JPS58149042A - Positive type photosensitive composition - Google Patents

Abstract

PURPOSE:To increase the sensitivity of a compound contg. a quinonediazido group, by using a specified heterocyclic compound contg. nitrogen as a sensitizer. CONSTITUTION:The sensitivity of a photosensitive composition is remarkably increased by combinedly using a compound contg. a quinonediazido group as a photosensitive substance and at least 1 kind of sensitizer for the compound selected from pyrrolidone, oxyindole, imidazolidone, benzimidazolinone, imidazolidinethione, oxazolidone, benzoxazolinone, isoindolinone, thioindole, pyrazolone, isatin, succinic acid imide, thiazolidinedione, rhodanine, oxazolidinedione, glutaric acid imide, piperidone and derivs. thereof.

Description

DETAILED DESCRIPTION OF THE INVENTION The invention provides a novel positive-working photosensitive composition 1. More specifically, the present invention relates to a highly sensitive positive-working photosensitive composition containing a novel combination of a quinonediazide group-containing compound and a special sensitizer as a photosensitive component.

Conventionally, it has been known that when a compound containing a quinonediazide group is irradiated with ultraviolet light through a Bonfilm mask, it turns into intenecarboxylic acid, which is soluble in a weakly alkaline aqueous solution.
Utilizing this property, quinone/azido group-containing compounds are widely used in positive-working photosensitive materials.

Quinonediazide group-containing compounds are often used in combination with tympanic membrane-shaped phenolic resins, and compounds in which phenol resins are directly chemically bonded as sulfonic acid esters of quinonediazide group-containing compounds are also used.

As described above, compounds containing quinone diacid groups are widely used as Bon type photosensitive materials in combination with film-forming substances, but since they require relatively long irradiation times with ultraviolet rays, improving their photosensitivity is a major challenge. It has become. In particular, in recent years, in the production of semiconductor devices such as LSI and VLSI and photosensitive printing plates, the image forming process (photo IJ)
As there is a strong demand for shortening the ultraviolet irradiation time of UV light irradiation of the photosensitive material, that is, for increasing the photosensitivity of positive-type photosensitive materials, there is a strong demand for drastic improvements.

To address these issues, many improvements have been made on the quinone diacid group-containing compound itself or on the selection of various resins to be combined with it, but satisfactory sensitivity has not yet been achieved.

The present inventors have conducted extensive research with the aim of developing an effective sensitizer that can increase the sensitivity of quinonediazide group-containing compounds, and as a result of their extensive research, they have achieved this goal by using a certain type of nitrogen-containing heterocyclic compound. They discovered scales and came up with the present invention.

That is, the present invention provides (a) a quinonediazide group-containing compound, and (b) pyrrolidone, oxindole, i.
Midazolid′・ ＜″Imipazoli″・
Imita'.

Lysinethione, oxazolidone, benzoxacylinone,
Contains at least one combination selected from isoindolinone, thioindole, pyrazolone, isatin, succinimide, thiazolidinedione, rhodanine, oxazolidinedione, °glutarimide, piperidone, and derivatives thereof as a photosensitive component. The present invention provides a positive photosensitive composition characterized by the following.

The compound used as component (a) of the composition of the present invention is a quinonediazide group-containing compound, such as orthobenzoquinonediazide, parabenzoquinonediazide, orthonaphthoquinonediazide, orthoantraquinonediazide and orthonaphthoquinonediazide. These include nuclear-substituted derivatives such as sulfonic acid esters, and compounds with orthoquinonediazide sulfonyl chloride and hydroxyl or amine groups, such as phenol, p-methoxyphenol,
Di, methylphenol, hydroquinone, bisphenol A1 naphthol, catechol pyrogallol, pyrocatechol, pyrogallol monomethyl ether, pyrogallol-1,3-dimethyl ether, gallic acid, gallic acid esterified or etherified with some hydroxyl groups remaining, aniline, Schiff Also included are reaction products with cyclnylamine and the like.

Moreover, in the composition of the present invention, the above-mentioned photosensitive pickle (a)
The middle component used in combination with is pyrrolidone, oxindole, imidazolitone, benzimidazolinone,
Imidazolidinethione, oxazolidone, benzoxacylinone, isoindolinone, thioindole, pyrazolone, isatin, conophosphate imide, thiazolidinedione, rhodanine, oxidase.

Sacilidinedione, glutarimide, piperidone and their derivatives are included, and these compounds include those with fused rings, lower alkyl groups, nitro groups, amine groups, hydroxyl groups, alkoxy groups, phenyl groups and It may have substituents such as. Specific examples of these sensitizers (b) include 2-pyrrolidone, 5-methyl-2-pyrrolidone, 5-nitro-2-pyrrolidone, 5-chloro-2-pyrrolidone, oxindole, 3.3 -dimethyl-oxindole, 3,3-
Dimethyl-oxindole, 5-hydroxyoxindole, 5-methoxyoxindole 5-methyloxindole, 5-ethylindole, 5-phenyloxindole, 3-hydroxy-2-indolinone, 2-imidazolitone, 3-hydroxy -2-indoline, 5,5-dimethyl-2-imidazolitone, 2-
Imidazolidinethione, 5,5-dimethyl-2-imidazolidinethione, 5-chloro-2-imidazolidinethione, 2-oxazolidone, 5-chloromethyl-2-oxazolidione, benzoxacylinone, 1-isoflatorinone, thioindole, 5-methylthioindole , 5
-chlorothioindole, 5-pyrazolone, 3-methyl-2-pyrazolin-5-one, isatin, 5-methylisatin, conolimide, α,α-dimethyl-β-methylsuccinimide, 2,4-thiazolidinedione , 5
, 5-dimethyl-2゜4-thiazolidinedione, rhodanine, p-dimethylaminobensyritene rhodanine, aminorhodanine, oxazolidinedione, 5,5-dimethyl-
2,4-oxazolidinedione, 515-diethyl-2
, 4-oxacylinone, glutarimide, 3.3
Examples include -dimethylglutarimide, 3,3-diethylglutarimide, 3-phenylglutarimide, piperidone, and the like.

It is effective to use these components in an amount of 0.1 to 25 parts by weight per 100 parts by weight of the quinonediazide group-containing compound and film-forming substance, and the preferred amount is 0.
．． It is 5 to 20 parts by weight. If the sweetness is too little, the sensitizing effect cannot be obtained, and even if the sweetness is too much, the sensitizing effect commensurate with the amount used cannot be obtained, which is uneconomical. The optimum amount to be used varies depending on the combination of photosensitizer and sensitizer used, but can be easily determined by simple experiments.

Alkali-soluble resins are preferably used as film-forming substances in the present invention, and specific examples thereof include novolac resins produced from phenol or cresol and aldehydes, polyvinyl alcohol, polyvinyl alkyl nityl, and styrene. Examples include copolymers of methacrylic acid and acrylic acid, copolymers of methacrylic acid and methacrylic acid alkyl esters, hydroxystyrene polymers, polyvinylhydroxybenzoate, polyvinylhydroxybensal, and the like.

The film-forming substance is 100 parts by weight or less per 10 parts by weight of the quinonediazide group-containing compound, and the preferred amount used is 55 parts by weight or less.
Parts by weight or less. If too much film-forming material is used, the mask pattern fidelity of the resulting image will be poor and the transferability will be poor. If the quinonediazide group-containing compound is not chemically bonded to the phenolic resin used for membrane rupture, it is desirable to use a film-forming substance in combination with the quinonediazide group-containing compound. The amount is preferably 25 parts by weight or more per 10 parts by weight of the compound. If the amount is less than that, the uniformity of the coating film will be poor and the resolution will also be reduced.

The composition of the present invention can be used in the form of a solution obtained by dissolving the quinonediazide group-containing compound as component (1) and the sensitizer as component (b) in a suitable solvent, and further dissolving the film-forming substance described above. is advantageous.

Examples of such solvents include ketones such as acetone, methyl ethyl ketone, cyclohexanone, and isoamyl ketone; Polyhydric alcohols such as probyl etherenope monobutyl ether or monophenyl ether;
/cyclic ethers such as oxane; and methyl acetate,
Examples include esters such as ethyl acetate and butyl acetate. These may be used alone or in combination of two or more of them.

The positive-working photosensitive compositions of the present invention may further contain compatible additives, such as additional resins, plasticizers, stabilizers or colorants to make the developed image more visible. It is possible to add and contain the following substances.

To give an example of a preferred method of using the composition of the present invention, first, a quinonediazide group-containing compound and the above-mentioned sensitizer are placed on a support such as silicone sea urchin, etc. together with a phenol novolac resin, as described above. A solution dissolved in a suitable solvent is applied using a spinner or the like and dried to form a photosensitive layer. Thereafter, exposure is performed using a light source that emits ultraviolet rays, such as a low-pressure mercury lamp, high-pressure mercury lamp, ultra-high-pressure mercury lamp, arc lamp, xenon lamp, etc. through a required mask pattern, or irradiation is performed while scanning an electron beam. . Next, when this is immersed in a developing solution, for example, a weakly alkaline aqueous solution such as a 1-2 hydroxide aqueous solution, the portions made solubilized by exposure are selectively dissolved and removed, making it possible to obtain an image faithful to the mask pattern. .

Since the positive-working photosensitive composition of the present invention has a significantly increased sensitivity of the photosensitive material, the time required to form an image by exposing it to ultraviolet light is shorter than that of conventionally known compositions.
It is a photosensitive material with improved workability and high practical value.

Next, the present invention will be explained in more detail with reference to Examples.

Comparative Example 1 Ethylene glycol monoethyl ether acetate, door 59, naphthoquinone-(1,2)-diazide-(2)-5-sulfonic acid triester of gallic acid n-propyl ester 5v and phenol Novorek resin 201 The solution was dissolved and filtered to prepare a photosensitive solution for forming a photosensitive film.

This solution was applied onto an aluminum substrate using a spinner and dried by placing it in a dryer kept at 80 to 90° C. for 30 minutes to obtain a photosensitive coating film with a film thickness of i and 0 μm. This film was coated with an ultra-high pressure mercury lamp exposure device (Canon PLA-300).
) and was exposed through a mask pattern and developed with x, 5% aqueous sodium hydroxide solution. The minimum exposure time required to faithfully reproduce the mask pattern and form an image during exposure (hereinafter referred to as "appropriate exposure time") was 5.2 seconds.

Example 1 A photosensitive solution was prepared in the same manner as in Comparative Example 1, and succinimide 2? After adding and dissolving the new 1
A photosensitive solution was prepared. This photosensitive solution was applied onto an aluminum substrate using a spinner and placed in a dryer kept at 80 to 90° C. for 30 minutes to obtain a photosensitive coating film with a thickness of 1.0 μm. Subsequently, PLA-
After exposure, the photoresist film was developed using a 1.5% aqueous sodium hydroxide solution as a developer. The appropriate exposure time for this positive photosensitive film was 3.7 seconds, and a comparison with Comparative Example 1 shows that succinimide has an excellent sensitizing effect.

Example 2 When oxindole was used as a sensitizer in place of succinimide in Example 1, the appropriate exposure time was determined.3
．． It was 4 seconds. This photosensitive composition exhibited a photosensitivity approximately 1.5 times higher than that of Comparative Example 1.

Comparative Example 2 Naphthoquinone-(1,2)-diazide-(2)-5-sulfonic acid diester 5f of 2.3.4-trihydroxybenzophenone and m-cresol novolak resin 20y
was dissolved in ethylene glycol monoethyl ether acetate 70f and filtered to prepare a photosensitive solution. This photosensitive liquid was applied onto a silicon wafer using a spinner.
The sample was placed in a dryer maintained at 0 to 90° C. for 30 minutes to obtain a photosensitive coating film with a thickness of 1.4 μm. Subsequently, as in Comparative Example 1, after exposure through a mask pattern, development was performed with a 1.8% sodium hydroxide aqueous solution to obtain a 1.0
An image with μm resolution was obtained. The appropriate exposure time for this photosensitive film was 3.2 seconds.

Example 3 A photosensitive solution was prepared in the same manner as in Comparative Example 1. Isatin 22 was added to the solution, dissolved, and filtered to prepare a photosensitive solution. This photosensitive liquid was applied onto a silicon wafer using a spinner and placed in a dryer maintained at 80 to 90° C. for 30 minutes to obtain a photosensitive coating film with a thickness of 1.4 μm. Subsequently, this film was exposed to light using PLA-300 through a mask pattern, and then developed using a 1.8 qb aqueous sodium hydroxide solution as a developer.

The appropriate exposure time at this time was 2.6 seconds, and comparison with Comparative Example 2 shows that isatin effectively acts as a sensitizer.

Example 4 When the same procedure as in Example 3 was performed except that the amount of isatin in Example 3 was increased from 22 to 42, the appropriate exposure time was 2.1 seconds. It was found that photosensitivity was further enhanced by increasing the amount of isatin, and it acted effectively as a sensitizer.

Example 5 Example 3 by changing the amount of isatin added in Example 3 to 1.2f
When the same operation was performed as above, the appropriate exposure time was 2.8 seconds. In this case as well, the effect of isatin as a sensitizer was fully recognized.

Example 6 5,5-dimethyl- in place of isatin in Example fl+3
When the appropriate exposure time was determined using 2,4-oxacylinedione 22, it was 1.6 seconds. This photosensitive composition has a photosensitivity about twice that of Comparative Example 2.

Example 7 Using 3,3-dimethylglutarimide 22 in place of isatin in Example 3, the appropriate exposure time was determined to be 1.6 seconds.

Example 8 A photosensitive solution was prepared in the same manner as in Comparative Example 2, and this photosensitive source was
2-pyrrolidone, 2-imidazolitone, 2 as a sensitizer
-Imidazolidinethione, 2-oxazolidone, 2,4
- After adding and dissolving 1.22% of either thiazolidineone, rhodanine, glutarimide, or benzoxacylinone,
A photosensitive solution was prepared by filtration. Then, a photosensitive coating film was formed in the same manner as in Comparative Example 2, exposed and developed, and the appropriate exposure times of the photosensitive compositions containing each sensitizer were as shown in the following table.

Claims (1)

[Claims] 1 H) A quinonediazide group-containing compound and (b) pyrrolidone, oxfindole, imidazolitone, benzimidazolinone, imidazolidinethione, oxanolitone, benzoxacillinone, isoindolinone, thioindole, pyrazolone, isatin, succinimide, thiazolidinedione, 1. A positive photosensitive composition containing as a photosensitive component at least one combination selected from the group consisting of rhodanine, oxazolidinedione, glutarimide, piperidone, and derivatives thereof.