JPH045378B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a positive photosensitive resin composition, and more specifically, to a positive photosensitive resin composition, and more specifically to an alkali-soluble resin and a specific one or two.
- A positive photosensitive resin composition containing a quinonediazide compound, which has high sensitivity, high resolution, and high residual film rate, has excellent developability, and is suitable as a heat-resistant photoresist for producing integrated circuits. . [Prior Art] Conventionally, as a photoresist for manufacturing integrated circuits, a negative photoresist in which a bisazide compound is blended with cyclized isoprene rubber is known. However, this negative type photoresist has a limitation in resolution, and therefore has the disadvantage that it cannot sufficiently respond to higher integration of integrated circuits. On the other hand, since positive photoresists have superior resolution in contrast to negative photoresists, they are considered to be able to fully respond to higher integration of integrated circuits. Currently, positive photoresists commonly used in this field are made by blending an alkali-soluble resin with a 1,2-quinonediazide compound as a photosensitizer. However, conventional positive photoresists
Satisfactory results have not always been obtained in various performances such as sensitivity, resolution, residual film rate, and heat resistance. [Problems to be Solved by the Invention] The purpose of the present invention is to eliminate the drawbacks of the above-mentioned prior art, and to provide a positive-working photosensitive material that has high sensitivity, high resolution, high residual film rate, excellent developability, and heat resistance. An object of the present invention is to provide a synthetic resin composition. As a result of extensive research to achieve this objective, the present inventors have discovered that the above-mentioned drawbacks can be improved by blending a specific 1,2-quinonediazide compound as a photosensitizer into an alkali-soluble resin. We have arrived at the present invention. [Means for Solving the Problems] The positive photosensitive resin composition of the present invention has the general formula () with respect to 100 parts by weight of the alkali-soluble resin. or general expression () [In the formula, a, b and c are the same or different, and 1
an integer of ~4, R ₁ , R ₂ and R ₃ are the same or different and each has 1 to 1 carbon atoms, such as a halogen atom such as a hydrogen atom, a chlorine atom, or a bromine atom, an alkyl group, preferably a methyl group, an ethyl group, a propyl group, etc. 4 alkyl group,
Aryl groups such as phenyl groups and naphthyl groups, aralkyl groups such as benzyl groups, alkoxy groups, preferably alkoxy groups having 1 to 3 carbon atoms such as methoxy groups,
an alloxyl group, preferably an alloxyl group having 6 to 9 carbon atoms such as a phenoxy group, an aralkoxy group, preferably an aralkoxy group having 7 to 10 carbon atoms such as a benzyloxy group, a cyano group or a nitro group, R ₄ is an alkyl group, preferably is an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, an aryl group such as a phenyl group, an aralkyl group such as a benzyl group, and Z is a residue of polyethylene glycol, polypropylene glycol, etc. An oxyalkylene group (-( _CpH2pO ) _rCpH2p- , in which p preferably means an integer of 1 to 4, and r preferably means an integer of 1 to 100) or methylene,
1,2 in all or part of the hydroxyl group of a compound represented by an alkylene group ( _-CqH2p- , q in the formula preferably means an integer of 1 to 4) such as ethylene, propylene, butylene, etc. -1 obtained by condensing quinonediazide sulfonyl chloride,
The present invention relates to a positive photosensitive resin composition containing 5 to 100 parts by weight of at least one 2-quinonediazide compound (A). The alkali-soluble resin used in the present invention is not particularly limited, but includes, for example, novolak resin obtained from phenol and formaldehyde, novolak resin obtained from cresol and formaldehyde, hydroxystyrene polymer, aminostyrene polymer, ethylenically unsaturated carboxylic acid. and other monoolefin compounds. The 1,2-quinonediazide compound (A) used in the present invention is a compound represented by the above general formula () or (), and a 1,2-naphthoquinonediazide-
After carrying out a condensation reaction of 1,2-quinonediazide sulfonyl chloride such as 4-sulfonyl chloride, 1,2-naphthoquinonediazide-5-sulfonyl chloride, and 1,2-benzoquinonediazide-4-sulfonyl chloride in the presence of a basic catalyst. , obtained by purification. The amount of 1,2-quinonediazide sulfonyl chloride used in the condensation reaction is appropriately adjusted depending on the number of hydroxyl groups in the compound represented by the general formula () or (), and is usually 1 equivalent per equivalent of the number of hydroxyl groups. , 1 mol of 2-quinonediazide sulfonyl chloride is used. Examples of the basic catalyst used in the condensation reaction include inorganic alkalis such as sodium hydroxide, potassium hydroxide, and sodium carbonate, and organic amines such as diethylamine and triethylamine. The amount of these basic catalysts used is usually 1 to 2 times the mole, preferably 1 to 1.3 times the mole of 1,2-quinonediazide sulfonyl chloride used. The condensation reaction is usually carried out in the presence of a solvent, and water, dioxane, diethyl ether, tetrahydrofuran, acetone, methyl ethyl ketone, etc. are used as the solvent. The amount of solvent used is determined by the compound represented by the general formula () or ().
It is usually 100 to 1000 parts by weight per 100 parts by weight. The condensation reaction temperature varies depending on the solvent used, but is generally -20 to 60°C, preferably 0 to 40°C.
It is. As the compound represented by the general formula (),
For example, ethylene glycol di(2-hydroxybenzoate), ethylene glycol di(3-hydroxybenzoate),
hydroxybenzoate), ethylene glycol di(4-hydroxybenzoate), ethylene glycol di(2,3-dihydroxybenzoate), ethylene glycol di(2,6-dihydroxybenzoate), ethylene glycol di(2,6-dihydroxybenzoate)
Di(3,5-dihydroxybenzoate), Ethylene glycol-di(3,4,5-trihydroxybenzoate), Ethylene glycol-di(2
-nitro-3,4,5-trihydroxybenzoate), ethylene glycol-di(2-cyano-
3,4,5-trihydroxybenzoate), ethylene glycol-di(2,4,6-trihydroxybenzoate), diethylene glycol-di(2,3-dihydroxybenzoate), diethylene glycol-di(2-hydroxy-3-methyl benzoate), triethylene glycol-di(3-hydroxy-4-methylbenzoate), tetraethylene glycol-di(4-chloro-2-
hydroxybenzoate), polyethylene glycol di(5-chloro-2-hydroxybenzoate), propylene glycol di(3-chloro-4-hydroxybenzoate), polypropylene glycol di(3-hydroxy-4-nitrobenzoate), polypropylene glycol-di(2-hydroxy-5-methoxybenzoate),
1,3-propanediol-di(4-hydroxy-3-methoxybenzoate), 1,3-propanediol-di(3,4,5-trihydroxybenzoate), 1,4-butanediol-di(3
-hydroxybenzoate), 1,4-butanediol-di(5-bromo-2-hydroxybenzoate), polytetrahydrofuran glycol-
di(3,4,5-trihydroxybenzoate),
Examples include neopentyl glycol di(3,4,5-trihydroxybenzoate). As the compound represented by the general formula (),
For example, ethylene glycol-monomethyl-mono(3,4,5-trihydroxybenzoate), ethylene glycol-monoethyl-mono(3,4,
5-trihydroxybenzoate), ethylene glycol monoethyl mono(2,4,6-trihydroxybenzoate), diethylene glycol monoethyl mono(2,3-dihydroxybenzoate), triethylene glycol monoethyl mono(3,5 -dihydroxybenzoate), ethylene glycol monophenyl mono(3,4,5-trihydroxybenzoate), and the like. The above 1,2-quinonediazide compound (A) can be used alone or in combination of two or more, and the blending amount of the 1,2-quinonediazide compound (A) is based on 100 parts by weight of the alkali-soluble resin. The amount is 5 to 100 parts by weight, preferably 10 to 50 parts by weight. If this amount is less than 5 parts by weight, the residual film rate after development will be insufficient, the resulting pattern will be easily deformed by heat, and it will not be possible to obtain a photosensitive resin composition with higher resolution. Also, if the amount added exceeds 100 parts by weight,
A highly sensitive photosensitive resin composition cannot be obtained. The positive photosensitive resin composition of the present invention contains 1,2
- A 1,2-quinonediazide compound other than the quinonediazide compound (A), for example, an alkali-soluble resin
100 parts by weight or less, preferably 50 parts by weight
It can be blended in an amount of not more than 20 parts by weight, more preferably not more than 20 parts by weight. These 1,2-quinonediazide compounds include US Pat. No. 3,046,118
2,3,4-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,3,4- 1,2-naphthoquinone diazide- in all or part of the hydroxy group of trihydroxyphenylmethylketone, 3,4,5-trihydroxyphenylmethylketone, 2,4,6-trihydroxyphenylmethylketone, etc. 4-sulfonyl chloride, 1,2-naphthoquinonediazide-5-sulfonyl chloride,
Examples include compounds obtained by subjecting 1,2-benzoquinonediazide-5-sulfonyl chloride to a condensation reaction. In order to improve developability, storage stability of the composition, etc., the composition of the present invention may contain, for example, a copolymer of styrene and maleic anhydride, a copolymer of styrene and maleic anhydride, a copolymer of styrene and maleic anhydride, a natural resin such as rosin or silica, etc. ,
Synthetic resins such as methacrylic acid or copolymers with these alkyl esters, acrylic acid ester polymers, vinyl ether polymers, vinyl acetate polymers, vinyl alcohol polymers, vinyl pyrrolidone polymers, etc. are added to 100 parts by weight of an alkali-soluble resin. It can be blended in an amount of 1 to 50 parts by weight, preferably 5 to 30 parts by weight. Furthermore, storage stabilizers, pigments, and the like may be added to the composition of the present invention, if necessary. A pattern is formed by applying the positive photosensitive resin composition of the present invention onto a substrate to be microfabricated, partially irradiating it with activating radiation, such as ultraviolet rays, and developing it with a developer. can do.
When applying the composition, depending on the selected substrate, an adhesion aid such as hexamethyldisilazane or chloromethylsilane may be applied to the substrate in order to improve the adhesion between the substrate and the composition. . As a method for applying the composition to the substrate, for example, the composition is dissolved by adding an appropriate solvent so that the concentration of the composition becomes 5 to 50% by weight, and then the composition is applied by spin coating, flow coating, roll coating, etc. An example of this method is to apply it by. Examples of solvents used in this case include ketones such as cyclopentanone, cyclohexanone, and diacetone alcohol, alcohols such as n-butanol, ethers such as dioxane, ethylene glycol dimethyl ether, and ethyl gelicol diethyl ether, and ethyl glycol. Alcohol ethers such as monomethyl ether and ethylene glycol monoethyl ether,
Esters such as butyl acetate, cellosolve acetate, methoxyethyl acetate, halogenated hydrocarbons such as 1,1,2-trichloroethylene, polar solvents such as dimethylacetamide, dimethylsulfoxide, dimethylformamide, N-methylpyrrolidone, etc. are used alone. used separately or in combination.
Furthermore, high boiling point solvents described in Japanese Patent Application No. 133108/1982, such as benzyl ethyl ether, diethylene glycol monomethyl ether, acetonyl acetone, caproic acid, 1-octanol, benzyl alcohol propylene carbonate, etc., may be used in combination. . Examples of the developer include aqueous solutions of inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, trisodium phosphate, and sodium hydrogen phosphate, n-propylamine, di-n -propylamine, di-n-butylamine, methyldiethylamine, pyrrole, 2,5-dimethylpyrrole,
Aqueous solutions of amines such as β-picoline, collidine, piperidine, piperazine, and triethylenediamine, aqueous solutions of alcohol amines such as dimethylethanolamine, triethanolamine, and diethylhydroxyamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, etc. Examples include aqueous solutions of quaternary ammonium salts and aqueous ammonia. Furthermore, an appropriate amount of alcohols such as methanol and ethanol, sulfite stabilizers, or surfactants may be added to the developer. [Examples] Hereinafter, the present invention will be explained in detail with reference to Examples, but the present invention is not limited to these Examples in any way. Example 1 (1) Synthesis of novolac resin In a 500 ml three-necked separable flask, m-
After charging 75 g of cresol and 25 g of p-cresol, 66 ml of a 37% by weight formalin aqueous solution and 0.04 g of oxalic acid were added. While stirring, immerse the separable flask in an oil bath to raise the reaction temperature to 100℃.
The temperature was adjusted to ℃ and allowed to react for 10 hours. After the reaction is complete,
Reduce the pressure to 30mmHg to distill off the water, and then lower the internal temperature.
The temperature was raised to 130°C to remove unreacted substances. The reaction product, molten alkali-soluble novolac resin, was then returned to room temperature and recovered. (2) Synthesis of photosensitizer A: 56.4 g of gallic acid in a 500 ml three-necked flask.
After adding 6.2g of ethylene glycol,
150 ml of dioxane, 150 ml of benzene and 5 ml of concentrated sulfuric acid were added. Next, this three-necked flask was immersed in an oil bath and reacted for 20 hours at an oil bath temperature of 120°C. The produced water was drained out of the reaction system using a water separator. After the reaction is complete, pour the reaction system into ice water,
The product ethylene glycol-di(3,4,5-trihydroxybenzoate) at around 0°C
was precipitated, separated by filtration, and purified by repeated washing with water. A 500ml three-necked separable flask under light-shielding conditions.
11.0 g of ethylene glycol di(3,4,5-trihydroxybenzoate), 1,2-naphthoquinonediazide-5-sulfonyl chloride
24.2 g and 200 ml of acetone were charged and dissolved. 10.9 g of triethylamine was gradually added to this solution while stirring, and the mixture was allowed to react at room temperature for 1 hour. After the reaction, the contents were dropped into a large amount of 1% by weight hydrochloric acid solution to precipitate the product, and after washing with water, the product was heated at 40°C.
After vacuum drying for 20 hours, ethylene glycol-di(3,4,5-trihydroxybenzoate)-
1,2-naphthoquinonediazide-5-sulfonic acid triester (sensitizer A) was obtained. (3) Preparation and evaluation of photosensitive resin composition 20 g of alkali-soluble novolak resin obtained in (1) and 5 g of photosensitizer A obtained in (2) under light shielding.
was dissolved in 75 g of cellosolve acetate and filtered through a membrane filter with a pore size of 0.2 μm to prepare a solution of a photosensitive resin composition. The obtained solution was applied onto a silicon oxide film wafer using a spinner, and then heated in an oven for 90 minutes.
A photosensitive resin composition film having a thickness of 1.2 μm was obtained by prebaking at °C for 25 minutes. A test pattern mask manufactured by Toppan Printing Co., Ltd. was placed in close contact with the wafer, irradiated with 18.9 mJ/cm ² of ultraviolet light (measured with a model 205 UV power meter manufactured by Optical Associates, Inc.), and treated with a 1.6% by weight aqueous solution of tetramethylammonium hydroxide. 60℃
When developed for seconds, a pattern with a line width of 0.5 μm could be resolved. The residual film rate in the unexposed area is extremely high at 98.8%, and there is no development residue, and the pattern is clear and has excellent developability.
After post-baking in an oven for a minute, no pattern collapse was observed. Examples 2 to 6 (1) Synthesis of photosensitizers B to F The following photosensitizers B to F were prepared in the same manner as in Example 1 (2).
F was synthesized. Photosensitizer B: 1,3-propanediol-di(3,4,5-trihydroxybenzoate)
11.4g and 1,2-naphthoquinonediazide-5
-1,3-propanediol-di(3,
4,5-trihydroxybenzoate)-1,
2-naphthoquinonediazide-5-sulfonic acid tetraester. Photosensitizer C: diethylene glycol-di(2,3
-dihydroxybenzoate) 11.3g and 1,
Diethylene glycol-di(2,3-dihydroxybenzoate)-1,2-naphthoquinonediazide-5-sulfonic acid triester, which is a reaction product with 24.2 g of 2-naphthoquinonediazide-5-sulfonyl chloride. Photosensitizer D: 1,4-butanediol-di(3-
hydroxybenzoate) 13.2g and 1,2-
1,4-butanediol-di(3-hydroxybenzoate)-1,2-naphthoquinonediazide-5, which is a reaction product with 21.5 g of naphthoquinonediazide-5-sulfonyl chloride.
-Sulfonic acid diester. Photosensitizer E: 9.1 g of ethylene glycol di(4-hydroxybenzoate) and 16.1 g of 1,2-naphthoquinonediazide-5-sulfonyl chloride
Ethylene glycol-di(4-hydroxybenzoate)-1, which is the reaction product with g
2-naphthoquinonediazide-5-sulfonic acid diester. Photosensitizer F: Ethylene glycol-monoethyl-
9.7 g of mono(3,4,5-trihydroxybenzoate) and 1,2-naphthoquinonediazide
Ethylene glycol monoethyl, the reaction product with 35.5 g of 5-sulfonyl chloride
Mono(3,4,5-trihydroxybenzoate)-1,2-naphthoquinonediazide-5
-Sulfonic acid triester (2) Preparation and evaluation of photosensitive resin composition 20 g of alkali-soluble novolak resin obtained in Example 1 (1) and 5 g each of photosensitizers B to F
A solution of a photosensitive resin composition was prepared in the same manner as in Example 1(3) using the following. This solution was evaluated in the same manner as in Example 1(3), and the results are shown in Table 1.

〔Effect of the invention〕

The positive photosensitive resin composition of the present invention has high sensitivity,
It has high resolution, high residual film rate, and excellent developability, and is particularly useful as a heat-resistant positive photoresist for integrated circuit manufacturing, as well as as a positive photoresist for mask production. is also useful.

Claims (1)

[Claims] 1 General formula () for 100 parts by weight of alkali-soluble resin or general expression () (In the formula, a, b and c are the same or different, and 1
an integer of ~4, R ₁ , R ₂ and R ₃ are the same or different, hydrogen atom, halogen atom, alkyl group, aryl group, aralkyl group, alkoxy group, alloxyl group, aralkoxy group, cyano group or nitro group, R ₄ is an alkyl group, an aryl group, or an aralkyl group, and Z is an alkylene group or an oxyalkylene group). 1,2
- at least one quinonediazide compound (A),
A positive photosensitive resin composition containing 5 to 100 parts by weight.