JPH0594012A - Positive type photosensitive resin composition - Google Patents

Abstract

PURPOSE:To obtain a positive type photosensitive resin composition capable of producing uniform film equally coated in thickness, excellent in flatening property and being usable for electronic parts manufacturing field. CONSTITUTION:In a positive type resist composition formed by dissolving an alkali solution soluble resin and compound containing quinone diazide group into an org. solvent, the org. solvent has properties of 160-180 deg.C b.p. (760mmHg), 1-2cP viscosity (20 deg.C) and <=70cal/g latent heat of evaporation to produce the positive type photosensitive resin composition.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive-type photosensitive resin composition, and more particularly to a positive-type photosensitive resin composition which is effectively used in the field of manufacturing electronic component materials and which has excellent coating properties and safety. ..

[0002]

2. Description of the Related Art In the manufacture of electronic component materials such as semiconductor devices and liquid crystal display devices, a pattern transfer method by photolithography is used as a method for forming a pattern on a substrate. In photolithography, a photoresist such as a wafer is coated on a substrate using a spinner and dried.
Then, an actinic ray is radiated through a mask and developed to transfer the mask pattern onto the wafer, followed by etching. The negative type photoresist was initially used as the photoresist used as a mask for this etching.However, the negative type photoresist is currently used because of the problems of resolution limit due to swelling in a developing solution and mask damage in contact exposure. A positive photoresist having excellent image quality is often used.

By the way, in recent years, wafers and glass substrates have become large in size, and when applying a photoresist onto a substrate, one having excellent uniformity and flatness of the coating film is required.
Various studies have been conducted on photoresist solvents.

Conventionally, many solvents for positive photoresists have been known, for example, ethylene glycol monoethyl ether acetate, cyclopentanone (JP-A-59-155838), monooxymonocarboxylic acid esters. (JP-A-62-123444), a combination of cyclic ketone and alcohol (US Pat. No. 4,526,856), propylene glycol alkyl ether acetate (JP-A-61-7837) and the like are known. However, there is a problem that none of the solvents has good uniformity and flatness and does not have practical coating properties.

[0005]

SUMMARY OF THE INVENTION The present invention has been made for the purpose of improving the above-mentioned problems and providing a positive type photosensitive resin composition having good coatability.

[0006]

DISCLOSURE OF THE INVENTION The inventors of the present invention have been keenly aware of a solvent capable of achieving the above-mentioned object with respect to a positive-type photosensitive resin composition in which an alkali-soluble resin is combined with a photosensitive component consisting of a quinonediazide group-containing compound. As a result of repeated research,
It has been found that the object can be achieved by using an organic solvent having a boiling point, a viscosity and a latent heat of vaporization within a specific range, and the present invention has been completed.

That is, the present invention provides a positive photoresist composition comprising an alkali-soluble resin and a quinonediazide group-containing compound dissolved in an organic solvent, wherein the organic solvent has a boiling point (760 mmHg) of 160 to 180 ° C. and a viscosity (20
C.) 1 to 2 cP and a latent heat of vaporization of 70 cal / g or less, a positive photosensitive resin composition is provided.

The present invention will be described in detail below. Examples of the alkali-soluble resin used in the composition of the present invention include novolac resins, acrylic resins, copolymers of styrene and acrylic acid, polymers of hydroxystyrene, polyvinylphenol, poly α-methylvinylphenol, and the like. Alkali-soluble novolac resin is particularly preferable. The alkali-soluble novolac resin is not particularly limited, and those conventionally used as a film-forming substance in a positive photoresist composition, such as aromatic hydroxy compounds such as phenol, cresol, and xylenol, and aldehydes such as formaldehyde are acidic. Those condensed in the presence of a catalyst are used. This alkali-soluble novolak resin has a weight average molecular weight of 2,000 to 2,000 with the low-molecular region cut.
The range of 0, preferably 5000-15000 is preferable.

In the composition of the present invention, a quinonediazide group-containing compound is used as a photosensitive component. Examples of the quinonediazide group-containing compound include orthobenzoquinonediazide, orthonaphthoquinonediazide, sulfonic acids of quinonediazides such as orthoanthraquinonediazide, and partial or complete esterification of a compound having a phenolic hydroxyl group or an amino group, or partial or complete esterification. Examples include amidated products. Examples of the compound having a phenolic hydroxyl group or an amino group include 2,3,4-trihydroxybenzophenone, 2,
2 ', 4,4'-tetrahydroxybenzophenone,
Polyhydroxybenzophenone such as 2,3,4,4′-tetrahydroxybenzophenone, alkyl gallate, aryl gallate, phenol, phenol resin,
p-methoxyphenol, dimethylphenol, hydroquinone, polyhydroxydiphenylalkane, polyhydroxydiphenylalkene, bisphenol A, α,
α ′, α ″ -tris (4-hydroxyphenyl) -1,
3,5-triisopropylbenzene, 1- [1- (4-
Hydroxyphenyl) isopropyl] -4- [1,1-
Bis (4-hydroxyphenyl) ethyl] benzene, tris (hydroxyphenyl) methane or its methyl-substituted product, naphthol, pyrocatechol, pyrogallol, pyrogallol monomethyl ether, pyrogallol-1,3-
Dimethyl ether, gallic acid, esterified or etherified gallic acid leaving some hydroxyl groups, aniline, p-
Amino diphenylamine etc. are mentioned. A particularly preferred quinonediazide group-containing compound is a complete or partial esterified product of polyhydroxybenzophenone and naphthoquinone-1,2-diazide-5-sulfonic acid or naphthoquinone-1,2-diazide-4-sulfonic acid, and The average degree of esterification is preferably 70% or more.

The composition of the present invention may contain, as the photosensitive component, one type of the above-mentioned quinonediazide group-containing compound or two or more types thereof.

This quinonediazide group-containing compound is obtained by using, for example, the above-mentioned polyhydroxybenzophenone, naphthoquinone-1,2-diazide-5-sulfonyl chloride or naphthoquinone-1,2-diazido-4-sulfonyl chloride in a suitable solvent such as dioxane. It can be produced by condensing in the presence of an alkali such as triethanolamine, an alkali carbonate or an alkali hydrogencarbonate to complete esterification or partial esterification.

The organic solvent used in the composition of the present invention has a boiling point (760 mmHg) of 160 to 18 as physical properties.
0 ° C, viscosity (20 ° C) 1-2 cP and latent heat of vaporization 70 ca
A solvent having an amount of 1 / g or less is used, and any organic solvent having such physical properties can be used. Specifically, ethyl 2-ethoxypropionate and ethyl 3-ethoxypropionate can be used. , 2-octanone, methylcyclohexanone and the like,
In practice, ethyl 3-ethoxypropionate is particularly preferably used. If even one of the physical property values deviates from the above range, a coating film having good coating properties cannot be formed, which is not preferable. Particularly when forming a coating film on a large-sized substrate using a roll coater, good leveling property is required, and the above range is an indispensable requirement.

In the composition of the present invention, the quinonediazide group-containing compound is used in an amount of usually 10 to 40 parts by weight, preferably 18 to 30 parts by weight, based on the alkali-soluble resin. If the amount of the quinonediazide group-containing compound is too small, it is difficult to obtain a resist pattern having a practical sectional shape, and if it is too large, the sensitivity tends to be significantly deteriorated, which is not preferable.

The amount of the organic solvent used is not limited, and may be used within the range where the coating film is formed. Specifically, the total amount of the alkali-soluble resin and the quinonediazide group-containing compound is 100% by weight. Usually 50 to 2 per set
It is used in an amount of 000 parts by weight, preferably 100 to 1000 parts by weight. If this amount is less than 50 parts by weight, the effect will not be sufficiently exhibited, and if it exceeds 2000 parts by weight, no effect will be obtained for the amount, and it is rather uneconomical, which is not preferable.

The composition of the present invention may further contain compatible additives such as an additional resin, a plasticizer, a stabilizer or a pattern obtained by development for improving the performance of the resist film. It is possible to add a colorant for making the composition more visible, and a commonly used additive such as a sensitizer for improving the sensitizing effect and a contrast enhancer.

It is advantageous that the composition of the present invention is used in the form of a solution by dissolving the alkali-soluble resin, the quinonediazide group-containing compound and the additional components used as necessary in the organic solvent in the required amounts.

About the preferred method of using the composition of the present invention 1
For example, first, on a support such as a silicon wafer,
A solution obtained by dissolving an alkali-soluble resin and a quinonediazide group-containing compound in the organic solvent is applied by a spinner, a roll coater or the like and dried to form a photosensitive layer, and then a light source that emits ultraviolet rays, for example, a low pressure mercury lamp, Whether to expose through a required mask pattern using a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, an arc lamp, a xenon lamp, a reduction projection exposure device, or an excimer laser or X-ray irradiation through the mask pattern, Alternatively, irradiation is performed while scanning the electron beam. Next, when this is immersed in a developing solution, for example, an alkaline aqueous solution such as a 1-10 wt% tetramethylammonium hydroxide aqueous solution, the portion solubilized by exposure is selectively dissolved and removed, and an image faithful to the mask pattern is obtained. Can be obtained.

Such a pattern is not limited to semiconductor processing, but is applied in the field of processing using lithography, such as LC.
The same excellent effect can be obtained for D, TAB, PCB, chemical milling, printing and the like. In particular, the composition of the present invention was not able to obtain a coating film excellent in uniformity with a conventional organic solvent, and in coating on a large substrate or a rectangular substrate using a roll coater, the leveling property can be greatly improved. It has a practical effect that a coating film having extremely high uniformity can be easily obtained.

[0019]

EFFECTS OF THE INVENTION The positive photosensitive resin composition of the present invention forms a coating film having extremely excellent uniformity and flatness by using an organic solvent having a specific physical property range as a preparation solvent. It can be used, and particularly, it has excellent coating properties even on a large substrate, and thus can be effectively used in practice.

[0020]

The present invention will be described in more detail with reference to the following examples, which should not be construed as limiting the invention thereto.

[0021]

Example 1 1 mol of 2,3,4,4'-tetrahydroxybenzophenone and naphthoquinone-1,2-diazide-
2 g of the esterification reaction product of 3 mol of 5-sulfonyl chloride and 8 g of cresol novolac resin were dissolved in 50 g of ethyl 3-ethoxypropionate to prepare a coating liquid for a positive photosensitive resin composition. This coating solution was spun on a 6-inch silicon wafer at 3000 rpm by a spinner.
A coating film having a thickness of 1.3 μm was formed by coating for 0 seconds and drying on a hot plate at 90 ° C. for 90 seconds.
As a result of observing the surface of the coating film, the surface was uniform and excellent in flattening property.

Next, a reduction projection exposure apparatus NSR-1505
G-4D (manufactured by Nikon Corporation) was used to selectively irradiate it with ultraviolet rays, and then it was heated on a hot plate at 110 ° C. for 90 seconds and developed with a 2.38 wt% tetramethylammonium hydroxide aqueous solution for 30 seconds. A good resist pattern could be obtained by washing with water and drying.

EXAMPLE 2 2 g of an esterification reaction product of 1 mol of 2,3,4, -trihydroxybenzophenone and 3 mol of naphthoquinone-1,2-diazide-5-sulfonyl chloride and 8 g of cresol novolak resin were treated with 3-ethoxy. It was dissolved in 50 g of ethyl propionate to prepare a coating solution of the positive photosensitive resin composition. An ITO film was formed on the surface of this coating solution 300
A roll coater RCP-352-P (manufactured by Dainippon Screen Co., Ltd.) was applied at a feed rate of 1 m / min onto a glass substrate (thickness 1.1 mm) of × 300 mm to form a linearly applied coating film on the substrate. The time required for the film to uniformly spread over the entire surface of the substrate was measured to be 30 seconds, and it was confirmed that the leveling property was excellent.

Then, on a hot plate at 100 ° C., 3
After drying for a minute, ultraviolet rays were selectively irradiated at an intensity of 50 mJ / cm ² and developed, and as a result, a good resist pattern was formed.

Comparative Example The preparation of the coating liquid for the positive type photosensitive resin composition used in Example 2 was repeated except that ethyl 3-ethoxypropionate was replaced with ethylene glycol monoethyl ether acetate and ethylene glycol monobutyl ether. Two types of coating liquids thus obtained were prepared. The two types of coating solutions were coated on a glass substrate in the same manner as in Example 2, and the time until the respective coating solutions spread evenly over the substrate was measured. As a result, ethylene glycol monoethyl ether acetate was used. The coating solution was 60 seconds, and the coating solution using ethylene glycol monobutyl ether was 5 minutes, both of which had poor leveling properties and were not practical.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hisashi Nakayama 26-404 Takamura housing complex 26-26 Takamura, Hiratsuka-shi, Kanagawa

Claims (2)

[Claims] 1. A positive resist composition comprising an alkali-soluble resin and a quinonediazide group-containing compound dissolved in an organic solvent, wherein the organic solvent has a boiling point (760 mmH).
g) A positive photosensitive resin composition, which exhibits physical properties of 160 to 180 ° C., viscosity (20 ° C.) of 1 to 2 cP and latent heat of vaporization of 70 cal / g or less. 2. The positive photosensitive resin composition according to claim 1, wherein the organic solvent is ethyl 3-ethoxypropionate.