JPH11231537A - Positive photosensitive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the positive photosensitive composition enhanced in sensitivity and resolution and pattern profiles without changing the pattern profiles and the sensitivity and the like by incorporating a compound for generating an acid and a resin having specified repeating structural units. SOLUTION: The positive photosensitive composition contains the compound to be allowed to generate an acid by irradiation with active light or radiation and the resin having the repeating structural units represented by formulae I and II and formulae I and III, and in formulae I-III, R1 is an H atom or a methyl group; each of R2 and R3 is, independently, an H atom or an optionally substituted alkyl or aryl group, but at least one of them is a group except an H atom; R4 is an optionally substituted cycloalkyl or alkenyl group or the like; R5 is a group represented by -C(R8 )(R9 )(R10 ) or the like; and each of (m) and (n) is, independently, an integer of 0-3.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a lithographic printing plate or an IC.
The present invention relates to a positive photosensitive composition used in a semiconductor manufacturing process such as the above, a circuit substrate such as a liquid crystal and a thermal head, and other photofabrication processes.

[0002]

2. Description of the Related Art As a positive photoresist composition, there is a chemically amplified resist composition described in U.S. Pat. No. 4,491,628 and EP 249,139. 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. This 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 Application Laid-Open No. 48-89003), a combination of an orthoester or an amide acetal compound ( Combination with a polymer having an acetal or ketal group in the main chain (JP-A-53-172014).
3429), a combination with an enol ether compound (JP-A-55-12995), a combination with an N-acyliminocarbonate compound (JP-A-55-126236),
Combination with a polymer having an orthoester group in the main chain (JP-A-56-17345), combination with a tertiary alkyl ester compound (JP-A-60-3625), combination with a silyl ester compound (JP-A-60-3625) Showa 60-10247
No.) and a combination with a silyl ether compound (Japanese Unexamined Patent Publication No.
0-37549, JP-A-60-112446) and the like. These have high photosensitivity because the quantum yield exceeds 1 in principle.

Similarly, systems which are stable under aging at room temperature, but are decomposed by heating in the presence of an acid and solubilized in alkali are disclosed in, for example, JP-A-59-45439, JP-A-60-3625, JP-A-62-2229242, JP-A-63-27829, JP-A-63-36240, JP-A-63-250542, Polym.Eng.Sce., Vol. 23, 101
2 (1983); ACS.Sym. 242, 11 (1984); Semicond
uctor World 1987, November, p. 91; Macromolecules, 2
Vol. 1, p. 1475 (1988); SPIE, vol. 920, p. 42 (1988);
Combination systems with esters or carbonate compounds of primary or secondary carbons (eg t-butyl, 2-cyclohexenyl). These systems also have high sensitivity and have a deep-UV compared to the naphthoquinonediazide / novolak resin system.
Since the absorption in the region is small, it can be an effective system for shortening the wavelength of the light source.

The above-mentioned positive chemically amplified resist comprises three components comprising an alkali-soluble resin, a compound capable of generating an acid upon exposure to radiation (photoacid generator), and a compound inhibiting dissolution of the alkali-soluble resin having an acid-decomposable group. It can be roughly classified into a two-component system comprising a resin having a group which is decomposed by the reaction with an acid and becomes alkali-soluble and a photoacid generator. In these two-component or three-component positive chemically amplified resists, an acid from a photoacid generator is interposed by exposure, decomposed by heat treatment, and then developed to obtain a resist pattern. Here, from exposure to heat treatment (PEB treatment)
As the standing time until the exposure becomes longer, the generated acid is diffused, and the acid on the resist surface is deactivated by basic impurities in the atmosphere, so that the sensitivity and the profile of the developed resist pattern (T -Top shape), line width, and the like. In particular, when the acid-decomposable group is a group having a relatively large acid-decomposition activation energy such as a t-BOC group or a t-butyl ester group, the sensitivity is reduced,
The formation of the T-top is a major problem. On the other hand, in a group having a small acid decomposition activation energy such as an acetal group, a tetrahydropyranyl ether group, and a silyl ether group,
While these problems are alleviated, a problem arises in that the line width of the pattern is reduced.

On the other hand, to solve these problems, a technique has been reported in which a group having a high activation energy for acid decomposition such as a t-BOC group is combined with a group having a low activation energy for acid decomposition such as an acetal group. For example, Japanese Unexamined Patent Publication No.
No. 4, No. 8-262721, No. 9-6002, No. 9
-6003, 9-179301, 9-2211
No. 7, No. 9-1227698, No. 9-222732,
Nos. 9-222733 and 9-244246, in which a resin having a t-BOC group and a resin having an acetal group are used in combination. Further, JP-A-6-273934, JP-A-8-123032, and No. 211864, 9-2
A system using a resin having a group having a large activation energy for acid decomposition such as a t-BOC group and a group having a small activation energy for acid decomposition such as an acetal group described in No. 11866 in the same molecule is exemplified. However, even in these systems, the profile (T-top shape) and the change in sensitivity are insufficiently improved due to the low acid decomposability of groups such as t-BOC, and the improvement in performance such as resolution is limited. Was.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a positive photosensitive composition in which the pattern shape and the sensitivity do not change over time after exposure, thereby improving the sensitivity, resolution and pattern profile. It is.

[0008]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies while paying attention to the above characteristics, and as a result, the object of the present invention is to use a resin containing the following specific structural unit in a positive-type chemical amplification system. It has been found that this is achieved by the above, and the present invention has been achieved. That is, the present invention has the following configuration. (1) (A) a compound that generates an acid upon irradiation with actinic rays or radiation, (B) a resin having a repeating structural unit represented by the following general formulas (I) and (II), and (C) a general formula shown below. A positive photosensitive composition comprising a resin having a repeating structural unit represented by (I) or (III).

[0009]

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In the general formulas (I) to (III), R _{1 to} R ₇ are as follows. R ₁ represents a hydrogen atom or a methyl group. R ₂ and R ₃ are the same or different and each represent a hydrogen atom or an optionally substituted alkyl group or aryl group. However, at least one of R ₂ and R ₃ is a group other than a hydrogen atom. R ₄ may have a substituent,
Represents a cycloalkyl group, an alkenyl group, an alkynyl group or an aryl group. R ₅ represents a group represented by —C (R ₈ ) (R ₉ ) (R ₁₀ ) or —C (R ₁₁ ) (R ₁₂ ) (OR ₁₃ ). Here, R ₈ to R ₁₂ are the same or different, a hydrogen atom, which may have a substituent, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group or an aryl group, R ₁₃ is, An alkyl group which may have a substituent,
Represents a cycloalkyl group or an aryl group. However, R ₈
At least two of R ₁₀ are groups other than a hydrogen atom.
R ₆ and R ₇ are the same or different and are each a halogen atom, a hydroxyl group, an alkyl group which may have a substituent,
Represents an aryl group, an aralkyl group, an alkoxy group, an acyl group or an acyloxy group. In addition, the above R _{2 to} R ₄ , R _{8 to} R
_And two of R _{11 to} R ₁₃ may combine to form a ring. m and n are the same or different,
Shows an integer of 0 to 3.

(2) A low-molecular acid-decomposable dissolution inhibiting compound having a molecular weight of 3,000 or less, which has a group decomposable by an acid and whose solubility in an alkali developing solution is increased by the action of an acid. The positive photosensitive composition as described in (1) above, which is characterized in that:

(3) The above (1) or (2), which contains a resin which is insoluble in water and soluble in an aqueous alkali solution.
4. The positive photosensitive composition according to item 1.

The positive photosensitive composition of the present invention comprises a resin containing a repeating structural unit having an acetal group or the like represented by the general formula (III) and a cycloalkyl compound represented by the general formula (II) Group, an alkenyl group, an alkynyl group, or a resin containing a repeating structural unit having a carbonate group to which an aryl group is bonded to form t-BO.
The acid-decomposability observed with a group such as C is appropriately improved, and a change in pattern shape (T-top shape) and a change in sensitivity over time after exposure are eliminated, thereby greatly improving sensitivity, resolution, and pattern profile.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, components used in the positive photosensitive composition of the present invention will be described in detail. First, the resin (B) having a repeating structural unit represented by the general formulas (I) and (II) and the resin (C) having a repeating structural unit represented by the general formulas (I) and (III) will be described. I do.

In the above formula, the alkyl group of R ₂ , R ₃ , R ₆ and R ₇ is preferably an optionally substituted methyl group, ethyl group, propyl group, n-butyl group, sec
Examples thereof include those having 1 to 8 carbon atoms such as -butyl group, hexyl group, 2-ethylhexyl group, and octyl group. R ₂ ,
The aryl group of R ₃ , R ₄ , R ₆ , and R ₇ is preferably an aryl group which may have a substituent, such as a phenyl group, a tolyl group, a xylyl group, a cumenyl group, a naphthyl group, and an anthracenyl group. 6-14. As the cycloalkyl group for R ₄ , those having 3 to 10 carbon atoms, such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and an adamantyl group, which may have a substituent, are preferably exemplified. As the alkenyl group, preferably a vinyl group which may have a substituent,
Propenyl group, allyl group, butenyl group, pentenyl group,
Examples thereof include those having 2 to 6 carbon atoms such as a hexenyl group and a cyclohexenyl group. The alkynyl group preferably has 2 to 6 carbon atoms, such as an acetyl group and a propargyl group, which may have a substituent.

As the halogen atom for R ₆ and R ₇ , fluorine, chlorine, bromine and iodine are preferred. The aralkyl group preferably has a carbon number of 7 to 1 such as a benzyl group, a naphthylmethyl group and a phenethyl group, which may have a substituent.
There are two. Examples of the alkoxyl group preferably include those having 1 to 8 carbon atoms such as a methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, and a butoxy group which may have a substituent. As the acyl group, a formyl group, an acetyl group, a propanoyl group, a butanoyl group, which may have preferably a substituent,
Those having 1 to 8 carbon atoms such as a benzoyl group are exemplified.
The acyloxy group preferably has 2 to 10 carbon atoms such as an acetoxy group, a propanoyloxy group, a butanoyloxy group and a benzoyloxy group which may have a substituent.
Individual ones.

The alkyl, cycloalkyl, alkenyl, alkynyl, aryl, and R _{8 to} R ₁₂
The alkyl group, cycloalkyl group and aryl group of ₁₃ are R ₂
Preferably the same as that shown in to R _7. R ₂ ~
2 of each of R ₄ , R _{8 to} R ₁₀ , and R _{11 to} R ₁₃
Examples of the ring formed by bonding one to another include a 3- to 8-membered ring such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl which may have a substituent.

[0018] As further substituents of the above substituents, preferably hydroxyl groups; halogen atoms (fluorine, chlorine, bromine, iodine), nitro groups, cyano groups, amide groups, sulfonamide group; R ₂ above , R ₃ , R ₆ , R ₇
Alkoxy group having 1 to 8 carbon atoms such as methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group, butoxy group; alkoxycarbonyl group such as methoxycarbonyl group, ethoxycarbonyl group; formyl group Acyl groups such as acetyl group, benzoyl group and the like; acyloxy groups such as acetoxy group and butyryloxy group; carboxy group.

The resin (B) having the repeating structural units represented by the general formulas (I) and (II) and the resin (C) having the repeating structural units represented by the general formulas (I) and (III) are: For example, it can be synthesized by the following method.

That is, the resin (B) is prepared by homopolymerizing or copolymerizing a polymerizable monomer giving a structural unit represented by the general formula (I) with a hydroxyl group in the resin. A method of modifying and converting to a group represented by a carbonate group; a method of copolymerizing a polymerizable monomer giving a structural unit represented by general formulas (I) and (II); a structure represented by general formula (II) After homopolymerization or copolymerization of a polymerizable monomer giving a unit, it can be synthesized by a method of hydrolyzing a part of a carbonate group of the general formula (II) to convert it into a structural unit of the general formula (I). .

Similarly, in the case of the resin (C), the compound represented by the general formula (I)
A hydroxyl group in a resin obtained by homopolymerizing or copolymerizing a polymerizable monomer giving a structural unit represented by
A method of modifying and converting to a group represented by R ₅ in the general formula (III); a method of copolymerizing a polymerizable monomer giving a structural unit represented by the general formulas (I) and (III); A method of homopolymerizing or copolymerizing a polymerizable monomer giving the structural unit represented by III), and then hydrolyzing a part of the R ₅ group of the general formula (III) to convert it into the structural unit of the general formula (I) Can be synthesized by

Specifically, a polymerizable monomer giving the structural unit represented by the above general formula (I) is prepared by using a suitable solvent and catalyst, for example, as described in JP-A-2-25850 and JP-A-3-22-22.
No. 3860, No. 4-211258, No. 5-24968
After homopolymerization or copolymerization with another polymerizable monomer by the radical polymerization method described in JP-A No. 2 (1993) -195, etc., the hydroxyl group in the obtained resin is replaced with, for example, JP-A-60-52845 and JP-A-5-19482. Nos. 4-219757 and 4-
No. 251259, No. 5-249682, No. 4-211
No. 258, No. 5-181279, No. 6-83059
No. 6,194,841 and the like, the resin (B) is modified and converted to a carbonate group of the general formula (II), and the OR ₅ group of the general formula (III) is modified.
By the conversion, the resin (C) is synthesized. Further, a monomer giving the structural units represented by the general formulas (I) and (II) or the general formulas (I) and (III), and if necessary, other polymerizable monomers are copolymerized by the above radical polymerization method or the like. By doing so, the resins (B) and (C) are synthesized. Further, a monomer giving the structural units represented by the general formulas (II) and (III) and, if necessary, other polymerizable monomers can be prepared by the radical polymerization method described in JP-A-4-350657;
-350658, 6-41221, 6-412
No. 22, No. 6-65332, No. 6-65333, etc., after homopolymerization or copolymerization by a living anionic polymerization method or the like, a part of the carbonate group of the general formula (II) is decomposed to give a hydroxyl group. By converting to resin (C)
However, the resin (B) is synthesized by hydrolyzing a part of the OR ₅ group of the general formula (III) to convert it into a hydroxyl group. In the case of this method, in order to adjust the hydroxyl group content,
The hydroxyl group may be modified and converted again into a carbonate group of the general formula (II) or an OR ₅ group of the general formula (III).

Specific examples of the polymerizable monomer giving the structural unit represented by the general formula (I) include the following, but are not limited thereto.

[0024]

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[0025]

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Specific examples of the polymerizable monomer giving the structural unit represented by the general formula (II) include the above-mentioned compound examples (I-
1) to (I-23) are converted to the following groups (a)
1) to (a16).

[0027]

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Further, as specific examples of the polymerizable monomer giving the structural unit represented by the general formula (III), the hydroxyl group of the above compound examples (I-1) to (I-23) is replaced with the following group (a17) To (a36), but not limited thereto.

[0029]

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Other polymerizable monomers copolymerizable with these polymerizable monomers 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, for example, acrylates such as alkyl (the alkyl group has 1 to 1 carbon atoms)
Acrylates (eg, methyl acrylate, ethyl acrylate, propyl acrylate, t-butyl acrylate, t-amyl acrylate, ethylhexyl acrylate, octyl acrylate, 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, 2
-Tetrahydropyranyl acrylate, etc.), aryl acrylate (eg, phenyl acrylate, etc.), silyl acrylate (eg, t-butyldimethylsilyl acrylate, etc.);

Methacrylic esters, for example, alkyl (alkyl having preferably 1 to 10 carbon atoms) methacrylate (for example, methyl methacrylate,
Ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, t-butyl methacrylate,
t-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, glycidyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, 2-
Tetrahydropyranyl methacrylate, etc.), aryl methacrylate (eg, phenyl methacrylate, cresyl methacrylate, naphthyl methacrylate, etc.), silyl methacrylate (eg, trimethylsilyl methacrylate, t-butyldimethylsilyl methacrylate, etc.);

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, (for example, phenyl group, tolyl group, nitrophenyl group, naphthyl group,
Examples include a cyanophenyl group and a hydroxyphenyl group. ), N, N-dialkylacrylamide (an alkyl group having 1 to 10 carbon atoms, for example, a methyl group, an ethyl group, a butyl group, an isobutyl group, an ethylhexyl group, a cyclohexyl group, etc.); N-diarylacrylamide (an aryl group includes, for example, a phenyl group), N-methyl-N-phenylacrylamide, N-hydroxyethyl-N-methylacrylamide, N-2-acetamidoethyl-N-acetylacrylamide and the like ;

Methacrylamides, for example, methacrylamide, N-alkyl methacrylamide (an alkyl group having 1 to 10 carbon atoms, for example, a methyl group,
Examples include an ethyl group, a t-butyl group, an ethylhexyl group, a hydroxyethyl group, and a cyclohexyl group. ), N-arylmethacrylamide (aryl groups include phenyl, hydroxyphenyl, carboxyphenyl, etc.), N, N-dialkylmethacrylamide (alkyl groups include ethyl, propyl, butyl) ), N, N-diarylmethacrylamide (the aryl group includes a phenyl group and the like), N-hydroxyethyl-N-methylmethacrylamide, N-methyl-N-phenylmethacrylamide, N- Ethyl-N-phenylmethacrylamide and the like;

Allyl compounds such as 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 such as alkyl vinyl ethers (for example, 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 aryl ethers (eg, vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-2,
4-dichlorophenyl ether, vinyl naphthyl ether, vinyl anthranyl ether, etc.);

Vinyl esters, for example, vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxy acetate, vinyl butoxy acetate , Vinylphenyl acetate, vinyl acetoacetate, vinyl lactate, vinyl-β-
Phenylbutyrate, vinylcyclohexylcarboxylate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate, and the like;

Styrenes such as styrene, alkyl styrene (eg, methyl styrene, dimethyl styrene,
Trimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, butylstyrene, hexylstyrene, cyclohexylstyrene, decylstyrene,
Benzylstyrene, chloromethylstyrene, trifluoromethylstyrene, ethoxymethylstyrene, acetoxymethylstyrene, etc.), alkoxystyrene (for example,
Methoxystyrene, 4-methoxy-3-methylstyrene, dimethoxystyrene and the like), halogen styrene (for example, chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, Fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, 4-fluoro-3-trifluoromethylstyrene, etc.), 4-acetoxystyrene, 4-carboxystyrene, α-methylstyrene;

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.) Dialkyl maleic acid or fumaric acid (eg, dimethyl maleate, dibutyl fumarate, etc.); acrylic acid, methacrylic acid, maleimide, acrylonitrile, methacrylonitrile, maleinonitrile, fumaronitrile, maleic anhydride, maleimide, N -Alkylmaleimide, N-arylmaleimide (as the aryl group, a phenyl group,
And a hydroxyphenyl group). In addition, copolymerizable addition-polymerizable unsaturated compounds can be used.

The repeating units represented by the general formulas (I), (II) and (III) in the resin (B) and the resin (C) may be used alone or in combination of two or more. Can be. The content of the structural unit represented by the general formula (I) in the resin (B) or the resin (C) is preferably 30.
-90 mol%, more preferably 40-85 mol%, still more preferably 50-80 mol%. The content of the structural unit represented by the general formula (II) in the resin (B) is preferably 3 to 70 mol%, more preferably 5 to 50 mol%, and still more preferably 10 to 35 mol%. The content of the structural unit represented by the general formula (III) in the resin (C) is preferably 5 to 70 mol%, more preferably 10 to 50 mol%, and still more preferably 15 to 45 mol%. In the copolymer, another polymerizable monomer can be selected so that an alkali-soluble group such as a phenolic hydroxyl group or a carboxyl group can be introduced in order to maintain good developability in an alkali developing solution.

The molecular weight of the resin (B) and the resin (C) of the present invention synthesized by the above method has a weight average (Mw: polystyrene standard) of 2,000 or more, preferably 3.0 or more.
00 to 200,000, more preferably 5,000.
0 to 50,000. The degree of dispersion (Mw / Mn)
Is preferably 1.0 to 4.0, more preferably 1.0 to 4.0.
-2.0, particularly preferably 1.0-1.6, and the smaller the degree of dispersion, the better the heat resistance.

The content of the resin (B) and the resin (C) in the photosensitive composition of the present invention (excluding the coating solvent) is preferably from 50 to 99% by weight, more preferably from 65 to 99% by weight. 97%. The weight ratio of the resins (B) and (C) ((B) / (C)) is preferably 5/1 to 1/10, more preferably 3/1 to 1/5, and still more preferably. 2/1 to 1/3.

Specific examples of the resin (B) having the repeating structural units represented by the general formulas (I) and (II) and the resin (C) having the repeating structural units represented by the general formulas (I) and (III) Are shown below, but the present invention is not limited to these. In the following specific examples, m / n is preferably a molar ratio of 85/15 to 65/35, and m / n
/ P is a molar ratio, preferably 75/15/10 to 40
/ 35/25.

[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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[0052]

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[0053]

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[0054]

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Next, the compound (A) which generates an acid upon irradiation with actinic rays or radiation will be described. The compound (A) that is decomposed by irradiation with actinic rays or radiation to generate an acid used in the present invention includes a photoinitiator for cationic photopolymerization,
A photoinitiator for photoradical polymerization, a photobleaching agent for dyes, a photochromic agent, or a compound capable of generating an acid by known light used in a microresist or the like and a mixture thereof are appropriately selected and used. be able to.

For example, SISchlesinger, Photogr.Sci.E
ng., 18,387 (1974), TSBal etal, Polymer, 21,423 (198
0) etc., U.S. Pat.No.4,069,055
No. 4,069,056, Re 27,992, Japanese Patent Application No. 3-140,140
Salt, DCNecker etal, Macrom
olecules, 17, 2468 (1984), CSwen et al, Teh, Proc. Con
f.Rad.Curing ASIA, p478 Tokyo, Oct (1988), U.S. Patent No.
Nos. 4,069,055 and 4,069,056, and phosphonium salts described in JVCrivello et al., Macromorecules, 10 (6), 1307 (19
77), Chem. & Eng. News, Nov. 28, p31 (1988), European Patent No. 10
No. 4,143, U.S. Pat.Nos. 339,049, 410,201, JP-A-2-150,848, iodonium salts described in JP-A-2-296,514, etc., JVCrivello et al., Polymer J. 17, 73 (1985),
JVCrivello et al. J. Org.Chem., 43, 3055 (1978), WRW
att etal, J. Polymer Sci., Polymer Chem. Ed., 22, 1789 (1
984), JVCrivello etal, Polymer Bull., 14,279 (198
5), JVCrivello etal, Macromorecules, 14 (5), 1141 (19
81), JVCrivello etal, J. PolymerSci., Polymer Chem.
Ed., 17,2877 (1979), European Patent Nos. 370,693, 3,902,1
No. 14, 233,567, 297,443, 297,442, U.S. Patent Nos. 4,933,377, 161,811, 410,201, 33
9,049, 4,760,013, 4,734,444, 2,833,827
No. 2,904,626, 3,604,580, 3,604,
No. 581 etc., sulfonium salt, JVCrivello etal, M
acromorecules, 10 (6), 1307 (1977), JVCrivello etal,
J. Polymer Sci., Polymer Chem. Ed., 17, 1047 (1979), etc., selenonium salts, CSwen et al., Teh, Proc. Conf.R
onium salts such as arsonium salts described in ad.Curing ASIA, p478 Tokyo, Oct (1988), U.S. Pat.No. 3,905,815,
JP-B-46-4605, JP-A-48-36281, JP-A-55-32070
No., JP-A-60-239736, JP-A-61-169835, JP-A-61-169835
No. 1-169837, JP-A-62-58241, JP-A-62-212401,
JP-A-63-70243, organic halogen compounds described in JP-A-63-298339, etc., K. Meier et al., J. Rad.Curing, 13 (4), 26
(1986), TPGilletal, Inorg.Chem., 19,3007 (1980), D.
Astruc, Acc.Chem.Res., 19 (12), 377 (1896), JP-A-2-161
Organometallic / organic halides described in No. 445, S. Hayas
e etal, J. Polymer Sci., 25, 753 (1987), E. Reichmanis et.
al, J.Pholymer Sci., Polymer Chem. Ed., 23, 1 (1985), Q.
Q. Zhu et al., J. Photochem., 36, 85, 39, 317 (1987), B. Amit
etal, Tetrahedron Lett., (24) 2205 (1973), DHRBarton
etal, J. Chem Soc., 3571 (1965), PMCollins etal, JC
hem.SoC., Perkin I, 1695 (1975), M. Rudinstein et al., Tet
rahedron Lett., (17), 1445 (1975), JWWalker etal J.A
m. Chem. Soc., 110, 7170 (1988), SCBusman et al., J. Imagi
ng Technol., 11 (4), 191 (1985), HM Houlihan et al, Maco
rmolecules, 21, 2001 (1988), PM Collins et al., J. Chem. S.
oc., Chem.Commun., 532 (1972), S.Hayase et al, Macromole
cules, 18, 1799 (1985), E. Reichmanis et al., J. Electroche
m.Soc., Solid State Sci.Technol., 130 (6), FMHoulih
an etal, Macromolcules, 21, 2001 (1988), EP 029
0,750, 046,083, 156,535, 271,851,
0,388,343, U.S. Pat.Nos. 3,901,710, 4,181,531
JP-A-60-198538, JP-A-53-133022 and the like, a photoacid generator having an o-nitrobenzyl-type protecting group, M.TU
NOOKA etal, Polymer Preprints Japan, 35 (8), G. Berner
etal, J.Rad.Curing, 13 (4), WJMijs etal, Coating Tech
nol., 55 (697), 45 (1983), Akzo, H. Adachi et al, Polymer
Preprints, Japan, 37 (3), European Patent Nos. 0199,672 and 8451
No. 5, No. 199,672, No. 044,115, No. 0101,122, U.S. Pat.Nos. 618,564, 4,371,605, 4,431,774, JP-A-64-18143, JP-A-2-245756, Japanese Patent Application No. 3 Compounds which generate sulfonic acid upon photolysis, such as iminosulfonate described in JP-A-140109, etc., and disulfone compounds described in JP-A-61-166544 are exemplified.

Further, a group that generates an acid by these lights,
Alternatively, a compound having a compound introduced into the main chain or side chain of a polymer, for example, MEWoodhouse et al., J. Am. Chem.
c., 104, 5586 (1982), SPPappas etal, J. Imaging Sc
i., 30 (5), 218 (1986), S. Kondo et al., Makromol.Chem., Ra.
pid Commun., 9,625 (1988), Y.Yamadaetal, Makromol.Che
m., 152, 153, 163 (1972), JVCrivello etal, J. Polymer
Sci., Polymer Chem. Ed., 17,3845 (1979), U.S. Pat.
No. 849,137, Dokoku Patent No. 3914407, JP-A-63-26653,
JP-A-55-164824, JP-A-62-69263, JP-A-63-1460
No. 38, JP-A-63-163452, JP-A-62-153853, JP-A-63-146029 and the like can be used.

Further, VNRPillai, Synthesis, (1), 1 (198
0), A. Abad etal, Tetrahedron Lett., (47) 4555 (1971),
Compounds that generate an acid by light described in DHR Barton et al., J. Chem. Soc., (C), 329 (1970), U.S. Pat. No. 3,779,778, and EP 126,712 can also be used.

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

[0060]

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In the formula, R ¹ represents a substituted or unsubstituted aryl group, alkenyl group, and R ² represents a substituted or unsubstituted aryl group, alkenyl group, alkyl group, or —CY ₃ . Y ₃ represents a chlorine atom or a bromine atom. Specific examples include the following compounds, but the present invention is not limited thereto.

[0062]

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[0063]

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[0064]

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

[0066]

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In the formula, Ar ¹ and Ar ² are the same or different and each represents a substituted or unsubstituted aryl group. here,
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 ³ , R ⁴ and R ⁵ are the same or different and each represents a substituted or unsubstituted alkyl group or aryl group. Preferably an aryl group having 6 to 14 carbon atoms, 1 carbon atom
To 8 alkyl groups and substituted derivatives thereof. Here, preferable 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. In contrast, an alkoxy group having 1 to 8 carbon atoms, a carboxyl group, and an alkoxycarbonyl group.

[0069] Z ^- represents a counter anion, for example BF ₄ ^{-,
_{AsF 6 -, PF 6 -,}} SbF 6 -, SiF 6 2-, ClO 4 -,
_{CF 3 SO 3 -, C 4} F 9 SO 3 - etc. perfluoroalkane sulfonate anion, halogen-substituted benzenesulfonic acid anion such as pentafluorobenzenesulfonic acid anion, a straight-chain, branched, or cyclic alkyl group, an alkoxy Examples thereof include, but are not limited to, a group-substituted benzenesulfonate anion, a condensed polynuclear aromatic sulfonic acid anion, and a sulfonic acid group-containing dye.

Further, two of R ³ , R ⁴ and R ⁵ and A
r ¹ and Ar ² may be bonded via a single bond or a substituent.

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

[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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[0077]

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[0078]

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[0079]

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[0080]

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[0081]

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[0082]

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[0083]

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The above onium salts represented by the general formulas (PAG3) and (PAG4) are known, for example, JWKnapcz
yk et al., J. Am. Chem. Soc., 91, 145 (1969), ALMaycok et.
al, J. Org. Chem., 35, 2532, (1970), E. Goethas et al., Bul
l.Soc.Chem.Belg., 73,546, (1964), HM Leicester, JA
me.Chem.Soc., 51,3587 (1929), JVCrivello etal, J.Po
Chem. Ed., 18, 2677 (1980), U.S. Pat. Nos. 2,807,648 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).

[0086]

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In the formula, Ar ³ and Ar ⁴ each independently represent a substituted or unsubstituted aryl group. R ⁶ 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.

[0088]

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[0089]

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[0090]

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[0091]

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[0092]

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The amount of the compound capable of decomposing upon irradiation with actinic rays or radiation to generate an acid is usually 0.01 to 0.01% based on the total weight of the photosensitive composition (excluding the coating solvent).
To 20% by weight, preferably 0.1 to 1% by weight.
0% by weight, more preferably 1 to 5% by weight.

Next, a water-insoluble resin which is preferably used in the present invention and is soluble in an aqueous alkali solution (hereinafter also referred to as an alkali-soluble resin) will be described. The addition of an alkali-soluble resin is preferred in terms of improving the heat resistance of the resist film, improving the sensitivity, improving and adjusting the alkali solubility during development, and the like. As the alkali-soluble resin used in the present invention, for example, a novolak resin, a hydrogenated novolak resin,
Acetone-pyrogallol resin, o-polyhydroxystyrene, m-polyhydroxystyrene, p-polyhydroxystyrene, hydrogenated polyhydroxystyrene, halogen- or alkyl-substituted polyhydroxystyrene, hydroxystyrene-N-substituted maleimide copolymer, o / p-
And m / p-hydroxystyrene copolymer, partially O-alkylated product relative to hydroxyl group of polyhydroxystyrene (for example, 5 to 30 mol% of O-methylated product, O- (1
-Methoxy) ethylated product, O- (1-ethoxy) ethylated product, O-2-tetrahydropyranylated product, O- (t-
Butoxycarbonyl) methylated product) or O-acylated product (for example, 5 to 30 mol% o-acetylated product,
O- (t-butoxy) carbonyl compound, etc.), styrene-
Maleic anhydride copolymer, styrene-hydroxystyrene copolymer, α-methylstyrene-hydroxystyrene copolymer, carboxyl group-containing methacrylic resin and derivatives thereof, but are not limited thereto. . Particularly preferred alkali-soluble resins are novolak resins and o-polyhydroxystyrene, m-polyhydroxystyrene, p-polyhydroxystyrene and copolymers thereof, alkyl-substituted polyhydroxystyrene, partial O-alkylation of polyhydroxystyrene, Or an O-acylated product, a styrene-hydroxystyrene copolymer, or an α-methylstyrene-hydroxystyrene copolymer. The novolak resin is obtained by subjecting a given monomer as a main component to addition condensation with an aldehyde in the presence of an acidic catalyst.

As the predetermined monomer, phenol, m
Cresols such as -cresol, p-cresol and o-cresol, xylenols such as 2,5-xylenol, 3,5-xylenol, 3,4-xylenol and 2,3-xylenol, m-ethylphenol, p- Alkylphenols such as ethylphenol, o-ethylphenol, pt-butylphenol, p-octylphenol, 2,3,5-trimethylphenol, p-methoxyphenol, m-methoxyphenol, 3,5-dimethoxyphenol, Alkoxyphenols such as -methoxy-4-methylphenol, m-ethoxyphenol, p-ethoxyphenol, m-propoxyphenol, p-propoxyphenol, m-butoxyphenol and p-butoxyphenol, 2-methyl-4-isopropyl Fenault Bis-alkylphenols etc., m
Hydroxychloro compounds such as -chlorophenol, p-chlorophenol, o-chlorophenol, dihydroxybiphenyl, bisphenol A, phenylphenol, resorcinol, and naphthol can be used alone or as a mixture of two or more, but are not limited thereto. It is not something to be done.

Examples of the aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, phenylacetaldehyde, α-phenylpropylaldehyde, β-
Phenylpropylaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, p-nitrobenzaldehyde, o -Methylbenzaldehyde, m-methylbenzaldehyde,
p-Methylbenzaldehyde, p-ethylbenzaldehyde, pn-butylbenzaldehyde, furfural, chloroacetaldehyde, and their acetal compounds, such as chloroacetaldehyde diethyl acetal, among which formaldehyde is used Is preferred. These aldehydes are used alone or in combination of two or more. As the acidic catalyst, hydrochloric acid, sulfuric acid, formic acid, acetic acid, oxalic acid and the like can be used.

The novolak resin thus obtained preferably has a weight average molecular weight in the range of 1,000 to 30,000. If it is less than 1,000, the film loss of the unexposed portion after development is large, and if it exceeds 30,000, the developing speed is reduced. Particularly preferred are 2,000-20,
000. In addition, the weight average molecular weight of the polyhydroxystyrene other than the novolak resin, its derivative, and the copolymer is 2,000 or more, preferably 5,000.
~ 200,000, more preferably 10,000-1000
00. Further, from the viewpoint of improving the heat resistance of the resist film, 25,000 or more is preferable. here,
The weight average molecular weight is defined as a value in terms of polystyrene by gel permeation chromatography. In the present invention, these alkali-soluble resins may be used as a mixture of two or more kinds. The amount of alkali-soluble resin used is
1 based on the total weight of the photosensitive composition (excluding the solvent)
It is 0 to 50% by weight, preferably 20 to 40% by weight.

Next, the acid-decomposable dissolution inhibiting compound preferably used in the present invention will be described. The use of an acid-decomposable dissolution inhibiting compound reduces film shrinkage upon heating after exposure, and improves dissolution inhibition of unexposed portions, and thus improves dissolution discrimination between exposed and unexposed portions. preferable. The acid-decomposable dissolution inhibiting compound used in the present invention has at least two acid-decomposable groups in its structure, and at the position where the distance between the acid-decomposable groups is farthest away, the acid-decomposable group Is a compound having at least 8 bonding atoms excluding. In the present invention, the acid-decomposable dissolution-inhibiting compound preferably has at least two groups capable of being decomposed by an acid in its structure, and at the position where the distance between the acid-decomposable groups is farthest away, the acid-decomposable group A compound having at least 10, preferably at least 11, and more preferably at least 12 bonding atoms excluding the above, or a position where the distance between the acid-decomposable groups is the longest, having at least three acid-decomposable groups Is a compound having at least 9, preferably at least 10, and more preferably at least 11 bonding atoms excluding an acid-decomposable group. The preferred upper limit of the number of the bonding atoms is 50, more preferably 30. In the present invention, the acid-decomposable dissolution inhibiting compound is
When the acid-decomposable group has three or more, preferably four or more, or two acid-decomposable groups, if the acid-decomposable groups are separated from each other by a certain distance or more, the alkali-soluble resin Significantly improves the dissolution inhibiting property against In addition, the distance between the acid-decomposable groups in the present invention is represented by the number of via bond atoms excluding the acid-decomposable groups. For example, in the case of the following compounds (1) and (2), the distance between the acid-decomposable groups is 4 bonding atoms, and in the compound (3), the bonding atom is 12 bonding atoms.

[0099]

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Further, the acid-decomposable dissolution-inhibiting compound of the present invention may have a plurality of acid-decomposable groups on one benzene ring, but preferably one compound on one benzene ring. A compound composed of a skeleton having an acid-decomposable group. Further, the molecular weight of the acid-decomposable dissolution inhibiting compound of the present invention is preferably 3,000 or less, more preferably 500 to
It is 3,000, more preferably 1,000 to 2,500.

In a preferred embodiment of the present invention, an acid-decomposable group, ie, -COO-A ⁰ , -OB ^0.
The group containing a group, -R ⁰ -COO-A ^0, or -Ar
Include groups represented by -O-B ^0. Where A ⁰ is −
C ( ^R01 ) ( ^R02 ) ( ^R03 ), -Si ( ^R01 ) ( ^R02 )
Shows the (R ^{0 3)} or ^{-C (R 04) (R 05} ) -O-R 06 group. B ⁰ represents A ⁰ or a —CO—OA ⁰ group.
R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R ⁰⁵ may be the same or different and each represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group;
⁰⁶ represents an alkyl group or an aryl group. Where R ⁰¹
At least two of to R ⁰³ is a group other than a hydrogen atom,
Further, two groups out of R ^{01 to} R ⁰³ and R ^{04 to} R ⁰⁶ may combine to form a ring. R ⁰ represents a divalent or higher valent aliphatic or aromatic hydrocarbon group which may have a substituent, and -Ar- represents a divalent or higher valent which may have a monocyclic or polycyclic substituent. Shows an aromatic group.

Here, the alkyl group is preferably an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group and a t-butyl group. Preferred are those having 3 to 10 carbon atoms such as cyclopropyl group, cyclobutyl group, cyclohexyl group and adamantyl group, and alkenyl groups having 2 to 2 carbon atoms such as vinyl group, propenyl group, allyl group and butenyl group. Preferably, the aryl group has 6 to 1 carbon atoms such as phenyl, xylyl, toluyl, cumenyl, naphthyl and anthracenyl.
Four are preferred. Further, as a substituent, a hydroxyl group,
Halogen atom (fluorine, chlorine, bromine, iodine), nitro group, cyano group, the above alkyl group, methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group, n-butoxy group, isobutoxy group, s
an alkoxy group such as an ec-butoxy group and a t-butoxy group,
Alkoxycarbonyl groups such as methoxycarbonyl group and ethoxycarbonyl group, aralkyl groups such as benzyl group, phenethyl group and cumyl group, aralkyloxy groups, acyl groups such as formyl group, acetyl group, butyryl group, benzoyl group, cyanamyl group, and valeryl group. Group, an acyloxy group such as a butyryloxy group, the above alkenyl group, a vinyloxy group.
Examples thereof include an alkenyloxy group such as a propenyloxy group, an allyloxy group, and a butenyloxy group, an aryloxy group such as the above-described aryl group and phenoxy group, and an aryloxycarbonyl group such as a benzoyloxy group.

Preferably, a silyl ether group, a cumyl ester group, an acetal group, a tetrahydropyranyl ether group, an enol ether group, an enol ester group,
And a tertiary alkyl ester group and a tertiary alkyl carbonate group. More preferred are a tertiary alkyl ester group, a tertiary alkyl carbonate group, a cumyl ester group, and a tetrahydropyranyl ether group.

As the acid-decomposable dissolution-inhibiting compound, those described in JP-A-1-289946 and JP-A-1-2899 are preferred.
No. 47, JP-A-2-2560, JP-A-3-12895
9, JP-A-3-158855, JP-A-3-1793
No. 53, JP-A-3-191351, JP-A-3-200
No. 251, JP-A-3-200252, JP-A-3-20
0253, JP-A-3-200254, JP-A-3-2
0255, JP-A-3-259149, JP-A-3-259
279958, JP-A-3-279959, JP-A-4
JP-A-1650, JP-A-4-1651, JP-A-4-11
No. 260, JP-A-4-12356, JP-A-4-123
No. 57, Japanese Patent Application No. 3-33229, Japanese Patent Application No. 3-2307
No. 90, Japanese Patent Application No. 3-320438, Japanese Patent Application No. 4-251
No. 57, Japanese Patent Application No. 4-52732, Japanese Patent Application No. 4-1032
No. 15, Japanese Patent Application No. 4-104542, Japanese Patent Application No. 4-107
No. 885, Japanese Patent Application No. 4-107889 and No. 4-1521
Compounds in which some or all of the phenolic OH groups of the polyhydroxy compound described in the specification such as No. 95 are bonded and protected by the above-mentioned groups, -R ⁰ -COO-A ⁰ or B ⁰ groups, included.

More preferably, JP-A-1-289946.
JP-A-3-128959, JP-A-3-15885
5, JP-A-3-179353, JP-A-3-2002
No. 51, JP-A-3-200252, JP-A-3-200
255, JP-A-3-259149, JP-A-3-27
9958, JP-A-4-1650, JP-A-4-112
No. 60, JP-A-4-12356, JP-A-4-1235
7, Japanese Patent Application No. 4-25157, Japanese Patent Application No. 4-10321
No. 5, Japanese Patent Application No. 4-104542, Japanese Patent Application No. 4-1078
No. 85, Japanese Patent Application Nos. 4-107889 and 4-15219
No. 5 using the polyhydroxy compound described in the specification.

More specifically, general formulas [I] to [XV]
The compound represented by I] is mentioned.

[0107]

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[0108]

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[0109]

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[0110]

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Here, R ¹ , R ² , R ³ , R ⁴ may be the same or different, and represent a hydrogen atom, a —R ⁰ —COO—A ⁰ or B ⁰ group, and R ₁ : —CO—, — COO-, -NHCONH-, -N
HCOO -, - O -, - S -, - SO -, - SO 2 -,
-SO _3- , or

[0112]

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[0113] Here, G = 2 to 6, provided that at least one alkyl group of R _4, R ₅ when the G = 2, R _4, R _5: may be the same or different, a hydrogen atom, an alkyl Group, alkoxy group, -OH, -COOH, -C
N, a halogen atom, —R ₆ —COOR ₇ , or —R ₈
—OH (R ₆ , R ₈ : alkylene group, R ₇ : hydrogen atom, alkyl group, aryl group or aralkyl group), R ₂ , R ₃ , R _{9 to} R ₁₂ , R ₁₅ , R _{17 to} R ₂₁ , R ₂₅ ~
_{R 27, R 30 ~R 32,} R 37 ~R 42, R 46 ~R 49 and R _51:
May be the same or different, and include a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, an acyl group, an acyloxy group, an aryl group, an aryloxy group, an aralkyl group, an aralkyloxy group, a halogen atom, a nitro group, a carboxyl group, a cyano group, or _{-N (R 13) (R 14} ) (R 13, R 14: H, alkyl or aryl group,), R _16: a single bond, an alkylene group or,

[0114]

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R ₂₂ and R ₂₄ may be the same or different and are a single bond, an alkylene group, —O—, —S—, —CO— or a carboxyl group; R ₂₃ : a hydrogen atom, an alkyl group, an alkoxy group; An acyl group, an acyloxy group, an aryl group, a nitro group, a hydroxyl group, a cyano group, or a carboxyl group, provided that the hydrogen of the hydroxyl group may be substituted with a t-butoxycarbonyl group. R ₂₈ , R ₂₉ : same or different A methylene group, a lower alkyl-substituted methylene group, a halomethylene group, or a haloalkyl group, provided that the lower alkyl group in the present application refers to an alkyl group having 1 to 4 carbon atoms, and R _{33 to} R ₃₆ may be the same or different. , A hydrogen atom, or an alkyl group, R _{43 to} R ₄₅ : may be the same or different, and represent a hydrogen atom, an alkyl group, an alkoxy group, an acyl group, or an Siloxy group, R ₅₀ : hydrogen atom, t-butoxycarbonyl group, or

[0116]

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R ₅₂ and R _53, which may be the same or different, are a hydrogen atom, a lower alkyl group, a lower haloalkyl group, or an aryl group; R _{54 to} R _57, which may be the same or different, a hydrogen atom;
Hydroxyl group, halogen atom, nitro group, cyano group, carbonyl group, alkyl group, alkoxy group, alkoxycarbonyl group, aralkyl group, aralkyloxy group, acyl group,
An acyloxy group, an alkenyl group, an alkenyloxy group, an aryl group, an aryloxy group, or an aryloxycarbonyl group, provided that the four substituents having the same symbol do not have to be the same group; Y: —CO—, Or —SO ₂ —, Z, B: a single bond or —O—, A: a methylene group, a lower alkyl-substituted methylene group, a halomethylene group, or a haloalkyl group; E: a single bond or an oxymethylene group; a1 to y1: When plural, the groups in parentheses may be the same or different. a to q, s, t, v, g1 to i1, k1 to m1, o1, q1, s1, u1: 0 or Integer of 1 to 5, r, u, w, x, y, z, a1 to f1, p1, r1, t1, v1 to x1: 0 or 1
An integer of 4, j1, n1, z1, a2, b2, c2, d2: an integer of 0 or 1 to 3, z1, a
2, at least one of c2, d2 is 1 or more, y1: an integer of 3 to 8, (a + b), (e + f + g), (k + l + m), (q + r + s ), (w + x + y), (c1 + d1), (g1 +
h1 + i1 + j1), (o1 + p1), (s1 + t1) ≧ 2, (j1 + n1) ≦ 3, (r + u), (w + z), (x + a1), (y + b1), (c1 + e1), (d1 + f1), (p1 + r1),
(t1 + v1), (x1 + w1) ≦ 4, provided that (w +
z), (x + a1) ≦ 5, (a + c), (b + d), (e + h), (f + i), (g + j), (k + n), (l + o), (m + p), (q
+ t), (s + v), (g1 + k1), (h1 + l1), (i1 + m1), (o1 + q1), (s1 + u1)
≦ 5.

[0118]

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[0119]

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[0120]

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[0121]

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Specific examples of preferred compound skeletons are shown below.

[0123]

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[0124]

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[0125]

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[0126]

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[0127]

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[0128]

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[0129]

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[0130]

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[0131]

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[0132]

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[0133]

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[0134]

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[0135]

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[0136]

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[0137]

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[0138]

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[0139]

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[0140]

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[0141]

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R in the compounds (1) to (63) represents a hydrogen atom,

[0143]

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Represents the following. However, at least two or three depending on the structure are groups other than hydrogen atoms, and each substituent R
May not be the same group.

The amount of the acid-decomposable dissolution inhibiting compound to be added is 3 to 50 based on the total weight of the photosensitive composition (excluding the solvent).
%, Preferably 5 to 35% by weight, more preferably 10 to 20% by weight.

In the photosensitive composition of the present invention, if necessary,
Further, dyes, pigments, plasticizers, surfactants, photosensitizers, organic basic compounds, compounds having two or more phenolic hydroxyl groups for promoting solubility in a developing solution, and the like can be contained.

The compound having two or more phenolic hydroxyl groups that can be used in the present invention is preferably a phenol compound having a molecular weight of 1,000 or more. Further, it is necessary to have at least two phenolic hydroxyl groups in the molecule, but if it exceeds 10, the effect of improving the development latitude is lost. When the ratio of the phenolic hydroxyl group to the aromatic ring is less than 0.5, the film thickness dependency is large, and the development latitude tends to be narrow. If this ratio exceeds 1.4, the stability of the composition deteriorates, and it becomes difficult to obtain high resolution and good film thickness dependency, which is not preferable.

The preferred addition amount of the phenol compound is 2 to 50% by weight, more preferably 5 to 30% by weight, based on the alkali-soluble resin. An addition amount exceeding 30% by weight is not preferable because the development residue deteriorates and a new defect that the pattern is deformed during development occurs.

Such a phenol compound having a molecular weight of 1000 or less can be prepared by, for example, referring to the methods described in JP-A-4-122938, JP-A-2-28531, US Pat. ,
It can be easily synthesized by those skilled in the art. Specific examples of the phenol compound are shown below, but the compounds that can be used in the present invention are not limited to these.

Resorcin, phloroglucin, 2, 3, 4
-Trihydroxybenzophenone, 2,3,4,4'-
Tetrahydroxybenzophenone, 2,3,4,3 ',
4 ', 5'-hexahydroxybenzophenone, acetone-pyrogallol condensation resin, fluoroglucoside,
4,2 ', 4'-biphenyltetrol, 4,4'-thiobis (1,3-dihydroxy) benzene, 2,2',
4,4'-tetrahydroxydiphenyl ether, 2,
2 ', 4,4'-tetrahydroxydiphenylsulfoxide, 2,2', 4,4'-tetrahydroxydiphenylsulfone, tris (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) Cyclohexane, 4,4- (α-methylbenzylidene) bisphenol, α, α ′, α ″ -tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene,
α, α ', α "-tris (4-hydroxyphenyl)-
1-ethyl-4-isopropylbenzene, 1,2,2-
Tris (hydroxyphenyl) propane, 1,1,2-
Tris (3,5-dimethyl-4-hydroxyphenyl)
Propane, 2,2,5,5-tetrakis (4-hydroxyphenyl) hexane, 1,2-tetrakis (4-hydroxyphenyl) ethane, 1,1,3-tris (hydroxyphenyl) butane, para [α, α , Α ', α'-tetrakis (4-hydroxyphenyl)]-xylene.

Preferred organic basic compounds that can be used in the present invention are compounds that are more basic than phenol. Among them, a nitrogen-containing basic compound is preferable. Preferred chemical environments include the following formulas (XVII) to (XXI).

[0152]

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Further preferred compounds are nitrogen-containing basic compounds having two or more nitrogen atoms having different chemical environments in one molecule, and particularly preferred is a ring structure containing a substituted or unsubstituted amino group and a nitrogen atom. Or a compound having an alkylamino group. 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 aminomorpholine, substituted or unsubstituted aminoalkylmorpholine and the like can be mentioned. Preferred substituents are an amino group,
An aminoalkyl group, an alkylamino group, an aminoaryl group, an arylamino group, an alkyl group, an alkoxy group, an acyl group, an acyloxy group, an aryl group, an aryloxy group, a nitro group, a hydroxyl group, and a cyano group. As particularly preferred compounds, guanidine, 1,1-dimethylguanidine, 1,1,3,3-tetramethylguanidine, 2-
Aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-dimethylaminopyridine, 4-dimethylaminopyridine, 2-diethylaminopyridine, 2- (aminomethyl) pyridine, 2-amino-3-methylpyridine, 2-amino -4-methylpyridine, 2-amino-5
-Methylpyridine, 2-amino-6-methylpyridine,
3-aminoethylpyridine, 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,
Examples include, but are not limited to, N-aminomorpholine, N- (2-aminoethyl) morpholine, and the like.

These nitrogen-containing basic compounds are used alone or in combination of two or more. The amount of the nitrogen-containing basic compound to be used is generally from 0.001 to 10 parts by weight, preferably from 0.01 to 10 parts by weight, per 100 parts by weight of the composition (excluding the solvent).
1 to 5 parts by weight. If the amount is less than 0.001 part by weight, the effects of the present invention cannot be obtained. On the other hand, if it exceeds 10 parts by weight, the sensitivity tends to decrease and the developability of the unexposed part tends to deteriorate.

Suitable dyes include oil dyes and basic dyes. Specifically, Oil Yellow # 101, Oil Yellow # 103, Oil Pink # 312, Oil Green BG, Oil Blue BOS, Oil Blue # 60
3. Oil black BY, oil black BS, oil black T-505 (all manufactured by Orient Chemical Co., Ltd.), crystal violet (CI42555), methyl violet (CI42535), rhodamine B
(CI45170B), malachite green (CI42
000), methylene blue (CI52015) and the like.

Further, the photosensitive composition of the present invention is sensitized by adding a spectral sensitizer as described below and sensitizing the photoacid generator to be used in a longer wavelength region than far ultraviolet where the photoacid generator has no absorption. Sensitivity can be given to i or g rays. Suitable spectral sensitizers include, specifically, benzophenone, p,
p'-tetramethyldiaminobenzophenone, p, p '
-Tetraethylethylaminobenzophenone, 2-chlorothioxanthone, anthrone, 9-ethoxyanthracene, anthracene, pyrene, perylene, phenothiazine, benzyl, acridine orange, benzoflavin,
Cetoflavin-T, 9,10-diphenylanthracene, 9-fluorenone, acetophenone, phenanthrene, 2-nitrofluorene, 5-nitroacenaphthene,
Benzoquinone, 2-chloro-4-nitroaniline, N-
Acetyl-p-nitroaniline, p-nitroaniline, N-acetyl-4-nitro-1-naphthylamine, picramide, anthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone 1,2-benzanthraquinone, 3- Methyl-1,3-diaza-1,
9-benzanthrone, dibenzalacetone, 1,2-
Naphthoquinone, 3,3′-carbonyl-bis (5,7-
Dimethoxycarbonylcoumarin) and coronene, but are not limited thereto. Further, these spectral sensitizers can also be used as a light absorbing agent for far ultraviolet light of a light source. In this case, the light absorber reduces the reflected light from the substrate and reduces the influence of multiple reflections in the resist film, thereby exhibiting the effect of improving the standing wave.

The photosensitive composition of the present invention is dissolved in a solvent in which each of the above components is dissolved, and coated on a support. Examples of the solvent used herein include ethylene dichloride, cyclohexanone, cyclopentanone, 2-heptanone, γ-butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, and ethylene glycol monoethyl ether acetate. , Propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, toluene, ethyl acetate, methyl lactate, ethyl lactate, methyl methoxypropionate,
Ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, N, N-dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, tetrahydrofuran and the like are preferable, and these solvents are used alone or in combination.

A surfactant may be added to the above solvents. Specifically, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether, polyoxyethylene octyl phenol ether,
Polyoxyethylene alkyl allyl ethers such as polyoxyethylene nonylphenol ether, 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, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate Surfactants such as polyoxyethylene sorbitan fatty acid esters such as acrylates and the like, F-top EF301, E 303, EF352 (manufactured by Shin Akita Kasei Co., Ltd.), Megafac F171, F173 (manufactured by Dainippon Ink Co., Ltd.), Flora - de FC430, FC43
1 (manufactured by Sumitomo 3M Limited), Asahi Guard AG71
0, Surflon S-382, SC101, SC102,
Fluorinated surfactants such as SC103, SC104, SC105 and SC106 (manufactured by Asahi Glass Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), and acrylic or methacrylic (co) polymerized polyflow No. 75, no. 95 (manufactured by Kyoeisha Yushi Kagaku Kogyo KK) and the like. The amount of these surfactants is usually 2 parts by weight or less, preferably 1 part by weight or less, per 100 parts by weight of the solids in the composition of the present invention. These surfactants may be added alone or in some combination.

The above-mentioned photosensitive composition is applied on a substrate (eg, silicon / silicon dioxide coating) to be used in the manufacture of precision integrated circuit devices by a suitable application method such as a spinner or a coater, and then passed through a predetermined mask. By exposing, baking and developing, a good resist pattern can be obtained.

Examples of the developer for the photosensitive composition of the present invention include:
Sodium hydroxide, potassium hydroxide, sodium carbonate,
Inorganic alkalis such as sodium silicate, sodium metasilicate and aqueous ammonia, primary amines such as ethylamine and n-propylamine, secondary amines such as diethylamine and di-n-butylamine, and triethylamine and methyldiethylamine Use alkaline aqueous solutions such as triamines, alcoholamines such as dimethylethanolamine and triethanolamine, quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, and cyclic amines such as pyrrole and pichelidine. be able to. Further, an appropriate amount of an alcohol or a surfactant may be added to the above alkaline aqueous solution.

[0161]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the contents of the present invention are not limited thereto.

[Synthesis Example 1 (Synthesis of Resin of Structural Example (b1))] Poly (p-hydroxystyrene) (weight average molecular weight 10,800, dispersity 1.1; polystyrene standard) 2
4.0 g (0.20 mol) were dissolved in 200 ml of anhydrous THF. 1.90 g (0.024 mol) of pyridine is added to this solution, and 10.8 g (0.040 mol) of di- (2-cyclopropyl-2-propyl) dicarbonate is further added.
Was added and stirred at room temperature for 12 hours. The reaction solution was poured into 3 L of ion-exchanged water with vigorous stirring, and the precipitated polymer was washed with water. Dry at 40 ° C under vacuum to obtain a white powder 2
7.4 g were obtained. By NMR measurement, it was confirmed that this powder was the resin (m / n = 81/19: molar ratio) of Structural Example (b1) of the present invention. When the molecular weight was measured by GPC measurement, the weight average was 11,400 (polystyrene standard) and the dispersity was 1.2.

[Synthesis Example 2 (Synthesis of Resin of Structural Example (b4))] In Synthesis Example 1, di- (2-cyclopropyl-
9.69 g of di- (2-vinyl-2-propyl) dicarbonate (0.
Except for using 040 mol), 27.1 g of a white powder was obtained in the same manner as in Synthesis Example 1. According to NMR measurement, this powder was found to be the resin (m / n = 82/1) of the structural example (b4) of the present invention.
8: molar ratio). When the molecular weight was measured by GPC measurement, the weight average was 11,200 (polystyrene standard) and the dispersity was 1.2.

[Synthesis Examples 3 to 10 (Synthesis of Resin (B))]
In the same manner as in Synthesis Examples 1 and 2, a resin (B) having a composition ratio shown in Table 1 below was synthesized.

[0165]

[Table 1]

[Synthesis Example 11 (Synthesis of Resin of Structural Example (c1))] Poly (p-hydroxystyrene) (weight average molecular weight 10,800, dispersity 1.1; polystyrene standard) 2
4.0 g (0.20 mol) were dissolved in 200 ml of anhydrous THF. 4.54 g of ethyl vinyl ether was added to this solution.
(0.063 mol) and 0.1 g of a 5% THF solution of p-toluenesulfonic acid as a catalyst.
Stirred for hours. Thereafter, the reaction solution was poured into 3 L of ion-exchanged water with vigorous stirring, and the precipitated polymer was washed with water. It was dried at 40 ° C. under vacuum to obtain 27.5 g of a white powder. By NMR measurement, it was confirmed that this powder was the resin of structural example (c1) of the present invention (m / n = 70/30: molar ratio). When the molecular weight was measured by GPC measurement, the weight average was 11,800 (polystyrene standard),
The dispersity was 1.2.

[Synthesis Example 12 (Synthesis of Resin of Structural Example (c2))] In Synthesis Example 1, except that 6.31 g (0.63 mol) of i-butylethyl ether was used instead of ethyl vinyl ether. White powder 2 as in Example 1
8.3 g were obtained. By NMR measurement, it was confirmed that this powder was the resin of structural example (c2) of the present invention (m / n = 69/31: molar ratio). When the molecular weight was measured by GPC measurement, the weight average was 11,600 (polystyrene standard) and the dispersity was 1.2.

[Synthesis Examples 13 to 22 (Resin (C) of the present invention)
In the same manner as in Synthesis Examples 11 and 12, a resin (C) having a composition ratio shown in Table 2 below was synthesized.

[0169]

[Table 2]

(Examples 1 to 12 and Comparative Examples 1 to 3) Resin (B) and resin (C) synthesized in the above synthesis examples (Examples)
Alternatively, a resist was prepared using another resin (Comparative Example). Table 3 shows the prescription at that time. The amount of the photoacid generator used was 0.1 g in all cases, and the amount of the additive was 0.3 g when used.

[0171]

[Table 3]

The abbreviations used in Table 3 represent the following contents. <Polymer> In parentheses, molar ratio is PHS / St p-hydroxystyrene / styrene copolymer (85/15) (weight average molecular weight: 25,000) PHS / EES p-hydroxystyrene / 1-ethoxyethoxystyrene copolymer Combined (70/30) (weight average molecular weight: 12,000) PHS / TBOCS p-hydroxystyrene / t-butoxycarbonyloxystyrene copolymer (80/20) (weight average molecular weight: 13,000)

[Preparation and Evaluation of Photosensitive Composition] To each of the components shown in Table 3 was added 0.03 g of 4-dimethylaminopyridine, dissolved in 9.5 g of propylene glycol monomethyl ether acetate, and filtered through a 0.2 μm filter. Thus, a resist solution was prepared. This resist solution is applied on a silicon wafer using a spin coater,
The resist film was dried on a vacuum adsorption type hot plate at 130 ° C. for 60 seconds to obtain a resist film having a thickness of 0.76 μm. This resist film was exposed using a 248 nm KrF excimer laser stepper (NA = 0.42). Immediately after exposure and one hour after exposure, heating was performed for 60 seconds on a vacuum suction type hot plate at 110 ° C., and immediately 2.3.
8% tetramethylammonium hydroxide (T
MAH) dipped in an aqueous solution for 60 seconds, rinsed with water for 30 seconds and dried. The profiles, sensitivities, and resolving powers of the thus-obtained patterns on the silicon wafer immediately after exposure and one hour after exposure were evaluated and compared as described below. Table 4 shows the results.

[Profile] The pattern on the silicon wafer thus obtained was observed with a scanning electron microscope to evaluate the resist profile. [Sensitivity] Sensitivity was evaluated based on the minimum exposure dose for reproducing a 0.30 μm mask pattern. [Resolving power] The resolving power was evaluated based on the minimum resolving power of the minimum exposure amount for reproducing a mask pattern of 0.30 μm.

[0175]

[Table 4]

From the results in Table 4, the following is clear. The positive photosensitive composition of the present invention has a good profile, high sensitivity, and high resolution, and does not change with time after exposure. On the other hand, in the cases of Comparative Examples 1 to 3, the changes in sensitivity, resolution, and profile over time after exposure were large, and were inferior to those of the positive photosensitive composition of the present invention.

[0177]

According to the chemical amplification type positive photosensitive composition of the present invention, there is no change in pattern shape and sensitivity with the passage of time after exposure, and as a result, sensitivity, resolution and pattern profile are improved.

Claims (3)

[Claims] (1) a compound capable of generating an acid upon irradiation with actinic rays or radiation; (B) a compound represented by the following general formulas (I) and (II):
And a resin having a repeating structural unit represented by the following general formulas (I) and (III): (C) a resin having a repeating structural unit represented by the following general formulas (I) and (III): Embedded image In the general formulas (I) to (III), R _{1 to} R ₇ are as follows. R ₁ represents a hydrogen atom or a methyl group. R ₂ and R
₃ represents the same or different and represents a hydrogen atom, an alkyl group or an aryl group which may have a substituent. Where R
_At least one of ₂ and R ₃ is a group other than a hydrogen atom. R ₄ represents a cycloalkyl group, an alkenyl group, an alkynyl group or an aryl group which may have a substituent. R _{5 is, -C (R 8) (R} 9) (R 10), or -C (R ₁₁₎ (R
₁₂ ) represents a group represented by (OR ₁₃ ). Here, R _{8 to} R
₁₂ is the same or different and represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group or an aryl group which may have a substituent, and R ₁₃ has a substituent Represents an alkyl group, a cycloalkyl group or an aryl group. However, at least two of R _{8 to} R ₁₀ are groups other than hydrogen atoms. R ₆ and R ₇ are the same or different and represent a halogen atom, a hydroxyl group, an alkyl group, an aryl group, an aralkyl group, an alkoxy group, an acyl group or an acyloxy group which may have a substituent. In addition, R _{2 to} R ₄ , R _{8 to} R ₁₀ , and R _{11 to} R
Two of each of ₁₃ may combine to form a ring. m and n are the same or different and each represent an integer of 0-3. 2. A low molecular weight acid-decomposable dissolution inhibiting compound having a molecular weight of 3,000 or less, which has a group decomposable by an acid and whose solubility in an alkaline developer is increased by the action of an acid. The positive photosensitive composition according to claim 1, wherein 3. The positive photosensitive composition according to claim 1, further comprising a resin which is insoluble in water and soluble in an aqueous alkali solution.