JPS61271354A - Ultraviolet-sensitive resin composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. which has excellent shelf stability and forms an image having high resolution while inhibiting halation during exposure in forming a film image on a substrate having a high reflectance, containing a methine dye having a nitrile group. CONSTITUTION:0.05-20wt% nitrile group-contg. methine dye (e.g. C, I, Disperse Yellow 31) which exhibits absorption due to CidenticalN stretching at nearly 2,160-2,260cm<-1> in infrared absorptiometry, exhibits 300-500 parent peaks showing its MW in mass spectrometry and has absorbance of at least 1 against light of 436nm in an acetone soln. of 0.01g/l is blended with an ultraviolet sensitive org. high-molecular resin compsn. consisting of 100pts.wt. alkali-soluble resin (e.g. alkali-soluble novolak resin having an MW of 400-900), 10-40pts.wt. quinone diazide of the formula (wherein n is 1-3; R is alkyl, aryl, aralkyl) and optionally 0.5-20pts.wt. sensitizing agent (e.g. benzotriazole), 1-50pts.wt. additives such as surfactant, plasticizer, etc.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention relates to an ultraviolet-sensitive resin composition, and more specifically, the present invention relates to an ultraviolet-sensitive resin composition that prevents halation during ultraviolet irradiation when forming a film image on a highly reflective substrate. The present invention relates to an ultraviolet-sensitive resin composition suitable as a resist for forming high-resolution images.

(Prior art) In recent years, integrated circuit manufacturing methods have made remarkable progress, and there has been a strong demand for improvements to the equipment and peripheral materials used. is desired.

Conventionally, a mixture of a diazide compound and a polyisoprene cyclized product has been used as a negative resist in the production of integrated circuits.
Further, a mixture of a quinonediazide compound and a novolak resin is used as a positive resist. When these resists are used on a highly reflective substrate such as aluminum, the ultraviolet rays reflected from the substrate surface when irradiated with ultraviolet rays go around to areas that are not desired to be irradiated with ultraviolet rays. It has the disadvantage that fine patterns cannot be accurately reproduced.

Conventionally, in order to improve this drawback, by adding a light-absorbing material to the photosensitive resin composition, the light transmittance of the photosensitive resin composition is reduced. Efforts have been made to prevent the composition from reacting (Japanese Patent Publication No. 51-37562, Japanese Patent Application Laid-Open No. 59-142538, etc.). The light-absorbing material added at this time belongs to a so-called dye, and the light energy absorbed by the dye is re-emitted as light with a wavelength that does not excite the photosensitizer and sensitizer in the photosensitive resin composition. , the purpose is achieved by reducing the light transmittance of the photosensitive resin composition and lowering the sensitivity.

However, among the conventionally used light-absorbing materials,
For example, when using oil yellow as shown in Japanese Patent Publication No. 59-142538, after applying the photosensitive resin composition to the substrate, a blending process is carried out to remove residual solvent and at the same time improve adhesion to the substrate. During baking, part of the light-absorbing material sublimes from the photosensitive resin composition film, resulting in a significant decrease in antihalation effect, and is greatly affected by the baking conditions, resulting in variations in resist performance such as sensitivity. There is a drawback. Furthermore, when using the Ab compound disclosed in JP-A-59-142538 as a light-absorbing material, there is no problem in terms of variations in sensitivity due to the light-absorbing material and anti-halation effect, but storage stability is poor. However, there are disadvantages in that resist performance such as sensitivity changes over time, and resist performance changes during the time from after coating to exposure.

(Problems to be Solved by the Invention) It is an object of the present invention to eliminate the drawbacks of the above-mentioned conventional techniques, and to improve resolution by preventing halation during exposure when forming a film image on a substrate with high reflectance. It is an object of the present invention to provide an ultraviolet-sensitive resin composition that can form images with high brightness and has excellent storage stability.

(Another means to solve the problem) The present invention provides an organic polymer photosensitive ultraviolet resin composition that includes:
The present invention provides an ultraviolet-sensitive resin composition characterized by containing a methine dye having a nitrile group.

Examples of the organic polymer photosensitive ultraviolet resin composition used in the present invention include positive type ultraviolet rays (sealing compositions) consisting of an alkali-soluble resin and a quinone diazide compound.

Examples of the alkali-soluble resin include phenol,
Alkali-soluble Nopola 7 resin, hydroxyl, obtained by addition condensation of phenols such as cresol, ethylphenol, xylenol, p-phenylphenol, resorcinol, pyrogallol, and phloroglucinol with aldehydes such as formaldehyde, acetaldehyde, and benzaldehyde. Examples include polymers of styrene and/or hydroxystyrene derivatives such as α-methylhydroxystyrene.

Among the alkali-soluble novolak resins, m-cresol is contained in an amount of 55 to 97% by weight, and p-cresol is contained in an amount of 3 to 45% by weight.
An alkali-soluble novolak resin obtained by condensing a cresol isomer mixture containing % by weight with formaldehyde, Samurai does not contain 0-cresol, and contains m-cresol and p-cresol.
An alkali-soluble novolac resin obtained by condensing a cresol isomer mixture containing only cresol and formaldehyde is preferable, and among these, an alkali-soluble novolak resin obtained by condensing m-cresol and p-cresol in a weight ratio of 97/3 to 80/20 is preferable. Particularly preferred are those obtained. In addition, the number average molecular weight of the alkali-soluble novolac resin is 400 to 90'O.
is preferable, and particularly preferably 500 to 900.

Alkali-soluble novolak resins are produced by condensing phenols and aldehydes in the presence of an acidic catalyst in a conventional manner. Examples of acidic catalysts used in this case include oxalic acid, acetic acid, hydrochloric acid, sulfuric acid, etc.
These are usually used in an amount less than the stoichiometric equivalent of the aldehyde to be subjected to the reaction. The condensation reaction is 8
It is preferably carried out at 0 to 150°C, particularly 95 to 120°C, under a pressure of 1 to 3 atmospheres, and is usually completed in about 1 to 7 hours.

The polymer of hydroxystyrene and/or hydroxystyrene derivatives is obtained by converting hydroxystyrene, hydroxystyrene derivatives, etc., from an azo compound such as azobisisobutyronitrile, or a peroxide such as benzoyl peroxide or lauroyl peroxide. A method of radical polymerization in the presence of a radical generator such as n-butyllithium, sec- It is produced by a method of polymerizing in the presence of an anionic polymerization initiator such as butyl lithium or sodium naphthalene, followed by desilylation or deacetylation.

These polymers of hydroxystyrene and/or hydroxystyrene derivatives may be copolymers with other polymerizable polymers. Examples of monomers that can be copolymerized include styrene monomers such as styrene and aminostyrene, methacrylic acid, methyl methacrylate, ethyl methacrylate, hydroxyethyl methacrylate, acrylic acid, methyl acrylate, and ethyl acrylate. Examples include (meth)acrylic acid monomers, butadiene, isolarene, and other diene thread polymers, and two or more of these polymers may be copolymerized in combination. The preferred (co)polymerization ratio of hydroxystyrene and/or hydroxystyrene derivative in the polymer of hydroxystyrene and/or hydroxystyrene derivative is 3
0 to 100 mol%, particularly preferably 40 to 100 mol%
It is.

The weight average molecular weight of the polymer of hydroxystyrene and/or hydroxystyrene derivative in terms of polystyrene is preferably 3,000 to 30,000.

The alkali-soluble resin may be one that has been given UV sensitivity, for example, 1,2-naphthoquinonediazide-4-sulfonyl group, 1,2-naphthoquinonediazide-
5-sulfonyl group, ■, 2-benzoquinone diazido 4
- An alkali-soluble novolac resin into which a quinonediazide sulfonyl group such as a sulfonyl group has been introduced, a polymer of hydroxystyrene and/or a hydroxystyrene derivative into which a quinonediazide sulfonyl group has been introduced, etc., but an alkali-soluble resin imparted with UV sensitivity of these may be used. teeth,
From the viewpoint of alkali solubility, the content of quinonediazide sulfonyl groups in the resin is preferably 10% by weight or less, particularly 1 to 8% by weight.

The alkali-soluble resin imparted with UV sensitivity includes the alkali-soluble resin, 1.2-naphthoquinonediazide-4-sulfonyl chloride, 1.2-naphthoquinonediazide-5-sulfonyl chloride, and 1.2-benzoquinonediazide. It is produced by condensing quinonediazide sulfonyl chloride such as -4-sulfonyl chloride in an appropriate solvent in the presence of a basic catalyst if necessary. Examples of the solvent used in this case include acetone, dioxane, ethyl acetate, cellosolve acetate, pyridine, etc., and examples of the basic catalyst used include triethylamine, potassium hydroxide, sodium hydroxide, etc. The condensation reaction is usually carried out at 10 to 50°C.

The alkali-soluble resins may be used alone or in combination of two or more kinds, and when used in combination, it is preferable that the resins have compatibility with each other. Examples of combinations of two or more alkali-soluble resins include an alkali-soluble novolac resin and a hydroxystyrene polymer, an alkali-soluble novolak resin and an α-methylhydroxystyrene polymer, an alkali-soluble novolac resin and an alkali-soluble resin that has been given UV sensitivity. Examples include novolac resins, hydroxystyrene polymers, and hydroxystyrene polymers imparted with UV sensitivity.

As the quinonediazide compound mixed with the alkali-soluble resin, various 1,2-benzoquinonediazide-4-
Sulfonic acid ester, 1,2-naphthoquinone diazide
Examples include 4-sulfonic acid ester, 1,2-naphthoquinonediazide-5-sulfonic acid ester, and specifically, for example, the above-mentioned esters of mono- or polyhydroxybenzene or derivatives of these compounds.

Specific examples of hydroxybenzene include p-cresol, resorcinol, pyrogallol, phloroglycitur, and the like.

Further, as a quinonediazide compound, for example, all or one of the hydroxyl groups of a compound represented by the following general formula (1), where n is an integer of 1 to 3 and R is an alkyl group, an aryl group, or an aralkyl group, may be used. In part,
A 1,2-quinonediazide compound obtained by subjecting 2-benzoquinonediazide-4-sulfonyl chloride to a condensation reaction can also be used. Examples of the compound represented by the general formula (1) include 2,3.4-1-lyhydroxyphenylmethylketone, 2,3.4-)lyhydroxyphenylethylketone, 2.3.4-)lyhydroxyphenyl Butyl ketone, 2,3,4-trihydroxyphenyl-
n-hexyl ketone, 3.4.5-1-lihydroxyphenylmethyl ketone, 3,4.5-1-lihydroxyphenylethyl ketone, 3. 4. 5-1-lihydroxyphenylbutyl ketone, 3.4.5-)lihydroxyphenyl-n-hexyl ketone, 2.4.6-trihydroxyphenylmethylketone, 2,4.6-)lihydroxyphenylethyl Ketone, 2,4.6-trihydroxyphenylbutylketone, 2.4゜6-trihydroxyphenyl-n-hexylketone, 2,3.4-trihydroxyphenyldecylketone, 2.3.4-) Hydroxyphenyldodecylketone, 2,3.4-trihydroxybenzophenone, 2.4.6-1-dihydroxybenzophenone, 2,3.4-1-lihydroxydiphenylbenzylketone, 3.4.5-trihydroxybenzylketone , 2.4.6-1-lihydroxyphenylbenzyl ketone, etc. (US Pat. No. 3,046,118 and Japanese Patent Publication No. 37-18015), as well as 2,4-dihydroxyphenylpropyl ketone, 2,4-dihydroxyphenyl-〇- Examples include hexyl ketone and 2,4-dihydroxybenzophenone.

Further, as a quinonediazide compound, for example, 2°4.2
',4'-tetrahydroxy-6,6'-dimethyl-diphenylmethane, 2,6.2',6'-tetrahydroxy-3,5,3',5'-tetrachloro-diphenylmethane, 2,2'-dihydroxy -4,4'-dimethyl-
diphenylmethane-(1,1), 2,2'-dihydroxy-4,4'-dimethoxy-diphenylethane-(1
, 1), 2.4.2', 4'-tetrahydroxy-diphenylethane-(1,1), 2.2'-dihydroxy-
4,4′-ditomexytriphenylmethane, 2.2′-dihydroxy-dinaphthylmethane, 2°4.2′,4
'-Tetrahydroxy-diphenyl sulfide, 2,4
．． 2',4'-Tetrahydroxy-diphenyl sulfoxide, 2,4.2'.

4'-tetrahydroxy-6,6'-dimethyl-diphenylethane-(1,1), 2,4.2'.

4'-tetrahydroxy-6,6'-dicarbomethoxydiphenylmethane, 2,4.2',4'-tetrahydroxy-6,6'-dimethyl-triphenylmethane, 2
．． 4. 2', 4'-tetrahydroxy-diphenylpropane-(1,1), 2°4.2', 4'-tetrahydroxy-diphenyl-n-butane-(1,1)
, 2,4.2', 4'-pentahydroxy-triphenylmethane, 2°4.2', 4'-tetrahydroxy-diphenylcyclohexane-(1,1), 2,2'-dihydroxy-4,4 ′-Dimethoxydipheni! Remethane, 2. 4. 2', 4'-tetrahydroxy-
Diphenylbencune-(1,1),2,4.2'.

4'-tetrahydroxy-diphenylpropane-(2,
2), 2,4.2',4'-tetrahydroxy-triphenylmethane, 2,2'-dihydroxy-5,5'-dibromo-diphenylmethane, 2,2'-dihydroxy-
5,51-dichloro-diphenylethane-(1,1),
2,2'-dihydroxy-5,51-dibromo-diphenylethane-(1,1), etc., are converted into 1,2-naphthoquinonediazide-4-sulfonyl chloride, 1,2-naphthoquinonediazide-5-sulfonyl chloride, or 1. It is also possible to use a 1,2-quinonediazide compound obtained by condensation reaction with 2-benzoquinonediazide-4-sulfonyl chloride (Japanese Patent Publication No. 37-1953).

Furthermore, lauryl 3,5-dihydroxybenzoate, 2.3
．． 4-) Phenyl hydroxybenzoate, 3', 4.5
-1 (poly)hydroxybenzoic acid alkyl ester or aryl ester such as propyl trihydroxybenzoate, phenyl 3,4.5-trihydroxybenzoate, etc.,
, 2-naphthoquinonediazide-4-sulfonyl chloride, 1,2-naphthoquinonediazide-5-sulfonyl chloride, or 1,2-quinonediazide compound obtained by condensation reaction with 1,2-benzoquinonediazide-4-sulfonyl chloride. You can also do it.

The amount of the quinonediazide compound added is 100 parts by weight of the alkali-soluble resin, considering the heat resistance, plasma resistance, solubility of unexposed areas, sensitivity range to ultraviolet rays, etc. when the obtained ultraviolet-sensitive resin composition is used as a resist. per unit, preferably 10 to 40 parts by weight, particularly preferably 15 to 35 parts by weight.
Parts by weight.

A sensitizer may be added to the positive ultraviolet resin composition, if necessary. Examples of the sensitizer include triazoles, indazoles, imidazoles, halides thereof, and 2H-pyrido(3,2-b)-1,4-oxazine-3(4H) represented by the following general formulas.
ons, 10H-pyrido(3,2-b)(1,4)-benzothiazines, urazoles, hydantoins, barbylic acids, glycine anhydrides, ■-bitroxybenzotriazoles, alloxanes, maleimides, etc. is used.

Benzotriazole and its halides 5-Methylbenzo1-lyazole and its halides 5.6-Dimethylbenzotriazole and its halides ■, 2-Naphthotriazole and its halides Indazole and its halides 5-Nitroindazole and its halides Compounds 6-aminoindazole and its halides cyclohexyltriazole and its halides 1.2.3-1-Riazole and its halides 1.2.4-) Riazole and its halides 4.5-dicyano-1, 2,3-Triazoleimidazole and its halide 4-Azabenzimidazole and its halide 2H-pyrido(3,2-b)-1,4oxazine-3(
4H) one 10-pyrido(3,2-b)Cl 4)-benzothiazine □ urazolehydantoin convex barbylic acid glycine anhydride 1-hydroxybenzotriazole (riH alloxan (in the above formula, X means a halogen atom, k, ffi
, m and n mean integers of O~4.0~3.0~2 and 0~5, respectively).

These compounds may be derivatives of these compounds, that is, these compounds, and examples of the derivatives of these compounds include 1-methylurazole, 1-phenylurazole, 3-methylurazole, 3-p-tolylurazole, 5゜5-diphenylhydantoin, 5
, 5-dimethylhydantoin, 5-methyl-5-phenylhydantoin, 5-methyl-5-p-)lylhydantoin, 1-methylhydantoin, 1-phenylhydantoin, ■-methyl-5-methylhydantoin, 5-methylhydantoin, 5-ethyl-5-p-tolylhydantoin, 5.5-diethylhydantoin, 5-ethyl-5
-p-1lylbarbituric acid, 5-nitrobarbituric acid, 5.5-dimethylbarbituric acid, 5.5-diphenylbarbituric acid, 1-methylglycine, 1-phenylglycine, Examples include 2-methylglycine, 2,2-dimethylglycine, 5-methyl-1-hydroxybenzotriazole, 5,6-dimethyl-1-hydroxybenzotriazole, 1-methylalloxane, 1-phenylloxane, 3-phenylmaleimide, etc. It will be done.

The blending amount of the sensitizer is 0.5 to 20 M parts, preferably 1 to 15 parts by weight, per 100 parts by weight of the alkali-soluble resin.

In addition, in order to improve developability, storage stability of the composition, coating properties, etc., the positive weight-sensitive ultraviolet resin composition may contain natural resins such as rosin, schlag, etc., styrene and maleic anhydride, if necessary. Copolymers, copolymers of styrene and alkyl acids, methacrylic acids, or alkyl esters thereof, copolymers of acrylic acid or methacrylic acid and alkyl esters or hydroxyalkyl esters thereof, acrylic ester polymers, vinylpyrrolidone A synthetic resin such as a polymer, a surfactant, a plasticizer such as diethyl phthalate, diisopropyl phthalate, di-t-butyl phthalate, etc., is preferably 1 to 50 parts by weight per ioo:i parts of the alkali-soluble resin. It may be blended in a proportion of 5 to 30 parts by weight.

Another example of the organic polymer photosensitive ultraviolet resin composition used in the present invention is a negative weight sensitive ultraviolet resin composition comprising a cyclized product of a conjugated diene polymer and an ultraviolet crosslinking agent.

The cyclized product of the conjugated diene polymer is a cyclized product of a polymer or copolymer having a unit represented by the following general formula (n) in the polymer chain.

[In the formula, R", R", R14% R"", R"6
, Rx1, R", R", Rx0, R21, R22 and Rx3 are the same or different and are a hydrogen atom, an alkyl group such as a methyl group, an ethyl group, a propyl group, etc., or an aryl group].

Specific examples of the unit represented by general formula (II) include cis-1,4-butadiene unit, trans-1゜4-butadiene unit, cis-1,4-isoprene unit, trans-
1,4-isoprene unit, cis-1,4-pentadiene unit, trans-1,4-pentadiene unit, 1.4-
Examples include 2-phenylbutadiene unit, 1,2-butadiene unit, 3,4-isoprene unit, 1.2-pentadiene unit, 3゜4-2-phenylbutadiene unit, etc., and these conjugated diene units Monomer units that can be copolymerized with include vinyl aromatic compound units such as styrene units and α-methylstyrene units, and ethylene! Examples include olefin units such as the 1st position, propylene units, and isobutylene units. The cyclized products of these conjugated diene polymers include cis-1,4-isoprene units, trans-1,4-isoprene units, 3,4-isoprene units,
A cyclized product of a polymer or copolymer having at least one unit selected from cis-1,4-butadiene units, trans-1,4-butadiene units and 1,2-butadiene units is preferred, and isoprene polymers are particularly preferred. Alternatively, a cyclized product of a butadiene polymer is preferred. The amount of residual double bonds in the cyclized product of the conjugated diene polymer is not particularly limited, but is preferably 5 to 95%, particularly preferably 10 to 9%.
0%, most preferably 15-50%. Note that the amount of remaining double bonds is represented by *. (*: Measured by NMR) The ultraviolet crosslinking agent is not particularly limited as long as it is an ultraviolet crosslinking agent soluble in an organic solvent, and may be an azide-based photosensitive substance, such as 4,4'-diazide F, l - Rubene, p-phenylenebisazide, 4゜4'-diazidebenzophenone, 4
．． 4'-Diazidiphenylmethane, 4,4'-diazidochalcone, 2,6-bis(4'-azidobenzal)cyclohexanone, 2,6-biX(4''-azidobenzal)-4-methylcyclohexanone, 4.4 '-Diazido diphenyl, 4,4'-diazido-3゜3-dimethyldiphenyl, 2,7-diacidofluorene, etc. can be used.These ultraviolet crosslinking agents are preferably used to 0.1 to 1 per 100 parts by weight of compound
It is used by adding 0 parts by weight, but particularly preferably 1 to 5 parts by weight.
It is used by adding parts by weight.

As the methine dye having a nitrile group used in the present invention, for example, C,1,Disperse Yellow
ow31,C,1,Disperse Yellow
49, C, 1, Disperse Yellow61
,C,1,Disperse Yellow201,
C11, Disperse Y6110W231, etc.
Furthermore, the following general formula (where R1 is C2,
Cycloalkyl group on J day, optionally substituted C1,
4 alkoxy group, 01-4 alkylthio group, C1-
C12. substituted with an alkylcarbonyloxy group of 4, an alkoxycarbonyloxy group of 01 to 4, or an alkoxycarbonyl group of C1, V4. . an alkyl group or an alkenyl group of C3AJ10, R3 is a hydrogen atom,
Halogen atom, 01-4 alkyl group, C1,,4 alkoxy group or C1y4 alkoxycarbonyl group, R4 is hydrogen atom, halogen atom, cyano group, trifluoromethyl group, C5/J B cycloalkyl group, C
1 to 4 alkoxy groups % C5 to e cycloalkoxy groups, C1 to 4 alkylthio groups, C5w +3 cycloalkylthio groups, phenyl groups, phenoxy groups, phenylthio groups, phenylthio-01 to 4 alkyl groups, phenyl-
01-4 alkyl group, phenoxy-CIA74 alkyl group, phenylazo group, C1-4 alkoxycarbonyl group, 05-8 cycloalkoxycarbonyl group, phenoxycarbonyl group, benzoyl group, benzoyloxy group, phenoxycarbonyloxy group, phenylsulfonyl It means an oxy group or a phenyl-C1,+4 alkylthio group, and R3 and R4 are on adjacent carbon atoms, and together with these carbon atoms, a 5- or 6-membered saturated or unsaturated carbocycle or heterocycle. , Rs means a hydrogen atom, a chlorine atom, a bromine atom, a methyl group or a methoxy group, and any alkyl or alkoxy group as R3 or R4 may be formed.
4 alkoxy group, phenyl group or 01-4 alkoxycarbonyl group may be optionally substituted,
Any cycloalkyl group as or contained in R4 may be substituted by up to 3 methyl groups or by C1~
4 alkoxy group, phenyl group or c I A, +
4 may be optionally substituted with an alkoxycarbonyl group, and any phenyl group as R4 or contained in R4 may be substituted with a halogen atom, a methyl group, a CIAJ4
may be optionally substituted with two or less substituents selected from the group consisting of an alkoxy group and an alkoxycarbonyl group of 01 to 4. However, any alkoxy group substituted by an alkoxy group also has at least 2 carbon atoms, and when R, R4 and R5 are hydrogen atoms at the same time, R2 has at least 6 carbon atoms. an alkyl group, an alkylthioalkyl group, an alkoxyalkyl group, or an alkenyl group of 03-1°) (see JP-A-51-63824), a compound represented by the following general formula (wherein R6 is a halogen atom, an ethylene group fused in the β-position to an alkoxy group, a lower alkyl group having up to 6 carbon atoms optionally substituted with a lower alkoxycarbonyl group or a nitrile group, a phenyl group, a benzyl group or a nuclear naphthalene ring;
R7 means a hydrogen atom, a lower alkoxy group, a halogen atom, a lower alkyl group, or -CH=CCN (see JP-A-54-95629).

Among these methine dyes having a nitrile group, dyes satisfying the following conditions are particularly preferred.

(1) 2160-226 by infrared absorption spectrophotometry
It has an absorption near 0 cm-'' that shows the expansion and contraction of C3N.

(2) According to the f-quantity analysis method, the parent peak indicating the molecular weight is found between 300 and 500.

(3) 0.01 g/i! 436 n in acetone solution
The absorbance for light of m is 1 or more.

In the ultraviolet-sensitive resin composition of the present invention, the amount of the methine dye having a nitrile group is 0.05 to 20% by weight, particularly preferably 0.1 to 15% by weight, based on the total solid content of the ultraviolet-sensitive resin composition. Weight%.

If the amount is too large, sensitivity tends to decrease.

When using the ultraviolet-sensitive resin composition of the present invention as a resist, it is applied onto a substrate to be microfabricated and partially irradiated with ultraviolet light having a wavelength of, for example, 180 to 450 through a mask pattern or reticle. A pattern can be formed by developing.

As a method for applying the ultraviolet-sensitive resin composition of the present invention to a substrate, for example, the composition of the present invention may be dissolved in a suitable organic solvent and applied by a method such as spin coating, flow coating, or roll coating. Can be mentioned. Examples of solvents used in this case include glycol ethers such as ethylene glycol 7-methyl ether, diethylene glycol 7-methyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, and diethylene glycol dibutyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, and butyl cellosolve. Cellosolve esters such as acetate, aromatic hydrocarbons such as toluene and xylene, ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetonylacetone, acetophenone, isophorone, hensyl ethyl ether, 1,2-dibutoxyethane , ethers such as dihexyl ether, caproic acid,
Fatty acids such as caprylic acid, alcohols such as 1-octatool, 1-nonanol, 1-decanol, and benzyl alcohol! , ethyl acetate, butyl acetate, 2-ethylhexyl acetate, benzyl acetate, benzyl benzoate,
Examples include esters such as diethyl oxalate, dibutyl oxalate, diethyl malonate, dibutyl maleate, diethyl maleate, dibutyl maleate, dimethyl phthalate, ethylene carbonate, propylene carbonate, and lactones such as T-butyrolactone. These organic solvents may be one or two types.
Used in combination of more than one species.

The amount of the organic solvent used varies depending on the required film thickness when applying the UV-sensitive resin composition solution, but is generally 100 to 2000 parts by weight, preferably 300 to 1500 parts by weight, per 100 parts by weight of the solid content of the composition. be.

In the case of the above-mentioned positive ultraviolet resin composition, examples of the developer used in the ultraviolet-sensitive resin composition of the present invention include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, phosphoric acid, etc. Aqueous solutions of inorganic alkalis such as trisodium and sodium hydrogen phosphate, n-propylamine, di-n-propylamine,
Aqueous solutions of amines such as di-n-butylamine, methyldiethylamine, virol, 2,5-dimethylvirol, β-picoline, collidine, piperidine, piperazine, triethylenediamine, dimethylethanolamine, triethanolamine, dimethylhydroxyl Examples include aqueous solutions of alcohol amines such as amines, aqueous solutions of quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, and developing solutions based on ammonia water. These developers further contain surfactants, stabilizers such as sodium sulfite and ammonium sulfite, alcohol, and ketones for the purpose of improving the developability and adjusting the sensitivity, residual film rate, etc. of the ultraviolet-sensitive resin composition. , esters, ethers and other hydrophilic organic solvents, tetrapropylammonium hydroxide, tetrapropylammonium bromide, tetra-n-butylammonium hydroxide, tetra-n-butylammonium chloride, trimethylbenzylammonium hydroxide, trimethylbenzylammonium iodine A quaternary ammonium hydroxide or a quaternary ammonium salt such as tetrapentylammonium hydroxide, tetrapentylammonium bromide, tetrapentylammonium bromide, etc. can be added.

In the case of the negative type ultraviolet resin composition, examples of the developer include benzene, toluene, xylene, n-hebutane,
Organic solvents such as cyclohexane, ethylcyclohexane, chloroform, carbon tetrachloride, chlorobenzene, dichlorobenzene, decalin, methanol, ethanol, acetone, ethyl ether, n-butyl acetate, n-amyl acetate, dioxane, and these organic solvents. Examples include mixed solvents mixed in appropriate ratios. Note that the developability can be further improved by adding a surfactant, such as a fatty acid ester nonionic surfactant, to these developers. Examples of fatty acid ester nonionic surfactants include sorbitan trioleate, sorbitan sesquioleate, sorbitan monooleate,
Examples include those having an HLB of 1 to 5, such as sorbitan monostearate, sorbitan distearate, stearic acid monoglyceride, and oleic acid monoglyceride.

(Example) The present invention will be explained below with reference to Examples.

Example 1 (1) 500m! ! In the three-piece adjustable flask, m
- After charging 75 g of cresol and 25 g of p-cresol, 65 m 12 of a 37% by weight aqueous formalin solution and 0.04 g of oxalic acid were added, and the separable flask was immersed in an oil bath while stirring to maintain the reaction temperature at 100°C. The reaction was continued for 10 hours. After the reaction is completed, 3001jH
Water was distilled off by reducing the pressure to 1.5 g, and the internal temperature was further raised to 130° C. to remove unreacted substances. Next, the reaction product, molten alkali-soluble novolak resin (hereinafter referred to as "novolak resin A"), was returned to room temperature and recovered.

Novolak resin A 15g, 2,4.6-1-lyhydroxybenzophenone-1,2-naphthoquinone diazide-5
- After dissolving 3.0 g of sulfonic acid triester and 0.30 g of methine-based disperse dye having a nitrile group shown below in 75 g of ethyl cellosolve acetate, the pore size was 0.2
A solution of the ultraviolet-sensitive resin composition of the present invention was prepared by filtration with a μm membrane filter.

Methine dye with nitrile group (C, 1, Dispe
rse Yel 1ow49 (Sand.

(manufactured by Z company)] (a) Parent Beeknia 4 showing molecular weight by mass spectrometry (0) 436 nm of 0.01 g/12 acetone solution
Absorbance for light = 1.4 (c) Infrared absorption spectrum: See Figure 11 (2) (1)
The composition obtained was spin-coated onto a silicon wafer having a step structure of 0.8 μm on which a 0.2 μm thick aluminum layer was deposited, and then prebaked for 2 minutes on a hot plate kept at 90°C. A UV-sensitive resin composition film having a thickness of 1.3 μm was obtained.

A test pattern mask with equal line width and space width (I L/IS pattern) was used on this ultraviolet-sensitive resin composition film, and a 436 nm reduction projection exposure apparatus GCA MANN 4800 equipped with a 150 W ultra-high pressure mercury lamp was used.
After exposure for 1.3 seconds using DSW (manufactured by Sumitomo OCA Co., Ltd.), the film was immersed in a 2.4% by weight aqueous solution of tetramethylammonium as a developer, developed at 25° C. for 1 minute, and rinsed with running water.

The obtained resist pattern has no breakage or chipping due to the effects of halation, and has a pattern of up to 0.8 μm.
Well resolved.

(3) Using the composition obtained in (1) and a silicon wafer having a silicon oxide film, a resist pattern was formed in the same manner as in (2) except that the exposure time was 1.4 seconds.

The residual film rate at this time was 97.4%, indicating a high residual film rate. In addition, after preparing the composition, store it at 25°C for 3 months,
When similar evaluations were made thereafter, it was found that equivalent resist performance was obtained and the composition of the present invention was also excellent in stability.

(4) Furthermore, the composition obtained in (1) was coated on a silicon wafer in the same manner as in (2), and then baked at 25°C.
When the same evaluation as in (2) was carried out by leaving it for 4 days and exposing it to light, the same resist performance was obtained, indicating that the UV-sensitive resin composition of the present invention also has excellent stability after application. I understand.

Comparative Example 1 0.30 g of 4-hydroxy-4'-dimethylaminoazobenzene was used as the light-absorbing material, and the rest was the same as Example 1.
A solution of the ultraviolet-sensitive resin composition was obtained by processing in the same manner as in (1).

The antihalation effect of this composition was examined in the same manner as in Example 1 (2), and the antihalation effect was found to be good. However, when the composition solution was evaluated after being stored at 25°C for 3 months in the same manner as in Example 1 (3) and compared with that immediately after preparation, it was found that the performance as a resist decreased, such as a decrease in the residual film rate. It was changing.

In addition, in the same manner as in Example 1 (4), after coating and pre-baking, it was left at 25°C for 4 days and evaluated by exposing it to light, and it was found that the residual film rate was lower than when it was not left. , the resist performance changed significantly.

Comparative Example 2 A solution of an ultraviolet-sensitive resin composition was obtained in the same manner as in Example 1, except that no light-absorbing material was added.

For this composition, except that the exposure time was 0.8 seconds'
When the halation prevention effect was investigated in the same manner as in Example 1 (2), it was found that the resist pattern had many chips and breaks at the bottom of the pattern due to the effect of halation from the side surface of the step.

Example 2 (1) 15 g of novolak resin A, 1,3.5-tri(
1',2'-naphthoquinonediazide-59-sulfoxy)benzene 1.5g and methine disperse dye (C,1,
After dissolving 0.31 g of Disperse Yellow 49) in 70 g of ethyl cellosolve acetate, the solution was filtered through a membrane filter with a pore size of 0.2 μm to obtain a solution of the ultraviolet-sensitive resin composition of the present invention.

(2) Using the composition obtained in ('1), Example 1 (2)
) to form a resist pattern. However, the exposure time was 0.9 seconds.

The resulting resist pattern showed no effect of halation at all, and was accurately resolved down to a pattern of 0.7 μm.

(3) Using the composition obtained in (1), Example 1 (3)
, The stability was investigated in the same manner as in (4), and there were no problems at all.

Example 3 (1) In a 500rnl Mitsuro separable flask, m
- 117 g of cresol, 13 g of p-cresol, 137% by weight formaldehyde aqueous solution 92 m! and oxalic acid 0.0
4 g was charged, the separable flask was immersed in an oil bath while stirring, and the reaction temperature was maintained at 100°C for 3 hours.
The reaction was allowed to proceed for 0 minutes. After the reaction was completed, the oil bath temperature was raised to 180° C., and at the same time the pressure inside the separable flask was reduced to remove water, unreacted cresol and formaldehyde, and oxalic acid. Next, the reaction product, molten alkali-soluble novolak resin (hereinafter referred to as "novolak resin B"), was returned to room temperature and collected.

815 g of novolac resin, 2,4.6-)lyhydroxybenzophenone-1,2-naphthoquinonediazide-5-
1.6 g of sulfonic acid triester and methine-based disperse dye (C, 1, Disperse Yellow)
49) 0.42g of ethyl cellosolve acetate 65
g, and filtered through a membrane filter with a pore size of 0.2 μm to obtain a solution of the ultraviolet-sensitive resin composition of the present invention.

(2) Using the composition obtained in (1), Example 1 (2)
A resist pattern was formed in the same manner as above.

However, the exposure time was 0.5 seconds. The obtained resist pattern showed no effect of halation at all and had a zero
．． Patterns down to 7 μm were accurately resolved.

(3) Using the composition obtained in (1), Example 1 (3)
The stability was also investigated in the same manner as above, and there were no problems at all.

Example 4 (1) 15 g of novolak resin A, 3.0 g of 2.4.6-)lyhydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid triester, and a methine-based dispersion having a nitrile group shown below. After dissolving 0.23 g of the dye in 75 g of ethyl cellosolve acetate, it was filtered through a membrane filter with a pore size of 0.2 μm to prepare a solution of the ultraviolet-sensitive resin composition of the present invention.

Methine dye with nitrile group (C, 1, Dispe
(manufactured by Rse Yellow)] (a) Parent peak showing molecular weight by mass spectrometry: (b) Absorbance of 0.01 g/β acetone solution to 436 nm light: 1.3 (c) Infrared absorption spectrum: Figure 2 Reference (2) The composition obtained in (1) was spin-coated onto a silicon wafer having a step structure of 0.8 μm on which a 0.2 μm thick aluminum layer was vapor-deposited, and then heated on a hot plate maintained at 90°C. A UV-sensitive resin composition film having a thickness of 1.3 μm was obtained by bre-baking for 2 minutes.

A test pattern mask with equal line width and space width (LL/IS pattern) was used on this ultraviolet-sensitive resin composition film, and a 436 nm reduction projection exposure device GC/;, MA・NN 4800 having a 150 W ultra-high pressure mercury lamp was used.
After exposure for 0.7 seconds using DSW (manufactured by Sumitomo OCA Co., Ltd.), the film was immersed in a 2.4% by weight aqueous solution of tetramethylammonium as a developer, developed at 25° C. for 1 minute, and rinsed with running water.

The resulting resist pattern had no disconnections or chips due to the effects of halation, and patterns down to 0.8 μm were accurately resolved.

(3) Using the composition obtained in (1) and a silicon wafer having a silicon oxide film, a resist pattern was formed in the same manner as in (2) except that the exposure time was 0.8 seconds.

The residual film rate at this time was 92.0%, indicating a high residual film rate. In addition, after preparing the composition, store it at 25°C for 3 months,
When similar evaluations were performed thereafter, it was found that equivalent resist performance was obtained, and the composition of the present invention was also found to be excellent in stability.

(4) Furthermore, the composition obtained in (1) was coated on a silicon wafer in the same manner as in (2), and then baked at 25°C.
When the same evaluation as in (2) was carried out by leaving it for 4 days and exposing it to light, the same resist performance was obtained, indicating that the UV-sensitive resin composition of the present invention also has excellent stability after application. I was angry.

Example 5 (1) 15 g of novolak resin A, 1.3.5-)
1',2''-naphthoquinonediazide-5'-sulfoxy)benzene and methine-based disperse dye (C,1,
Disperse Yellow201) 0.45g
After dissolving in 70 g of ethyl cellosolve acetate,
It was filtered through a membrane filter with a pore size of 0.2 μm to obtain a solution of the ultraviolet-sensitive resin composition of the present invention.

(2) Using the composition obtained in (1), Example 4 (2)
A resist pattern was formed by processing in the same manner as above. However, the exposure time was 0.9 seconds.

The resulting resist pattern showed no effect of halation at all, and was accurately resolved down to a pattern of 0.7 μm.

(3) Using the composition obtained in (1), Example 4 (3)
The stability, which was investigated in the same manner as in (4), showed no problems at all.

(Effects of the Invention) The ultraviolet-sensitive resin composition of the present invention can prevent halation during exposure and form a high-resolution image even when forming a film image on a substrate with high reflectance. It has excellent coating film uniformity and storage stability, and has a high residual film rate after development. Therefore, by using the ultraviolet-sensitive resin composition of the present invention as a resist, it is possible to accurately reproduce fine patterns necessary for manufacturing integrated circuit elements.

[Brief explanation of the drawing]

FIGS. 1 and 2 are diagrams showing infrared absorption spectra of a compound that is an example of a methine-based disperse dye having a nitrile group used in the ultraviolet-sensitive resin composition of the present invention. Agent Patent Attorney Takeshi Kawakita Long Procedural Amendment July 2, 1985 Commissioner of the Patent Office Michibe Uga 1, Indication of the Case 1985 Patent Application No. 111686 2, Title of Invention Ultraviolet-sensitive resin composition・3. Relationship with the case of the person making the amendment Patent applicant address: 2-11-24 Tsukiji, Chuo-ku, Tokyo Name:
(41?) Japan Synthetic Rubber Co., Ltd. Representative Hisashi Yoshimitsu 4, Agent 103 Address 11-8 Nihonbashi Kayabacho, Chuo-ku, Tokyo (
Benimoe Building) Telephone 03 (639) 5592 Number Name (7658) Patent Attorney Takeshi Kawakita Cho 5,
wi Date of positive instruction Vol. 7, [Correct content (1) "Grisitoul" on page 10, line 13 of the specification]
Change to Glucinol J. (2) Add "per r light path law" after "for light" on page 31, line 12 of the specification. (3) Add "J per optical path 1aa" next to "for light" on page 37, line 18 of the specification. (4) Add "J per optical path 1aa" next to "for light" on page 43, line 20 of the specification. Add 1 per optical path 11. (5) rYell on page 43, line 16 of the specifications. that's all

Claims (1)

[Claims] (1) An ultraviolet-sensitive organic polymer-based ultraviolet-sensitive resin composition characterized by containing a methine-based dye having a nitrile group.