not containing a hydroxyl group is particularly preferred from the viewpoint of coating uniformity.

≪ (F) Acid-decomposable dissolution inhibiting compound≫
The positive photosensitive composition of the present invention further has (F) a group that decomposes by the action of an acid to increase the solubility in an alkaline developer, and has a molecular weight of 3000 or less, preferably 100 or more and 3000 or less. It is preferable to contain a blocking low molecular weight compound (hereinafter also referred to as “(F) acid-decomposable dissolution blocking compound”).
In particular, an alicyclic group containing an acid-decomposable group, such as a cholic acid derivative containing an acid-decomposable group described in Proceeding of SPIE, 2724,355 (1996), in order not to lower the permeability of 220 nm or less. Aliphatic compounds are preferred as (F) acid-decomposable dissolution inhibiting compounds. Examples of the acid-decomposable group and alicyclic structure are the same as those described for the acid-decomposable resin.
(F) The addition amount of the acid-decomposable dissolution inhibiting compound is preferably 3 to 50% by weight, more preferably 5 to 40% by weight, based on the solid content of the total composition of the positive photosensitive composition. .
Specific examples of the (F) acid-decomposable dissolution inhibiting compound are shown below, but are not limited thereto.

≪ (G) Alkali-soluble resin≫
The positive photosensitive composition of the present invention can further contain a resin that does not contain an acid-decomposable group, (G) is insoluble in water, and is soluble in an alkaline developer, thereby improving sensitivity. To do.
In the present invention, a novolak resin having a molecular weight of about 1000 to 20000 and a polyhydroxystyrene derivative having a molecular weight of about 3000 to 50000 can be used as such a resin, since these have a large absorption with respect to light of 250 nm or less. It is preferable to use a partially hydrogenated amount or 30 wt% or less of the total resin amount.
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 methacrylic acid ester and (meth) acrylic acid copolymer having an alicyclic hydrocarbon structure that does not exhibit acid decomposability, or a (meth) acrylic acid ester having an alicyclic hydrocarbon group having a carboxyl group at the terminal 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 component (D), a photosensitizer, a compound that promotes solubility in a developer, and the like. It can be included.
The dissolution accelerating compound for the developer that can be used in the present invention is a low molecular weight 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.
A preferable addition amount of these dissolution promoting compounds is 2 to 50% by weight, more preferably 5 to 30% by weight with respect to the resin (B) which decomposes by the action of an acid and increases the solubility in an alkaline developer. %. When the amount exceeds 50% by weight, the development residue is deteriorated, and a new defect that the pattern is deformed during development is not preferable.

Such a phenol compound having a molecular weight of 1000 or less can be easily synthesized by those skilled in the art with reference to the methods described in, for example, JP-A-4-1222938, JP-A-2-28531, US Pat. No. 4,916,210, European Patent 219294, and the like. can do.
Specific examples of alicyclic or aliphatic compounds having a carboxyl group include carboxylic acid derivatives having a steroid structure such as cholic acid, deoxycholic acid, lithocholic acid, adamantane carboxylic acid derivatives, adamantane dicarboxylic acid, cyclohexane carboxylic acid, cyclohexane Examples thereof include, but are not limited to, dicarboxylic acids.

In the present invention, a surfactant other than the above (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 octylphenol ether, polyoxyethylene nonylphenol ether, etc. Sorbitans such as polyoxyethylene alkyl allyl ethers, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate Fatty acid esters, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopal Te - DOO, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, may be mentioned polyoxyethylene sorbitan tristearate nonionic surfactants of polyoxyethylene sorbitan fatty acid esters such as such.
These surfactants may be added alone or in some combination.

≪How to use≫
The positive photosensitive composition of the present invention is used by dissolving the above components in a predetermined organic solvent, preferably the mixed solvent, and applying the solution on a predetermined support as follows.
That is, the positive photosensitive composition is applied onto a substrate (eg, silicon / silicon dioxide coating) used for manufacturing a precision integrated circuit element by an appropriate application method such as a spinner or a coater.
After coating, exposure is performed through a predetermined mask, baking and development are performed. In this way, a good resist pattern can be obtained. Here, the exposure light is preferably far ultraviolet rays having a wavelength of 250 nm or less, more preferably 220 nm or less. Specific examples include a KrF excimer laser (248 nm), an ArF excimer laser (193 nm), an F ₂ excimer laser (157 nm), an X-ray, and an electron beam.

In the development process, a developer is used as follows. As the developer of the positive photosensitive composition, inorganic hydroxides such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia, and primary amines such as ethylamine and n-propylamine are used. Secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide Alkaline aqueous solutions of cyclic amines such as quaternary ammonium salts such as pyrrole and pihelidine can be used.
Furthermore, alcohols and surfactants can be added in appropriate amounts to the alkaline aqueous solution.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, the scope of the present invention is not restrict | limited at all by an Example.

<Example of resin synthesis>
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 dissolved in methyl ethyl ketone / tetrahydrofuran = 5/5 to prepare 100 mL of a 20% solid content solution. To this solution, 2 mol% of V-65 manufactured by Wako Pure Chemical Industries, Ltd. was added dropwise to 10 mL of methyl ethyl ketone heated to 60 ° C. over 4 hours under a nitrogen atmosphere. After completion of the dropwise addition, 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 the resin (1) which was a white powder crystallized and precipitated in 3 L of a mixed solvent of distilled water / ISO propyl alcohol = 1/1 was recovered.
The polymer composition ratio determined from C ¹³ NMR was 46/54. Moreover, the weight average molecular weight of standard polystyrene conversion calculated | required by GPC measurement was 10700.

Resins (2) to (18) were synthesized by the same operation as in Synthesis Example (1).
The composition ratios and molecular weights of the resins (2) to (18) are shown below. (Repeating units 1, 2, 3, and 4 are the order from the left of the structural formula.)

  The structures of the resins (1) to (18) are shown below.

Synthesis Example (2) Synthesis of Resin (19) (Main Chain Type)
Norbornenecarboxylic acid tbutyl ester, norbornenecarboxylic acid butyrolactone ester, maleic anhydride (molar ratio 40/10/50) and THF (reaction temperature 60 wt%) were charged into 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 initiate the reaction. Heated for 12 hours. The resulting reaction mixture was diluted twice with tetrahydrofuran and then poured into a mixed solution of hexane / isopropyl alcohol = 1/1 to precipitate a white powder. The precipitated powder was filtered out and dried to obtain the desired resin (19).
When the molecular weight analysis by GPC of the obtained resin (19) was tried, it was 8300 (weight average) in terms of polystyrene. Further, from the NMR spectrum, it was confirmed that the molar ratio of the norbornenecarboxylic acid tbutyl ester / norbornenecarboxylic acid butyrolactone ester / maleic anhydride repeating unit of the resin (1) was 42/8/50.

Resins (20) to (30) were synthesized in the same manner as in Synthesis Example (2).
The composition ratios and molecular weights of the resins (20) to (30) are shown below. (The alicyclic olefin units 1, 2, and 3 are the order from the left of the structural formula.)

  Moreover, the structure of the said resin (19)-(30) is shown below.

Synthesis Example (3) Synthesis of Resin (31) (Hybrid Type)
Norbornene, maleic anhydride, t-butyl acrylate and 2-methylcyclohexyl-2-propyl acrylate were charged into a reaction vessel at a molar ratio of 35/35/20/10 and dissolved in tetrahydrofuran to prepare a solution having a solid content of 60%. . This was heated at 65 ° C. under a nitrogen stream. When the reaction temperature was stabilized, 1 mol% of radical initiator V-601 manufactured by Wako Pure Chemical Industries, Ltd. was added to initiate the reaction. After heating for 8 hours, the reaction mixture was diluted 2 times with tetrahydrofuran and then poured into hexane having a volume 5 times that of the reaction mixture to precipitate a white powder. The precipitated powder was filtered out, dissolved in methyl ethyl ketone, reprecipitated in a 5-fold volume of hexane / t-butyl methyl ether = 1/1 mixed solvent, and the precipitated white powder was collected by filtration, dried and dried. Resin (31) which is a thing was obtained.
When the molecular weight analysis by GPC of the obtained resin (31) was tried, it was 12100 (weight average) in terms of polystyrene. From the NMR spectrum, the composition of the resin (1) was norbornene / maleic anhydride / tbutyl acrylate / 2-methylcyclohexyl-2-propyl acrylate according to the present invention in a molar ratio of 32/39/19/10.

Resins (32) to (44) were synthesized in the same manner as in Synthesis Example (3).
The composition ratios and molecular weights of the resins (32) to (44) are shown below.

  Moreover, the structure of the said resin (31)-(44) is shown below.

Synthesis Example (4) Synthesis of Resin (45) (Hybrid Type)
Norbornene carboxylic acid t-butyl ester, maleic anhydride, 2-methyl-2-adamantyl acrylate, norbornene lactone acrylate is charged into a reaction vessel at a molar ratio of 20/20/35/25, and dissolved in methyl ethyl ketone / tetrahydrofuran = 1/1 solvent. And a 60% solids solution was prepared. This was heated at 65 ° C. under a nitrogen stream. When the reaction temperature was stabilized, 3 mol% of radical initiator V-601 manufactured by Wako Pure Chemical Industries, Ltd. was added to initiate 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 again dissolved in methyl ethyl ketone / tetrahydrofuran = 1/1 solvent and charged into 5 volumes of hexane / methyl tBu ether to precipitate a white powder, which was taken out by filtration. This operation was repeated again and dried to obtain the desired resin (45).
When the molecular weight analysis (RI analysis) by GPC of the obtained resin (45) was attempted, it was 11600 (weight average) in terms of polystyrene, and the amount of residual monomer was 0.4%. From the NMR spectrum, the composition of the resin (1) was 18/23/34/25 in terms of the molar ratio of norbornene / maleic anhydride / 2-methyl-2-adamantyl acrylate / norbornene lactone acrylate of the present invention.

Resins (46) to (69) were synthesized in the same manner as in Synthesis Example (4).
The composition ratios and molecular weights of the resins (46) to (69) are shown below.

  The structures of the resins (45) to (69) are shown below.

[Reference Examples 1 to 13, Example 14, Reference Examples 15 to 19, Examples 20 to 21, Reference Examples 22 to 27, Examples 28 to 29, Reference Examples 30 to 35, Example 36, Reference Example 37, Implementation Example 38, Reference Example 39, Example 40, Reference Examples 41 to 54, Examples 55 to 56, Reference Examples 57 to 61, Example 62, Reference Examples 63 to 66, Examples 67 to 71, Reference Example 72, Implementation Examples 73 to 76 and Comparative Examples 1 to 4]
The resin synthesized in the above synthesis example and each component described in Tables 5-7 below were dissolved in the solvent described in Tables 5-7 at a solid content concentration of 12% by weight, and then 0.1 μm Teflon (registered) A positive photosensitive composition was prepared by filtration through a trademark filter. The prepared composition was evaluated by the following method, and the results are shown in Tables 5-7.

  The abbreviations in Tables 5 to 7 are as follows.

Photoacid generator:
Specific examples of the component (A) z1 to z40

Abbreviations for basic compounds are as follows. In addition, the ratio in the case of multiple use in Tables 5-7 is a weight ratio.
C1: tridecylamine C2: tetradecylamine C3: pentadecylamine C4: hexadecylamine C5: octadecylamine C6: didecylamine C7: methyloctadecylamine C8: triisodecylamine C9: N, N-dimethylundecylamine C10: N, N-dimethyldodecylamine C11: tridodecylamine C12: methyldioctadecylamine C13: trioctylamine 1: 1,5-diazabicyclo [4.3.0] -5-nonene 2: bis (1,2,2 , 6,6-pentamethyl-4-piperidyl) sebacate 3: tri-n-butylamine 4: triphenylimidazole 5: antipyrine 6: 2,6-diisopropylaniline

Surfactant:
W-1: Megafuck F176 (Dainippon Ink Co., Ltd.) (Fluorine)
W-2: Megafuck R08 (Dainippon Ink Co., Ltd.)
(Fluorine and silicon)
W-3: Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Silicon)
W-4: Troisol S-366 (manufactured by Troy Chemical Co., Ltd.)

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>
[Sidelobe resistance evaluation]
An anti-reflective coating DUV-42 manufactured by Brewer Science Co., Ltd. was uniformly applied to 600 angstroms on a silicon substrate subjected to hexamethyldisilazane treatment with a spin coater, dried on a hot plate at 100 ° C. for 90 seconds, and then at 190 ° C. Heat drying was performed for 240 seconds. Thereafter, each photosensitive resin composition was applied by a spin coater and dried at 120 ° C. for 90 seconds to form a 0.30 μm resist film. The resist film was exposed with an ArF excimer laser stepper (NA = 0.6 manufactured by ISI) through a mask, and immediately after the exposure, it was heated on a hot plate at 120 ° C. for 90 seconds. Further, the resist line pattern was obtained by developing with a 2.38% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 60 seconds, rinsing with pure water for 30 seconds, and drying.
Sidelobe resistance was evaluated by using a halftone phase shift mask, resolving 0.22 μm to 0.20 μm, observing the pattern at 0.18 μm, and no sidelobe was observed. A sample was shown as ◯, a sample showing some signs of side lobes was shown as △, and a sample where side lobes were clearly confirmed was shown as ×.
These evaluation results are shown in Tables 8-10.

  As is apparent from the results in Tables 8 to 10, the composition of the present invention is excellent in suitability for halftone exposure (side lobe resistance).

Claims (7)

(A) a compound that generates an acid upon irradiation with an actinic ray or radiation,
(B) a resin having a monocyclic or polycyclic alicyclic hydrocarbon structure, decomposed by the action of an acid, and increased in solubility in an alkali developer,
(C) A basic compound containing a substituted or unsubstituted aliphatic hydrocarbon group having at least 8 carbon atoms in the molecule and a nitrogen-containing basic compound other than the basic compound of component (C) A positive photosensitive composition.   The positive photosensitive composition according to claim 1, wherein the basic compound of component (C) contains a substituted or unsubstituted aliphatic hydrocarbon group having at least 10 carbon atoms in the molecule.   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. The resin of the component (B) is a repeating unit having a partial structure containing an alicyclic hydrocarbon represented by the following general formula (pI) to general formula (pVI) and a repeating unit represented by the general formula (II-AB) The positive photosensitive composition according to claim 1, which is a resin containing at least one selected from the group.

In the formula, R ₁₁ represents a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group or a sec-butyl group, and Z forms an alicyclic hydrocarbon group together with a carbon atom. Represents the atomic group necessary to do.
R _{12 to} R ₁₆ each independently represents a linear or branched alkyl group or alicyclic hydrocarbon group having 1 to 4 carbon atoms, provided that at least one of R _{12 to} R ₁₄ , or Either R ₁₅ or R ₁₆ represents an alicyclic hydrocarbon group.
R _{17 to} R ₂₁ each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or an alicyclic hydrocarbon group, 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 alicyclic hydrocarbon group having 1 to 4 carbon atoms.
R _{22 to} R ₂₅ each independently represents a linear or branched alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group, provided that at least one of R _{22 to} R ₂₅ is a fat Represents a cyclic hydrocarbon group. R ₂₃ and R ₂₄ may be bonded to each other to form a ring.

In 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 contains two bonded carbon atoms (C—C) and may have a substituent.   Furthermore, the positive photosensitive composition in any one of Claims 1-4 containing (D) fluorine and / or a silicon-type surfactant.   Furthermore, (F) it has a group which decomposes | disassembles by the effect | action of an acid and increases the solubility in an alkali developing solution, and contains the molecular weight 3000 or less dissolution prevention low molecular weight compound in any one of Claims 1-5. A positive photosensitive composition.   A pattern forming method comprising: forming a film with the positive photosensitive composition according to claim 1, and exposing and developing the film.