JPH0733855A - Radiation-sensitive resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition useful for negative type resist, having excellent sensitivity, residual film ratio and adhesivity to a substrate, comprising a specific copolymer, a phenolic compound, a melamine, a triazine and an onium salt. CONSTITUTION:(A) A copolymer of an unsaturated carboxylic acid, an epoxy group-containing radically polymerizable compound and another radically polymerizable compound, (B) a phenolic compound, (C) a melamine of formula I [R1 to R6 are H or CH2OR (R is H or 1-6C alkyl)] and (D) a trihalomethyltriazine of formula II {X is halogen; A is CX3 or group of formula III [B, D and E are H, 1-10C alkyl, thioalkyl, (thio)aryl, alkoxy, aryloxy, halogen, cyano, nitro, 1-10C alkyl bonded tertiary amino, carboxyl, etc.; (m) is 1-5] or an onium salt of formula IV (A)nZ<+>Y<-> (Z is sulfur or iodine; Y is BF4, PF6, SbF6, AsF6, etc.; (n) is 2-3).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a radiation-sensitive resin composition. Specifically, ultraviolet rays, far ultraviolet rays, X-rays, electron beams,
Semiconductor integrated circuit sensitive to radiation such as molecular beam, γ-ray, synchrotron radiation, and proton beam, TF for LCD
The present invention relates to a radiation-sensitive resin composition suitable as a negative resist for producing a T circuit or a mask for producing a circuit.

[0002]

2. Description of the Related Art Positive resists, which are a combination of a quinonediazide compound and a novolac resin, give a pattern of high resolution and are therefore widely used in the manufacture of integrated circuits. In recent years, in the field of the semiconductor industry, patterns have become finer with the progress of higher integration, and high-resolution resists have been actively developed. However, in the actual manufacturing process, the ratio of processing steps requiring submicron resolution is about 10 to 20% of the whole,
The resolution required in the rough process, which occupies most of the rest, is
It is on the order of a few microns to a few tens of microns. The resist used in these rough processes is strongly required to have high sensitivity rather than high resolution. Further, in the rough process, the etching process of the base substrate is often performed by a wet etching method which enables large-scale batch processing, and therefore reactive ion etching (RI
The dry etching resistance required in the case of the E) method is more important than the adhesiveness to the substrate and the chemical resistance not attacked by the etchant. In addition, the resist used in the rough process is required to have heat resistance that can withstand high temperature heating in the ion implantation process and the like. The positive resist, which is a combination of a quinonediazide compound and a novolac resin, is excellent in terms of resolution and RIE resistance, but it is often pointed out that its performance is insufficient in terms of sensitivity, adhesion to a substrate, and heat resistance. Has been done. Especially in today's situation where the substrate diameter is increasing for the purpose of improving the yield and the throughput must be increased, the demand for the development of a high-sensitivity rough process resist is equal to the demand for the development of a high-resolution fine processing resist. High as well.

Such a situation also applies to the field of the liquid crystal display (LCD) industry, which has seen rapid development in recent years. Among the liquid crystal displays, the active matrix (AM) type LCD, in which a thin film transistor (TFT) is incorporated in each pixel, is considered to be a favorite of the next-generation display device that changes from its fast response speed to a CRT. The screen area is steadily increasing. The design rule of the TFT of AM-LCD is about several microns, and the resolution that the resist for rough process has is sufficient for manufacturing, but because of the use of a substrate larger than that used for semiconductor manufacturing, As long as a positive resist in which a quinonediazide compound and a novolac resin are combined is used, the above-mentioned problems such as sensitivity, adhesion to a substrate, and heat resistance become more remarkable.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a radiation sensitive resin composition. Another object of the present invention is to provide a radiation sensitive resin composition for a negative resist, which is excellent in sensitivity, residual film rate, heat resistance and adhesion to a substrate. Further objects and advantages of the present invention will be apparent from the following description.

[0005]

According to the present invention, the above objects and advantages of the present invention include (A) (a) an unsaturated carboxylic acid, and (b) a radically polymerizable compound containing an epoxy group, (C) a copolymer with another radically polymerizable compound,
(B) Phenolic compound, (C) General formula (I)

[0006]

[Chemical 4]

(In the formula, R _{1 to} R ₆ may be the same or different and each represents a hydrogen atom or a group —CH ₂ OR, and R represents a hydrogen atom or a C _{1 to} C ₆ alkyl group.) Melamines represented by, and (D) general formula (II)

[0008]

[Chemical 5]

(In the formula, X represents halogen and A represents CX.
₃ or a group represented by the following general formula, and B,
D and E are each independently a hydrogen atom, a C _{1 to} C ₁₀ alkyl group, an aryl group, an alkoxy group, an aryloxy group, a thioalkyl group, a thioaryl group, a halogen, a cyano group, a nitro group, a C _{1 to} C ₁₀ A tertiary amino group having an alkyl group, a carboxyl group, a hydroxyl group, a C _{1 to} C ₁₀ ketoalkyl group, or a ketoaryl group, a C _{1 to} C ₂₀ alkoxycarbonyl group, or an alkylcarbonyloxy group, and m is 1 Indicates an integer of ˜5. )

[0010]

[Chemical 6]

Trihalomethyl triazines represented by [0011], or the general formula ^{(III) (A) nZ +} Y - ..................... (III) ( wherein definitions of A are the same as the above formula, Z Represents sulfur or iodine, Y represents BF ₄ , PF ₆ , SbF ₆ , As
It represents F ₆ , p-toluenesulfonate, trifluoromethanesulfonate or trifluoroacetate, and n represents 2 or 3. And a radiation-sensitive resin composition containing an onium salt functioning as a photoacid generator represented by the formula (1).

The components of the present invention will be described below. 1. Component (A) (hereinafter referred to as "copolymer I") The copolymer I used in the present invention is a copolymer which is soluble in an aqueous alkaline solution and which can be crosslinked by heating. . The copolymer I is obtained by radically copolymerizing (a) an unsaturated carboxylic acid and (b) a radically polymerizable compound containing an epoxy group with (c) another radically polymerizable compound in a solvent. To be Examples of the unsaturated carboxylic acid (a) include methacrylic acid,
Acrylic acid, maleic acid, itaconic acid, citraconic acid,
Mesaconic acid, fumaric acid, crotonic acid, 1,4-cyclohexene dicarboxylic acid, o-, m-, p-vinylbenzoic acid and the like can be mentioned, preferably methacrylic acid,
Mention may be made of acrylic acid. These unsaturated carboxylic acids may be used either individually or in combination of two or more. The proportion of unsaturated carboxylic acid in the copolymer I is preferably 5 to 50% by weight, more preferably 10 to 40% by weight. 5 unsaturated carboxylic acids
When the content is less than wt%, the resulting copolymer I becomes difficult to dissolve in an alkaline aqueous solution, resulting in deterioration of sensitivity and deterioration of developability. If it exceeds 50% by weight, the solubility of the copolymer in an alkaline aqueous solution becomes too high, and the residual film ratio of the unexposed portion is lowered.

As the radically polymerizable compound (b) containing an epoxy group, glycidyl acrylate, glycidyl methacrylate, α-ethylglycidyl acrylate, α-n-propylglycidyl acrylate, α-n
-Butylglycidyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 3,4-epoxyheptyl acrylate, 3,4
-Epoxyheptyl methacrylate, α-ethyl-6,
7-epoxyheptyl acrylate, allyl glycidyl ether, vinyl glycidyl ether, etc. can be mentioned, Preferably, glycidyl acrylate, glycidyl methacrylate, vinyl glycidyl ether can be mentioned. These radically polymerizable compounds containing an epoxy group can be used alone or in combination of two or more kinds. The proportion of the radically polymerizable compound containing an epoxy group in the copolymer I is preferably 5 to 70% by weight, more preferably 10 to 50% by weight. If the radical-polymerizable compound containing an epoxy group is less than 5% by weight, the heat resistance of the pattern obtained from the composition will not be sufficient, and if it exceeds 70% by weight, the storage stability of the copolymer I will be improved. Becomes worse.

Next, the other radically polymerizable compound (c) will be described. Generally, when radical polymerization of an unsaturated carboxylic acid and a radically polymerizable compound containing an epoxy group is carried out in a two-component system, the carboxyl group and the epoxy group react during the polymerization reaction to cause gelation. Therefore, in order to obtain the copolymer I, it is necessary to suppress the gelation by copolymerizing another radically polymerizable compound as the third component. Examples of the other radically polymerizable compound (c) having such a purpose include olefins such as butadiene, 2,3-dimethylbutadiene and isoprene, styrene, α-,
o-, m-, p-methylstyrene, p-methoxystyrene, p-tertbutoxystyrene, chloromethylstyrene, methacrylic acid or methacrylic acid methyl, ethyl, n-propyl, i-propyl, n-butyl, sec
-Butyl, ter-butyl, 2-ethylhexyl, lauryl, dodecyl, dicyclopentanyl, isobornyl,
Cyclohexyl, 2-methylcyclohexyl, dicyclohexyl, adamantyl, allyl, propargyl, phenyl, naphthyl, anthracenyl, cyclopentyl, furyl, tetrahydrofuryl, pyranyl, benzyl, phenesyl, cresyl, 1,1,1-trifluoroethyl, perfluoroethyl, Perfluoro-n-propyl, perfluoro-i-propyl, triphenylmethyl, adamantyl, cumyl ester, methacrylic acid or acrylic acid amide, N, N-dimethyl, N, N-propylamide, anilide, acrylonitrile, acrolein, Methacrylonitrile, vinyl chloride, vinylidene chloride, N-vinylpyrrolidone, vinyl acetate and the like can be mentioned.
Preferably, ter of styrene, butadiene, p-tert-butoxystyrene, methacrylic acid or acrylic acid is used.
-Butyl, dicyclopentanyl, pyranyl, benzyl esters may be mentioned. These radically polymerizable compounds can be used alone or in combination of two or more kinds. The proportion of the other radically polymerizable compound in the copolymer I is preferably 10 to 70% by weight,
More preferably, it is 20 to 60% by weight. When the proportion of the other radically polymerizable compound is less than 10% by weight, gelation is likely to occur during the polymerization reaction, and when it exceeds 70% by weight, the solubility of the copolymer I in an alkaline aqueous solution is lowered, or the composition is decreased. The heat resistance of the product deteriorates.

Examples of the solvent used for producing the copolymer I include alcohols such as methanol, ethanol, propanol and butanol, or cyclic ethers such as tetrahydrofuran and dioxane, and fragrances such as benzene, toluene and xylene. Group hydrocarbons, DM
Aprotic polar solvent such as F, NMP, ethyl acetate,
Examples thereof include acetic acid esters such as butyl acetate, glycol ethers such as diethylene glycol dimethyl ether, and cellosolve esters such as methyl cellosolve acetate. The amount of these reaction media used is usually
It is 20 to 1,000 parts by weight per 100 parts by weight of the reaction raw material.

Examples of the polymerization initiator include 2,2'-
Azobisisobutyronitrile, 2,2'-azobis (2,4-methylvaleronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile)
Examples thereof include azo compounds such as benzoyl peroxide, lauroyl peroxide, ter-butylperoxypivalate, and organic peroxides such as 1,1-bis (ter-butylperoxy) cyclohexane, and hydrogen peroxide. When a peroxide is used as an initiator, it may be used as a redox type initiator in combination with a reducing agent.

The polystyrene reduced weight average molecular weight of the copolymer I used in the present invention is usually 2,000 to
100,000, preferably 5,000 to 50,000
Is. If the average molecular weight is less than 2,000, the pattern shape, residual film rate, developability and heat resistance deteriorate, resulting in 100,000.
If it exceeds, the pattern shape and the phenomenological property are deteriorated, and particularly the sensitivity is deteriorated.

(B) Phenolic compound Examples of the phenolic compound used in the composition of the present invention include phenol, o-, m-, p-cresol, hydroquinone, catechol, resorcinol, pyrogallol, gallic acid, and floric acid. Logricinol, bisphenol A, P, S, F, AF, methylene bisphenol,
4,4'-ethylidene bisphenol, 4,4'-cyclohexylidene bisphenol, 4,4 '-(1-phenylethylidene) bisphenol, 4,4'-(1-methylethylidene) bis [2- (2-propenyl) ) Phenol], 4,4'-oxybisphenol, 4,4 ',
4 "-ethylidyne tris [2-methylphenol],
4,4 '-(3,4-diolbenzylidene) bis [2,6-dimethylphenol], 4,4'-(1-phenylethylidene) bis [2-methylphenol],
4,4 '-[(4-hydroxyphenyl) methylene] bis [2-methylphenol], 4,4'-[(3,4-
Dihydroxyphenyl) methylene] bis [2-methylphenol], 4,4 ′-[(4-hydroxyphenyl)
Methylene] bis [2,6-dimethylphenol], 2,
2 '-[(2-hydroxyphenyl) methylene] bis [3,5-dimethylphenol], 4,4'-[(3-
Hydroxyphenyl) methylene] bis [2,6-dimethylphenol], 2,2 ′-[(4-hydroxyphenyl) methylene] bis [3,5-dimethylphenol],
4,4 '-[(2-hydroxyphenyl) methylene] bis [2,4,6-trimethylphenol], 4,4',
4 ", 4 '"-(1,2-ethanedilidene) tetrakis [2-methylphenol], 4,4', 4 ", 4 '"-
(1,4-phenylene dimethylidine) tetrakisphenol, 4,4 ′, 4 ″, 4 ′ ″-(1,2-ethanedilidene) tetrakis [2,6-dimethylphenol],
4,4 ', 4 ", 4'"-(1,4-phenylene dimethylidine) tetrakis (2,6-dimethylphenol),
4,4'-isopropylidene bis [2-fluorophenol], 4,4 '-[(4-fluorophenyl) methylene] bis [2-fluorophenol], 4,4'-(phenylmethylene) bis [2- Fluorophenol],
4,4 '-[(4-fluorophenyl) methylene] bisphenol], bis (2,4-dihydroxyphenyl)
Methane, bis (p-hydroxyphenyl) methane, tri- (p-hydroxyphenyl) methane, 1,1,1-tri- (p-hydroxyphenyl) ethane, bis (2,2
3,4-trihydroxyphenyl) methane, 2,2-bis (2,3,4-dihydroxyphenyl) propane,
1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane, 4,4 '-[1
-[4- [1- [4-Hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol, bis (2,5-dimethyl-4-hydroxyphenyl) -2
-Hydroxyphenylmethane, 3,3,3 ', 3'-tetramethyl-1,1'-spirobiindene-5,6
7,5 ', 6', 7'-hexanol, 2,2,4-trimethyl-7,2 ', 4'-trihydroxyflavan,
Resorcin flavan 2,3,4-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,3,4,3'-tetrahydroxybenzophenone, 2 , 3,4,4'-tetrahydroxybenzophenone, 2,3,4,2'-tetrahydroxy-4'-methylbenzophenone, 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone, 2, 3, 4,
2 ', 6'-pentahydroxybenzophenone, 2,
4,6,3 ', 4', 5'-hexahydroxybenzophenone, 3,4,5,3 ', 4', 5'-hexahydroxybenzophenone and the like can be mentioned, preferably bisphenol A, P, S, F, AF, 4,4 '-(1-phenylethylidene) bisphenol, 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3
-Phenylpropane, 4 '-[1- [4- [1- [4-
Hydroxyphenyl] -1-methylethyl] phenyl]
Ethylidene] bisphenol, 2,2,4-trimethyl-7,2 ', 4'-trihydroxyflavan, 1,1,
1-tri- (p-hydroxyphenyl) ethane, 3,
Mention may be made of 3,3 ', 3'-tetramethyl-1,1'-spirobiindene-5,6,7,5', 6 ', 7'-hexanol. These may be used alone or in combination of two or more.

The amount of the phenolic compound added is usually 5 to 200 parts by weight, preferably 20 to 100 parts by weight, based on 100 parts by weight of the copolymer I. If the amount added is less than 5 parts by weight, the crosslinking between the phenolic compound and the melamine will be insufficient, resulting in severe swelling during development,
Patterning is difficult. On the other hand, when it exceeds 200 parts by weight, the film forming property as a film cannot be maintained.

(C) Melamines represented by the general formula (I) (hereinafter referred to as "melamines") Examples of the melamines include hexamethylolmelamine, hexabutyrolmelamine, partially methylolated melamine and alkylation thereof. Body, tetramethylol benzoguanamine, partially methylolated benzoguanamine and alkylated forms thereof.

The amount of these melamines added is the amount of the copolymer I
It is 1 to 100 parts by weight, preferably 5 to 50 parts by weight, relative to 100 parts by weight. If the addition amount is less than 1 part by weight, the crosslinking of the system is insufficient and patterning becomes difficult. On the other hand, if the amount exceeds 100 parts by weight, the alkali solubility of the entire composition becomes too high, which causes a problem that the residual film rate after development decreases.

(D) Trihalomethyltriazines represented by the general formula (II) (hereinafter referred to as "triazines") or onium salts represented by the general formula (III) (hereinafter referred to as "onium salts"). Examples of triazines include tris (2,4,6-
Trichloromethyl) -s-triazine, 2-phenyl-
Bis (4,6-trichloromethyl) -s-triazine,
2- (4-chlorophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (3-chlorophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (2-chlorophenyl) ) -Bis (4,6-trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -bis (4,6-trichloromethyl) -s
-Triazine, 2- (3-methoxyphenyl) -bis (4,6-trichloromethyl) -s-triazine, 2-
(2-Methoxyphenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4-methylthiophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (3-methylthio Phenyl) -bis (4,
6-trichloromethyl) -s-triazine, 2- (2-
Methylthiophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl)
-Bis (4,6-trichloromethyl) -s-triazine, 2- (3-methoxynaphthyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (2-methoxynaphthyl) -bis (4 , 6-Trichloromethyl) -s
-Triazine, 2- (4-methoxy-β-styryl)-
Bis (4,6-trichloromethyl) -s-triazine,
2- (3-Methoxy-β-styryl) -bis (4,6-
Trichloromethyl) -s-triazine, 2- (2-methoxy-β-styryl) -bis (4,6-trichloromethyl) -s-triazine, 2- (3,4,5-trimethoxy-β-styryl)- Bis (4,6-trichloromethyl) -s-triazine, 2- (4-methylthio-β-styryl) -bis (4,6-trichloromethyl) -s-triazine, 2- (3-methylthio-β-styryl ) -Bis (4,6-trichloromethyl) -s-triazine, 2
-(2-Methylthio-β-styryl) -bis (4,6-
Trichloromethyl) -s-triazine and the like.

Examples of onium salts include diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluorophosphonate, diphenyliodonium hexafluoroarsenate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium trifluoroacetate, diphenyliodonium-p-toluenesulfonate. 4-methoxyphenylphenyliodonium tetrafluoroborate, 4-methoxyphenylphenyliodonium hexafluorophosphonate, 4-methoxyphenylphenyliodonium hexafluoroarsenate, 4-methoxyphenylphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylferiodonium trioxide Fluoroace Over DOO, 4-methoxyphenyl iodonium -p- toluenesulfonate, bis (4-te
r-Butylphenyl) iodonium tetrafluoroborate, bis (4-ter-butylphenyl) iodonium hexafluorophosphonate, bis (4-ter-butylphenyl) iodonium hexafluoroarsenate, bis (4-ter-butylphenyl) iodonium trifluoro Rmethanesulfonate, bis (4-ter-
Butylphenyl) iodonium trifluoroacetate, diaryliodonium salts such as bis (4-ter-butylphenyl) iodonium-p-toluenesulfonate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphonate, triphenylsulfonium hexafluoroacene , Triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate, triphenylsulfonium-p-toluenesulfonate, 4-methoxyphenyldiphenylsulfonium tetrafluoroborate, 4-methoxyphenyldiphenylsulfonium hexafluorophosphonate, 4-methoxy Phenyldiphenylsulfonium hexafluoroarsene , 4-methoxyphenyl diphenyl sulfonium trifluoromethanesulfonate, 4
-Methoxyphenyldiphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium-p-toluenesulfonate, 4-phenylthiophenyldiphenyltetrafluoroborate, 4-phenylthiophenyldiphenylhexafluorophosphonate, 4-phenylthiophenyldiphenylhexafluoro Examples thereof include triarylsulfonium salts such as arsenate, 4-phenylthiophenyldiphenyltrifluoromethanesulfonate, 4-phenylthiophenyldiphenyltrifluoroacetate, and 4-phenylthiophenyldiphenyl-p-toluenesulfonate.

Among these compounds, 2- (3-chlorophenyl) -bis (4,6-trichloromethyl) -s-
Triazine, 2- (4-methoxyphenyl) -bis (4,6-trichloromethyl) -s-triazine, 2-
(4-Methylthiophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4-methoxy-β
-Styryl) -bis (4,6-trichloromethyl) -s
-Triazine, 2- (4-methoxynaphthyl) -bis (4,6-trichloromethyl) -s-triazine, diphenyliodonium trifluoroacetate, diphenyliodonium trifluoromethanesulfonate, 4-
Methoxyphenylphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium trifluoroacetate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate, 4-methoxyphenyldiphenyl Sulfonium trifluoroacetate, 4-phenylthiophenyldiphenyltrifluoromethanesulfonate, 4-phenylthiophenyldiphenyltrifluoroacetate and the like are preferably used in the present invention.

The amount of the compound represented by the general formula (II) or (III) added is 0.001 to 30 parts by weight, preferably 0.01 to 100 parts by weight of the copolymer I.
10 to 10 parts by weight. If the addition amount is less than 0.001 part by weight, the amount of acid generated by exposure is small, so that the crosslinking of the phenolic compound and the melamines does not proceed sufficiently, the residual film rate after development, the heat resistance of the pattern, the chemical resistance. Sex decreases. Further, if the addition amount exceeds 30 parts by weight, the sensitivity is lowered.

The compounds represented by the general formula (II) or (III) can be used in combination with a sensitizer. As the sensitizer, for example,
Coumarins, flavones, dibenzalacetones, dibenzalcyclohexanes, chalcones, xanthenes, thioxanthenes, porphyrins, acridines and the like having a substituent at the 3-position and / or the 7-position can be mentioned. To be

In the composition of the present invention, a compound containing two or more epoxy groups in the molecule other than the polymer I can be blended mainly for the purpose of improving heat resistance and adhesion. Examples of the compound containing two or more epoxy groups in the molecule include Epicoat 1001, 1002,
1003, 1004, 1007, 1009, 1010,
828 [Okaka Shell Epoxy Co., Ltd.] and other bisphenol A type epoxy resin commercial products, Epicoat 807 [Okaka Shell Epoxy Co., Ltd.] and other bisphenol F type epoxy resin commercial products, Epicoat 152, 154 [Okaka Shell Epoxy Co., Ltd.], EPPN201, 202
Commercially available phenol novolac type epoxy resin such as [Nippon Kayaku Co., Ltd.], EOCN-102, 103S, 10
4S, 1020, 1025, 1027 [Nippon Kayaku Co., Ltd.
, EIZO Shell 180S75 (produced by Yuka Shell Epoxy Co., Ltd.) and other commercially available cresol novolac type epoxy resins, CY-175, 177, 179 [CIBA-G].
EIGY A. G] ERL-4234, 4299, 4
221, 4206 [U. C. Made by Company C], Shoredyne 5
09 [Showa Denko KK], Aldalite CY-18
2, 192, 184 [CIBA-GEIGY A. G
Made], Epicron 200, 400 [Dainippon Ink Co., Ltd.
Products], Epicoat 871, 872 [produced by Yuka Shell Epoxy Co., Ltd.], ED-5661, 5662 [produced by Celanese Coating Co., Ltd.], commercial products of cycloaliphatic epoxy resins, Epolite 100MF [Kyoeisha Yushi-Kagaku Kogyo] Commercially available products of aliphatic polyglycidyl ether such as Epiol TMP (produced by NOF Corporation), and preferably bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy. Examples thereof include resins, cresol novolac type epoxy resins, and aliphatic polyglycidyl ethers. Most of the epoxy compounds listed here are high molecular weight compounds, but the epoxy compounds used in the present invention are not limited to the molecular weight, and even low molecular weight compounds such as glycidyl ethers of bisphenol A and bisphenol F can be used. Can be used. The addition amount of these epoxy compounds is usually 1 to 100 parts by weight, preferably 5 to 50 parts by weight of the copolymer I.

Further, a surfactant may be added to the composition of the present invention in order to improve coatability, for example, developability of a radiation-irradiated portion after striation or formation of a dry coating film. Examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether and other polyoxyethylene alkyl ethers, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether and other polyoxyethylene alkyl ethers. Nonionic surfactants such as polyethylene glycol dialkyl esters such as oxyethylene aryl ethers, polyethylene glycol dilaurate, polyethylene glycol distearate, F-top EF301, 303, 35
2 [manufactured by Shin-Akita Kasei Co., Ltd.], Megafac F171, 1
72, 173 [Dainippon Ink Co., Ltd.], Florard F
C430, 431 [Sumitomo 3M Limited], Asahi Guard AG710, Surflon S-382, SC10
1, 102, 103, 104, 105, 106 (manufactured by Asahi Glass Co., Ltd.) and other fluorine-based surfactants, organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), acrylic acid-based or methacrylic acid-based (co) Polymer Polyflow No. 57, 95 (produced by Kyoei Yushi Kagaku Kogyo Co., Ltd.) and the like. The content of these surfactants is usually 2 parts by weight or less, preferably 1 part by weight or less, based on the solid content of the composition.

Further, the composition of the present invention may contain an adhesion aid for improving the adhesion to the substrate. In addition, an antistatic agent, a storage stabilizer, an antihalation agent, an antifoaming agent and the like can be added to the composition of the present invention, if necessary.

As a method for applying the composition of the present invention to a substrate such as a silicon wafer, a predetermined amount of Copolymer I, a phenolic compound, melamines, triazines or onium salts and various compounding agents, for example, solid A method may be mentioned in which the solvent is dissolved in a solvent to a concentration of 20 to 40% by weight, filtered through a filter having a pore size of about 0.2 μm, and then applied by rotation, pouring or roll coating. As the solvent used in this case, ethylene glycol monomethyl ether, glycol ethers such as ethylene glycol monoethyl ether, ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoether. Diethylene glycol alkyl ethers such as ethyl ether, diethylene glycol diethyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol alkyl ether acetates such as propylene glycol propyl ether acetate, aromatics such as toluene and xylene Hydrogen acids, methyl ethyl ketone, cyclohexanone, 2-heptanone, methyl ethyl ketone, methyl isobutyl ketone, 2-hydroxy propionic acid methyl, ethyl 2-hydroxypropionate, 2-
Ethyl hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl oxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methyl-3-methoxybutylacetate, 3- Methyl-3-methoxybutyl propionate, 3-methyl-3-methoxybutyl butyrate, ethyl acetate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, butyl 3-methoxypropionate, 3- Methyl ethoxypropionate,
Esters such as ethyl 3-ethoxypropionate and butyl 3-ethoxypropionate can be used.
These solvents can be used alone or as a mixture. Furthermore, if necessary, benzyl ethyl ether,
Dihexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether,
Diethylene glycol monobutyl ether, acetonylacetone, isophorone, caproic acid, caprylic acid, 1-
Octanol, 1-nonanol, benzyl alcohol,
Benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate,
It is also possible to add a high boiling point solvent such as carbitol acetate.

The developer of the composition of the present invention is, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, inorganic alkaline water such as aqueous ammonia, ethylamine, n-propylamine. Primary amines such as diethylamine, di-n
-Secondary sphere amines such as propylamine, tertiary sphere amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline and the like Quaternary sphere ammonium salt or pyrrole, piperidine, 1,8-diazabicyclo- (5,4,0) -7-
Undecene, 1,5-diazabicyclo- (4,3,0)
An alkaline aqueous solution prepared by dissolving cyclic amines such as -5-nonane is used. In addition, a water-soluble organic solvent, for example, alcohols such as methanol and ethanol or a surfactant may be added to the developer in an appropriate amount.

[0032]

EXAMPLES The present invention is described below by dividing it into synthetic examples and examples, but the present invention is not limited to these synthetic examples and examples. In addition,% means weight%.

(1) Synthesis Example of Copolymer I Synthesis Example 1 of Copolymer I In a separable flask equipped with a stirrer, a cooling tube, a nitrogen introducing tube and a thermometer, 1.0 g of butadiene and 1 styrene were added.
0.0 g, methacrylic acid 20.0 g, dicyclopentanyl methacrylate 29.0 g, glycidyl methacrylate 40.0 g, N, N'-azobisisobutyronitrile 4.0 g, diethylene glycol dimethyl ether 30
After charging 0.0 g and purging with nitrogen for 30 minutes, the separable flask was immersed in an oil bath, the internal temperature was kept at 80 ° C., and polymerization was carried out for 3 hours while stirring to synthesize a resin. The obtained resin solution was poured into 10 liters of methanol, and the obtained precipitate was reprecipitated and purified twice with tetrahydrofuran / methanol. It was dried under reduced pressure at 50 ° C. overnight to obtain a white resin powder (hereinafter referred to as “resin (1)”). When the polystyrene-converted weight average molecular weight of the resin (1) was measured by GPC chromatograph HLC-8020 manufactured by Toyo Soda, it was 2.1.
It was 1 × 10 ⁴ .

Synthesis Example 2 of Copolymer I In a separable flask equipped with a stirrer, a cooling tube, a nitrogen introducing tube and a thermometer, 5.0 g of butadiene and 1 styrene were added.
0.0 g, methacrylic acid 20.0 g, dicyclopentanyl methacrylate 25.0 g, glycidyl methacrylate 40.0 g, N, N'-azobisisobutyronitrile 4.0 g, diethylene glycol dimethyl ether 30
After charging 0.0 g and purging with nitrogen for 30 minutes, the separable flask was immersed in an oil bath, the internal temperature was kept at 80 ° C., and polymerization was carried out for 4 hours while stirring to synthesize a resin. The obtained resin solution was poured into 10 liters of methanol, and the obtained precipitate was reprecipitated and purified twice with tetrahydrofuran / methanol. It was dried under reduced pressure at 50 ° C. overnight to obtain a white resin powder (hereinafter referred to as “resin (2)”). When the polystyrene-converted weight average molecular weight of the resin (2) was measured by GPC chromatograph HLC-8020 manufactured by Toyo Soda, it was found to be 1.5.
It was 1 × 10 ⁴ .

Synthetic Example 3 of Copolymer I 5.0 g of butadiene and styrene of 5.0 g in a separable flask equipped with a stirrer, a cooling tube, a nitrogen introducing tube and a thermometer.
0 g, methacrylic acid 16.0 g, dicyclopentanyl methacrylate 34.0 g, glycidyl methacrylate 4
0.0 g, N, N'-azobisisobutyronitrile 4.
0 g, diethylene glycol dimethyl ether 200.
After charging 0 g and purging with nitrogen for 30 minutes, the separable flask was immersed in an oil bath, the internal temperature was kept at 80 ° C., and polymerization was carried out for 4 hours while stirring to synthesize a resin. The obtained resin solution was poured into 10 liters of methanol, and the obtained precipitate was reprecipitated and purified twice with tetrahydrofuran / methanol. It was dried under reduced pressure at 50 ° C. overnight to obtain a white resin powder (hereinafter, referred to as “resin (3)”). When the polystyrene-converted weight average molecular weight of the resin (3) was measured by GPC chromatograph HLC-8020 manufactured by Toyo Soda, it was 1.73 ×.
It was 10 ⁴ .

Synthesis Example 4 of Copolymer I In a separable flask equipped with a stirrer, a cooling tube, a nitrogen introducing tube and a thermometer, 5.0 g of butadiene, 22.0 g of methacrylic acid and 3 of dicyclopentanyl methacrylate were placed.
3.0 g, glycidyl methacrylate 40.0 g, N,
Charge 4.0 g of N'-azobisisobutyronitrile and 250.0 g of diethylene glycol dimethyl ether,
After purging with nitrogen for 30 minutes, the separable flask was immersed in an oil bath, the internal temperature was kept at 80 ° C., and polymerization was carried out for 4 hours while stirring to synthesize a resin. The obtained resin solution was poured into 10 liters of methanol, and the obtained precipitate was reprecipitated and purified twice with tetrahydrofuran / methanol. After drying under reduced pressure at 50 ° C. overnight, a white resin powder was obtained (hereinafter referred to as “resin (4)”). Resin (4) made by Toyo Soda GPC
The polystyrene-reduced weight average molecular weight was measured by Chromatograph HLC-8020 and found to be 1.43 × 10 ⁴ .

(2) Examples Example 1 100 parts by weight of the resin (1) was mixed with 100 parts by weight of the phenolic compound (1), 20 parts by weight of the melamines (1) and 2 parts by weight of the photo-acid generator. , The total solids concentration is 35%
After being dissolved with diethylene glycol dimethyl ether so as to be, the mixture was filtered through a membrane filter having a pore size of 0.2 μm to prepare a composition solution of the present invention. The obtained solution was patterned according to (3) -1, and evaluated and observed according to (3) -2. The results are shown in Table 1. further,
When this solution was stored at 5 ° C. for 3 months and evaluated and observed previously, the same performance was obtained, and it was found that the composition of the present invention has excellent storage stability.

[0038]

[Table 1]

Examples 2 to 12 Example 1 except that the resins and compounds listed in Table 1 were used
Evaluation was carried out in the same manner as. The results are summarized in Table 1.

Comparative Example 1 OFPR-800 manufactured by Tokyo Ohka Kogyo Co., Ltd. was patterned according to (3) -1 and evaluated and observed according to (3) -2.
The results are shown in Table 1.

Comparative Example 2 OFPR-5000 manufactured by Tokyo Ohka Kogyo Co., Ltd. was patterned according to (3) -1 and evaluated and observed according to (3) -2. The results are shown in Table 1.

(3) Negative Resist Performance (3) -1: Evaluation Conditions The negative resist evaluation conditions were set as follows. Evaluation conditions: Copolymer I, phenolic compound, melamines represented by general formula (I) on a 6-inch silicon substrate,
A composition of the present invention comprising a compound represented by the general formula (II) or (III) and a solvent was spin-coated to a film thickness of 2.00 μm, and prebaked at 90 ° C. for 2 minutes on a hot plate. Nikon NSR175517A
After exposure was performed by changing the exposure time with a reduction projection exposure machine (NA = 0.50, λ = 365 nm), the exposure was performed at 100 ° C. for 2 hours.
Post exposure bake was performed on a hot plate for minutes. Development was carried out for 1 minute at 25 ° C. in an aqueous tetramethylammonium hydroxide solution having the concentration shown in Table 1.
After rinsing with water and drying, a pattern was formed on the wafer, and the performance evaluation shown below was performed.

(3) -2: Performance of Negative Resist Regarding the performance of the negative resist, the following items were evaluated and observed. Sensitivity: 2.00 μm line and space (L / S) of the negative resist pattern created under the above evaluation conditions
The exposure time required for the pattern line width of the pattern to be 2.00 μm (hereinafter referred to as “optimal exposure time” or “sensitivity”) was determined. Resolution: The size of the smallest space pattern resolved at the optimum exposure time was examined with a scanning electron microscope. Development degree: The surface roughness of the line portion after development and the presence or absence of undeveloped residue (scum) in the space portion were examined with a scanning electron microscope. Pattern shape: The cross-sectional shape of the resist pattern at the optimum exposure time was examined by an investigative electron microscope, and the quality of the cross-sectional shape was judged according to FIG. Heat resistance: The substrate on which a pattern formed according to 3- (1) is heated on a hot plate at 10 ° C. intervals for 5 minutes,
The temperature at which the 100 μm bulk pattern causes thermal deformation was investigated. 160 ℃ or more ○, 150 ~ 130 ℃ △, 120
The temperature below ℃ was marked as ×. Residual film rate: (film thickness after development / initial film thickness) × 100 is calculated,
90 or more was evaluated as ◯, and 89 or less as x. Adhesiveness: A pattern was formed on a silicon substrate with a thermal oxide film of 0.66 μm in the same manner as in 3- (1), and heated on a hot plate at 150 ° C. for 5 minutes. 40 heated substrates
% Ammonium fluoride aqueous solution / 50% hydrogen fluoride aqueous solution,
It was immersed in an etchant mixed at a volume ratio of 6: 1 at 25 ° C. for 6 minutes, and the undercut of 5.00 μmL / S pattern was examined by a scanning electron microscope.
1.01 to 1.30 μm was evaluated as Δ, and 1.31 μm or more was evaluated as x.

[0044]

INDUSTRIAL APPLICABILITY A radiation sensitive resin composition for a negative resist having excellent sensitivity, residual film rate, heat resistance and adhesion to a substrate can be obtained.

[Brief description of drawings]

FIG. 1 is a schematic diagram of a cross-sectional shape of a resist pattern.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI Technical display location G03F 7/038 505 H01L 21/027 // C08F 220/32 MMP (72) Inventor Bessho Nobuo Tokyo 2-11-24 Tsukiji, Chuo-ku, Japan Synthetic Rubber Co., Ltd.

Claims (1)

[Claims] 1. (A) (a) an unsaturated carboxylic acid,
(B) a radically polymerizable compound containing an epoxy group,
(C) Copolymer with other radically polymerizable compound, (B)
Phenolic compound, (C) general formula (I) (In the formula, R _{1 to} R ₆ may be the same or different and each represents a hydrogen atom or a group —CH ₂ OR, and R represents a hydrogen atom or a C _{1 to} C ₆ alkyl group). Melamines, and (D) general formula (II) (Wherein X represents halogen, A represents CX ₃ or a group represented by the following general formula, and B, D and E
Are each independently a hydrogen atom, C ₁ -C ₁₀ alkyl group, aryl group, alkoxy group, aryloxy group, thioalkyl group, thioaryl group, halogen, cyano group,
Nitro group, tertiary amino group with C ₁ -C ₁₀ alkyl group, carboxyl group, hydroxyl group, C ₁ -C ₁₀ ketoalkyl group, or ketoaryl group, C ₁ -C ₂₀ alkoxycarbonyl group, or alkylcarbonyl It represents an oxy group, and m represents an integer of 1 to 5. ) [Chemical 3] Or a general formula (III) (A) nZ ⁺ Y ⁻ ... ………… (III) (wherein A is the same as the above formula, Z is sulfur or Represents iodine, and Y is BF ₄ , PF ₆ , SbF ₆ , As
It represents F ₆ , p-toluenesulfonate, trifluoromethanesulfonate or trifluoroacetate, and n represents 2 or 3. ) A radiation-sensitive resin composition containing an onium salt functioning as a photoacid generator represented by the formula (1).