JP2629814B2 - Positive radiation-sensitive resin composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a positive-type radiation-sensitive resin composition. More specifically, an ultraviolet ray, a far ultraviolet ray, an X ray containing an alkali-soluble resin and a specific 1,2-quinonediazide compound.
The present invention relates to a positive-type radiation-sensitive resin composition that is sensitive to radiation such as radiation, electron beam, molecular beam, γ-ray, synchrotron radiation, and proton beam, and can be particularly preferably used as a resist for producing an integrated circuit.

[Prior art] In a positive resist composed of an alkali-soluble resin and a 1,2-quinonediazide compound, the radiation-irradiated portion of 1,2-quinonediazide compound
The quinonediazide compound changes to indenecarboxylic acid and dissolves in a developing solution composed of an alkaline aqueous solution. However, the 1,2-quinonediazide compound in the unirradiated portion serving as a resist pattern does not change and does not dissolve in the developing solution. The unirradiated portion has very little deformation and gives a resist pattern with high resolution that is faithful to the mask.

In recent years, where higher integration of integrated circuits is required, positive resists such as those described above are often used. However, with the improvement in integration of integrated circuits, the resolution, heat resistance, and developability of resist have been increasing. There is a further demand for improvements in sensitivity and the like.

Conventionally, as the above-mentioned positive resist, a positive photoresist comprising an alkali-soluble novolak resin and a 1,2-quinonediazide compound has been known (for example, JP-A-58-149042, JP-A-58-182633). Gazette, JP
58-150948, etc.).

JP-A-58-149042 and JP-A-58-182633 disclose a method of adding a sensitizer for the purpose of improving the sensitivity of the resist, and JP-A-58-150948 discloses the method. Discloses a method using a 1,2-naphthoquinone-2-diazide-sulfonic acid ester compound of polyhydroxybenzophenone in which the 2-position and the 2'-position adjacent to the carbonyl group of the benzophenone nucleus are substituted with hydroxyl groups.

Also, Japanese Patent Publication No. 62-28457 discloses the following formula: Here, D is naphthoquinone-1,2-diazido-5-sulfonyl or naphthoquinone-1,2-diazido-4-sulfonyl. A positive photoresist in which a photosensitive component containing a compound represented by the formula is mixed with an alkali-soluble resin. A composition is disclosed.

Further, Japanese Patent Application Laid-Open No. 62-280737, which is filed by the same applicant as the present applicant, discloses that 1,2-quinonediazidesulfonic acid ester of tetrahydroxybenzophenone is 10 to 8%.
A positive-type radiation-sensitive resin composition of an alkali-soluble resin and the quinonediazidesulfonic acid ester, which is contained at 0% by weight, is disclosed.

However, in each of the above publications, 2,2 ', 3,
A positive radiation-sensitive resin composition containing a 1,2-quinonediazide compound mainly composed of 1,2-quinonediazidosulfonic acid ester of 4-tetrahydroxybenzophenone (a mixture of mono-, di-, tri- and tetraesters) is specifically described. Is not described.

[Problems to be Solved by the Invention] An object of the present invention is to provide a positive radiation-sensitive resin composition having a novel composition.

Another object of the present invention is to provide a radiation-sensitive resin composition suitable for a positive resist having high sensitivity, high resolution, high residual film ratio and excellent developability.

Still other objects and advantages of the present invention will be apparent from the following description.

(Means for Solving the Problems) According to the present invention, the above objects and advantages of the present invention are as follows: (A) an alkali-soluble resin and (B) 2,2 ', 3,4-tetrahydroxybenzophenone. It contains a 1,2-quinonediazide compound mainly composed of 1,2-quinonediazidesulfonic acid ester, and the 1,2-quinonediazidesulfonic acid ester contains 0 to 10% by weight of a monoester and 0 to 10% by weight of a diester.
This is achieved by a positive-type radiation-sensitive resin composition comprising 30% by weight, 20 to 70% by weight of a triester and 5 to 70% by weight of a tetraester.

The 1,2-quinonediazide compound (B) used in the present invention mainly consists of 1,2-quinonediazidesulfonic acid ester of 2,2 ', 3,4-tetrahydroxybenzophenone.

Such 1,2-quinonediazidesulfonic acid esters include, for example, 2,2 ', 3,4-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,2', 3,4- Tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,2 ', 3,4-tetrahydroxybenzophenone-1,2
-Benzoquinonediazide-4-sulfonic acid ester;

Examples of these 1,2-quinonediazidosulfonic acid esters include a mixture of two or more esters of a monoester, a diester, a triester, and a tetraester. % By weight, 0 to 30% by weight of diester, 20 to 70% by weight of triester, 5 to 70% by weight of tetraester
It is.

1,2-quinonediazide sulfonic acid ester is, for example,
2,2 ', 3,4-tetrahydroxybenzophenone and 1,2-naphthoquinonediazide-5-sulfonic acid chloride, 1,2-
Naphthoquinonediazide-4-sulfonic acid chloride, 1,2
It can be obtained by subjecting one or more kinds of 1,2-quinonediazidesulfonic acid halides such as -benzoquinonediazide-4-sulfonic acid chloride to a condensation reaction in the presence of a basic catalyst.

As the basic catalyst, for example, amines such as trimethylamine, triethylamine, tripropylamine, pyridine and tetramethylammonium hydroxide and inorganic alkalis such as sodium hydroxide, potassium hydroxide and sodium carbonate are used. The amount of the basic catalyst to be used is generally 0.8 to 2 mol, preferably 1 to 1.5 mol, per 1 mol of 1,2-quinonediazidesulfonic acid halide used. The condensation reaction is usually performed in the presence of a solvent. As the solvent used at this time, for example, water, dioxane, diethyl ether, tetrahydrofuran, acetone, methyl ethyl ketone, γ-butyrolactone, N-methylpyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, ethylene carbonate, propylene carbonate And the like. The amount of these solvents used is usually from 100 to 1,000 based on 100 parts by weight of the reaction raw materials.
0 parts by weight.

The temperature of the condensation reaction varies depending on the solvent used, but is usually -20 to 60C, preferably 0 to 40C.

As a purification method after the condensation reaction, the by-product hydrochloride is filtered or water is added to dissolve the hydrochloride, followed by reprecipitation purification with a large amount of acidic water such as a dilute hydrochloric acid aqueous solution,
A method for drying can be exemplified.

In these reactions, usually, all of the hydroxyl groups contained in 2,2 ', 3,4-tetrahydroxybenzophenone are converted from the monosulfonic acid ester of 2,2', 3,4-tetrahydroxybenzophenone. The reacted tetrasulfonic acid ester is formed.

In the present invention, 1,2-quinonediazidesulfonic acid ester is, for example, preferably 100 parts by weight of alkali-soluble resin, preferably 5 to 100 parts by weight, more preferably 10 to 5 parts by weight.
Used at 0 parts by weight.

When the amount is less than 5 parts by weight, the 1,2-quinonediazide compound absorbs radiation and generates a small amount of carboxylic acid, so that patterning tends to be difficult.
When the amount exceeds 100 parts by weight, it is difficult to decompose all of the added 1,2-quinonediazide compound by short-time irradiation, and it becomes difficult to perform development with a developing solution composed of an alkaline aqueous solution.

The 1,2-quinonediazidosulfonic acid ester of 2,2 ', 3,4-tetrahydroxybenzophenone used in the present invention may be optionally used, for example, as described in JP-A-62-178562. Thus, they can be used after being modified by acylation or sulfonylation to such an extent that the performance is not impaired.

As described above, the composition of the present invention is mainly composed of 1,2-quinonediazidesulfonic acid ester of 2,2 ', 3,4-tetrahydroxybenzophenone as the 1,2-quinonediazide compound (B). That is, the 1,2-quinonediazidesulfonic acid ester can be used alone, and the 1,2-diazidosulfonic acid ester can be used in combination with another 1,2-quinonediazide compound.

When used in combination, 1,2-quinonediazidosulfonic acid ester of 2,2 ', 3,4-tetrahydroxybenzophenone 1
The other 1,2-quinonediazide compound is used in an amount of 100 parts by weight or less, preferably 40 parts by weight or less based on 00 parts by weight. Other 1,2-quinonediazide compounds used at this time include, for example, 1,2-quinonediazide compounds such as p-cresol, resorcinol, pyrogallol, and the like.
-Benzoquinonediazide-4-sulfonic acid ester, 1,
2-naphthoquinonediazide-4-sulfonic acid ester and 1,2-naphthoquinonediazide-5-sulfonic acid ester; 2,4-dihydroxyphenyl-propyl ketone, 2,
4-dihydroxyphenyl-n-hexyl ketone, 2,4-
Dihydroxybenzophenone, 2,3,4-trihydroxyphenyl-n-hexyl ketone, 2,3,4-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,2 ′, 4,4'-tetrahydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,
3,4,4'-tetrahydroxy-3'-methoxybenzophenone, 2,2 ', 3,4-tetrahydroxy-4'-methylbenzophenone, 2,3,4,2', 4'- Pentahydroxybenzophenone, 2,3,4,2 ', 5'-pentahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,3,4,2', 6'-pentane Hydroxybenzophenone, 2,3,4,3 ', 4'-pentahydroxybenzophenone, 2,3,4,3', 5'-pentahydroxybenzophenone, 2,3,4,2 ', 3 ', 4'-hexahydroxybenzophenone, 2,3,4,3', 4 ', 5'-hexahydroxybenzophenone, 2,3,4,2', 4 ', 6'-hexahydroxy Benzophenone, 2,4,6,2 ', 4'-pentahydroxybenzophenone, 2,4,6,2', 5'-pentahydroxybenzophenone, 2,4,6,2 ', 6 '-Pentahydroxybenzophenone, 2,4,6,3', 4'- Hydroxybenzophenone, 2,4,6,3 ', 5'-pentahydroxybenzophenone, 2,4,6,3', 4 ', 5'-hexahydroxybenzophenone, 2,4,6 , 2 ', 4', 6'-hexahydroxybenzophenone, 2,3,4,5,2'-pentahydroxybenzophenone, 2,3,4,5,3'-pentahydroxybenzophenone,
2,3,4,5,4'-pentahydroxybenzophenone, 2,3,
4,5,2 ', 4'-hexahydroxybenzophenone, 2,3,
4,5,2 ', 5'-hexahydroxybenzophenone, 2,3,
4,5,2 ', 6'-hexahydroxybenzophenone, 2,3,
4,5,3 ', 4'-hexahydroxybenzophenone, 2,3,
4,5,3 ', 5'-hexahydroxybenzophenone, 2,3,
4,5,2 ', 3', 4'-heptahydroxybenzophenone,
2,3,4,5,3 ', 4', 5'-heptahydroxybenzophenone, 2,3,4,5,2 ', 4', 6'-heptahydroxybenzophenone, 2,3, 4,2 ', 4'-pentahydroxy-5-methylbenzophenone, 2,3,4,2', 4'-pentahydroxy-5-ethylbenzophenone, 2,3,4,2 ', 4 '-Pentahydroxy-5-n-propylbenzophenone, 2,3,4,
2 ', 4'-pentahydroxy-5-n-butylbenzophenone, 2,3,4,2', 5'-pentahydroxy-5-methylbenzophenone, 2,3,4,2 ', 5 '-Pentahydroxy-5-n-propylbenzophenone, 2,3,4,2', 6'-
Pentahydroxy-5-methylbenzophenone, 2,3,4,
2 ', 6'-pentahydroxy-5-n-propylbenzophenone, 2,3,4,3', 4'-pentahydroxy-5-methylbenzophenone, 2,3,4,3 ', 4 '-Pentahydroxy-5-n-propylbenzophenone, 2,3,4,3', 5 '
-Pentahydroxy-5-methylbenzophenone, 2,3,
4,3 ', 5'-pentahydroxy-5-n-propylbenzophenone, 2,3,4,2', 3 ', 4'-hexahydroxy-
5-methylbenzophenone, 2,3,4,2 ', 3', 4'-hexahydroxy-5-n-propylbenzophenone, 2,3,
4,3 ', 4', 5'-hexahydroxy-5-methylbenzophenone, 2,3,4,3 ', 4', 5'-hexahydroxy-5
-N-propylbenzophenone, 2,3,4,2 ', 4', 6'-
Hexahydroxy-5-methylbenzophenone, 2,3,4,
2 ', 4', 6'-hexahydroxy-5-n-propylbenzophenone, 2,3,2 ', 3', 4'-pentahydroxy-
4-methoxybenzophenone, 2,3,2 ', 3', 4'-pentahydroxy-4-ethoxybenzophenone, 2,3,2 ',
3 ', 4'-pentahydroxy-4-n-propoxybenzophenone, 2,3,2', 3 ', 4'-pentahydroxy-4
-N-butoxybenzophenone, 2,3,3 ', 4', 5'-pentahydroxy-4-methoxybenzophenone, 2,3,
3 ', 4', 5'-pentahydroxy-4-n-propoxybenzophenone, 2,3,2 ', 4', 6'-pentahydroxy-4-methoxybenzophenone, 2,3,2 ' , 4 ', 6'-pentahydroxy-4-n-propoxybenzophenone,
2,3,4,2 ', 4'-pentahydroxy-5-chlorobenzophenone, 2,3,4,2', 4'-pentahydroxy-5-bromobenzophenone, 2,3,4, 2 ', 6'-pentahydroxy-5-chlorobenzophenone, 2,3,4,2', 6'-pentahydroxy-5-bromobenzophenone, 2,3,4,3 ',
4 ', 5'-hexahydroxy-5-chlorobenzophenone, 2,3,4,3', 4 ', 5'-hexahydroxy-5-bromobenzophenone, 2,3,4,2', 4'-pentahydroxy-5-cyanobenzophenone, 2,3,4,3 ', 4', 5'-hexahydroxy-5-cyanobenzophenone, 2,3,4,
2 ', 4'-pentahydroxy-5-nitrobenzophenone, 2,3,4,3', 4 ', 5'-hexahydroxy-5-nitrobenzophenone, 2,4,3', 4 '5,5'-pentahydroxy-5-acetylbenzophenone, 2,4,3 ', 4', 5'-
Pentahydroxy-5-benzoylbenzophenone, 2,
3,4,3 ', 4', 5'-hexahydroxy-5-acetylbenzophenone, 2,3,4,3 ', 4', 5'-hexahydroxy-5-benzoylbenzophenone, 2, 4,3 ', 4', 5'-
Pentahydroxy-5-benzylbenzophenone, 2,3,
4,3 ', 4', 5'-Hexahydroxy-5-benzylbenzophenone, 2,3,4,2 ', 4'-pentahydroxybenzophenone, 2,3,4,2', 6 ' -Pentahydroxybenzophenone, 2,3,4,3 ', 4', 5'-hexahydroxybenzophenone, 2,4,6,2 ', 6'-pentahydroxybenzophenone, 2,4, 6,3 ', 4', 5'-hexahydroxybenzophenone, 2,3,4,5,4'-pentahydroxybenzophenone, 2,3,4,5,2 ', 6'-hexahydroxy Benzophenone, 2,3,4,5,3 ', 4', 5'-heptahydroxybenzophenone, 2,3,4,2 ', 4'-pentahydroxy-5-methylbenzophenone, 2 , 3,4,2 ', 6'-pentahydroxy-5-methylbenzophenone, 2,3,4,3', 4 ', 5'-
Hexahydroxy-5-methylbenzophenone, 2,3,
3 ', 4', 5'-pentahydroxy-4-methoxybenzophenone, 2,3,4,3 ', 4', 5'-hexahydroxy-5
-Chlorobenzophenone, 2,3,4,3 ', 4', 5'-hexahydroxy-5-acetylbenzophenone, 2,3,4,3 ',
4 ', 5'-hexahydroxy-5-benzoylbenzophenone, 2,3,4,2', 6'-pentahydroxybenzophenone, 2,3,4,3 ', 4', 5'-hexa Hydroxybenzophenone, 2,4,6,3 ', 4', 5'-hexahydroxybenzophenone, 2,3,4,3 ', 4', 5'-hexahydroxy-5
-Methylbenzophenone, 2,3,3 ', 4', 5'-pentahydroxy-4-methoxybenzophenone, 2,3,4,3 ',
Of (poly) hydroxyphenylalkylketone or (poly) hydroxyphenylarylketone such as 4 ', 5'-hexahydroxy-5-benzoylbenzophenone
1,2-benzoquinonediazide-4-sulfonic acid ester, 1,2-naphthoquinonediazide-4-sulfonic acid ester and 1,2-naphthoquinonediazide-5-sulfonic acid ester: bis (p-hydroxyphenyl) methane,
Bis (2,4-dihydroxyphenyl) methane, bis (2,
3,4-trihydroxyphenyl) methane, 2,2-bis (p
Bis [(poly) such as -hydroxyphenyl) propane, 2,2-bis (2,4-dihydroxyphenyl) propane and 2,2-bis (2,3,4-trihydroxyphenyl) propane
1,2-benzoquinonediazide-4-sulfonic acid ester, 1,2-naphthoquinonediazide-4-sulfonic acid ester and 1,2-naphthoquinonediazide-5-sulfonic acid ester of hydroxyphenyl] alkane; 3,5-dihydroxy Alkyl (poly) hydroxybenzoates such as lauryl benzoate, phenyl 2,3,4-trihydroxybenzoate, propyl 3,4,5-trihydroxybenzoate, phenyl 3,4,5-trihydroxybenzoate or 1,2- of (poly) hydroxybenzoic acid aryl ester
Benzoquinonediazide-4-sulfonic acid ester, 1,2
-Naphthoquinonediazide-4-sulfonic acid ester and 1,2-naphthoquinonediazide-5-sulfonic acid ester; bis (2,5-dihydroxybenzoyl) methane, bis (2,3,4-trihydroxybenzoyl) methane, bis ( 2,4,6-trihydroxybenzoyl) methane, p-bis (2,5-dihydroxybenzoyl) benzene, p-bis (2,3,4-trihydroxybenzoyl) benzene, p
1,2-benzoquinonediazido-4-sulfonic acid ester of bis [(poly) hydroxybenzoyl] alkane or bis-[(poly) hydroxybenzoyl] benzene, such as -bis (2,4,6-trihydroxybenzoyl) benzene; 1,2-naphthoquinonediazide-4-sulfonic acid ester and 1,2-naphthoquinonediazide-5-sulfonic acid ester; ethylene glycol-di (3,5-dihydroxybenzoate), polyethylene glycol-di (3,4,5- 1,2-benzoquinonediazide-4-sulfonic acid ester, 1,2-naphthoquinonediazide-4-sulfonic acid ester and 1,2 of (poly) ethylene glycol-di [(poly) hydroxybenzoate] such as trihydroxybenzoate) -Naphthoquinonediazide-5
-Sulfonic acid esters and the like. In addition to these compounds, "Light-Sensitive Systems" by J. Kosar, 339-3
52 (1965), John Wile & Sons (New York) and WSD
"Photoresist" by eForest, 50, (1975), McGraw-Hill I
nc., (New York) can also be used.

These other 1,2-quinonediazide compounds can also be used after acylation or sulfonylation modification by, for example, the method described in JP-A-62-178562.

A typical example of the alkali-soluble resin (A) used in the present invention is an alkali-soluble novolak resin (hereinafter, simply referred to as “novolak resin”). The novolak resin is obtained by polycondensing phenols and aldehydes in the presence of an acid catalyst.

Examples of the phenols include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol,
p-butylphenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 3,4-xylenol, 3,
5-xylenol, 2,3,5-trimethylphenol, p-
Phenylphenol, hydroquinone, catechol, resorcinol, 2-methylresorcinol, pyrogallol, α-naphthol, bisphenol A, dihydroxybenzoic acid ester, gallic acid ester and the like are used.
Of these phenols, phenol, o-cresol, m-cresol, p-cresol, 2,5-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, resorcinol, 2-methylresorcinol and bisphenol A is preferred. These phenols are used alone or in combination of two or more.

Examples of the aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, propylaldehyde, 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 and the like are used. Of these compounds, formaldehyde, acetaldehyde and benzaldehyde are preferred. These aldehydes are used alone or in combination of two or more.

The aldehyde is used preferably in a ratio of 0.7 to 3 mol, particularly preferably 0.7 to 2 mol, per mol of the phenol.

As the acid catalyst, for example, an inorganic acid such as hydrochloric acid, nitric acid or sulfuric acid, or an organic acid such as formic acid, acid or acetic acid is used. The use amount of these acid catalysts is preferably 1 × 10 ^{-4 to} 5 × 10 ^-1 mol per 1 mol of phenols.

In the condensation reaction, water is usually used as a reaction medium, but when the phenols used in the condensation reaction do not dissolve in the aqueous solution of the aldehyde and become heterogeneous from the beginning of the reaction, a hydrophilic medium is used as the reaction medium. Solvents can also be used. Examples of these hydrophilic solvents include alcohols such as methanol, ethanol, propanol and butanol, and cyclic ethers such as tetrahydrofuran and dioxane. The amount of these reaction media used is usually 20 to 1000 per 100 parts by weight of the reaction raw materials.
Parts by weight.

The reaction temperature of the condensation reaction can be appropriately adjusted according to the reactivity of the reaction raw materials, but is usually 10 to 200 ° C, preferably 70 to 150 ° C.

After the completion of the condensation reaction, the internal temperature is generally raised to 130 ° C. to remove unreacted raw materials, acid catalyst and reaction medium present in the system.
The temperature is raised to 230230 ° C., and the volatile components are distilled off under reduced pressure.

After completion of the condensation reaction, the reaction mixture is dissolved in the hydrophilic solvent, water, n-hexane, and added to a precipitant such as n-heptane to precipitate a novolak resin,
The precipitate can be separated and collected.

Examples of the alkali-soluble resin (A) other than the novolak resin used in the present invention include, for example, polyhydroxystyrene or a derivative thereof, a styrene-maleic anhydride copolymer, polyvinylhydroxybenzoate, a carboxyl group-containing methacrylic resin, and the like. .

These alkali-soluble resins (A) may be used alone or
Used as a mixture of more than one species.

The composition of the present invention may contain a sensitizer in order to improve the sensitivity as a resist. Examples of the sensitizer include 2H-pyrido [3,2-b] -1,4-oxazin-3 [4H] ones and 10H-pyrido [3,2-b] [1,4]-.
Benzothiazines, urazoles, hydantoins, barbituric acids, glycine anhydrides, 1-hydroxybenzotriazoles, alloxanes, maleimides and the like can be mentioned. The compounding amount of the sensitizer is usually 1 to 100 parts by weight, preferably 4 to 60 parts by weight, based on 100 parts by weight of the 1,2-quinonediazide compound.

Further, a surfactant may be added to the composition of the present invention in order to improve coatability, for example, striation or developability of a radiation-irradiated portion after formation of a dried coating film. Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether and polyoxyethylene oleyl ether; polyoxyethylenes such as polyoxyethylene octyl phenol ether and polyoxyethylene nonyl phenol ether. Ethylene alkyl phenol ethers; and polyethylene glycol dialkyl ethers such as polyethylene glycol dilaurate and polyethylene glycol distearate (nonionic surfactants); Eftup EF301, EF303, EF352 (manufactured by Shin-Akita Chemical Co., Ltd.), MegaFac F171 F-172, F17
3 (Dainippon Ink Co., Ltd.), Florado FC430, FC431
(Manufactured by Sumitomo 3M Limited), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC10
5, fluorine-based surfactant such as SC106 (manufactured by Asahi Glass Co., Ltd.); organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), acrylic acid-based or methacrylic acid-based (co)
Polymer polyflow Nos. 75 and 95 (manufactured by Kyoeisha Yushi Kagaku Kogyo KK) and the like are used. The amount of the surfactant to be added depends on the amount of the alkali-soluble resin (A) and 1,2 in the composition of the present invention.
The amount is usually at most 2 parts by weight, preferably at most 1 part by weight, per 100 parts by weight of the quinonediazide compound (B).

Further, the composition of the present invention may contain a coloring agent, an adhesion aid, a storage stabilizer, an antifoaming agent, and the like, if necessary.

The composition of the present invention is prepared by dissolving a predetermined amount of the alkali-soluble resin (A), the 1,2-quinonediazide compound (B) and the various compounding agents in a solvent, for example, in a solvent having a pore size of 0.1.
It is prepared by filtering through a filter of about 2 μm.

Examples of the solvent used in this case include ethylene glycol alkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol dipropyl ether. ,
Diethylene glycol dialkyl ethers such as diethylene glycol dibutyl ether; ethylene glycol alkyl acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; propylene glycol alkyl ether acetate such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and propylene glycol propyl ether acetate. Aromatic hydrocarbons such as toluene and xylene; ketones such as methyl ethyl ketone and cyclohexanone; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate;
Ethyl hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl oxyacetate, 2-hydroxy-3-
Methyl methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate,
Use esters such as methyl-3-methoxybutyl propionate, 3-methyl-3-methoxybutyl butyrate, ethyl acetate, butyl acetate, methyl acetoacetate, and ethyl acetoacetate; and amides such as dimethylformamide and dimethylacetamide. be able to. These solvents may be used alone or in combination of two or more. Furthermore, benzyl ethyl ether, dihexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, acetonylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate And high boiling solvents such as diethyl maleate, [gamma] -butyrolactone, ethylene carbonate, propylene carbonate, and phenyl cellosolve acetate.

Further, in the composition of the present invention, to visualize the latent image of the radiation-irradiated portion, a colorant to reduce the influence of the radiation upon irradiation, and an adhesion aid to improve the adhesiveness, Further, an antifoaming agent or the like can be added as needed.

Examples of the developing solution of the composition of the present invention include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia, and primary amines such as ethylamine and n-propylamine.
Secondary amines such as tertiary amines, diethylamine and di-n-propylamine; tertiary amines such as triethylamine and methyldiethylamine; alcohol amines such as dimethylethanolamine and triethanolamine; tetramethylammonium hydroxide Quaternary ammonium salts such as tetraethylammonium hydroxide, trimethyl-hydroxyethylammonium hydroxide, or pyrrole, piperidine, 1,8-diazabicyclo (5,4,0) -7-undecene, 1,5-diazabicyclo ( An alkaline aqueous solution obtained by dissolving a cyclic amine such as (4,3,0) -5-nonane is used.

Further, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent, for example, an alcohol such as methanol or ethanol or a surfactant to the developer may be used as the developer.

 Hereinafter, the present invention will be described in detail with reference to examples.

[Examples] Example 1 (1) In a light-shielded flask equipped with a stirrer, a dropping funnel and a thermometer, 12.2 g of 2,2 ', 3,4-tetrahydroxybenzophenone and 1,2-naphtho were added. Quinonediazide-5
-47.0 g of sulfonic acid chloride [equivalent to 1,2-naphthoquinonediazide-5-sulfonic acid chloride / 2,2 ', 3,4-tetrahydroxybenzophenone = 3 (molar ratio)]
Further, 277 g of dioxane was added and dissolved with stirring. Separately, 19.5 g of triethylamine was charged into a dropping funnel, and the separable flask was immersed in a water bath maintained at 30 ° C. When the internal temperature became constant at 30 ° C, triethylamine was slowly added dropwise. After adding triethylamine so that the internal temperature does not exceed 35 ° C., water was added to and dissolved in the precipitated triethylamine hydrochloride, and the filtrate was poured into a large amount of diluted hydrochloric acid to precipitate a 1,2-quinonediazide compound. .
This was filtered, recovered and vacuum dried at 40 ° C. overnight. The yield obtained by measuring the dry weight was 98%.

As a result of composition analysis of the thus obtained 1,2-quinonediazide compound, the proportion of triester was 66% by weight, the proportion of tetraester was 29% by weight, and the proportion of diester was 4%.
% By weight, and the proportion of monoester was 1% by weight.

The composition distribution of the 1,2-quinonediazide compound was determined by gel permeation chromatography (hereinafter referred to as “GP
C "). The GPC measurement conditions are as follows.

Separation column: Column with an inner diameter of 20 mm and a length of 60 cm packed with polystyrene gel having an average pore size of 7 mm Eluent: Tetrahydrofuran Flow rate: 2 ml / min Detector: Showa Denko Shodex RISE-31 differential refractometer Separation column temperature: 25 ° C Sample injection amount: About 1.0% by weight of tetradrofuran solution in 100
μl (2) 54 g (0.5 mol) of m-cresol, 3,5-xylenol 2 in a flask equipped with a stirrer, condenser and thermometer
44 g (2.0 mol), 385 g of 37% by weight formaldehyde aqueous solution
After charging 0.22 g of oxalic acid, the flask was immersed in an oil bath and reacted for 1 hour while maintaining the internal temperature at 100 ° C. Thereafter, m-cresol 216 g (2.0 mol), 3,5
-61 g (0.5 g mol) of xylenol was continuously charged into the flask as the reaction proceeded, and reacted for 2 hours. Next, the novolak resin was dissolved in methanol, water was gradually added thereto to precipitate the novolak resin, and the precipitate was dried to obtain a novolak resin.

(3) 20 g of the novolak resin obtained in (2), (1)
6 g of the 1,2-quinonediazide compound and 60 g of ethyl cellosolve acetate obtained in the above were dissolved by sufficiently stirring at room temperature, followed by filtration through a membrane filter having a pore size of 0.2 μm to prepare a solution of the composition of the present invention. This solution was applied on a silicon wafer by a spinner and prebaked at 90 ° C. for 2 minutes to form a 1.2 μm thick resist layer. Then
Exposure was performed with a stepper (NSR1505G4D, manufactured by Nippon Kogaku Kogyo Co., Ltd.), development was performed with a 2.38% by weight aqueous solution of tetramethylammonium hydroxide at 25 ° C. for 60 seconds, and rinsing with water to form a resist pattern. Here the resist pattern is 1.
Exposure time (hereinafter referred to as “sensitivity”) for accurately forming a line and space pattern of 2 μm or more was determined to be 0.29 seconds, which was good, and no scum (resist residue) was observed in the irradiated area. A resist pattern having a line width of 0.55 μm could be resolved. The remaining film ratio (resist film thickness after development / resist film thickness before development × 100%) is also 98%.
And it was excellent.

Examples 2-3 In a light-shielded flask equipped with a stirrer, a dropping funnel and a thermometer, the compounds shown in Table 1 were used in the proportions shown in Table 1 in the same manner as in Example 1 (1). A 1,2-quinonediazide compound was obtained.

Table 1 shows the results of a composition analysis by GPC of the 1,2-quinonediazide compound thus obtained.

Next, a solution of the composition of the present invention was prepared in the same manner as in Example 1 (3) except that the novolak resin obtained in Example 1 (2) and the 1,2-quinonediazide compound were used.

Next, exposure, development and rinsing were performed in the same manner as in Example 1 (3) to form a resist pattern. The results are shown in Table 1.

Comparative Example 1 In Example 1 (1), 1,2-naphthoquinonediazide was used in which 11.5 g of 2,3,4-trihydroxybenzophenone was used instead of 2,2 ', 3,4-tetrahydroxybenzophenone. The amount of -5-sulfonic acid chloride used was 34.9 g, the amount of triethylamine used was 14.5 g, and the others were as in Example 1.
A 1,2-quinonediazide compound was obtained in the same manner as in (1).

Next, a solution of a resist composition was prepared in the same manner as in Example 1 (3) except that the novolak resin obtained in Example 1 (2) and the 1,2-quinonediazide compound were used.

Next, exposure, development and rinsing were performed in the same manner as in Example 1 (3) to form a resist pattern. The results are shown in Table 1.

Comparative Example 2 In Example 1 (1), except that instead of 2,2 ', 3,4-tetrahydroxybenzophenone, 12.3 g of 2,3,4,4'-tetrahydroxybenzophenone was used. Example 1
A 1,2-quinonediazide compound was obtained in the same manner as in (1).

Next, a solution of a resist composition was prepared in the same manner as in Example 1 (3) except that the novolak resin obtained in Example 1 (2) and the 1,2-quinonediazide compound were used.

Next, exposure, development and rinsing were performed in the same manner as in Example 1 (3) to form a resist pattern. The results are shown in Table 1.

Examples 4 to 5 A flask equipped with a stirrer, a condenser and a thermometer was charged with phenols, 385 g of a 37% by weight aqueous solution of formaldehyde and 0.22 g of oxalic acid having a mixing ratio shown in Table 3, and then charged.
This flask was immersed in an oil bath and reacted for 1 hour while maintaining the internal temperature at 100 ° C. Thereafter, additional phenols shown in Table 3 were continuously charged into the flask with the progress of the reaction and reacted for 2 hours. Next, the novolak resin was dissolved in methanol, water was gradually added to the solution to precipitate the novolak resin, and the precipitate was dried to obtain a novolak resin. Next, the novolak resin and Example 1 were used.
Using the 1,2-quinonediazide compound obtained in (1), a solution of the composition of the present invention was prepared in the same manner as in Example 1 (3) except for the above.

Next, exposure, development and rinsing were performed in the same manner as in Example 1 (3) to form a resist pattern. The results are shown in Table 2.

(Effects of the Invention) The positive-type radiation-sensitive resin composition of the present invention has high sensitivity, high resolution, high residual film ratio, and excellent developability, and can be composed of ultraviolet rays, far ultraviolet rays, X-rays, electron beams, and molecules. It is sensitive to radiation such as X-rays, γ-rays, synchrotron radiation, and proton beams, and is suitable as a resist for producing integrated circuits, particularly a positive resist for high integration.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Takao Miura 2-11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd. (56) References JP-A-63-180947 (JP, A) JP-A Sho 62-280737 (JP, A) JP-A-58-150948 (JP, A) JP-A-57-135947 (JP, A) JP-A-62-150245 (JP, A) JP-A-62-153950 (JP, A) A)

Claims (1)

(57) [Claims] (1) A 1,2-quinonediazide compound mainly comprising (A) an alkali-soluble resin and (B) a 1,2-quinonediazidesulfonic acid ester of 2,2 ', 3,4-tetrahydroxybenzophenone. And the 1,2-quinonediazidesulfonic acid ester contains 0 to 10% by weight of a monoester and 0 to 10% by weight of a diester.
A positive radiation-sensitive resin composition comprising 30% by weight, 20 to 70% by weight of a triester and 5 to 70% by weight of a tetraester.