JP2003021905A - Positive photosensitive composition - Google Patents

Abstract

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

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive type photosensitive composition used in the process of manufacturing semiconductors such as ICs, the manufacture of circuit boards such as liquid crystals and thermal heads, and other photofabrication processes. . More specifically, the present invention relates to a positive photosensitive composition that is suitable when using far ultraviolet rays of 250 nm or less as an exposure light source.

[0002]

2. Description of the Related Art A chemically amplified positive resist composition produces an acid in an exposed area by irradiation with radiation such as far-ultraviolet light.
It is a pattern-forming material that forms a pattern on a substrate by changing the solubility of a portion irradiated with actinic radiation and a portion not irradiated with actinic radiation with a developer by the reaction using the acid as a catalyst.

When a KrF excimer laser is used as an exposure light source, the absorption mainly in the 248 nm region is small,
Since a resin having a basic skeleton of poly (hydroxystyrene) is used as a main component, it has a high sensitivity, high resolution, and forms a good pattern, and is a better system than the conventional naphthoquinone diazide / novolak resin system. ing.

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

Further, as an acid generator for a chemically amplified positive resist composition, a triarylsulfonium salt-based acid generator and a phenacylsulfonium salt-based acid generator are known, but the triarylsulfonium salt-based acid generator is known. The agent is 19
The phenacylsulfonium salt-based acid generator had a low absorption rate at 3 nm and the acid generation ability was low.

In recent years, with the demand for miniaturization of semiconductor chips, the design pattern of the fine semiconductor is 0.13.
It reaches a fine region of 0.35 μm. However, the conventional techniques cannot satisfy various characteristics such as suitability for halftone exposure. Here, the halftone exposure suitability means whether or not a side lobe (a phenomenon in which the surface of the unexposed portion becomes weak and a hole starts to be formed) that occurs when exposure is performed using a halftone phase shift mask, Or it shows that it is hard to occur and is also called side lobe resistance.

[0007]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a positive type photosensitive composition excellent in halftone exposure suitability (sidelobe resistance).

[0008]

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

(1) (A) a compound capable of generating an acid upon irradiation with actinic rays or radiation; and (B) having a monocyclic or polycyclic alicyclic hydrocarbon structure, which is decomposed by the action of an acid to give an alkaline developer. Positive type photosensitivity characterized by containing a resin having an increased solubility in (C) and (C) a basic compound containing at least a substituted or unsubstituted aliphatic hydrocarbon group having 8 or more carbon atoms in the molecule. Composition. (2) The positive photosensitive composition as described in (1) above, which further contains (D) fluorine and / or a silicon-based surfactant. (3) Further, (F) has a group which decomposes by the action of an acid to increase the solubility in an alkaline developer and has a molecular weight of 30
(1) containing a dissolution inhibiting low molecular weight compound of 00 or less
Alternatively, the positive photosensitive composition as described in (2). (4) The positive photosensitive composition as described in (1) to (3) above, which further contains (E) a mixed solvent obtained by mixing a solvent containing a hydroxyl group and a solvent not containing a hydroxyl group.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The compounds used in the present invention are described in detail below. << (A) Compound that generates an acid upon irradiation with actinic rays or radiation >>

The composition of the present invention contains, as the component (A), a compound capable of generating an acid upon irradiation with actinic rays or radiation (photoacid generator). Such photo-acid generators include photo-initiators for photo-cationic polymerization, photo-initiators for photo-radical polymerization, photo-decoloring agents for dyes, photo-color-changing agents, or actinic rays used for micro resists or the like. Known compounds that generate an acid upon irradiation with radiation and mixtures thereof can be appropriately selected and used.

For example, onium salts such as diazonium salts, ammonium salts, phosphonium salts, iodonium salts, sulfonium salts, selenonium salts and arsonium salts,
Organic halogen compounds, organic metal / organic halides, o
Examples thereof include a photoacid generator having a nitrobenzyl-type protecting group, a compound represented by iminosulfonate and the like, which photolyzes to generate a sulfonic acid, and a disulfone compound.

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

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

Among the compounds which decompose to generate an acid upon irradiation with actinic rays or radiation, those which are particularly effectively used are described below.

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

[0017]

[Chemical 1]

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 represent a substituted or unsubstituted alkyl group or aryl group. Of these, an aryl group having 6 to 14 carbon atoms, an alkyl group having 1 to 8 carbon atoms, and a substituted derivative thereof are preferable. Preferred substituents are an alkoxy group having 1 to 8 carbon atoms, an alkyl group having 1 to 8 carbon atoms, a nitro group, a carboxyl group, a hydroxy group and a halogen atom for an aryl group,
The alkyl group is an alkoxy group having 1 to 8 carbon atoms, a carboxyl group or an alkoxycarbonyl group.

Z ⁻ represents a counter anion, for example, BF ₄ ⁻ ,
_{^{AsF 6 -, PF 6 -,}} SbF 6 -, SiF 6 2-, ClO 4 -,
Perfluoroalkane sulfonate anions such as CF ₃ SO ₃ ⁻ , pentafluorobenzene sulfonate anions, condensed polynuclear aromatic sulfonate anions such as naphthalene-1-sulfonate anions, anthraquinone sulfonate anions, sulfonate group-containing dyes, etc. Examples thereof include, but are not limited to:

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

Specific examples include the compounds shown below, but the invention is not limited thereto.

[0023]

[Chemical 2]

[0024]

[Chemical 3]

[0025]

[Chemical 4]

[0026]

[Chemical 5]

[0027]

[Chemical 6]

[0028]

[Chemical 7]

[0029]

[Chemical 8]

[0030]

[Chemical 9]

[0031]

[Chemical 10]

[0032]

[Chemical 11]

[0033]

[Chemical 12]

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

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

[0036]

[Chemical 13]

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 thereof include the compounds shown below, but the invention is not limited thereto.

[0038]

[Chemical 14]

[0039]

[Chemical 15]

[0040]

[Chemical 16]

[0041]

[Chemical 17]

[0042]

[Chemical 18]

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

[0044]

[Chemical 19]

Here, R represents a linear, branched or cyclic alkyl group or an aryl group which may be substituted. Specific examples include the compounds shown below,
It is not limited to these.

[0046]

[Chemical 20]

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.

[0048]

[Chemical 21] 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 or more of R _{1 to} R ₅ are It may combine with each other to form a ring structure. R
₆ and R ₇ represent a hydrogen atom, an alkyl group, a cyano group or an aryl group. Y ₁ and Y ₂ represent an alkyl group, an aryl group, an aralkyl group or an aromatic group containing a hetero atom, and Y ₁ and Y ₂ may be bonded to each other 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 combined 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 combined. To form a ring. In addition, R ₁
To R ₇ or any of Y ₁ or Y ₂ via a linking group to form a structure of formula (I)
You may have one or more.

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, and examples of the unsubstituted alkyl group include a methyl group and an ethyl group. Group, propyl group, n-butyl group,
Examples thereof include sec-butyl group and t-butyl group. The alkoxy group of R _{1 to} R _{5 and} the alkoxy group in the alkyloxycarbonyl group are substituted or unsubstituted alkoxy groups, preferably alkoxy groups having 1 to 5 carbon atoms, and examples of the unsubstituted alkoxy group include , A methoxy group, an ethoxy group, a propoxy group, a butoxy group and the like. The aryl group represented by 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, and examples of the unsubstituted aryl group include phenyl. Group, tolyl group,
Examples thereof include a naphthyl group. Examples of the halogen atom of 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 having 1 to 30 carbon atoms.
Is an alkyl group. As the unsubstituted alkyl group, for example, a linear or branched alkyl group such as methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, t-butyl group, and cyclopropyl group, Examples thereof include cyclic alkyl groups such as cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group and boronyl group.

The aralkyl group of Y ₁ and Y ₂ is a substituted or unsubstituted aralkyl group, preferably having 7 to 7 carbon atoms.
Examples of the aralkyl group of 12 and the unsubstituted aralkyl group include a benzyl group, a phenethyl group, and a cumyl group.

The aromatic group containing a hetero atom means a group having a hetero atom such as a nitrogen atom, an oxygen atom or a sulfur atom 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, and examples of the unsubstituted group include furan, thiophene, pyrrole, pyridine and indole. And a heterocyclic aromatic hydrocarbon group.

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

Each of the above-mentioned 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 a carbon number. 1-5) etc. may be substituted. Further, the aryl group and aralkyl group may be substituted with an alkyl group (preferably having 1 to 5 carbon atoms). Moreover, a halogen atom is preferable as a substituent of the alkyl group.

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

[0056] X ^- include the non-nucleophilic anion, for example, may be mentioned sulfonic acid anion, a carboxylic acid anion. The non-nucleophilic anion is an anion having an extremely low ability to cause a nucleophilic reaction, and is an anion capable of suppressing decomposition 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 carboxylic acid anion include an alkylcarboxylic acid anion, an arylcarboxylic acid anion, and an aralkylcarboxylic acid anion.

The alkyl group in the alkyl sulfonate anion is preferably an alkyl group having 1 to 30 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 Group, cyclopropyl group, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, boronyl group and the like. The aryl group in the aryl sulfonate anion is preferably an aryl group having 6 to 14 carbon atoms, for example, a phenyl group, a tolyl group, a naphthyl group and the like.

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

Examples of the halogen atom include chlorine atom, bromine atom, fluorine atom, iodine atom and the like. As the alkyl group, for example, an alkyl group preferably having 1 to 15 carbon atoms, for example, a methyl group, an 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,
Examples thereof include a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, and an eicosyl group. As the alkoxy group, for example, preferably an alkoxy group having 1 to 5 carbon atoms,
For example, methoxy group, ethoxy group, propoxy group, butoxy group and the like can be mentioned. The alkylthio group is, 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,
Examples thereof include nonadecylthio group and eicosylthio group. 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 alkylcarboxylic acid anion include those similar to the alkyl group in the alkylsulfonic acid anion. Examples of the aryl group in the arylcarboxylic acid anion include the same as the aryl group in the arylsulfonic acid anion. The aralkyl group in the aralkylcarboxylate anion is preferably an aralkyl group having 6 to 12 carbon atoms, for example, a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group, a naphthylmethyl group and the like.

The alkyl group, aryl group and aralkyl group in the above alkylcarboxylic acid anion, arylcarboxylic acid anion and aralkylcarboxylic acid anion may have a substituent, and examples of the substituent include:
The same halogen atom, alkyl group, alkoxy group, alkylthio group and the like as in the aryl sulfonate anion 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 combined to form a ring, or a ring of R ₁ to R ₅ is formed. At least one and at least one of R _{6 and} R ₇ are combined to form a ring. By forming a ring, the compound represented by the formula (I) has a fixed three-dimensional structure and improves optical resolution. Any _one of R ₁ to R ₇ or Y ₁
Or at any position of Y ₂ is bonded via a linking group,
It may have two or more structures of formula (I).

Further, the compound of formula (I) is preferably of the following general formula (IA) or (IB).

[0065]

[Chemical formula 22]

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

Y represents a single bond or a divalent linking group, and 2
As the valent linking group, an optionally substituted alkylene group, alkenylene group, -O-, -S-, -CO-, -C
ONR- (R is hydrogen, an alkyl group, or an acyl group), and a linking group which may include two or more of these are 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, and specifically, a methylene group, an ethylene group, a propylene group, —CH ₂ —O—, —CH. ₂ -S- are preferred, and most preferably an ethylene group, -CH ₂ -O-,
A connecting group forming a 6-membered ring such as —CH ₂ —S—. By forming a 6-membered ring, the carbonyl plane and C-
The S + sigma bond becomes closer to vertical, and the photolysis efficiency is improved by the orbital interaction.

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

[0070]

[Chemical formula 23]

[0071]

[Chemical formula 24]

[0072]

[Chemical 25]

[0073]

[Chemical formula 26]

[0074]

[Chemical 27]

[0075]

[Chemical 28]

[0076]

[Chemical 29]

[0077]

[Chemical 30]

[0078]

[Chemical 31]

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

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

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

Of the compounds (A) used in the present invention which generate an acid upon irradiation with actinic rays or radiation, particularly preferred examples are shown below.

[0083]

[Chemical 32]

[0084]

[Chemical 33]

[0085]

[Chemical 34]

[0086]

[Chemical 35]

<< (B) Resin whose dissolution rate in an alkali developing solution is increased by the action of acid (also referred to as "acid-decomposable resin") >>

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

[0089]

[Chemical 36]

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

[0091]

[Chemical 37]

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 carbon atoms (C-C) bonded and may have a substituent.

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

[0094]

[Chemical 38]

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, -COOR _5, group decomposable by the action of an acid, -C (= O) -X- A'-R 17', or substituted It represents an alkyl group which may have a group or a cyclic hydrocarbon group. Here, R ₅ represents an alkyl group which may have a substituent, a cyclic hydrocarbon group or the following —Y group. X
It represents an oxygen atom, a sulfur atom, -NH -, - NHSO ₂ - or an -NHSO ₂ NH-. A'represents a single bond or a divalent linking group. It is also possible to form at least two members to the ring of R _l3 '~R _16'. n represents 0 or 1.
R ₁₇ 'is —COOH, —COOR ₅ , —CN, hydroxyl group,
An alkoxy group which may have a substituent, -CO-NH
-R _6, represents a -CO-NH-SO ₂ -R ₆ or -Y group shown below. R ₆ represents an alkyl group or a cyclic hydrocarbon group which may have a substituent. -Y group;

[0096]

[Chemical Formula 39]

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

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

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

[0100]

[Chemical 40]

[0101]

[Chemical 41]

[0102]

[Chemical 42]

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

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

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

[0106]

[Chemical 43]

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

[0108]

[Chemical 44]

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, alone or in combination of two or more. 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.

[0111]

[Chemical formula 45]

[0112]

[Chemical formula 46]

[0113]

[Chemical 47]

[0114]

[Chemical 48]

[0115]

[Chemical 49]

[0116]

[Chemical 50]

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

Examples of the halogen atom in R ₁₁ ′ and R ₁₂ ′ include chlorine atom, bromine atom, fluorine atom and iodine atom. Above R ₁₁ ', R ₁₂ ', R ₂₁ '~ R
The alkyl group in ₃₀ 'is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, more preferably a linear or branched alkyl group having 1 to 6 carbon atoms, and further preferably Methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group,
a sec-butyl group and 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 chlorine atom, bromine atom, fluorine atom, iodine atom and the like,
Examples of the alkoxy group include those having 1 to 4 carbon atoms such as methoxy group, ethoxy group, propoxy group and butoxy group, examples of the acyl group include formyl group, acetyl group and the like, and examples of the acyloxy group include Can include an acetoxy group and the like.

The atomic group for forming the alicyclic structure of Z ′ is an atomic group for forming a repeating unit of an alicyclic hydrocarbon which may have a substituent in the resin, and is particularly a bridged group. An atomic group for forming a bridged alicyclic structure forming a repeating unit of the alicyclic hydrocarbon of the formula is preferable. Examples of the alicyclic hydrocarbon skeleton to be formed include those shown by the following structures.

[0121]

[Chemical 51]

[0122]

[Chemical 52]

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

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.

The above general formula (II-A) or (II-B)
In the formula, R ₁₃ ′ to R ₁₆ ′ are each independently a hydrogen atom, a halogen atom, a cyano group, —COOH, —COOR ₅ , a group decomposable by the action of an acid, —C (═O) —XA ′. -R
₁₇ ', or an alkyl group which may have a substituent or a cyclic hydrocarbon group. R ₅ may have a substituent, an alkyl group, cyclic hydrocarbon group or said group -Y. X is an oxygen atom, a sulfur atom, -NH-, -NH
It represents SO ₂ — or —NHSO ₂ NH—. A'represents a single bond or a divalent linking group. It is also possible to form at least two members to the ring of R _l3 '~R _16'. n is 0
Or represents 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
Alternatively, it represents the following —Y group. 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 represent a hydrogen atom or an alkyl group which may have a substituent, and
b represents 1 or 2.

In the resin according to the present invention, the acid-decomposable group may be contained in the above-mentioned —C (═O) —X—A′—R ₁₇ ′ or Z ′ of the general formula (II-AB). May be included as a substituent of The structure of the acid-decomposable group, -C (= O) -X ₁
It is represented by -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
1-alkoxyethyl groups such as isobutoxyethyl group and 1-cyclohexyloxyethyl group, alkoxymethyl groups such as 1-methoxymethyl group and 1-ethoxymethyl group, 3
-Oxoalkyl group, tetrahydropyranyl group, tetrahydrofuranyl group, trialkylsilyl ester group, 3
-Oxocyclohexyl ester group, 2-methyl-2-
Examples thereof include an adamantyl group and a mevalonic lactone residue. X ₁ has the same meaning as X above.

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

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 1 to 10 carbon atoms.
Six linear or branched alkyl groups, more preferably methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group.

The cyclic hydrocarbon group for R ₅ , R ₆ , and R ₁₃ 'to R ₁₆ ' is, for example, a cyclic alkyl group or a bridged hydrocarbon, and is a cyclopropyl group, a cyclopentyl group,
Cyclohexyl group, adamantyl group, 2-methyl-2-
Examples thereof include an adamantyl group, a norbornyl group, a boronyl group, an isobornyl group, a tricyclodecanyl group, a dicyclopentenyl group, a nobornane epoxy group, a menthyl group, an isomenthyl group, a neomenthyl group, and a tetracyclododecanyl group. The ring formed by combining at least two members out of R ₁₃ ′ to R ₁₆ ′ is cyclopentene,
Examples thereof include rings having 5 to 12 carbon atoms such as cyclohexene, cycloheptane, and cyclooctane.

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

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

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

In the resin according to the present invention, the group capable of decomposing under the action of an acid is one of the above general formulas (pI) to (pV).
I) a repeating unit having a partial structure containing an alicyclic hydrocarbon, a repeating unit represented by the general formula (II-AB), and at least one repeating unit of the repeating units of the copolymerization component described below. Can be included.

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

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

[0136]

[Chemical 53]

[0137]

[Chemical 54]

[0138]

[Chemical 55]

[0139]

[Chemical 56]

[0140]

[Chemical 57]

[0141]

[Chemical 58]

[0142]

[Chemical 59]

[0143]

[Chemical 60]

[0144]

[Chemical formula 61]

[0145]

[Chemical formula 62]

[0146]

[Chemical formula 63]

[0147]

[Chemical 64]

[0148]

[Chemical 65]

[0149]

[Chemical formula 66]

[0150]

[Chemical formula 67]

[0151]

[Chemical 68]

[0152]

[Chemical 69]

[0153]

[Chemical 70]

[0154]

[Chemical 71]

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

[0156]

[Chemical 72]

In 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, an ester group, or a combination of two or more groups selected from the group consisting of. Ra ₁ , Rb ₁ , Rc ₁ , Rd ₁ and Re ₁ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. m and n each independently represent an integer of 0 to 3, 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 methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group and the like. Can be mentioned.

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

Further substituents in the above 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, 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 and the like. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as methoxy group, ethoxy group, propoxy group and butoxy group. An acetoxy group etc. are mentioned as an acyloxy group. Examples of the halogen atom include chlorine atom, bromine atom, fluorine atom, iodine atom and the like.

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

[0162]

[Chemical formula 73]

[0163]

[Chemical 74]

[0164]

[Chemical 75]

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

Further, the following general formulas (V-1) to (V-4)
You may contain the repeating unit which has the group represented by either of these.

[0167]

[Chemical 76]

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

In the general formulas (V-1) to (V-4),
Examples of the alkyl group for R _{1b to} R _5b include linear and branched alkyl groups, which may have a substituent. The linear or branched alkyl group has 1 to 1 carbon atoms.
12 straight chain or branched alkyl groups are preferred,
More preferably, it is a linear or branched alkyl group having 1 to 10 carbon atoms, and even 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,
It is a decyl group. The cycloalkyl group for R _{1b to} R _5b is preferably a cycloalkyl group having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group. The alkenyl group in R _{1b to} R _5b is preferably an alkenyl group having a carbon number of 2 to 6, such as a vinyl group, a propenyl group, a butenyl group and a hexenyl group. Examples of the ring formed by combining two members out of R _{1b to} R _5b include a 3- to 8-membered ring such as a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, and a cyclooctane ring. The general formula (V-1)
R _{1b to} R _5b in to (V-4) may be bonded to any of the carbon atoms constituting the cyclic skeleton.

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

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

[0172]

[Chemical 77]

In formula (AI), R _b0 represents a hydrogen atom, a halogen atom, or a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms. Preferable substituents that the alkyl group represented by R _b0 may have include those represented by the general formula (V-1) to
Examples of the preferable substituent that the alkyl group as R _1b in (V-4) may have include those exemplified above. Examples of the halogen atom of 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 combining these. B ₂ represents a group represented by any one of formulas (V-1) to (V-4). In A ′, examples of the combined divalent group include those represented by the following formulas.

[0174]

[Chemical 78]

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 or an alkoxy group, and they may be the same or different. The alkyl group is preferably a lower alkyl group such as methyl group, ethyl group, propyl group, isopropyl group and butyl group, and more preferably selected from methyl group, ethyl group, propyl group and 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 methoxy group, ethoxy group, propoxy group and butoxy group. Examples of the halogen atom include chlorine atom, bromine atom, fluorine atom, iodine atom and the like. r
1 represents an integer of 1 to 10, preferably an integer of 1 to 4.
m represents an integer of 1 to 3, preferably 1 or 2.

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

[0177]

[Chemical 79]

[0178]

[Chemical 80]

[0179]

[Chemical 81]

[0180]

[Chemical formula 82]

[0181]

[Chemical 83]

[0182]

[Chemical 84]

[0183]

[Chemical 85]

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

[0185]

[Chemical 86]

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

In formula (VI), examples of the alkylene group represented by A ₆ include groups represented by the following formula. -[C (Rnf) (Rng)] r- In the above formula, Rnf and Rng are each a hydrogen atom, an alkyl group,
It represents a substituted alkyl group, a halogen atom, a hydroxyl group, or an alkoxy group, and they may be the same or different. The alkyl group is preferably a lower alkyl group such as methyl group, ethyl group, propyl group, isopropyl group and butyl group, and more preferably selected from methyl group, ethyl group, propyl group and 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 methoxy group, ethoxy group, propoxy group and butoxy group. Examples of the halogen atom include chlorine atom, bromine atom, fluorine atom, iodine atom and the like. r is an integer of 1-10. General formula (VI)
In the above, examples of the cycloalkylene group represented by A ₆ include those having 3 to 10 carbon atoms.
Examples thereof include a cyclohexylene group and a cyclooctylene group.

The bridged alicyclic ring containing Z ₆ may have a substituent. Examples of the substituent include a halogen atom, an alkoxy group (preferably having 1 to 4 carbon atoms), an alkoxycarbonyl group (preferably having 1 to 5 carbon atoms), an acyl group (eg, formyl group, benzoyl group), an acyloxy group ( Examples thereof include a propylcarbonyloxy group, a benzoyloxy group), an alkyl group (preferably having a carbon number of 1 to 4), a carboxyl group, a hydroxyl group, an alkylsulfonylsulfamoyl group (-CONHSO ₂ CH ₃ etc.). still,
The alkyl group as a substituent may be further substituted with a hydroxyl group, a halogen atom, an alkoxy group (preferably having a carbon number of 1 to 4) 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 atoms constituting the bridged alicyclic ring structure containing Z _6. Good.

The specific examples of the repeating units represented by formula (VI) are shown below, but the invention is not limited thereto.

[0191]

[Chemical 87]

[0192]

[Chemical 88]

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

[0194]

[Chemical 89]

In formula (VII), R _{2c to} R _4c each independently represent 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 body or a monohydroxy body, more preferably a dihydroxy body.

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

[0198]

[Chemical 90]

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

The specific examples of the repeating units having the structure represented by formula (AII) are shown below, but the invention is not limited thereto.

[0201]

[Chemical Formula 91]

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

[0203]

[Chemical Formula 92]

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

In the above general formula (VIII), Z ₂ is-
Represents O- or -N (R ₄₁ )-. Here, R ₄₁ is a hydrogen atom, a hydroxyl group, an alkyl group, a haloalkyl group, or —OS.
Representing the O ₂ -R _42. R ₄₂ represents an alkyl group, a haloalkyl group, a cycloalkyl group or a camphor residue.

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

The alkyl group and haloalkyl group as R ₄₁ and R ₄₂ , the cycloalkyl group 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 a carbon number of 1 to 1).
4, for example, methoxy group, ethoxy group, propoxy group, butoxy group, etc.), acyl group (preferably having 2 to 5 carbon atoms, for example, formyl group, acetyl group, etc.), acyloxy group (preferably having 2 to 5 carbon atoms, for example, An acetoxy group), an aryl group (preferably having a carbon number of 6 to 14, for example, a phenyl group), and the like.

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

[0209]

[Chemical formula 93]

[0210]

[Chemical 94]

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

Examples of such repeating units 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-forming property (glass transition point), (3)
Alkali developability, (4) Membrane slippage (hydrophobicity, selection of alkali-soluble groups), (5) Adhesion of unexposed area to substrate,
(6) Fine adjustment of dry etching resistance and the like becomes possible. Examples of such monomers include acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers,
Examples thereof include compounds having one addition-polymerizable unsaturated bond selected from vinyl esters and the like.

Specifically, the following monomers can be mentioned. Acrylic esters (preferably alkyl acrylates having 1 to 10 carbon atoms in the alkyl group): methyl acrylate, ethyl acrylate, propyl acrylate, amyl acrylate, cyclohexyl acrylate, ethylhexyl acrylate, octyl acrylate, acrylic Acid-t-octyl, chloroethyl acrylate, 2-hydroxyethyl acrylate 2,2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate,
Trimethylolpropane monoacrylate, pentaerythritol monoacrylate, benzyl acrylate,
Methoxybenzyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, etc.

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

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

Methacrylamides: Methacrylamides,
N-alkylmethacrylamide (alkyl group having 1 to 10 carbon atoms, for example, methyl group, ethyl group, t-
Butyl group, ethylhexyl group, hydroxyethyl group, cyclohexyl group, etc.), N, N-dialkylmethacrylamide (alkyl groups include ethyl group, propyl group, butyl group, etc.), N-hydroxyethyl-N-
Methylmethacrylamide, etc.

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

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

Vinyl esters: vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl barrate, 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 and the like. Dialkyl esters or monoalkyl esters of fumaric acid; dibutyl fumarate and the like.

Others Crotonic acid, itaconic acid, maleic anhydride, maleimide, acrylonitrile, methacrylonitrile, maleironitrile and the like.

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

In the acid-decomposable resin, the molar ratio of each repeating unit depends on the dry etching resistance of the resist, suitability for a standard developing solution, substrate adhesion, resist profile, and resolution and heat resistance, which are generally required performances of a resist. ,
It is appropriately set to adjust the sensitivity and the like.

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

In the acid-decomposable resin, one of the general formulas (pI) to (pV)
The content of the repeating unit having a partial structure containing an alicyclic hydrocarbon represented by I) is 30 to 70 in all repeating units.
Mol% is preferable, more preferably 35 to 65 mol%,
More preferably, it is 40 to 60 mol%. The content of the repeating unit represented by the general formula (II-AB) in the acid-decomposable resin is preferably 10 to 60 mol% in all repeating units, more preferably 15 to 55 mol%, and further preferably 20 to
It is 50 mol%.

The content of the repeating unit based on the monomer of the additional copolymerization component in the resin can be appropriately set according to the desired performance of the resist, but in general, the above general formula is used. 99 moles based on the total number of moles of the repeating units having a partial structure containing an alicyclic hydrocarbon represented by (pI) to (pVI) and the repeating units represented by the general formula (II-AB). % Or less, more preferably 90 mol% or less, still more preferably 80 mol% or less. When the composition of the present invention is for ArF exposure, ArF
From the viewpoint of transparency to light, it is preferable that the resin does not have an aromatic group.

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

The weight average molecular weight of the resin according to the present invention is G
The polystyrene conversion value by the PC method is preferably 1,000 to 200,000. When the weight average molecular weight is less than 1,000, heat resistance and dry etching resistance are deteriorated, which is not preferable, and when it exceeds 200,000, developability is deteriorated and film forming property is deteriorated due to extremely high viscosity. It produces less favorable results.

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

<< (C) Basic Compound >> The positive photosensitive composition of the present invention comprises (C) a substituted or unsubstituted aliphatic hydrocarbon group having at least 8 and preferably 8 to 19 carbon atoms in the molecule. Contains a basic compound containing.

These basic compounds may have 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 and 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-
Examples thereof include a nonadecanyl group and a t-nonadecanyl group, and these groups may be further substituted with other substituents. As the substituent, an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group and a t-butyl group, an aralkyl group such as a benzyl group, a phenyl group, Examples thereof include an aryl group such as a tolyl group, an allyl group, and a halogen atom. It is more preferable that these aliphatic hydrocarbon groups have 10 or more carbon atoms.

Examples of the basic compound having an aliphatic hydrocarbon group include, but are not limited to, those described below. Octylamine, dioctylamine,
Trioctylamine, dioctylmethylamine, nonylamine, dinonylamine, trinonylamine, dinonylmethylamine, decylamine, didecylamine, tridecylamine, didecylmethylamine, undecylamine, diundecylamine, triundecylamine, diundecylmethyl Amine, dodecylamine, didodecylamine, tridodecylamine, didodecylmethylamine,
Tridecylamine, ditridecylamine, tritridecylamine, ditridecylmethylamine, tetradecylamine, ditetradecylamine, tritetradecylamine, ditetradecylmethylamine, pentadecylamine, dipentadecylamine, tripentadecylamine ,
Dipentadecylmethylamine, hexadecylamine, dihexadecylamine, trihexadecylamine, dihexadecylmethylamine, heptadecylamine, diheptadecylamine, triheptadecylamine, diheptadecylmethylamine, octadecylamine, di Octadecylamine, trioctadecylamine, dioctadecylmethylamine, 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-undecyl Amine, 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-tetradecylamine, 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,
Examples thereof include di-i-octadecylmethylamine, i-nonadecylamine, di-i-nonadecylamine, tri-i-nonadecylamine and di-i-nonadecylmethylamine. 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 can also be used in combination. Examples of the basic compound 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, and JP-A 5-127
369, JP-A-5-289322, JP-A-5-249683, JP-A-5
-289340, JP-A-5-232706, JP-A-5-257282, JP-A-6-242605, JP-A-6-242606, JP-A-6-266100
No. 6-266110, No. 6-317902, No. 7-1
20929, JP 7-146558, JP 7-319163, JP 7-508840, JP 7-333844, JP 7-219217,
JP-A-7-92678, JP-A-7-28247, JP-A-8-22120
No. 8-110638, No. 8-123030, No. 9-27
4312, JP 9-166871, JP 9-292708, JP
9-325496, Tokuyohei 7-508840, USP5525453, USP562
Basic compounds described in 9134, USP 5667938 and the like can be used.

The nitrogen-containing basic compound is preferably 1,5-diazabicyclo [4.3.0] -5-nonene, 1,8-diazabicyclo [5.4.0] -7-undecene, 1, 4-diazabicyclo [2.2.2] octane, 4-dimethylaminopyridine, 1-naphthylamine, piperidine, hexamethylenetetramine, imidazoles, hydroxypyridines, pyridines, 4,4 '
-Diaminodiphenyl ether, pyridinium p-toluenesulfonate, 2,4,6-trimethylpyridinium p-toluenesulfonate, tetramethylammonium p-toluenesulfonate, tetrabutylammonium lactate, triethylamine, tributylamine and the like. 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 preferable.

These basic compounds may be used alone or
Used in seeds and above. The amount of the basic compound (C) used is
A basic compound which can be used in combination with the basic compound containing at least 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 is usually 0.001 to 10
%, Preferably 0.01 to 5% by weight. 0.0
If it is less than 01% by weight, the effect of adding the basic compound cannot be obtained. On the other hand, if it exceeds 10% by weight, the sensitivity tends to decrease and the developability of the unexposed area tends to deteriorate. Further, the mixing ratio of the basic compound containing at least a substituted or unsubstituted aliphatic hydrocarbon group having at least 8 carbon atoms in the molecule of the present invention and the basic compound usable in combination is usually 10 by weight.
/ 90 to 90/10, preferably 15/85 to 8
It is 5/15, 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-mentioned components (A) to (C). And / or silicon-based surfactant (fluorine-based surfactant and silicon-based surfactant, surfactant containing both fluorine atom and silicon atom), or 2
It is preferable to contain one or more species. Since the positive photosensitive composition of the present invention contains the above-mentioned (D) surfactant, when an exposure light source of 250 nm or less, particularly 220 nm or less is used, good sensitivity and resolution are obtained, and adhesion and development defects of It is possible to give a small resist pattern. Examples of these (D) surfactants include those disclosed in JP-A-62-62.
-36663, JP-A-61-226746, JP-A-61-226745,
JP 62-170950 A, JP 63-34540 A, JP 7-23016 A
5, JP 8-62834A, JP 9-54432A, JP 9-598A
8, U.S. Pat.Nos. 5,405,720, 5,360,692, 5,528,981,
5296330, 5436098, 5576143, 5294511
No. 5824451, and the following commercially available surfactants can be used as they are. As commercially available surfactants that can be used, for example, F-top EF301, EF303, (manufactured by Shin-Akita Kasei Co., Ltd.), Florard FC
430, 431 (Sumitomo 3M Limited), MegaFac F171,
F173, F176, F189, R08 (manufactured by Dainippon Ink Co., Ltd.), Surflon S-382, SC101, 102, 103, 104, 105, 106 (manufactured by Asahi Glass Co., Ltd.), Troisol S-366 (Troy Chemical Co., Ltd.) )) Or a fluorine-based surfactant or a silicon-based surfactant. Further, polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon-based surfactant.

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

<< (E) Organic Solvent >> The positive photosensitive composition of the present invention is used by dissolving the above components in a predetermined organic solvent. Examples of usable organic solvents include ethylene dichloride, cyclohexanone, cyclopentanone, and 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, lactic acid Methyl, ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate,
Methyl pyruvate, ethyl pyruvate, propyl pyruvate, N, N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, tetrahydrofuran and the like can be mentioned.

In the present invention, it is preferable to use a mixed solvent in which a solvent having a hydroxyl group in the structure and a solvent having no hydroxyl group are mixed as the organic solvent. This can reduce the generation of particles during storage of the resist solution. As the solvent containing a hydroxyl group, for example,
Examples thereof include ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and ethyl lactate. Of these, propylene glycol monomethyl ether and ethyl lactate are particularly preferable. preferable. Examples of the solvent containing no hydroxyl group include propylene glycol monomethyl ether acetate, ethylethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, butyl acetate, N-methylpyrrolidone, N, N-dimethylacetamide and dimethyl sulfoxide. Among these, propylene glycol monomethyl ether acetate, ethyl ethoxy propionate, 2-heptanone,
γ-Butyrolactone, cyclohexanone and butyl acetate are particularly preferable, and propylene glycol monomethyl ether acetate, ethylethoxypropionate and 2-heptanone are most preferable. 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 containing no hydroxyl group is particularly preferable from the viewpoint of coating uniformity.

<< (F) Acid-decomposable dissolution inhibiting compound >> The positive photosensitive composition of the present invention further has a group (F) which is decomposed by the action of an acid to increase the solubility in an alkali developing solution. However, the molecular weight is 3000 or less, preferably 100 or more and 300
It is preferable to contain a dissolution inhibiting low molecular weight compound of 0 or less (hereinafter, also referred to as “(F) acid-decomposable dissolution inhibiting compound”). In particular, because it does not reduce the transmittance below 220 nm,
An alicyclic or aliphatic compound containing an acid-decomposable group, such as a cholic acid derivative containing an acid-decomposable group described in Proceeding of SPIE, 2724,355 (1996), is (F) an acid-decomposable solution. Preferred as a blocking compound. Examples of the acid-decomposable group and the alicyclic structure include the same ones as described above for the acid-decomposable resin. The amount of the acid-decomposable dissolution inhibiting compound (F) added is preferably 3 to 50% by weight, and more preferably 5 to 40% by weight, based on the solid content of the entire positive photosensitive composition. . Specific examples of the acid-decomposable dissolution inhibiting compound (F) are shown below, but the invention is not limited thereto.

[0241]

[Chemical 95]

<< (G) Alkali-Soluble Resin >> The positive photosensitive composition of the present invention further comprises (G) a water-insoluble and alkali-developable resin which does not contain an acid-decomposable group. Can be included, which improves sensitivity. In the present invention, novolak resins having a molecular weight of about 1,000 to 20,000 and polyhydroxystyrene derivatives having a molecular weight of about 3,000 to 50,000 can be used as such resins, but they have large absorption for light of 250 nm or less. It is preferable to use it by partially hydrogenating it, or to use it in an amount of 30% by weight or less based on the total amount of the resin.
A resin containing a carboxyl group as an alkali-soluble group can also be used. In the resin containing carboxyl group, a single ring to improve dry etching resistance,
Alternatively, it preferably has a polycyclic alicyclic hydrocarbon group. Specifically, a copolymer of methacrylic acid ester having an alicyclic hydrocarbon structure which does not exhibit acid decomposability and (meth) acrylic acid, or a (meth) acrylic acid ester of an alicyclic hydrocarbon group having a carboxyl group at the terminal. And the like.

<< Other Additives >> The positive photosensitive composition of the present invention may further contain a dye, a plasticizer, a surfactant other than the above-mentioned component (D), a photosensitizer, and a developer, if necessary. A compound or the like which promotes the solubility of the compound may be contained. The compound capable of accelerating dissolution in a developer usable 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 above. The preferred addition amount of these dissolution accelerating compounds is 2 to 50% by weight, more preferably 5 to 50% by weight, with respect to the resin that is decomposed by the action of the acid (B) and the solubility in the alkali developing solution is increased.
It is 30% by weight. If the addition 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 prepared by those skilled in the art by referring to the methods described in, for example, JP-A-4-122938, JP-A-2-28531, US Pat. No. 4,916,210, and European Patent 219294. It can be easily synthesized. Specific examples of the alicyclic or aliphatic compound having a carboxyl group include carboxylic acid derivatives having a steroid structure such as cholic acid, deoxycholic acid, and lithocholic acid, adamantanecarboxylic acid derivatives, adamantanedicarboxylic acid, cyclohexanecarboxylic acid, and cyclohexane. Examples thereof include, but are not limited to, dicarboxylic acids.

In the present invention, a surfactant other than the (D) fluorine-based and / or silicon-based surfactant may be added. Specifically, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, polyoxyethylene nonylphenol ether, etc. Polyoxyethylene alkyl allyl ethers, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate,
Sorbitan fatty acid esters such as sorbitan tristearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate,
Examples thereof include nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate and polyoxyethylene sorbitan tristearate. These surfactants may be added alone or in some combinations.

<< Method of 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 described above, and coating the solution on a predetermined support as follows. . That is, the positive type photosensitive composition is used in a substrate (eg, silicon / silicon) used for manufacturing precision integrated circuit devices.
It is coated on the silicon dioxide coating) by a suitable coating method such as a spinner or coater. After coating, it is exposed through a predetermined mask, baked and developed. By doing so, a good resist pattern can be obtained. Here, the exposure light is far ultraviolet rays having a wavelength of preferably 250 nm or less, more preferably 220 nm or less. Specifically, KrF excimer laser (248 nm), Ar
Examples thereof include F excimer laser (193 nm), F ₂ excimer laser (157 nm), X-ray, and electron beam.

In the developing step, the developing solution is used as follows. Examples of the developer for the positive photosensitive composition include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, inorganic alkalis such as aqueous ammonia, primary amines such as ethylamine and n-propylamine. , Secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide It is possible to use an alkaline aqueous solution of a quaternary ammonium salt such as the above, a cyclic amine such as a pyrrole or a pyrhelidine, or the like. Furthermore, alcohols and surfactants may be added in appropriate amounts to the alkaline aqueous solution before use.

[0248]

EXAMPLES The present invention will be specifically described below based on examples, but the scope of the present invention is not limited to the examples.

<Synthesis Example of Resin> Synthesis Example (1) Synthesis of Resin (1) (Side Chain Type) 2-Ethyl-2-adamantyl methacrylate and butyrolactone methacrylate were charged at a ratio of 55/45 methyl ethyl ketone / tetrahydrofuran = 5 / It was dissolved in 5 to prepare 100 mL of a solution having a solid content concentration of 20%. 2 mol% of V-65 manufactured by Wako Pure Chemical Industries, Ltd. was added to this solution, and this 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 dropping, the reaction solution was heated for 4 hours, V-65 was added again at 1 mol% and the mixture was stirred for 4 hours. After completion of the reaction, the reaction solution was cooled to room temperature and distilled water / ISO propyl alcohol = 1/1 mixed solvent 3 L
The resin (1), which is a white powder that was crystallized and precipitated in the above, was recovered. Polymer composition ratio determined from C ¹³ NMR is 46/54
Met. Further, the weight average molecular weight in terms of standard polystyrene determined by GPC measurement was 10700.

Resins (2) to (18) were synthesized in the same manner as in Synthesis Example (1) above. Below, the above resin (2)
The composition ratio and molecular weight of (18) are shown. (Repeating unit 1,
2, 3 and 4 are the order from the left of the structural formula. )

[0251]

[Table 1]

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

[0253]

[Chemical 96]

[0254]

[Chemical 97]

[0255]

[Chemical 98]

[0256]

[Chemical 99]

[0257]

[Chemical 100]

Synthesis Example (2) Synthesis of Resin (19) (Main Chain Type) Norbornenecarboxylic acid t-butyl ester, norbornenecarboxylic acid butyrolactone ester, maleic anhydride (molar ratio 40/10/50) and THF (reaction temperature 6
0 wt%) was charged into a separable flask and heated at 60 ° C. under a nitrogen stream. When the reaction temperature became stable, 2 mol% of radical initiator V-601 manufactured by Wako Pure Chemical Industries, Ltd. was added to start the reaction. Heated for 12 hours. The resulting reaction mixture was diluted twice with tetrahydrofuran and then diluted with hexane /
It was put into a mixed solution of isopropyl alcohol = 1/1 to precipitate a white powder. The precipitated powder is filtered out,
After drying, the target resin (19) was obtained. When the molecular weight analysis of the obtained resin (19) by GPC was attempted, it was 8300 (weight average) in terms of polystyrene. Further, it was confirmed from the NMR spectrum that the molar ratio of norbornenecarboxylic acid t-butyl 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 following resin (2
The composition ratios and molecular weights of 0) to (30) are shown. (Alicyclic olefin units 1, 2, and 3 are in order from the left in the structural formula.)

[0260]

[Table 2]

Further, the following resins (19) to (30)
Shows the structure of.

[0262]

[Chemical 101]

[0263]

[Chemical 102]

Synthesis Example (3) Synthesis of Resin (31) (Hybrid Type) Norbornene, maleic anhydride, t-butyl acrylate and 2-methylcyclohexyl-2-propyl acrylate were reacted at a molar ratio of 35/35/20/10. It was charged in a container and dissolved in tetrahydrofuran to prepare a solution having a solid content of 60%. This was heated at 65 ° C. under a nitrogen stream. When the reaction temperature became stable, 1 mol% of radical initiator V-601 manufactured by Wako Pure Chemical Industries, Ltd. was added to start the reaction. After heating for 8 hours, the reaction mixture was diluted twice with tetrahydrofuran and then poured into hexane in an amount 5 times the volume of the reaction mixture to precipitate a white powder. The precipitated powder was taken out by filtration, dissolved in methyl ethyl ketone, reprecipitated in a mixed solvent of 5 volumes of hexane / t-butyl methyl ether = 1/1, and the precipitated white powder was collected by filtration, dried, and purposed. A resin (31) which is a product was obtained. When the molecular weight analysis of the obtained resin (31) by GPC was tried, it was 1 in terms of polystyrene.
It was 2100 (weight average). Further, from the NMR spectrum, the composition of the resin (1) was as follows: norbornene / maleic anhydride / t-butyl acrylate / 2-methylcyclohexyl-2-propyl acrylate of the present invention in a molar ratio of 32 /
It was 39/19/10.

Resins (32) to (44) were synthesized in the same manner as in Synthesis Example (3). The following resin (3
The composition ratios and molecular weights of 2) to (44) are shown.

[0266]

[Table 3]

Further, the following resins (31) to (44)
Shows the structure of.

[0268]

[Chemical 103]

[0269]

[Chemical 104]

[0270]

[Chemical 105]

[0271]

[Chemical formula 106]

Synthesis Example (4) Synthesis of Resin (45) (Hybrid Type) Norbornenecarboxylic acid t-butyl ester, maleic anhydride, 2-methyl-2-adamantyl acrylate, norbornene lactone acrylate in a molar ratio of 20/20.
/ 35/25 was charged into a reaction vessel and dissolved in a solvent of methyl ethyl ketone / tetrahydrofuran = 1/1 to give a solid content of 6
A 0% solution was prepared. This was heated at 65 ° C. under a nitrogen stream. When the reaction temperature became stable, 3 mol% of radical initiator V-601 manufactured by Wako Pure Chemical Industries, Ltd. was added to start the reaction. After heating for 12 hours, the reaction mixture was poured into 5 times the amount of hexane to precipitate a white powder. The precipitated powder was redissolved in a solvent of methyl ethyl ketone / tetrahydrofuran = 1/1 and put into 5 times the amount 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 target Resin (45). When the molecular weight analysis (RI analysis) of the obtained resin (45) by GPC was tried, it was 11 in terms of polystyrene.
600 (weight average), the amount of residual monomer was 0.4%. Further, from the NMR spectrum, the composition of the resin (1) was found to be norbornene / maleic anhydride / 2-methyl- of the present invention.
The molar ratio of 2-adamantyl acrylate / norbornene lactone acrylate was 18/23/34/25.

Resins (46) to (69) were synthesized in the same manner as in Synthesis Example (4). The following resin (4
The composition ratios and molecular weights of 6) to (69) are shown.

[0274]

[Table 4]

In addition, the following resins (45) to (69)
Shows the structure of.

[0276]

[Chemical formula 107]

[0277]

[Chemical 108]

[0278]

[Chemical 109]

[0279]

[Chemical 110]

[0280]

[Chemical 111]

[Examples 1 to 76 and Comparative Examples 1 to 4] The resins synthesized in the above Synthesis Example and the components shown in Tables 5 to 7 below were added in Tables 5 to 7 at a solid content concentration of 12% by weight. 0.1 μm Teflon (registered trademark) after being dissolved in the solvent described in
A positive photosensitive composition was prepared by filtering with a filter.
The prepared composition was evaluated by the following methods, and the results are shown in Table 8 to
Shown in 10.

[0282]

[Table 5]

[0283]

[Table 6]

[0284]

[Table 7]

Abbreviations in Tables 5 to 7 are as follows.

Photo-acid generator: Specific example of component (A) z1
~ Z40

The abbreviations for basic compounds are as follows. In addition, the ratio in the case of multiple use in Tables 5 to 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: Megafac F176 (Dainippon Ink and Chemicals, Inc.)
(Manufactured) (fluorine-based) W-2: Megafac R08 (manufactured by Dainippon Ink Co., Ltd.) (fluorine and silicon-based) W-3: polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) (silicon-based) ) W-4: Troisol S-366 (Troy Chemical Co., Ltd.)
Made)

Abbreviations for solvents are as follows. In addition, the ratio in the case of multiple use in Tables 5 to 7 is a weight ratio. A1: Propylene glycol methyl ether acetate A2: 2-heptanone A3: Ethyl ethoxy propionate A4: γ-butyrolactone A5: Cyclohexanone B1: Propylene glycol methyl ether B2: Ethyl lactate

<Image Evaluation Method> [Evaluation of Sidelobe Resistance] An antireflection film DUV-42 manufactured by Brewer Science Co., Ltd. is uniformly applied at 600 angstrom on a silicon substrate treated with hexamethyldisilazane with a spin coater, and the temperature is 100 ° C. After drying on a hot plate for 90 seconds at 190 ° C., heat drying was performed at 190 ° C. for 240 seconds. Then, each photosensitive resin composition was applied with a spin coater and dried at 120 ° C. for 90 seconds to give 0.30 μm.
m resist film was formed. For this resist film,
ArF excimer laser stepper (I
Exposure is made with SI company NA = 0.6), and immediately after exposure, 12
Heated on a hot plate for 90 seconds at 0 ° C. Further, it was developed with a 2.38% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 60 seconds, rinsed with pure water for 30 seconds and then dried to obtain a resist line pattern. The sidelobe resistance was evaluated by using a halftone phase shift mask and resolving 0.22 μm to 0.20 μm.
The pattern at 0.18 μm was observed, and a good one in which the expression of side lobes was not observed was indicated as ◯, a sign in which some side lobe signs were observed was marked as Δ, and a side lobe clearly confirmed was marked as x. . The evaluation results are shown in Tables 8 to 10.

[0291]

[Table 8]

[0292]

[Table 9]

[0293]

[Table 10]

As is clear from the results of Tables 8 to 10, the composition of the present invention is excellent in halftone exposure suitability (sidelobe resistance).

[0295]

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

Claims (4)

[Claims] 1. An alkali developing solution comprising: (A) a compound capable of generating an acid upon irradiation with actinic rays or radiation; and (B) having a monocyclic or polycyclic alicyclic hydrocarbon structure, which is decomposed by the action of an acid. A positive type photosensitive composition comprising: a resin having an increased solubility in water; and (C) a basic compound containing at least a substituted or unsubstituted aliphatic hydrocarbon group having 8 or more carbon atoms in the molecule. object. 2. The positive photosensitive composition according to claim 1, which further comprises (D) fluorine and / or a silicon-based surfactant. 3. The method according to claim 1, further comprising (F) a dissolution-inhibiting low-molecular compound having 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. The positive photosensitive composition as described in 1. 4. The positive photosensitive composition according to claim 1, further comprising (E) a mixed solvent obtained by mixing a solvent containing a hydroxyl group and a solvent not containing a hydroxyl group.