JP2002236359A - Positive type photosensitive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enhance performance proper to microphotofabrication using far ultraviolet light, particularly ArF excimer laser light, to solve technical problems proper to the microphotofabrication and to provide a positive type photosensitive composition excellent in sensitivity and resolving power. SOLUTION: The positive type photosensitive composition contains (A) at least one compound having at least one carbonyl group and generating an acid when irradiated with active light to cause decomposition accompanied by intramolecular hydrogen radical transfer and (B) a resin having a mono- or polycyclic alicyclic hydrocarbon structure and having solubility in an alkali developing solution increased when decomposed by the action of the acid.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

2. Description of the Related Art When a conventional resist comprising a novolak and a naphthoquinonediazide compound is used for lithographic pattern formation using far ultraviolet light or excimer laser light, novolak and naphthoquinonediazide have a strong absorption in the far ultraviolet region. Light hardly reaches the bottom of the resist, and only a low-sensitivity, tapered pattern can be obtained.

One of the means for solving such a problem is as follows.
U.S. Pat. No. 4,491,628, EP 249,1
No. 39 or the like. The chemically amplified positive resist composition generates an acid in the exposed portion by irradiation with radiation such as far ultraviolet light, and the reaction using the acid as a catalyst dissolves the active radiation-irradiated portion and the non-irradiated portion in the developing solution. It is a pattern forming material that changes the properties and forms a pattern on a substrate.

Examples of such a combination include a combination of a compound capable of generating an acid by photolysis with an acetal or an O, N-acetal compound (Japanese Patent Laid-Open No. 48-89003), a combination of an orthoester or an amide acetal compound. (JP-A-51-120714), combination with a polymer having an acetal or ketal group in the main chain (JP-A-53-133429), combination with an enol ether compound (JP-A-55-12995) ), N-acyliminocarbonate compounds (JP-A-55-126)
236), a combination with a polymer having an orthoester group in the main chain (JP-A-56-17345), and a combination with a tertiary alkyl ester compound (JP-A-60-1985).
No. 3625), combinations with silyl ester compounds (JP-A-60-10247), combinations with silyl ether compounds (JP-A-60-37549 and JP-A-60-12446). Can be mentioned. These have high photosensitivity because the quantum yield exceeds 1 in principle.

[0005] Similarly, a system which is decomposed by heating in the presence of an acid and solubilized in an alkali is disclosed in, for example,
-45439, JP-A-60-3625, JP-A-62
JP-A-229242, JP-A-63-27829, JP-A-63-36240, JP-A-63-250642, JP-A-5-181279, Polym. Eng.
Sce. 23, 1012 (1983); ACS.
Sym. 242, 11 (1984); Semico
nductor World, November 1987,
91, Macromolecules, 21, 14
75 (1988); SPIE, vol. 920, p. 42 (1
988), etc., and a tertiary or secondary carbon (for example, t-butyl, 2-
Combination system of cyclohexenyl) with an ester or carbonate compound, JP-A-4-219775, JP-A-5-24
Combination systems with acetal compounds described in JP-A Nos. 9682 and 6-65332, and
No. 11,258, 6-65333, etc., and a combination system with a t-butyl ether compound, and the like.

Since these systems mainly use a resin having a poly (hydroxystyrene) basic skeleton, which has a small absorption in the 248 nm region, as a main component, a high sensitivity is obtained when a KrF excimer laser is used as an exposure light source. A high-resolution and good pattern can be formed, and it can be a good system as compared with the conventional naphthoquinonediazide / novolak resin system.

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

On the other hand, the polymer having an alicyclic hydrocarbon group has the same dry etching resistance as an aromatic group and has a small absorption in the 193 nm region.
c. of SPIE, 1672, 66 (1992), and the use of the polymer has been energetically studied in recent years. Specifically, JP-A-4-39665 and JP-A-5-8
0515, 5-265212, 5-29759
No. 1, 5-346668, 6-289615,
6-324494, 7-49568, 7-1
No. 85046, No. 7-191463, No. 7-1994
Polymers described in JP-A Nos. 67, 7-234511, 7-252324 and the like can be mentioned. JP-A-3-28959 describes a positive photosensitive composition containing an alkali-soluble resin, an acid-decomposable dissolution inhibitor and α-sulfonyloxyacetophenone. JP-A-4-60551 describes that sensitivity is improved by applying a composition containing an α-sulfonyloxyacetophenone derivative to a substrate and then exposing the composition to water vapor or alcohol. However, these compositions require extraction of hydrogen radicals (intermolecular hydrogen transfer) from a material other than the acid generator, such as a resin, for the photolysis of the acid generator. There was a problem that it would be lower. In particular, when a resin having an alicyclic group is used, there is a problem that the sensitivity is significantly lowered because there is no hydrogen donor.

[0009]

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to improve the performance and technical problems inherent in the above-described microphotofabrication using far ultraviolet light, particularly ArF excimer laser light. An object of the present invention is to provide a positive photosensitive composition excellent in sensitivity and resolution.

[0010]

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

(1) (A) The carbonyl group has at least one
Having at least one compound that decomposes upon irradiation with actinic rays with intramolecular hydrogen radical transfer to generate an acid, and (B) a monocyclic or polycyclic alicyclic hydrocarbon structure, A positive photosensitive composition comprising a resin that decomposes by action to increase solubility in an alkaline developer. (2) The positive photosensitive composition according to the above (1), wherein the component (A) is a compound represented by the general formula (I) or (II).

[0012]

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R ₁ and R ₂ may be the same or different and represent a hydrogen atom or a monovalent organic group. Or, R ₁ and R ₂ are bonded to form a heteroatom, a multiple bond, -CO-,
A monocyclic or polycyclic ring structure which may contain -COO- may be formed. R ₃ and R ₄ may be the same or different and represent a hydrogen atom or a monovalent organic group.

X represents a monovalent organic group having a hydrogen radical donating group. X may combine with R ₁ or R ₂ to form a monocyclic or polycyclic ring structure. Y ₁ in the general formula (I) represents R′SO ₃ —, R′COO—, or a halogen atom. R ′ represents an optionally substituted linear, branched, or cyclic alkyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, or an optionally substituted camphor group. General formula (I
Y ₂ in I) ^- represents a non-nucleophilic anion. Ra and Rb represent an optionally substituted linear, branched or cyclic alkyl group, an optionally substituted aryl group, or an optionally substituted aralkyl group. In addition, Ra and Rb
May combine with each other to form a ring. R _{1 to} R ₄ , Ra, R
b, X, Y ₁ , and Y ₂ ^— may be bonded via a linking group at any position to have two structures of the general formula (I) or (II).

(3) (C) A low molecular weight dissolution inhibiting compound having a molecular weight of 3000 or less, which has a group decomposable by an acid and whose dissolution rate in an alkali developing solution is increased by the action of an acid. Features (1) or (2) above
4. The positive photosensitive composition according to item 1. (4) The positive photosensitive composition as described in any of (1) to (3) above, wherein the resin (B) is a resin having a lactone structure.

(5) (A) a carbonyl group having at least 1
(C) having at least one compound capable of decomposing by the irradiation of actinic rays with the transfer of intramolecular hydrogen radicals to generate an acid, and (C) a group decomposable by an acid, and a dissolution rate in an alkaline developer. Is increased by the action of an acid.
000 or less low molecular weight dissolution inhibiting compound; and (D) a resin having a monocyclic or polycyclic alicyclic hydrocarbon structure, containing a resin which is insoluble in water and soluble in an alkali developing solution. Photosensitive composition.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

(A) A compound having at least one carbonyl group, which decomposes upon irradiation with actinic rays with the transfer of intramolecular hydrogen radicals to generate an acid. Compounds represented by II) are preferred. In the above formulas (I) and (II), the monovalent organic group for R ₁ , R ₂ , R ₃ and R ₄ is an alkyl group (preferably having 1 to 10 carbon atoms, more preferably 1 to 10 carbon atoms). 5, for example, a methyl group, an ethyl group, n
-Propyl group, isopropyl group, n-butyl group, sec
-Butyl group, t-butyl group, pentyl group), alkoxy group (preferably having 1 to 10 carbon atoms, more preferably having 1 to 5 carbon atoms, for example, methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group) , N
-Butoxy group, isobutoxy group, sec-butoxy group,
t-butoxy group, etc.), alkoxycarbonyl group (preferably having 2 to 6 carbon atoms, methoxycarbonyl group, ethoxycarbonyl group, etc.), aryl group (preferably having 6 to 6 carbon atoms)
9, phenyl group, xylyl group, toluyl group, cumenyl group), aryloxy group (preferably having 6 to 12 carbon atoms,
A phenoxy group or the like), an aryloxycarbonyl group (preferably having 7 to 12 carbon atoms, a benzoyloxy group or the like), an acyl group (preferably having 1 to 12 carbon atoms, for example, an aralkyloxy group, a formyl group, an acetyl group, a butyryl group, Benzoyl group, cyanamyl group, valeryl group, etc.), acyloxy group (preferably having 1 to 12 carbon atoms, such as butyryloxy group), alkenyl group (preferably having 2 to 4 carbon atoms, such as nyl group, propenyl group, allyl group, butenyl) Group), an alkenyloxy group (having 2 to 5 carbon atoms, such as a vinyloxy group, a propenyloxy group, an allyloxy group, a butenyloxy group, etc.), a carboxyl group, a nitro group, and a cyano group.

The monocyclic or polycyclic ring structure which may be formed by combining R ₁ and R ₂ and which may contain a hetero atom, a multiple bond, --CO--, --COO-- is preferable. Has 2 to 15 carbon atoms, such as benzene, naphthalene, cyclopentene, cyclopropene, cyclohexene, cycloheptene, cyclooctene, adamantene, norbornene,
Examples include isobornane, camphanene, dicyclopentene, and tricyclodecanene. These may have a substituent. Preferred substituents include an alkyl group having 1 to 5 carbon atoms, alkoxy, a halogen atom, a hydroxyl group and the like. Among them, R ₁ and R ₂ are preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a benzene ring or a naphthalene ring which may have a substituent to which R ₁ and R ₂ are bonded. And those forming a pentene ring. As R ₃ and R ₄ , a hydrogen atom and an alkyl group having 1 to 5 carbon atoms are preferable.

The substituted or unsubstituted linear, branched or cyclic alkyl group, the optionally substituted aryl group, or the optionally substituted aralkyl group as R ′ in R ₁ and Ra and Rb will be described. I do. The alkyl group is, for example, an alkyl group having 1 to 15 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a cyclopentyl group, a hexyl group,
-Ethylhexyl group, cyclohexyl group, octyl group,
An adamantyl group and a norbornyl group can be preferably exemplified. The alkyl group may further have a substituent. Examples of the substituent include a hydroxyl group, a halogen atom such as a fluorine atom, an alkoxy group (preferably having 1 to 5 carbon atoms) which may be substituted by fluorine, and an alkoxy group. Examples include a carbonyl group (preferably having 2 to 6 carbon atoms). The aryl group is, for example, an aryl group having 6 to 15 carbon atoms, specifically, a phenyl group, a tolyl group, a dimethylphenyl group, a 2,4,6-trimethylphenyl group, a naphthyl group, an anthryl group, Preferred are 9,10-dimethoxyanthryl groups and the like. The aryl group may further have a substituent, for example, a halogen atom such as a fluorine atom, an alkyl group which may be substituted by fluorine (preferably having 1 carbon atom).
To 5), an alkoxy group which may be substituted by fluorine (preferably having 1 to 5 carbon atoms), an alkoxycarbonyl group which may be substituted by fluorine (preferably having 2 to 6 carbon atoms), and the like. The aralkyl group is, for example, an aralkyl group having 7 to 12 carbon atoms, and specific examples thereof include a benzyl group, a phenethyl group, and a naphthylmethyl group. The aralkyl group may further have a substituent, for example, a halogen atom such as a fluorine atom, an alkyl group (preferably having 1 to 5 carbon atoms) which may be substituted with fluorine, or an alkoxy group which may be substituted with fluorine. (Preferably having 1 to 5 carbon atoms), and an alkoxycarbonyl group (preferably having 2 to 6 carbon atoms) which may be substituted by fluorine.

Examples of the substituent which the camphor group as R ′ may have include a halogen atom such as a fluorine atom, an alkyl group which may be substituted by fluorine (preferably having 1 carbon atom).
To 5), an alkoxy group which may be substituted by fluorine (preferably having 1 to 5 carbon atoms), an alkoxycarbonyl group which may be substituted by fluorine (preferably having 2 to 6 carbon atoms), and the like.

In the general formula (I), Y ₁ is R′SO
₃ -, R'COO-, or a halogen atom. Specific examples of the non-nucleophilic anion of Y ₂ ⁻ in the general formula (II) include R′SO ₃ ⁻ , R′COO ⁻ , halogen anion, and B
F ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , ClO ₄ ^{− and the} like can be mentioned. Y ₂ ^- as the perfluoro alkanesulfonic acid anion sensitivity, resolution, and most preferable from the viewpoint of transparency of the resist film.

The ring which may be formed by combining Ra and Rb is particularly preferably a 5- or 6-membered ring, wherein an alkylene group or -O-, -S-, -CO- or the like is linked. Those which form a ring structure via an alkylene group contained as a group are preferred. Most preferred alkylene groups include a butylene group and a pentylene group.
R _{1 to} R ₄ , Ra, Rb, X, Y ₁ , or a bond via a linking group at any position of Y ₂ ^— to form a compound represented by formula (I) or (II)
May have two structures.

The monovalent organic group having a hydrogen radical-donating group as X is a group having a hydrogen atom represented by -X'-H, and has a small bond dissociation energy of X'-H bond. Group. The bond dissociation energy of the X'-H bond is 150 kcal or less and 100 kcal
/ Mol or less, more preferably 90 kca
1 / mol or less. By using a group having a small bond dissociation energy, the hydrogen radical donating property is increased, the acid generation efficiency is improved, and the sensitivity is improved. The bond dissociation energy can be determined by a thermodynamic calculation from the heat of formation of free radicals, a kinetic method such as a toluene carrier method, or an electron impact method. These are Free Radicals in Solution,
p.40, Chem.Revs., 59, 239 (1959), Chem.Revs., 61,
247 (1961), Chem. Revs., 66, 465 (1966). In addition, Handbook of Chemistry and Physics 66th e
d. F185 describes bond dissociation energies of various functional groups. In addition, it is preferable that the X'-H group and the carbonyl group are bonded to a position forming a 5- to 7-membered ring via a linking group. In the case of the general formula (I), it is most preferable to have a structure capable of forming a 6-membered ring with a carbonyl group as shown in the following figure. This increases the intramolecular hydrogen transfer rate,
Photolysis efficiency is improved. The same applies to general formula (II).

[0025]

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Examples of the group having a small bond dissociation energy of the X'-H bond include a benzyl C-H bond, an ether α-CH bond, an alcohol α-CH bond, and an amine or amide N-CH bond. Examples include, but are not limited to, an H bond, an allyl C—H bond, an O—H bond of a phenolic hydroxyl group, and a C—H bond at the 2-position of an isopropyl group.

The reaction mechanism of the compound as the component (A) will be described below together with the reaction mechanism of a known acid generator.

[0028]

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[0029]

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

[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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The amount of the component (A) added to the composition is generally from 0.1 to 20% by weight, preferably from 0.5 to 10% by weight, more preferably from 0.5 to 10% by weight, based on the total solids of the composition. Preferably it is 1 to 7% by weight. If the ratio is less than the lower limit, the sensitivity tends to be remarkably low. If the ratio exceeds the upper limit, the transparency of the resist film tends to decrease, resulting in a pattern called taper.

The compound of the component (A) can be synthesized by a known method, and can generally be obtained by the following synthesis method. The compound of the general formula (I) can be obtained by reacting the corresponding ketone compound with [hydroxy (sulfonyloxy) iodo] benzene. [Hydroxy (sulfonyloxy) iodo] benzene is described in J. Am. Chem. Soc. 1987, 109, 228-235 or Tet.
rahedron, 1992, 48, 7149-7156, by reacting iodobenzene diacetate or iodosylbenzene with sulfonic acid. The compound of the general formula (II) is obtained by reacting an α-halogen-substituted ketone compound with a sulfide compound, if necessary, using a silver compound such as AgBF, to synthesize a sulfonium salt, and then performing salt exchange with a desired counter anion. Can be synthesized by

Acid-generating compounds other than component (A) which can be used in combination In the present invention, compounds which decompose upon irradiation with actinic rays or radiation to generate an acid may be used in addition to component (A). The amount of the photoacid generator that can be used in combination with the component (A) of the present invention is a molar ratio (component (A) / other acid generator).
And usually 100/0 to 20/80, preferably 100/0
0/40/60, more preferably 100/0 to 50/5
0. Such photoacid generators that can be used together include:
Photo-initiators for photo-cationic polymerization, photo-initiators for photo-radical polymerization, photo-decolorants for dyes, photo-discolorants, or known acids that generate acids by irradiation with actinic rays or radiation used in micro resists and the like Compounds 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, arsonium salts, etc.
Organic halogen compound, organic metal / organic halide, o
-Photoacid generators having a nitrobenzyl-type protecting group, compounds that generate sulfonic acid upon photolysis, such as iminosulfonate, and disulfone compounds.

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

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

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

[0046]

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

[0048]

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[0049]

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

[0051]

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

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

[0054 Z ^- represents a counter anion, for example BF ₄ ^{-,
_{AsF 6 -, PF 6 -,}} SbF 6 -, SiF 6 2-, ClO 4 -,
CF ₃ SO ₃ ^-, etc. perfluoroalkane sulfonate anion, pentafluorobenzenesulfonic acid anion, condensed polynuclear aromatic sulfonic acid anion such as naphthalene-1-sulfonic acid anion, anthraquinone sulfonic acid anion, a sulfonic acid group-containing dyes Examples include, but are not limited to:

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

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

[0057]

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[0058]

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[0059]

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[0060]

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[0061]

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[0062]

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[0063]

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[0064]

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[0065]

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[0066]

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[0067]

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

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

[0070]

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

[0072]

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[0073]

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[0074]

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[0075]

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[0076]

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

[0078]

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

[0080]

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

[0082]

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[0083]

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[0084]

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{(B) Resin whose solubility in an alkali developing solution is increased by the action of an acid}
A resin whose solubility in an alkaline developer is increased by the action of an acid (hereinafter also referred to as “acid-decomposable resin”) has a group that is decomposed by the action of an acid. A group that decomposes under the action of an acid (hereinafter, also referred to as an “acid-decomposable group”) is, for example, a group that hydrolyzes under the action of an acid to form an acid, and further, a carbon cation is eliminated under the action of an acid to form an acid Group. Preferred are groups represented by the following general formulas (x) and (y), acid-decomposable groups having a lactone structure, and acid-decomposable groups having an alicyclic structure. Thereby, the stability over time becomes excellent.

[0086]

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Here, Ra, Rb and Rc each independently represent a hydrogen atom or an alkyl group, a cycloalkyl group or an alkenyl group which may have a substituent.
However, at least one of Ra, Rb and Rc in the formula (x) is a group other than a hydrogen atom. Rd represents an alkyl group, a cycloalkyl group or an alkenyl group which may have a substituent. Further, two groups out of Ra, Rb and Rc in the formula (x) or two groups out of Ra, Rb and Rd in the formula (y) are bonded to each other to form a ring composed of 3 to 8 carbon atoms. A structure may be formed, or a ring structure containing a hetero atom may be formed. Specific examples of such a ring include a cyclopropyl group, a cyclopentyl group,
Examples thereof include a cyclohexyl group, a cycloheptyl group, a 1-cyclohexenyl group, a 2-tetrahydrofuranyl group, and a 2-tetrahydropyranyl group. Za and Zb each independently represent an oxygen atom or a sulfur atom. As the alkyl group of Ra to Rd, preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, which may have a substituent,
Those having 1 to 8 carbon atoms such as sec-butyl group, hexyl group, 2-ethylhexyl group and octyl group are exemplified. The cycloalkyl group preferably has 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group and a cyclohexyl group, which may have a substituent. The alkenyl group preferably has 2 to 6 carbon atoms such as a vinyl group, a propenyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group, and a cyclohexenyl group which may have a substituent. No.

Further substituents in each of the above-mentioned substituents are preferably a hydroxyl group, a halogen atom (fluorine, chlorine, bromine, iodine), a nitro group, a cyano group, an amide group, a sulfonamide group, a methyl group. , Ethyl group, propyl group, n-butyl group, sec-butyl group, hexyl group, 2-ethylhexyl group, alkyl group such as octyl group, methoxy group, ethoxy group, hydroxyethoxy group,
Propoxy group, hydroxypropoxy group, alkoxy group such as butoxy group, methoxycarbonyl group, alkoxycarbonyl group such as ethoxycarbonyl group, formyl group, acetyl group, acyl group such as benzoyl group, acetoxy group,
Examples include an acyloxy group such as a butyryloxy group and a carboxy group.

Specific examples of the repeating unit having an acid-decomposable group are shown below, but the present invention is not limited thereto.

[0090]

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[0091]

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[0092]

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[0093]

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Among the above, (c1), (c7), (c
11) is particularly excellent in acid decomposability. In the present invention, the acid-decomposable resin preferably contains a lactone structure. Here, as the lactone structure, those having a lactone structure in the side chain of the resin are preferable. Specifically, the repeating units (a1) to (a2
0) can be exemplified. As described above, each of the alicyclic hydrocarbon structure and the lactone structure may or may not have acid-decomposability.

[0095]

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[0096]

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Of the above (a1) to (a20), for example, (a1), (a12), (a15) and the like are usually preferred because of their acid decomposability. As the monocyclic or polycyclic alicyclic hydrocarbon structure contained in the acid-decomposable resin, as a monocyclic type, a monocyclic alicyclic skeleton having 3 or more carbon atoms, preferably 3 to 8 carbon atoms. And a cyclic hydrocarbon skeleton such as cyclopropane, cyclobutane, cyclopentane and cyclohexane. Examples of the polycyclic type include those having an alicyclic skeleton having 5 or more carbon atoms, preferably 7 to 25 carbon atoms. For example, an alicyclic cyclic hydrocarbon skeleton such as bicyclo, tricyclo and tetracyclo may be mentioned.
More specifically, those exemplified in the structure described later are exemplified.

On the other hand, the acid-decomposable group which may be contained in the alicyclic hydrocarbon group may be linked by an acid-decomposition structure, decomposed by the action of an acid, and the alicyclic hydrocarbon group may be eliminated. ,
Alternatively, the group represented by the above formula (x) or (y) may be bonded to the alicyclic hydrocarbon group directly or via a linking group. When a monocyclic or polycyclic alicyclic hydrocarbon group is provided on the side chain of the resin, it is preferable that the resin main chain and the alicyclic hydrocarbon group are connected by a tertiary ester group.

The repeating unit having a monocyclic or polycyclic alicyclic hydrocarbon structure is preferably a structural unit represented by the following general formulas (II) to (V).

[0100]

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[0101]

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Formulas (II) to (IV) will be described.
Formula (V) will be described. In formulas (II) to (IV),
A substituent attached to the main chain of the repeating unit, ie, R ¹¹,
R¹², R¹⁴~ R¹⁶Is hydrogen, halogen, cyano
Represents a group, an alkyl group or a haloalkyl group. R¹¹,
R¹², R¹⁴~ R¹⁶May be the same or different
It may be. R¹¹, R¹², R¹⁴~ R¹⁶Above
As the alkyl group, a methyl group, an ethyl group, a propyl group,
1-4 carbon atoms such as n-butyl group and sec-butyl group
Hydrocarbon groups. The above haloalk
As the alkyl group, a part of an alkyl group having 1 to 4 carbon atoms or
A group in which all halogen atoms are substituted can be mentioned.
Wear. Here, as the halogen atom, preferably fluorine
Atoms, chlorine atoms or bromine atoms. C
Specific examples of the loalkyl group include, for example, fluoromethyl
Group, chloromethyl group, bromomethyl group, fluoroethyl
Group, chloroethyl group, bromoethyl group and the like.
These alkyl groups and haloalkyl groups are a halogen atom
May further have a substituent other than the above.

The substituent R ¹³ is a cyano group, —CO—OR ²³
Or an -CO-NR ²⁴ R ^25. Here, R ²³ represents a hydrogen atom, an alkyl group, a cycloalkyl group or an alkenyl group, or an acid-decomposable group. Examples of the acid-decomposable group include the same groups as described above. For example, a compound having the same repeating structural unit as described above is preferable. Of the R ^23,
The alkyl group, cycloalkyl group and alkenyl group may further have a substituent.

R ²⁴ and R ²⁵ are each a hydrogen atom or
Represents an alkyl group, a cycloalkyl group or an alkenyl group. The alkyl group, cycloalkyl group, and alkenyl group may have a substituent. R ²⁴ and R ²⁵ may be the same or different. Combine with each other,
A ring may be formed together with the nitrogen atom. In such a case, the ring structure is preferably a 5- to 8-membered ring, and specific examples include pyrrolidine, piperidine, and piperazine skeletons. R
^The alkyl group represented by ^{23 to} R ²⁵ is preferably an alkyl group having 1 to 8 carbon atoms, specifically, a methyl group, an ethyl group,
Examples include a propyl group, an n-butyl group, a sec-butyl group, a hexyl group, a 2-ethylhexyl group, and an octyl group. As the cycloalkyl group, a cycloalkyl group having 3 to 8 carbon atoms is preferable, and specific examples include a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group. The alkenyl group is preferably an alkenyl group having 2 to 6 carbon atoms, specifically, a vinyl group, a propenyl group,
Allyl group, butenyl group, pentenyl group, hexenyl group,
And cyclohexenyl group. The alkyl group, cycloalkyl group, and alkenyl group may have a substituent.

In the formulas (II) to (IV), X ₁ -A, X ₂
-A or X ₃ -A, X _{1 to} X ₃
Represents a single bond or a divalent group. Examples of the divalent group, such as an alkylene group, an alkenylene group, a cycloalkylene _{group, -O -, - SO 2 -} , - O-CO-R 26 -, - CO
—O—R ²⁷ — and —CO—NR ²⁸ —R ²⁹ — and the like. X _{1 to} X ₃ may be the same or different.

X₁~ X_ThreeOf which, an alkylene group, an alkenyl
Rene group and cycloalkylene group are represented by R ¹¹, R¹², R¹⁴~ R
¹⁶Alkyl, alkenyl, and cycloalkyl groups represented by
And the carbon skeleton can each be the same divalent group
Wear. X₁~ X_ThreeOf the above -O-CO-R²⁶-, -CO-
OR²⁷-And -CO-NR^{Two 8}-R²⁹R in-²⁶,
R²⁷, R²⁹Represents a single bond or a divalent group, respectively. 2
Examples of the valent group include an alkylene group and an alkenylene
And cycloalkylene groups. This
Alkylene group, alkenylene group and cycloal
For the kylene group, R¹¹, R¹², R¹⁴~ R¹⁶A
Alkyl, alkenyl, cycloalkyl and carbon skeleton
Can be the same divalent group. These groups
Further includes ether groups, ester groups, amide groups,
Combined with a tan group or ureido group
It may form a group. R²⁶, R²⁷, R²⁹Of the three
However, they may be the same or different. X₁~
X_Three-CO-NR within²⁸-R²⁹-Substituent R²⁸Is on
R^{twenty three}~ R^{twenty five}The same applies to hydrogen atoms, alkyl groups,
Represents a loalkyl group or an alkenyl group. These archi
Groups, cycloalkyl groups, and alkenyl groups have a substituent.
It may be. R²⁸Is R^{twenty four}And R^{twenty five}Same as any of
It may be one or different. R²⁸Al represented by
Specific examples of kill, cycloalkyl and alkenyl groups
Is R^{twenty three}~ R^{twenty five}An alkyl group represented by the formula
This is the same as in the case of a kill group or an alkenyl group.

The substituent A bonded indirectly to the main chain of the repeating unit via X ₁ or the like represents a monocyclic or polycyclic hydrocarbon group. Examples of the monocyclic hydrocarbon group represented by A include groups having an alicyclic skeleton having 3 or more carbon atoms, preferably 3 to 8 carbon atoms. For example, a cyclic hydrocarbon skeleton such as cyclopropane, cyclobutane, cyclopentane and cyclohexane can be mentioned. Examples of the polycyclic hydrocarbon group include a group having an alicyclic skeleton having 5 or more carbon atoms, preferably 7 to 25 carbon atoms. For example, an alicyclic cyclic hydrocarbon skeleton such as bicyclo, tricyclo and tetracyclo may be mentioned. These monocyclic or polycyclic cyclic hydrocarbon skeleton groups may further have a substituent to increase the number of carbon atoms.

Preferred substituents of the polycyclic alicyclic group include a hydroxyl group, a halogen atom, a nitro group, a cyano group, an amide group, a sulfonamide group, and the alkyl group described for R ²³ as they are. it can. Halogen is fluorine, chlorine, bromine or iodine. As a substituent, an alkoxy group, an alkoxycarbonyl group,
Examples include an acyl group, an acyloxy group, and a carboxy group.
Examples of the alkoxy group include an alkoxy group having 1 to 8 carbon atoms such as a methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, a hydroxypropoxy group, and a butoxy group. As the alkoxycarbonyl group,
Examples thereof include an alkoxycarbonyl group such as a methoxycarbonyl group and an ethoxycarbonyl group. Examples of the acyl group include a formyl group, an acetyl group and a benzoyl group. Examples of the acyloxy group include an acetoxy group and a butyryloxy group.

Representative examples of the polycyclic or monocyclic alicyclic moiety of the polycyclic or monocyclic cyclic hydrocarbon group, ie, A, include the following. .

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[0111]

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Next, the general formula (V) will be described. In the general formula (V), n is 0 or 1. X
a and Xb represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Ya and Yb represent a hydrogen atom, a hydroxyl group, or -COO
Represents a group represented by Xc. Here, Xc represents, in one embodiment, a hydrogen atom or an alkyl group. Examples of the alkyl group include an alkyl group having 1 to 8 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, and specifically, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a tert group -Butyl group and the like. These alkyl groups are a hydroxyl group, a halogen group or a cyano group,
Some or all of the hydrogen atoms may be substituted. In another embodiment of Xc, -COOXc represents a group constituting an acid-decomposable group as a whole. Specifically, the above equation (x),
The group represented by (y) can be mentioned. In addition, a group containing an acid-decomposable lactone structure and a group containing an acid-decomposable alicyclic structure can also be mentioned. Also,
The resin of the present invention is preferably a copolymer resin of the repeating unit represented by the general formula (V) and maleic anhydride, or a resin obtained by further copolymerizing an acrylic ester or a methacrylic ester.

Specific examples of the repeating structural units represented by formulas (II) to (V) are shown below, but the present invention is not limited thereto.

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[0121]

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[0123]

[Of 60]

Among these specific examples, for example, (b1)
(B2), (b5), (b9), (b47), (b4)
8), (b49), (b50), (b54), (b5)
8), (b60) and the like are usually preferred because of their acid decomposability. In particular, (b1), (b47), and (b4) in which an adamantyl group is linked to the resin main chain by an acid-decomposable structure.
8) and (b49) are preferred. When these are used, dry etching resistance and resolution are improved.

The acid-decomposable resin as described above may further contain a carboxyl group. The carboxyl group may be contained in each of the above repeating structural units, or may be contained in another repeating structural unit other than these. Furthermore, these structural units may be included in a plurality of positions.

The content of all the repeating units having a carboxyl group in the acid-decomposable resin contained in the positive photosensitive composition of the present invention depends on the performance such as alkali developability, substrate adhesion, and sensitivity. Although it is adjusted, it is preferably 0 to 6 with respect to all repeating structural units of the acid-decomposable resin.
The range is 0 mol%, more preferably 0 to 40 mol%, and still more preferably 0 to 20 mol%. Specific examples of the repeating structural unit having a carboxyl group are shown below,
The present invention is not limited to this.

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[0128]

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For the purpose of improving the performance of the acid-decomposable resin,
Other polymerizable monomers may be further copolymerized within a range that does not significantly impair the transmittance of the resin at 220 nm or less and the dry etching resistance. Copolymerizable monomers that can be used include those shown below. For example, it has one addition polymerizable unsaturated bond selected from acrylates, acrylamides, methacrylates, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, crotonates, and the like. Compound.

Specifically: acrylates, for example, alkyl (preferably having 1 to 10 carbon atoms in the alkyl group) acrylate (for example, methyl acrylate, ethyl acrylate, propyl acrylate, t-acrylate)
Butyl, 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, glycidyl acrylate, benzyl acrylate, methoxybenzyl Acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, etc.), aryl acrylate, methoxyethoxyethyl acrylate;

Methacrylic esters, for example, alkyl (the alkyl group preferably has 1 to 10 carbon atoms)
Methacrylate (e.g., methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, t-butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, octyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, Hydroxypentyl methacrylate, 2,2-dimethyl-3
-Hydroxypropyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, glycidyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate and the like, aryl methacrylate (for example, phenyl methacrylate, naphthyl methacrylate and the like), methoxyethoxyethyl methacrylate;

Acrylamides, for example, acrylamide, N-alkylacrylamide, (where the alkyl group has 1 to 10 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a t-butyl group, a heptyl group Octyl group, cyclohexyl group, benzyl group, hydroxyethyl group, benzyl group, etc.), N-arylacrylamide, N, N-dialkylacrylamide (alkyl group having 1 to 10 carbon atoms, for example, methyl group, Ethyl group, butyl group, isobutyl group, ethylhexyl group, cyclohexyl group, etc., N, N-arylacrylamide, N-hydroxyethyl-N-methylacrylamide, N-2-acetamidoethyl-N-acetylacrylamide, etc .; methacrylamides, For example, methacrylamide, N- The Le Kill methacrylamide (the alkyl group, those having 1 to 10 carbon atoms, e.g., methyl, ethyl, t- butyl group, ethylhexyl group,
Hydroxyethyl group, cyclohexyl group, etc.), N-aryl methacrylamide, N, N-dialkyl methacrylamide (an alkyl group such as ethyl group, propyl group, butyl group, etc.), N-hydroxyethyl-N-methyl methacrylamide , N-methyl-N-phenylmethacrylamide, N-ethyl-N-phenylmethacrylamide and the like; allyl compounds such as allyl esters (for example, allyl acetate, allyl caproate, allyl caprylate, allyl laurate, palmitic acid) Allyl, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate), allyloxyethanol and the like;

Crotonic esters, for example, alkyl crotonates (for example, butyl crotonate, hexyl crotonate, glycerin monocrotonate, etc.); dialkyl itaconates (for example, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, etc.) And dialkyl esters of maleic acid or fumaric acid (eg, dimethyl maleate, dibutyl fumarate, etc.), maleic anhydride, maleimide, acrylonitrile, methacrylonitrile, maleilenitrile, and the like. In addition, generally, any addition-polymerizable unsaturated compound that can be copolymerized may be used.

Among them, methoxyethoxyethyl methacrylate and methoxyethoxyethyl acrylate are particularly preferred. (B) The content of the repeating structural unit derived from another polymerizable monomer in the acid-decomposable resin is preferably 50 mol% or less based on all repeating structural units,
It is more preferably at most 30 mol%. From the viewpoint of ensuring the transparency to the ArF laser, it is preferable that the acid-decomposable resin (B) does not contain an aromatic ring. This is because if the transparency is reduced due to the introduction of the aromatic ring, the exposure light hardly reaches the bottom of the resist film, resulting in a pattern profile called a taper.

(B) In the acid-decomposable resin, the content of the repeating structural unit having an acid-decomposable group is adjusted by the balance between dry etching resistance, alkali developability and the like. The content is preferably at least 10 mol%, more preferably at least 15 mol%, further preferably at least 20 mol%. The structural unit having the cyclic hydrocarbon group (preferably, any of the general formulas (II) to (IV)
The content of the repeating structural unit represented by the formula (I) is adjusted according to the balance between dry etching resistance, alkali developability, and the like, but is preferably 20 mol% or more based on all repeating structural units. The content is more preferably 3
0-80 mol%, more preferably 35-70 mol%,
More preferably, it is in the range of 40 to 60 mol%.
The content of the repeating structural unit having a lactone structure in the acid-decomposable resin (B) is adjusted by a balance between dry etching resistance, alkali developability, and the like. % Is preferable. The content is more preferably at least 10 mol%, further preferably at least 20 mol%. In the present invention, the content of the resin (B) whose solubility in an alkali developer is increased by the action of an acid (B) is 20 to 99.8% by weight, preferably 50%, based on the total composition or the solid content excluding the solvent. ９９99.5% by weight is good.

(B) The weight-average molecular weight of the acid-decomposable resin is
As a polystyrene conversion value measured by the GPC method, 100
It is preferably in the range of 0 to 100,000, more preferably 2000 to 50,000, and still more preferably 300 to 50,000.
The range is from 0 to 30,000. Also, the degree of dispersion is 1.0 to
5.0 is preferred, and more preferably 1.0 to 3.0.

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

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<(D) Alkali-Soluble Resin> The positive photoresist composition of the present invention contains (D) a resin which is insoluble in water and soluble in an alkali developing solution and which does not contain an acid-decomposable group. And thus the sensitivity is improved. In the present invention, a novolak resin having a molecular weight of about 1,000 to 20,000 and a polyhydroxystyrene derivative having a molecular weight of about 3,000 to 50,000 can be used as such a resin. However, these resins have large absorption for light having a wavelength of 250 nm or less. It is preferable to use a partially hydrogenated product or to use it in an amount of 30% by weight or less of the total resin amount. Further, a resin containing a carboxyl group as an alkali-soluble group can also be used. The carboxyl group-containing resin preferably has a monocyclic or polycyclic alicyclic hydrocarbon group for improving dry etching resistance. Specifically, a copolymer of a methacrylic acid ester having an alicyclic hydrocarbon structure that does not show acid-decomposability and a (meth) acrylic acid or a (meth) acrylic acid ester of an alicyclic hydrocarbon group having a terminal carboxyl group Resin, an optionally substituted norbornene derivative and maleic anhydride copolymer, or an optionally substituted norbornene derivative and maleic anhydride and (meth) acrylate copolymer.

{(E) Nitrogen-Containing Basic Compound} The positive photosensitive composition of the present invention contains (E) a nitrogen-containing basic compound in order to reduce a change in performance over time from exposure to heating. Is preferred. Preferred structures include those represented by the following formulas (A) to (E).

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Here, R ²⁵⁰ , R ²⁵¹ and R ²⁵² each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms,
Or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, wherein R ²⁵⁰ and R ²⁵¹ are bonded to each other to form a ring. Good.

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(Wherein R ²⁵³ , R ²⁵⁴ , R ²⁵⁵ and R
²⁵⁶ independently represents an alkyl group having 1 to 6 carbon atoms). Preferred specific examples include substituted or unsubstituted guanidine, substituted or unsubstituted aminopyridine, substituted or unsubstituted aminoalkylpyridine, substituted or unsubstituted aminopyrrolidine, substituted or unsubstituted indazol, substituted or unsubstituted Pyrazole, substituted or unsubstituted pyrazine, substituted or unsubstituted pyrimidine, substituted or unsubstituted purine, substituted or unsubstituted imidazoline, substituted or unsubstituted pyrazoline, substituted or unsubstituted piperazine, substituted or unsubstituted amino Examples include morpholine, substituted or unsubstituted aminoalkyl morpholine, and the like, and include mono, di, trialkylamine, substituted or unsubstituted aniline, substituted or unsubstituted piperidine, mono and diethanolamine, and the like. Preferred substituents are an amino group, aminoalkyl group, alkylamino group, aminoaryl group, arylamino group, alkyl group, alkoxy group, acyl group, acyloxy group, aryl group, aryloxy group, nitro group, hydroxyl group, cyano group It is.

As particularly preferred compounds, guanidine,
1,1-dimethylguanidine, 1,1,3,3-tetramethylguanidine, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-dimethylaminopyridine, 4-dimethylaminopyridine, 2-diethylamino Pyridine, 2- (aminomethyl) pyridine, 2-amino-3-methylpyridine, 2-amino-4-methylpyridine, 2-amino-5-methylpyridine, 2-amino-6-methylpyridine, 3-aminoethyl Pyridine, 4
-Aminoethylpyridine, 3-aminopyrrolidine, piperazine, N- (2-aminoethyl) piperazine, N-
(2-aminoethyl) piperidine, 4-amino-2,
2,6,6-tetramethylpiperidine, 4-piperidinopiperidine, 2-iminopiperidine, 1- (2-aminoethyl) pyrrolidine, pyrazole, 3-amino-5-methylpyrazole, 5-amino-3-methyl -1-p-tolylpyrazole, pyrazine, 2- (aminomethyl) -5
-Methylpyrazine, pyrimidine, 2,4-diaminopyrimidine, 4,6-dihydroxypyrimidine, 2-pyrazoline, 3-pyrazoline, N-aminomorpholine, N-
(2-aminoethyl) morpholine, 1,5-diazabicyclo [4.3.0] non-5-ene, 1,8-diazabicyclo [5.4.0] undec-7-ene, 2,4,4
5-triphenylimidazole, tri (n-butyl) amine, tri (n-octyl) amine, N-phenyldiethanolamine, N-hydroxyethylpiperidine,
Examples include, but are not limited to, 2,6-diisopropylaniline, N-cyclohexyl-N'-morpholinoethylthiourea, and the like.

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

{(F) Fluorine and / or Silicon Surfactant} The positive photosensitive resin composition of the present invention comprises a fluorine and / or silicon surfactant (a fluorine surfactant and a silicon surfactant). Surfactant or a surfactant containing both a fluorine atom and a silicon atom), or two or more kinds. When the positive photosensitive composition of the present invention contains the surfactant (F) described above, when using an exposure light source of 250 nm or less, particularly 220 nm or less, excellent sensitivity and resolution, adhesion and development defects can be obtained. It is possible to provide a small number of resist patterns. These (F) surfactants include, for example,
-36663, JP-A-61-226746, JP-A-61-226745, JP-A-62-170950, JP-A-63-34540, JP-A-7-230165
No., JP-A-8-62834, JP-A-9-54432, JP-A-9-5988
No., U.S. Pat.No. 5,405,720, No. 5,360,692, No. 5,529,881,
No. 5296330, No. 5436098, No. 5576143, No. 5294511
And No. 5824451. The following commercially available surfactants can also be used as they are. As commercially available surfactants that can be used, for example, F-top EF301, EF303, (manufactured by Shin-Akita Chemical Co., Ltd.), Florad FC
430, 431 (Sumitomo 3M Limited), Mega Fuck F171,
F173, F176, F189, R08 (manufactured by Dainippon Ink and Chemicals, Inc.), Surflon S-382, SC101, 102, 103, 104, 105, 106 (manufactured by Asahi Glass Co., Ltd.), Troysol S-366 (Troy Chemical Corp.) )) Or a silicon-based surfactant. Also, polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can be used as a silicon-based surfactant.

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

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

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 EP 219294. It can be easily synthesized. Specific examples of the alicyclic group having a carboxyl group or an aliphatic compound include carboxylic acid derivatives having a steroid structure such as cholic acid, deoxycholic acid, and lithocholic acid, adamantanecarboxylic acid derivatives, adamantanedicarboxylic acid, cyclohexanecarboxylic acid, and cyclohexane. Examples include, but are not limited to, dicarboxylic acids.

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

{Method of Use} The photosensitive composition of the present invention is obtained by dissolving the above components in a predetermined solvent in a mixed state. It is used by coating on a predetermined support. As the solvent used here, ethylene dichloride, cyclohexanone, cyclopentanone, 2-heptanone, γ-butyrolactone,
Methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-
Methoxyethyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, toluene, ethyl acetate, methyl lactate, ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate, ethyl pyruvate, methyl pyruvate , Pyruvate, N, N-dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, tetrahydrofuran, etc., and these solvents are used alone or in combination. Among them, cyclohexanone, 2-heptanone, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, and ethyl ethoxypropionate may be used alone or as a mixture of two kinds in a ratio of 1/9 to 9/1. preferable.

The positive photosensitive composition dissolved in a solvent is applied on a predetermined substrate as follows. That is, the above-mentioned photosensitive composition is applied onto a substrate (eg, silicon / silicon dioxide coating) which is used for manufacturing a precision integrated circuit device by an appropriate application method such as a spinner or a coater.
After the application, the film is exposed through a predetermined mask, baked and developed. By doing so, a good resist pattern can be obtained. Here, the exposure light is preferably far ultraviolet light having a wavelength of 250 nm or less, more preferably 220 nm or less. Specifically, a KrF excimer laser (248 nm) and an ArF excimer laser (193n)
m), F ₂ excimer laser (157 nm), X-ray, electron beam and the like.

In the developing step, a developing solution is used as follows. As the developer of the photosensitive composition, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, inorganic alkalis such as ammonia water, ethylamine, primary amines such as n-propylamine, Secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcoholamines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide and the like An alkaline aqueous solution such as a quaternary ammonium salt, a cyclic amine such as pyrrole, or pyrhelidine can be used. Further, an appropriate amount of an alcohol or a surfactant may be added to the above alkaline aqueous solution for use.

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

<Synthesis Example of Component (A)> Synthesis of Compound (I-1) 12.8 g (95.6 mmol) of 2′-methylacetophenone
l) was dissolved in 200 ml of acetonitrile, and [hydroxy (p-tosyloxy) iodo] benzene 2 was added thereto.
5 g (63.7 mmol) was added and the mixture was distilled for 1 hour. The reaction solution was concentrated, dissolved in 300 ml of ethyl acetate, and washed twice with 100 ml of distilled water. The organic phase was concentrated, and the obtained crude product was purified by column chromatography to obtain 17 g of a compound (I-1). I-
1 to I-49 were synthesized using the same method.

Synthesis of Compound (II-1) 41.2 g of aluminum chloride and 80 ml of p-xylene were mixed, and bromoacetyl chloride 44.1 was added thereto under ice cooling.
g was added over 1 hour. After completion of the dropwise addition, the mixture was heated to room temperature and stirred for 2 hours. The reaction solution was poured into ice (500 ml), the aqueous solution was extracted twice with 200 ml of diisopropyl ether, and the organic phase was washed five times with 100 ml of distilled water. The organic phase was concentrated, and the remaining p-xylene was distilled off under reduced pressure to obtain a crude product. This was distilled under reduced pressure (5 mmHg, bp 1
27 ° C) to give 2-bromoacetyl-p-xylene 39
g was obtained. 10 g of tetrahydrothiophene was dissolved in 15 ml of acetonitrile, and 2-bromoacetyl-p was added thereto.
13.6 g of xylene were slowly added. After the addition, the mixture was stirred at room temperature to precipitate a powder, which was collected by filtration and washed with acetonitrile to obtain 9.8 g of 2,5-dimethylphenacyltetrahydrothiophenium bromide. 2,5
-5 g of dimethylphenacyltetrahydrothiophenium bromide was dissolved in methanol, 5.63 g of potassium nonafluorobutanesulfonate was added thereto, and this solution was poured into 500 ml of distilled water. The precipitated powder was collected by filtration and washed with water to obtain 7 g of a compound II-1. II-2 to II-38
Was also synthesized by synthesizing the corresponding sulfonium halide and then performing salt exchange.

<Synthesis Example of Resin> [Synthesis of Resin (P1) (a1) / (b1) = 50/5
0] 5.0 g of 2-methyl-2-adamantane methacrylate, 4.23 g of mevalonic lactone methacrylate, 7.02 g of N, N-dimethylacetamide heated to 60 ° C. in a nitrogen stream, polymerization initiator 2,2′-azobis (2,4
-Dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries; V-65)
0.534 g of N, N-dimethylacetamide 30.0
g was added dropwise over 4 hours. 6 more
After reacting at 0 ° C. for 2 hours, 0.267 g of V-65 was added, and the mixture was further reacted for 2 hours. The reaction solution was deionized water 1
000 ml, and the precipitated powder was collected by filtration. This is T
The resin was dissolved in HF, poured into 1500 ml of hexane, and the obtained powder was dried to obtain a resin (I-1). The obtained resin has a weight average molecular weight of 5,500 and a degree of dispersion (Mw / Mn).
Was 1.9. The weight average molecular weight and the degree of dispersion are polystyrene equivalent values measured by the GPC method.

[Synthesis of Resin (P2) to Resin (P15)]
In substantially the same manner, the resins (P2) to
Resin (P15) was synthesized in order. Table 1 shows the molecular weight and the degree of dispersion of these resins.

[0160]

[Table 1]

Further, the following resins (P16) to (P1)
8) was synthesized. Resin Used monomer ratio Molecular weight (dispersion degree) (P16) b53 / maleic anhydride / b43 / b42 (30/30/30/10) 11000 (1.9) (P17) b54 / maleic anhydride / b48 / b44 (30/30 / 10/20) 13000 (2.1) (P18) b53 / maleic anhydride / b45 (35/35/30) 8500 (1.7)

<Adjustment of Resist> [Examples 1 to 24 and Comparative Examples 1 and 2] A solution having a solid content of 15% by weight was prepared by dissolving the materials shown in Table 2, and this was then 0.1 μm Teflon (registered trademark). ) The mixture was filtered through a filter to prepare a photosensitive composition. The prepared composition was evaluated by the following method, and the results are shown in Table 3.

[0163]

[Table 2]

[0164]

[Table 3]

The symbols of each component in Table 2 are as follows. Further, the ratio in the case of plural use in Table 2 is a weight ratio.

[0166]

Embedded image

[Basic compound] (1): 1,5-diazabicyclo [4.3.0] -5-
Nonene (2): 2,4,5-triphenylimidazole (3): Tri-n-octylamine (4): Antipyrine (5): 2,6-diisopropylaniline [Surfactant] W-1: Megafax F176 (Dainippon Ink Co., Ltd.)
(Fluorine) W-2: Megafac R08 (Dai Nippon Ink Co., Ltd.)
(Fluorine and silicon type) W-3: Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) (silicon type) W-4: Troysol S-366 (Troy Chemical Co., Ltd.)
Made) (fluorine)

[Solvent] PGMEA: propylene glycol monomethyl ether acetate PGME: propylene glycol monomethyl ether EL: ethyl lactate EEP: ethyl ethoxypropionate BL: γ-butyrolactone CH: cyclohexanone

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

[Sensitivity]: Sensitivity indicates an exposure amount for reproducing a mask pattern of 0.16 μm. [Resolution]: The resolving power indicates a critical resolving power at an exposure amount for reproducing a mask pattern of 0.16 μm.

[0171]

[Table 4]

From the results shown in Table 3, Examples 1 to 24 were obtained.
It can be seen that the composition of Example 1 is clearly superior in sensitivity and resolution as compared with Comparative Example.

[0173]

According to the present invention, a positive photosensitive composition having excellent sensitivity and resolution can be provided. The positive photosensitive composition of the present invention is suitably used for microphotofabrication using far ultraviolet light, particularly ArF excimer laser light.

Claims (5)

[Claims] 1. A compound having at least one carbonyl group (A), which decomposes upon irradiation with actinic rays together with intramolecular hydrogen radical transfer to generate an acid, and (B) a monocyclic or polycyclic compound. A positive photosensitive composition comprising a resin having a cyclic alicyclic hydrocarbon structure, which is decomposed by the action of an acid, and which has an increased solubility in an alkaline developer. 2. The positive photosensitive composition according to claim 1, wherein the component (A) is a compound represented by the general formula (I) or (II). Embedded image R ₁ and R ₂ may be the same or different and represent a hydrogen atom or a monovalent organic group. Alternatively, R ₁ and R ₂ may combine to form a monocyclic or polycyclic ring structure which may contain a heteroatom, a multiple bond, —CO—, or —COO—. R ₃ and R ₄ may be the same or different and represent a hydrogen atom or a monovalent organic group. X represents a monovalent organic group having a hydrogen radical donating group. X may combine with R ₁ or R ₂ to form a monocyclic or polycyclic ring structure. Y ₁ in the general formula (I) is R′SO ₃ —,
R'COO- or a halogen atom. R ′ represents an optionally substituted linear, branched, or cyclic alkyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, or an optionally substituted camphor group. Y ₂ in the general formula (II) ^- represents a non-nucleophilic anion. Ra and Rb represent an optionally substituted linear, branched or cyclic alkyl group, an optionally substituted aryl group, or an optionally substituted aralkyl group. Ra and Rb may combine to form a ring. R ₁
To R ₄ , Ra, Rb, X, Y ₁ , or Y ₂ ^— , which may be bonded via a linking group at any position to have two structures of the general formula (I) or (II). 3. A low molecular weight dissolution inhibiting compound having a molecular weight of 3000 or less, which has a group decomposable by an acid and whose dissolution rate in an alkaline developer is increased by the action of an acid. The positive photosensitive composition according to claim 1 or 2, wherein 4. The positive photosensitive composition according to claim 1, wherein the resin (B) is a resin having a lactone structure. 5. A compound having at least one carbonyl group (A) which decomposes upon irradiation with an actinic ray together with intramolecular hydrogen radical transfer to generate an acid,
(C) having a group decomposable by an acid, wherein the dissolution rate in an alkaline developer is increased by the action of an acid;
0 or less low molecular dissolution inhibiting compound; and (D) a resin having a monocyclic or polycyclic alicyclic hydrocarbon structure, containing a resin that is insoluble in water and soluble in an alkali developing solution. Photosensitive composition.