JPH04242256A - Positive type photoresist composition - Google Patents

Abstract

PURPOSE:To form a resist pattern superior in dimensional stability by adding a kind of benzotriazole derivative to the positive type photosensitive resin composition comprising a specified quinonediazido compound and an alkali- soluble novolak resin. CONSTITUTION:The photosensitive resin composition comprising at least (A) the alkali-soluble resin and (B) 1,2-naphthoquinonediazido-5- (and/or -4-) sulfonic acid ester of an aromatic polyhydroxy compound having >=3 hydroxyl groups (but except pyrogallic acid ester and polyhydroxybenzophenone), and further contains (C) at least one of the benzotriazole derivative represented by formula I (each of R1, R2, and R3 may be independently H or halogen or 1-10C alkyl) in an amount of 0.1-10wt.% of the total solid, thus permitting the obtained resist to have high sensitivity and not to be deteriorated by prebaking conditions and to form a resist pattern high in resolution.

Description

[0001] The present invention relates to an improvement in a positive photoresist composition comprising an alkali-soluble resin and a 1,2-naphthoquinone diazide compound. In particular, the present invention relates to a positive photoresist composition that has excellent ability to form fine patterns even on substrates having irregularities or high reflectance. The positive photoresist composition according to the present invention can be applied to semiconductor wafers or glass,
It is applied to a thickness of 0.5 to 3 μm onto a substrate such as ceramics or metal by spin coating or roller coating. Thereafter, it is heated and dried, and a circuit pattern and the like are printed by UV irradiation through an exposure mask and developed to form a positive image. Further, by etching this positive image as a mask, it is possible to process a pattern on the substrate. Typical fields of application are the manufacturing process of semiconductors such as ICs, the manufacturing of circuit boards such as liquid crystals and thermal heads, and other photoabsorption processes. [0002] As a positive photoresist composition,
Generally, a composition containing an alkali-soluble resin and a naphthoquinone diazide compound as a photosensitive material is used. For example, USP-3,666,473 as "Novolak type phenolic resin/naphthoquinone diazide substituted compound"
No., USP-4,115,128 and USP-4,1
No. 73,470, etc., and as the most typical composition “
An example of "novolac resin consisting of cresol-formaldehyde/trihydroxybenzophenone-1,2 naphthoquinone diazide sulfonic acid ester" is given by Thompson "
"Introduction to Microlithography" (L.F. Thompson "Introduct")
ion to Microlithography
) (ACS Publishing, No. 219, P112-121
)It is described in. Novolak resin as a binder can be dissolved in alkaline aqueous solution without swelling,
It is also particularly useful in this application because it provides high resistance to plasma etching, especially when the generated image is used as an etching mask. In addition, the naphthoquinonediazide compound used in photosensitive materials itself acts as a dissolution inhibitor that reduces the alkali solubility of novolak resin, but when it decomposes upon exposure to light, it produces alkali-soluble substances and rather reduces the alkali solubility of novolak resin. It is unique in that it acts as a light enhancer, and because of its large change in properties with respect to light, it is particularly useful as a photosensitive material for positive photoresists. From this point of view, many positive photoresists containing novolak resins and naphthoquinone diazide photosensitive materials have been developed and put into practical use. However, although positive photoresists boast such high resolution, when patterned on a highly reflective substrate such as an aluminum substrate, the image is affected by the reflected light (halation) from the substrate. becomes blurry and line width control becomes extremely difficult. This phenomenon becomes even more noticeable when there are steps on the substrate. In order to solve such problems (prevent halation), it is known to add light-absorbing materials. For example, in Japanese Patent Publication No. 51-37562, there is a dye oil yellow (having the following structural formula) that has light-absorbing properties in the ultraviolet region.
[0004] [Chemical formula 2] [0005] The light transmittance of the photoresist layer is reduced, and the light reflected on the substrate surface and transmitted through the photoresist layer is reduced, and the area where ultraviolet light should not be irradiated is reduced. A method has been disclosed for reducing the amount of light that goes around the screen and preventing a decrease in resolution. However, when using this dye, the light absorbing property is Since a part of the material sublimes from within the photoresist film, the antihalation effect is significantly reduced, and the resist performance in terms of sensitivity varies due to the large influence of prebaking conditions. JP-A-55-36838 discloses a light absorbing agent (1-alkoxy-
4-(4'-N,N-diallaminophenyl azo)benzene) derivatives have been disclosed, but when this light absorbing agent is added to a normal positive photoresist, the sensitivity is significantly reduced. It was hot. Also, JP-A-59-14
When using the alkali-soluble azo compound disclosed in No. 2538, there is little decrease in sensitivity and variation in sensitivity due to light-absorbing materials, but it is not fully satisfactory in terms of anti-halation effect, and it is difficult to use in the semiconductor industry in recent years. Currently, it is not possible to respond to the rapid miniaturization of processing dimensions. Furthermore, JP-A-1-241546 discloses a system in which an ultraviolet absorber and a gallic acid ester or a polyhydroxybenzophenone and a 1,2 naphthoquinone diazide (and/or -4-) sulfonic acid ester are used in combination. However, even with these systems, it cannot be said that sufficient antihalation ability is achieved. SUMMARY OF THE INVENTION It is an object of the present invention to improve the conventional photosensitive material as described above in order to cope with the rapidly progressing miniaturization of processing dimensions in the field of semiconductor device manufacturing. The object of the present invention is to provide a positive photoresist composition that can overcome the drawbacks of the composition and form a resist pattern with extremely excellent dimensional stability. That is, the purpose of the present invention is to
It is an object of the present invention to provide a positive photoresist composition that is highly sensitive, does not have resist performance deteriorated by prebaking conditions, has a high halation prevention effect, and can therefore form a resist pattern with high resolution. . [Means for Solving the Problems] As a result of intensive studies, the present inventors added a certain type of benzotriazole type to a positive photosensitive resin composition containing a specific quinone diazide compound and an alkali-soluble novolak resin. It was discovered that the above object could be achieved by adding a compound, and the present invention was completed based on this finding. That is, the object of the present invention is to at least produce (A) an alkali-soluble resin, (B) an aromatic polyhydroxy compound having three or more hydroxyl groups in one molecule (excluding gallic acid esters and polyhydroxybenzophenones). ) of 1,2 naphthoquinone diazide-5-(and/or -4-) sulfonic acid ester and (C) at least one compound represented by general formula (I) in a total solid content of 0.1 to This was achieved with a positive photoresist composition containing 10% by weight of ##STR3##. Here, R1, R2, and R3 may be the same or different and represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 10 carbon atoms. The present invention will be explained in detail below. In R1, R2, and R3 of the above general formula (I), the halogen atom is preferably a chlorine atom, a bromine atom, or an iodine atom, and the alkyl group is a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group,
Alkyl having 1 to 10 carbon atoms such as sec-butyl group, t-butyl group, pentyl group, isopentyl group, neopentyl group, t-pentyl group, hexyl group, isohexyl group, heptyl group, octyl group, nonyl group or decyl group Groups are preferred. The compound represented by general formula (I) acts as a light absorbing agent, and specific examples thereof include 2-(2'-hydroxy-5'-methylphenyl)-benzotriazole, 2
-(2'-hydroxy-3',5'-di-t-butylphenyl)-5-chlorobenzotriazole, 2-(2'
-Hydroxy-3'-t-butyl-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3
',5'-di-t-amyl phenyl)-benzotriazole, 2-(2'-hydroxy-3',5'-di-t-
butylphenyl)-benzotriazole, 2-(2'-
Examples include hydroxy-5'-t-butylphenyl)-benzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)-benzotriazole, but needless to say, they are not limited to these. do not have. These compounds are described in Chem. Prum. ,19,
Kauvas. 109 (1969). M. The method of Chem. Zversti, 28,673 (1
Belusa, J. 974). It can be easily synthesized by methods such as those described above, and is also provided on the market by Ciba-Geigy, Cipro Kasei, and others. These compounds can be added alone or in combination of two or more in an amount of 0.1 to 10% by weight, preferably 0.3 to 5% by weight of the total solid content. If the amount added is less than this, the antihalation effect will not be sufficient, and if it is more than this, precipitation will occur, which is not preferable. Examples of the alkali-soluble novolac resin used in the present invention include novolac resin, acetone-pyrogallol resin, polyhydroxystyrene and derivatives thereof. Particularly preferred are novolak resins, which are obtained by condensing a predetermined monomer as a main component with an aldehyde in the presence of an acidic catalyst. The predetermined monomers include cresols such as phenol, m-cresol, p-cresol, and o-cresol, and xylenol such as 2,5-xylenol, 3,5-xylenol, 3,4-xylenol, and 2,3-xylenol. Alkylphenols such as o-ethylphenol, m-ethylphenol, p-ethylphenol, pt-butylphenol, p-methoxyphenol, m-methoxyphenol, 3,5-dimethoxyphenol, 2-methoxyphenol 4-methylphenol/m-ethoxyphenol/p
-Ethoxyphenol, m-propoxyphenol/p
-Propoxyphenol/m-butoxyphenol/p
- Alkoxyphenols such as butoxyphenol, 2
- Bisalkylphenols such as methyl-4-isopropylphenol, hydroxy aromatic compounds such as o-chlorophenol, m-chlorophenol, p-chlorophenol, dihydroxybiphenyl, bisphenol A, phenylphenol, resorcinol, naphthol, etc. These can be used alone or in combination of two or more, but the invention is not limited thereto. Examples of aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, propylaldehyde, benzaldehyde, phenylaldehyde,
α-phenylpropylaldehyde, β-phenylpropylaldehyde, o-hydroxybenzaldehyde, m-
Hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde,
p-Nitrobenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-ethylbenzaldehyde, p-n-butylbenzaldehyde, furfural, chloroacetaldehyde, and acetals thereof, such as chloroacetaldehyde diethyl acetal, can be used. Of these, formaldehyde is preferred. These aldehydes may be used alone or in combination of two or more. As the acidic catalyst, hydrochloric acid, sulfuric acid, formic acid, acetic acid, oxalic acid, etc. can be used. The weight average molecular weight of the novolak resin thus obtained is preferably in the range of 2,000 to 30,000. If it is less than 2,000, film loss in unexposed areas after development will be large, and if it exceeds 30,000, the development speed will become low. Particularly preferred is a range of 6,000 to 20,000. Here, the weight average molecular weight is defined by the polystyrene equivalent value determined by gel permeation chromatography. The photosensitive material used in the present invention uses an esterified product of the following polyhydroxy compound with 1,2-naphthoquinonediazide-5-sulfonyl chloride and/or 1,2-naphthoquinonediazide-4-sulfonyl chloride. be able to. The polyhydroxy compounds include 2,3,4-trihydroxyacetophenone, 2
, 3,4-trihydroxyphenylpentyl ketone, 2
, polyhydroxyphenyl alkyl ketones such as 3,4-trihydroxyphenylhexyl ketone, bis(2,
4-dihydroxyphenyl)methane, bis(2,3,4
-trihydroxyphenyl)methane, bis(2,4
-dihydroxyphenyl)propane-1, bis(2,3
, 4-trihydroxyphenyl)propane-1, bis((poly)hydroxyphenyl)alkanes such as nordihydroguaiaretic acid, bis(2,3,4-trihydroxybenzoyl)methane, bis(3- Acetyl-4,5
,6-trihydroxyphenyl)methane, bis(2,3
,4-trihydroxybenzoyl)benzene, bis(2
, 4,6-trihydroxybenzoyl)benzene or other bis(polyhydroxybenzoyl)aryls, ethylene glycol-di(3,5-dihydroxybenzoate), ethylene glycol-di(3,4 , 5-trihydroxybenzoate), 2,3,4-biphenyltriol, 3,
4,5-biphenyltriol, 3,5,3',5'-
Biphenyltetrol, 2,4,2',4'-biphenyltetrol, 2,4,6,3',5'-biphenylpentol, 2,4,6,2',4',6 Polyhydroxybiphenyls such as '-biphenylhexol, 2,3,4,2',3',4'-biphenylhexol, 4,4
Bis(polyhydroxy) sulfides such as '-thiobis(1,3-dihydroxy)benzene, 2,2',4,4
Bis(polyhydroxyphenyl) ethers such as '-tetrahydroxydiphenyl ether, 2,2',4,4
Bis(polyhydroxyphenyl) sulfoxides such as '-tetrahydroxydiphenyl sulfoxide, 2,
Bis(polyhydroxyphenyl)sulfones such as 2',4,4'-diphenylsulfone, 4,4',3''
,4''-tetrahydroxy-3,5,3',5'-tetramethyltriphenylmethane, 4,4',2'',3
'',4''-pentahydroxy-3,5,3',5'
-tetramethyltriphenylmethane, 2,3,4,2'
,3',4'-hexahydroxy-5,5'-diacetyltriphenylmethane, 2,3,4,2',3',4'
,3'',4''-octahydroxy-5,5'-diacetyltriphenylmethane, 2,4,6,2',4',
Polyhydroxytriphenylmethanes such as 6'-hexahydroxy-5,5'-dipropionyltriphenylmethane, 3,3,3',3'-tetramethyl-1,1'-
spirobi-indane-5,6,5',6'-tetrol, 3,3,3',3'-tetramethyl-1,1'-spirobi-indane-5,6,7,5',6', 7'-hexol, 3,3,3',3'-tetramethyl-1,1
'-spirobiindane-4,5,6,4',5',6'
-hexol, 3,3,3',3'-tetramethyl-
1,1'-spirobi-indan-4,5,6,5',6
',7'-Hexol and other polyhydroxy spirobi-
Indanes, 3,3-bis(3,4-dihydroxyphenyl)phthalide, 3,3-bis(2,3,4-trihydroxyphenyl)phthalide, 3',4',5',6'-
Polyhydroxyphthalides such as tetrahydroxyspiro[phthalide-3,9'-xanthene], 2-(3,4-
dihydroxyphenyl)-3,5,7-trihydroxybenzopyran, 2-(3,4,5-trihydroxyphenyl)-3,5,7-trihydroxybenzopyran, 2
-(3,4-dihydroxyphenyl)-3-(3,4,
5-trihydroxybenzoyloxy)-5,7-dihydroxybenzopyran, 2-(3,4,5-trihydroxyphenyl)-3-(3,4,5-trihydroxybenzoyloxy)-5,7- Polyhydroxybenzopyrans such as dihydroxybenzopyran, or morin,
Flavonoid pigments such as quercetin and rutin can be used. These naphthoquinone diazide ester photosensitive materials of polyhydroxy compounds may be used alone or in combination of two or more. The ratio of photosensitive material and alkali-soluble resin used is 5 to 10 parts by weight of photosensitive material to 100 parts by weight of resin.
0 parts by weight, preferably 10 to 50 parts by weight. If the usage ratio is less than 5 parts by weight, the residual film rate will drop significantly, while if it exceeds 100 parts by weight, sensitivity and solubility in solvents will drop. The composition of the present invention may further contain a polyhydroxy compound to promote dissolution in a developer. Preferred polyhydroxy compounds include phenols, resorcinol, phloroglucin, acetone-pyrogallol condensation resin, phloroglucide, 2,4,2',
4'-biphenyltetrol, 4,4'-thiobis(1
,3-dihydroxy)benzene, 2,2',4,4'-
Tetrahydroxy diphenyl ether, 2,2',4,
4'-tetrahydroxydiphenyl sulfoxide, 2
, 2',4,4'-diphenylsulfone and the like. The amount of the polyhydroxy compound blended is usually 100 parts by weight or less, preferably 5 to 50 parts by weight, based on 100 parts by weight of the quinonediazide compound. Examples of the solvent for dissolving the photosensitive material and alkali-soluble novolak resin of the present invention include ketones such as methyl ethyl ketone and cyclohexanone, and 4-ethoxy-2
- Keto ethers such as butanone and 4-methoxy-4-methyl-2-pentanno, alcohol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether, ethers such as dioxane and ethylene glycol dimethyl ether, methyl cellosolve acetate, ethyl Cellosolve esters such as cellosolve acetate, fatty acid esters such as butyl acetate, methyl lactate, ethyl lactate, halogenated hydrocarbons such as 1,1,2-trichloroethylene, dimethylacetamide,
Examples include highly polar solvents such as N-methylpyrrolidone, dimethylformamide, and dimethylsulfoxide. These solvents can be used alone or in combination. A surfactant may be added to the positive photoresist composition of the present invention in order to further improve the coating properties such as striation. Examples of surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether, polyoxyethylene octyl phenol ether, and polyoxyethylene nonyl. Polyoxyethylene alkyl allyl ethers such as phenol ether, polyoxyethylene/polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristear Sorbitan fatty acid esters such as esters, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, etc. Nonionic surfactants such as ethylene sorbitan fatty acid esters, EFTOP EF3
01, EF303, EF352 (manufactured by Shin Akita Kasei Co., Ltd.)
, Megafuck F171, F173 (manufactured by Dainippon Ink Co., Ltd.), Florado FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103,
Fluorine-based surfactants such as SC104, SC105, and SC106 (manufactured by Asahi Glass Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), and acrylic or methacrylic acid (co)polymerized polyflow No. 7
5, No. 95 (manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.). The blending amount of these surfactants is usually 2 parts by weight or less, preferably 1 part by weight or less, per 100 parts by weight of the alkali-soluble resin and quinonediazide compound in the composition of the present invention. These surfactants may be added alone or in some combination. The positive photoresist composition of the present invention may contain dyes, plasticizers, adhesion aids, surfactants and the like, if necessary. Specific examples include dyes such as methyl violet, crystal violet, and malachite green; plasticizers such as stearic acid, acetal resin, phenoxy resin, and alkyd resin; adhesive aids such as hexamethyldisilazane and chloromethylsilane; and nonylphenoxypoly(ethyleneoxy)ethanol,
There are surfactants such as octylphenoxy poly(ethyleneoxy)ethanol. The above positive photoresist composition is coated onto a substrate (eg silicon/silicon dioxide coated) such as that used in the manufacture of precision integrated circuit elements by a suitable coating method such as a spinner or coater, and then coated in a predetermined manner. A resist image can be obtained by exposing to light through a mask and developing it. When the composition of the present invention is used, a good resist image can be obtained even when a high reflectance substrate is used. [0020]
The developing solution for the positive photoresist composition of the present invention includes inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, etc. Primary amines, secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethyl Aqueous solutions of alkalis such as quaternary ammonium salts such as ammonium hydroxide and cyclic amines such as pyrrole and piperidine can be used. Furthermore, appropriate amounts of alcohols and surfactants may be added to the aqueous alkali solution. Hereinafter, the present invention will be explained in more detail based on Examples, but the present invention is not limited thereto. Note that % indicates weight % unless otherwise specified. [Example] [Synthesis of novolak resin and photosensitive material] Synthesis Example 1 Synthesis of novolak resin a 40 g of m-cresol, 60 g of p-cresol, 37%
54 g of formalin aqueous solution and 0.05 g of oxalic acid were placed in a three-necked flask, heated to 100° C. with stirring, and reacted for 7 hours. After the reaction, cool to room temperature and cut into 30mm
The pressure was reduced to Hg. Then, the temperature was gradually raised to 150°C,
Water and unreacted monomers were removed. The obtained novolak resin a had an average molecular weight of 7900 (in terms of polystyrene). Synthesis Example 2 Synthesis of novolac resin b m-
Cresol and 3,5-dimethylphenol were condensed with formalin using oxalic acid as a catalyst in the same manner as in Synthesis Example 1.
-dimethylphenol = 60/40 (mole ratio), average molecular weight = 6700). Synthesis Example 3 Synthesis of Photosensitive Material A 5.7 g of phloroglucin, 30.2 g of 1,2-naphthoquinonediazide-5-sulfonyl chloride and 300 ml of acetone were
The mixture was poured into a neck flask and dissolved uniformly. Then triethylamine/acetone=11.4g/50
ml of the mixed solution was gradually added dropwise and reacted at 25° C. for 3 hours. The reaction mixture was poured into 1500 ml of a 1% aqueous hydrochloric acid solution, and the resulting precipitate was filtered, washed with water and dried (40°C), and 1,2-naphthoquinonediazide-5 of phloroglucin was removed.
-22.4 g of sulfonic acid ester (photosensitive material A) was obtained. Synthesis Example 4 Synthesis of Photosensitive Material B 11.7 g of 4,4'-thiobis(1,3-dihydroxy)benzene,
40.3 g of 1,2-naphthoquinonediazide-5-sulfonyl chloride and 300 ml of acetone were charged into a three-necked flask and uniformly dissolved. Then triethylamine/
A mixed solution of 15.2 g/50 ml of acetone was gradually added dropwise, and the mixture was reacted at 25° C. for 3 hours. The reaction mixture was poured into 1500 ml of 1% aqueous hydrochloric acid solution, and the resulting precipitate was filtered off.
After washing with water and drying (40℃), 4,4'-thiobis(1
, 3-dihydroxy)benzene 1,2-naphthoquinonediazide-5-sulfonic acid ester (photosensitive material B) 36.
4g was obtained.
Synthesis Example 5 Synthesis of Photosensitive Material C 11.5 g of 2,3,4-trihydroxybenzophenone
, 30.2 g of 1,2-naphthoquinonediazide-5-sulfonyl chloride and 300 ml of acetone were charged into a three-necked flask and uniformly dissolved. Next, a mixed solution of triethylamine/acetone=11.4 g/50 ml was gradually added dropwise, and the mixture was reacted at 25° C. for 3 hours. The reaction mixture was poured into 1500 ml of a 1% aqueous hydrochloric acid solution, and the resulting precipitate was filtered, washed with water and dried (40°C), and 1,2-naphthoquinone diazide of 2,3,4-trihydroxybenzophenone was obtained. 29.8 g of -5-sulfonic acid ester (photosensitive material C) was obtained. Synthesis Example 6 Synthesis of Photosensitive Material D 2, 3, 4,
4'-tetrahydroxybenzophenone 12.3g, 1
, 40.3 g of 2-naphthoquinonediazide-5-sulfonyl chloride and 300 ml of acetone were charged into a three-necked flask and uniformly dissolved. Next, a mixture of triethylamine/acetone (15.2 g/50 ml) was gradually added dropwise, and the mixture was reacted at 25° C. for 3 hours. The reaction mixture was poured into 1500 ml of a 1% aqueous hydrochloric acid solution, the resulting precipitate was filtered, washed with water and dried (40°C), and 1,2 of 2,3,4,4'-tetrahydroxybenzophenone was removed. -Naphthoquinone diazide-5-sulfonic acid ester (photosensitive material D) 39.7 g
I got it.
Synthesis Example 7 Synthesis of Photosensitive Material E Propyl 3,4,5-trihydroxybenzoate 20.3
40.3 g of 1,2-naphthoquinonediazide-5-sulfonyl chloride and 300 ml of acetone were placed in a three-necked flask and uniformly dissolved. Next, a mixture of triethylamine/acetone (15.2 g/50 ml) was gradually added dropwise, and the mixture was reacted at 25° C. for 3 hours. 1% reaction mixture
Pour into 1500 ml of aqueous hydrochloric acid solution, filter the resulting precipitate, wash with water and dry (40°C) to obtain 1,2-naphthoquinonediazide-5-sulfonic acid ester of propyl 3,4,5-trihydroxybenzoate. (Photosensitive material E) 39.4g
I got it. [Preparation of positive photoresist] Example 1
~5 Novolac resins (a, b) obtained in Synthesis Examples 1 and 2, photosensitive materials (A, B) obtained in Synthesis Examples 3 and 4, and the compound of the present invention were mixed into 18 g of ethyl lactate in the composition shown in Table 1. dissolves in 0
．． After filtration with a 2 μm microfilter, it was applied onto a silicon wafer with an aluminum film using a spinner and dried at 90°C for 30 minutes in a convection oven under a nitrogen atmosphere to obtain a photoresist film with a film thickness of 1.5 μm. Ta. In this membrane Co., Ltd.
Using a reduction projection exposure device LD-5010 manufactured by Hitachi, Ltd., the resist pattern was exposed through a test chart mask, developed with a 2.38% tetramethylammonium hydroxide aqueous solution for 1 minute, washed with water for 30 seconds, dried, and formed a resist pattern. I got it. Comparative Examples 1 to 5 Novolak resins (a, b) obtained in Synthesis Examples 1 and 2, photosensitive materials (A, B, C, D, E) obtained in Synthesis Examples 3 to 7, and light absorbent was dissolved in 18 g of ethyl lactate with the composition shown in Table 1, and a resist pattern was obtained in the same manner as in the example. [Evaluation of Resist Patterns] The resist patterns obtained in the Examples and Comparative Examples were observed with a scanning electron microscope to evaluate the performance of the photoresist compositions. The results are shown in Table 2. The sensitivity was defined as the reciprocal of the exposure amount for reproducing a 1.0 μm mask pattern, and was expressed as a relative value to the sensitivity of Comparative Example 1. The resolution is expressed as the limit resolution at an exposure dose that reproduces a 1.0 μm mask pattern.
Sublimation resistance is determined by applying the resist composition to a glass wafer and prebaking it in a convection oven at 90°C for 30 minutes.The absorbance at 365 nm is measured using a spectrophotometer.The ratio is the value (after prebaking/before prebaking). expressed. The anti-halation ability was expressed by the appearance of the side surface of the pattern observed with an electron microscope. As is clear from the results in Table 2, the positive photoresist composition of the present invention was excellent in sensitivity, resolution, sublimation resistance, and antihalation ability. Further, even when the solution for the positive photoresist composition of the present invention was left at 40° C. for 30 days, no precipitation of the light absorbing agent was observed in the solution. [Table 1] [Table 2] [Table 2] [Table 3] [Effects of the Invention] According to the composition of the present invention, line width controllability is achieved even on a high reflectance substrate. A photoresist with excellent properties such as sensitivity, resolution, and sublimation resistance can be obtained, and is suitably used as a photoresist for microfabrication.

Claims (1)

[Claims] Claim 1: At least the following (A), (B) and (C)
) A positive photoresist composition comprising: (A) Alkali-soluble resin, (B) 1,2 naphthoquinone diazide-5, an aromatic polyhydroxy compound having three or more hydroxyl groups in one molecule (excluding gallic acid ester and polyhydroxybenzophenone) -(and/or -4-) sulfonic acid ester, (C) 0.1 to 10% by weight of the total solid content of at least one compound represented by general formula (I). [Formula 1] Here, R1, R2, and R3 may be the same or different,
Represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 10 carbon atoms.