JPH06148879A - Positive type radiation sensitive resin composition - Google Patents

Abstract

PURPOSE:To provide the positive type radiation sensitive resin composition especially adapted to a resist for forming an integrated circuit. CONSTITUTION:This positive type resin composition comprises an alkali-soluble resin and 1, 2-quinonediazidosulfonic acid ester obtained by condensing tetrahydroxybenzophenone with 1, 2-quinonediazidosulfohalide in the presence of an amine thus permitting the obtained resin composition to be high in the proportion of tetraester, freed of mixing of fine metallic residues derived from a used basic catalyst, and to form a resist pattern superior in developability and high in resolution, to be sensitive to ultraviolet rays, far ultraviolet rays, X-rays, electron beams, molecular beams, gamma rays, synchrotron beams, proton beams, on the like, and especially suitable for the resist for forming integrated circuits.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive-type radiation-sensitive resin composition, more specifically, ultraviolet rays, far-ultraviolet rays, X-rays, electrons, which are composed of an alkali-soluble resin and a specific 1,2-quinonediazidesulfonic acid ester. Ray, molecular ray, γ ray,
The present invention relates to a positive-type radiation-sensitive resin composition which is sensitive to radiation such as synchrotron radiation and proton beam and which has good developability and is particularly suitable as a resist for producing integrated circuits.

[0002]

2. Description of the Related Art Conventionally, as a resist for producing an integrated circuit, a negative resist in which a bisazide compound is mixed with a cyclized rubber and a positive resist in which a 1,2-quinonediazide compound is mixed with an alkali-soluble resin are known. . In the negative resist, the bisazide compound desorbs nitrogen to become nitrene by UV irradiation, and three-dimensionally crosslinks the cyclized rubber, so that the solubility of the UV-irradiated part and the non-irradiated part in the developing solution composed of the solvent of the cyclized rubber is improved. There is a difference, and patterning is caused by this, but even if it is said that crosslinking does not completely cure the ultraviolet irradiation portion, there is a drawback that the resist pattern swells greatly in the developer and the resolution of the resist pattern is poor. .

On the other hand, the positive type resist contains an alkali-insoluble 1,2-quinonediazide compound in an alkali-soluble resin, is hardly dissolved in a developing solution composed of an alkaline aqueous solution, and hardly swells. 1,2-quinonediazide compound is changed to indenecarboxylic acid, and even if it is developed with a developing solution consisting of an alkaline aqueous solution, since there is extremely little change in the unirradiated portion to be the resist pattern, it is true to the mask pattern,
In addition, a high resolution resist pattern can be obtained. As a result, in recent years, where high integration of integrated circuits is required, positive resists having excellent resolution are often used. However, even in the case of this positive type resist, it is difficult to obtain a resist pattern faithful to the mask unless the exposed portion is rapidly developed to the portion in contact with the wafer. When the width is as narrow as 1 μm or less, the developability of the hem portion of the resist pattern is large and the resolution is affected. Therefore, as the degree of integration increases year by year, there is a strong demand for development of a positive resist which has good developability and can resolve a resist pattern of 1 μm or less.

[0004]

SUMMARY OF THE INVENTION The object of the present invention is to solve the above-mentioned problems of the prior art, developability is good, and a positive-type impression suitable as a positive-type resist for producing an integrated circuit having high resolution. It is to provide a radioactive resin composition.

[0005]

The present invention provides a positive-type radiation-sensitive resin composition comprising an alkali-soluble resin and a 1,2-quinonediazide compound, wherein the 1,2-quinonediazide compound is tetrahydroxybenzophenone and 1 The present invention provides a positive-type radiation-sensitive resin composition, which is a 1,2-quinonediazidesulfonic acid ester obtained by subjecting 2,2-quinonediazidesulfonic acid halide to a condensation reaction in the presence of amines. is there.

The 1,2-quinonediazide compound used in the present invention is tetrahydroxybenzophenone 1,2-quinonediazide compound.
A quinonediazide sulfonate. This one
2-quinonediazide sulfonic acid ester is 2,3
4,4'-tetrahydroxybenzophenone, 2,
2 ', 4,4'-tetrahydroxybenzophenone,
One or several tetrahydroxybenzophenones such as 2,2 ′, 4,6-tetrahydroxybenzophenone, 1,2-naphthoquinonediazide-5-sulfonic acid chloride and 1,2-naphthoquinonediazide-4-sulfonic acid It can be obtained by subjecting one or several 1,2-quinonediazidesulfonic acid halides such as chloride and 1,2-benzoquinonediazide-4-sulfonic acid chloride to condensation reaction in the presence of amines.

As the amines, for example, trimethylamine, triethylamine, tripropylamine, pyridine, tetramethylammonium hydroxide and the like are used. The amount of these amines used is 1,2-
The amount is usually 0.8 to 2 mol, preferably 1 to 1.5 mol, per 1 mol of quinonediazide sulfonic acid halide.

The condensation reaction is usually carried out in the presence of a solvent. Examples of the solvent used at this time include dioxane, tetrahydrofuran, acetone, methyl ethyl ketone, γ-butyrolactone, N-methylpyrrolidone,
Examples include N, N-dimethylacetamide, N, N-dimethylformamide, ethylene carbonate, propylene carbonate and the like. The amount of these solvents used is usually 100 to 1000 parts by weight with respect to 100 parts by weight of the reaction raw material. Although the temperature of the condensation reaction varies depending on the solvent used, it is usually -20.
-60 ° C, preferably 0-40 ° C. As a purification method after the condensation reaction, the by-produced hydrochloride is filtered, or water is added to dissolve the hydrochloride, followed by reprecipitation purification with a large amount of acidic water such as dilute hydrochloric acid aqueous solution, followed by drying. The method of doing can be illustrated. By using amines as the basic catalyst for the condensation reaction, the trace amount of metal based on the trace amount of the residue of the catalyst is not mixed in the condensation reaction product.

The 1,2-quinonediazide compound used in the present invention is, for example, 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,3,4,4. 4'-Tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4,4'-
Examples thereof include tetrahydroxybenzophenone-1,2-benzoquinonediazide-4-sulfonic acid ester.
In the condensation reaction of tetrahydroxybenzophenone and 1,2-quinonediazide sulfonic acid halide,
From the monosulfonic acid ester of tetrahydroxybenzophenone, a tetrasulfonic acid ester in which all the hydroxyl groups contained in tetrahydroxybenzophenone have reacted is produced.

The 1,2-quinonediazide sulfonic acid ester used in the present invention has a tetraester ratio of 10 to 80% by weight, preferably 20 to 70% by weight. When the proportion of the tetraester is less than 10% by weight, it is easy to dissolve in a developer consisting of an alkaline aqueous solution even when it is not irradiated with radiation when used as a positive-type radiation-sensitive resin composition, and high-resolution patterning is possible. If it exceeds 80% by weight, residual development may occur. As described above, in the positive-type radiation-sensitive resin composition, the ratio of the tetraester in the 1,2-quinonediazidesulfonic acid ester plays an important role in obtaining a resist pattern with high resolution. The 1,2-quinonediazidesulfonic acid ester used in the present invention is a 1,2-quinonediazidesulfonic acid ester obtained by subjecting tetrahydroxybenzophenone and a 1,2-quinonediazidesulfonic acid halide to a condensation reaction in the presence of amines. Based on the feature that it was obtained by the condensation reaction in the presence of amines, the condensation reaction was generated as compared with the case of using other basic catalysts, for example, inorganic alkalis such as sodium carbonate and sodium hydrogen carbonate. The ratio of the tetraester in the product is high, and the use of such a 1,2-quinonediazide sulfonic acid ester is a positive-type radiation-sensitive resin composition for obtaining a resist pattern with excellent developability and high resolution. Of technical significance for the preparation of Further, there is an advantage that a 1,2-quinonediazide sulfonic acid ester that does not have a metal residue based on a very small amount of an inorganic alkali catalyst which is very difficult to purify, which affects the performance of an integrated circuit, can be used. As the proportion of triester, diester and monoester other than tetraester, the proportion of the total amount of diester and triester is usually 20 to 60% by weight, preferably 30 to 60%.
% By weight, the proportion of monoester is usually 30% by weight or less,
It is preferably 20% by weight or less.

In the present invention, the compounding amount of 1,2-quinonediazide sulfonic acid ester is 1
It is usually 5 to 100 parts by weight with respect to 00 parts by weight,
It is preferably 10 to 50 parts by weight. When the amount is less than 5 parts by weight, the amount of carboxylic acid produced by the 1,2-quinonediazide sulfonic acid ester is small due to absorption of radiation, which makes patterning difficult, while when it exceeds 100 parts by weight. However, it is impossible to decompose all of the added 1,2-quinonediazide sulfonic acid ester by irradiation with radiation for a short time, which makes it difficult to develop with a developer containing an alkaline aqueous solution.

In the composition of the present invention, the above 1,2-
An amount of 1,2-quinonediazide sulfonic acid ester of tetrahydroxybenzophenone, which is an amount that does not impair the effects of the present invention on quinone diazide sulfonic acid ester 1,
100 parts by weight or less, preferably 40 parts by weight with respect to 00 parts by weight
Less than 1 part by weight of another 1,2-quinonediazide compound can be added.

Other 1,2-quinonediazide compounds used in this case include, for example, p-cresol-1,2-
1,2- (poly) hydroxybenzene such as benzoquinone diazide-4-sulfonic acid ester, resorcinol-1,2-naphthoquinone diazide-4-sulfonic acid ester, pyrogallol-1,2-naphthoquinone diazide-5-sulfonic acid ester Quinone diazide sulfonic acid esters; 2,4-dihydroxyphenyl-propyl ketone-1,2-benzoquinone diazide-4-sulfonic acid ester, 2,4-dihydroxyphenyl-n-hexyl ketone-1,2-naphthoquinone diazide-4- Sulfonic acid ester, 2,4-dihydroxybenzophenone-
1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,3,4-trihydroxyphenyl-n-hexylketone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4-trihydroxybenzophenone -1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,4,6-trihydroxybenzophenone-
1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,4,6-trihydroxybenzophenone-1,
2,2-naphthoquinonediazide-5-sulfonic acid ester or other (poly) hydroxyphenylalkylketone or (poly) hydroxyphenylarylketone 1,2-
Quinonediazide sulfonates; bis (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonate, bis (2,4-dihydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfonate Ester, bis (2,3,4-trihydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,2-bis (p-hydroxyphenyl) propane-1,2-naphthoquinonediazide-4 -Sulfonic acid ester, 2,2-bis (2,2
4-dihydroxyphenyl) propane-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,2-bis (2,3,4-trihydroxyphenyl) propane-
1,2-naphthonequinonediazide-5-sulfonic acid ester and other bis [(poly) hydroxyphenyl] alkane 1,2-quinonediazidesulfonic acid esters; 3,5
-Dihydroxybenzoic acid lauryl-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4-trihydroxybenzoic acid phenyl-1,2-naphthoquinonediazide-5-sulfonic acid ester, 3,4,5- (Poly) hydroxybenzoic acid such as propyl-1,2-naphthoquinonediazide-5-sulfonic acid ester of trihydroxybenzoic acid, phenyl-1,2-naphthoquinonediazide-5-sulfonic acid ester of 3,4,5-trihydroxybenzoic acid 1,2-quinonediazide sulfonic acid esters of acid alkyl esters or (poly) hydroxybenzoic acid aryl esters; bis (2,5-dihydroxybenzoyl) methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (2 , 3,4-trihydroxybenzoyl) meta 1,2-naphthoquinonediazide -
5-sulfonic acid ester, bis (2,4,6-trihydroxybenzoyl) methane-1,2-naphthoquinonediazide-5-sulfonic acid ester, p-bis (2,5-dihydroxybenzoyl) benzene-1,2- Naphthoquinonediazide-4-sulfonic acid ester, p-bis (2,2
3,4-trihydroxybenzoyl) benzene-1,2
-Naphthoquinonediazide-5-sulfonic acid ester, p
1-bis [(poly) hydroxybenzoyl] alkane such as bis (2,4,6-trihydroxybenzoyl) benzene-1,2-naphthoquinonediazide-5-sulfonic acid ester or bis [(poly) hydroxybenzoyl] benzene , 2-quinonediazide sulfonates; and ethylene glycol di (3,5-dihydroxybenzoate) -1,2-naphthoquinonediazide-
5-sulfonic acid ester, polyethylene glycol di (3,4,5-trihydroxybenzoate) -1,2
Examples include 1,2-quinonediazidesulfonic acid esters of (poly) ethylene glycol-di [(poly) hydroxybenzoate] such as naphthoquinonediazide-5-sulfonic acid ester.

Typical examples of the alkali-soluble resin used in the present invention include alkali-soluble novolac resins (hereinafter simply referred to as "novolac resins"). The novolak resin is obtained by polycondensing phenols and aldehydes in the presence of an acid catalyst. Examples of phenols include phenol, o-cresol, m-
Cresol, p-cresol, o-ethylphenol,
m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-butylphenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 3,4-xylenol,
3,5-xylenol, 2,3,5-trimethylphenol, p-phenylphenol, hydroquinone, catechol, resorcinol, 2-methylresorcinol, pyrogallol, α-naphthol, bisphenol A, dihydroxybenzoic acid ester, gallic acid ester, etc. Of these phenols, phenol, o-cresol, m-cresol, p-cresol, 2,5-
Xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, resorcinol, 2-methylresorcinol and bisphenol A are preferred. These phenols may be used alone or in admixture of two or more.

Examples of the aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, propylaldehyde, benzaldehyde, phenylacetaldehyde, α-phenylpropylaldehyde, β-phenylpropylaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde. , O-chlorobenzaldecht,
m-chlorobenzaldehyde, p-chlorobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, p-nitrobenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-
Methylbenzaldehyde, p-ethylbenzaldehyde, pn-butylbenzaldehyde and the like are used, and formaldehyde, acetaldehyde and benzaldehyde are preferable among these compounds. These aldehydes may be used alone or in admixture of two or more.
Aldehydes are used in a ratio of preferably 0.7 to 3 mol, particularly preferably 0.7 to 2 mol, per mol of phenols.

As the acid catalyst, for example, inorganic acids such as hydrochloric acid, nitric acid and sulfuric acid, or organic acids such as formic acid, oxalic acid and acetic acid are used. The amount of these acid catalysts used is preferably 1 × 10 ^{−4 to} 5 × 10 ⁻¹ mol per mol of phenols. In the condensation reaction, water is usually used as the reaction medium, but when the phenols used in the condensation reaction do not dissolve in the aqueous solution of aldehydes and become a heterogeneous system from the initial stage of the reaction, hydrophilicity is used as the reaction medium. It is also possible to use a solvent. Examples of these hydrophilic solvents include alcohols such as methanol, ethanol, propanol and butanol, and cyclic ethers such as tetrahydrofuran and dioxane. The amount of these reaction media used is usually 20 to 1 per 100 parts by weight of the reaction raw material.
000 parts by weight. The reaction temperature of the condensation reaction can be appropriately adjusted depending on the reactivity of the reaction raw materials, but usually,
The temperature is 10 to 200 ° C, preferably 70 to 150 ° C. After the condensation reaction is completed, in order to remove the unreacted raw materials, the acid catalyst and the reaction medium existing in the system, the internal temperature is generally set to 130 to
The temperature is raised to 230 ° C., the volatile components are distilled off under reduced pressure, and then the molten novolac resin is drowned on a steel belt or the like and collected.

After the completion of the condensation reaction, the reaction mixture is dissolved in the hydrophilic solvent and added to a precipitating agent such as water, n-hexane or n-heptane to precipitate the novolac resin, and the precipitate is separated. It can also be recovered by heating and drying. Examples of the alkali-soluble resin other than the novolak resin used in the present invention include polyhydroxystyrene or a derivative thereof, a styrene-maleic anhydride copolymer, polyvinyl hydroxybenzoate, and a methacrylic resin containing a carboxyl group.

These alkali-soluble resins may be used alone or in admixture of two or more. The composition of the present invention includes
To improve the sensitivity as a resist, a sensitizer can be added. Examples of the sensitizer include 2H-pyrido [3,2-b] -1,4-oxazine-3 [4H] one, 10H-pyrido [3,2-b] [1,4] -benzothiazine, Urazoles, hydantoins, barbituric acids, glycine anhydrides, 1-hydroxybenzotriazoles, alloxans, maleimides and the like can be mentioned. The compounding amount of the sensitizer is usually 100 parts by weight of 1,2-quinonediazide sulfonic acid ester,
It is 100 parts by weight or less, preferably 60 parts by weight or less.

Further, the composition of the present invention may contain a surfactant in order to improve the coating property, for example, the developability of the irradiation area after striation or dry film formation. Examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether and other polyoxyethylene alkyl ethers, polyoxyethylene octylphenol ether, polyoxyethylene nonylphenol ether and other polyoxyethylene alkylphenols. Nonionic surfactants of ethers and polyethylene glycol dialkyl ethers such as polyethylene glycol dilaurate and polyethylene glycol distearate, Ftop EF301, EF30
3, EF352 (manufactured by Shin-Akita Kasei Co., Ltd.), Megafac F171, F173 (manufactured by Dainippon Ink Co., Ltd.), Florard FC430, FC431 (Sumitomo 3M Ltd.)
Made), Asahi Guard AG710, Surflon S-38
2, SC101, SC102, SC103, SC10
4, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.) and other fluorine-based surfactants, organosiloxane polymer KP3
41 (manufactured by Shin-Etsu Chemical Co., Ltd.) or acrylic acid-based or methacrylic acid-based (co) polymer Polyflow No. 75, N
o. 95 (manufactured by Kyoeisha Oil and Fat Chemical Co., Ltd.) and the like are used. The blending amount of the surfactant is 10% by weight of the alkali-soluble resin and the 1,2-quinonediazide compound 10 in the composition of the present invention.
It is usually 2 parts by weight or less, preferably 1 part by weight or less, based on 0 parts by weight. Further, the composition of the present invention may contain a colorant, an adhesion aid, a storage stabilizer, an antifoaming agent, etc., if necessary.

In the composition of the present invention, the alkali-soluble resin, the 1,2-quinonediazide sulfonic acid ester, and the above-mentioned various compounding agents are dissolved in a solvent in predetermined amounts, and filtered with a filter having a pore size of about 0.2 μm. It is prepared by Examples of the solvent used at this time include glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; cellosolve esters such as methyl cellosolve acetate and ethyl cellosolve acetate; methyl 2-oxypropionate and 2-oxypropione. Examples thereof include monooxymonocarboxylic acid esters such as ethyl acidate; aromatic hydrocarbons such as toluene and xylene; ketones such as methyl ethyl ketone and cyclohexanone; esters such as ethyl acetate and butyl acetate. These solvents may be used alone or in admixture of two or more.

If necessary, benzyl ethyl ether, dihexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, acetonylacetone, isophorone, caprons, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, It is also possible to add a high boiling point solvent such as ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate and the like.

As a method for applying the composition of the present invention to a substrate such as a silicon wafer, the composition of the present invention is dissolved in the above solvent to a concentration of, for example, 5 to 50% by weight, filtered, and then Examples of the method include spin coating, flow coating, and roll coating.

The developer of the composition of the present invention includes, for example, sodium hydroxide, potassium hydroxide, sodium carbonate,
Inorganic alkalis such as sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxy And tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo (5,4,0) -7-undecene, 1,5-diazabicyclo (4,3,0) -5-nonane are dissolved. An alkaline aqueous solution is used. An alkaline aqueous solution prepared by adding an appropriate amount of a water-soluble organic solvent, for example, alcohols such as methanol and ethanol or a surfactant to the developer can also be used as the developer.

[0024]

The present invention will be described in more detail with reference to the following examples. Example 1 (1) In a 500 ml separable flask equipped with a stirrer, a dropping funnel, and a thermometer under light shielding, 2, 3, 4,
10.5 g of 4'-tetrahydroxybenzophenone and 34.5 g of 1,2-naphthoquinonediazide-5-sulfonic acid chloride [1,2-naphthoquinonediazide-5-
Sulfonic acid chloride / 2,3,4,4′-tetrahydroxybenzophenone = 3 (molar ratio)],
Further, 240 g of dioxane was added and dissolved while stirring. Separately, 14.3 g of triethylamine was charged into the dropping funnel, the separable flask was immersed in a water bath kept at 30 ° C., and when the internal temperature became constant at 30 ° C., triethylamine was slowly added dropwise. After adding triethylamine so that the inner temperature does not exceed 35 ° C., the precipitated triethylamine hydrochloride was removed by filtration, and the filtrate was poured into a large amount of dilute hydrochloric acid to precipitate 1,2-quinonediazidesulfonic acid ester. . This was filtered, collected, and dried at 40 ° C. for one day. The yield obtained by measuring the dry weight was 98%. The compositional analysis of the 1,2-quinonediazide sulfonic acid ester thus obtained showed that the proportion of tetraester was 63% by weight, the proportion of the total amount of diester and triesrel was 32% by weight, and the proportion of monoester was 5% by weight. Met. The composition distribution of the 1,2-quinonediazide sulfonic acid ester used in the present invention was measured by gel permeation chromatography (hereinafter abbreviated as GPC). The measurement conditions of GPC are as follows. Separation column: Column having an inner diameter of 20 mm and a length of 60 cm filled with polystyrene gel having an average pore diameter of 7 μm Eluent: tetrahydrofuran Flow rate: 2 ml / min Detector: Showa Denko's differential refractometer SHODEX SE3
Type 1 separation column temperature: 25 ° C. Sample injection amount: 100 μl of about 1.0 wt% tetrahydrofuran solution

(2) After charging 50 g of m-cresol and 50 g of p-cresol in a 500 ml flask,
66 ml of 37% by weight formaldehyde aqueous solution and 0.04 g of oxalic acid were added, the flask was immersed in an oil bath with stirring, the reaction temperature was kept at 100 ° C., and polycondensation was performed for 6 hours to obtain a novolak resin. It was After the reaction, the system was depressurized to 30 mmHg to remove water, and the internal temperature was further raised to 130 ° C. to distill off unreacted substances. Then, the molten novolac resin was returned to room temperature and recovered.

(3) Novolak resin 2 obtained in (2)
0 g, 2,3,4,4′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester 5 g obtained in (1) and ethyl cellosolve acetate 60 g were well stirred at room temperature and dissolved, The solution of the composition of the present invention was prepared by filtering with a membrane filter having a pore size of 0.2 μm. After coating this solution on a silicon wafer having a silicon oxide film with a spinner,
Prebaking was performed at 2 ° C. for 2 minutes to form a 1.2 μm thick resist layer. Next, a stepper is used to irradiate ultraviolet rays for 0.58 seconds through a pattern mask, and tetramethylammonium hydroxide (hereinafter abbreviated as TMA).
Develop with 2.4 wt% aqueous solution for 60 seconds, rinse with water,
Dried. When the obtained resist pattern was observed with a scanning electron microscope, a portion that could not be completely developed at the joint between the silicon wafer and the resist pattern, that is, no development residue was observed, and a resist pattern with a line width of 0.8 μm was resolved. It was The results are shown in Table 1.

Examples 2 to 4 The amount of triethylamine shown in Table 1 was used in place of 14.3 g of triethylamine, and the same procedure as in Example 1 (1) was carried out otherwise to obtain 1,2-quinonediazidesulfonic acid ester. Table 1 shows the amount of raw material charged and the compositional analysis results of the obtained 1,2-quinonediazide sulfonic acid ester by GPC. Next, the novolak resin obtained in Example 1 (2) and the 1,2-quinonediazide sulfonic acid ester were used, and the other treatments were performed in the same manner as in Example 1 (3), and a positive type radiation sensitive resin composition was obtained. A solution of the product was prepared. Then
A resist layer was formed on a silicon wafer in the same manner as in Example 1 (3), and a stepper was used to interpose a pattern mask,
It was irradiated with ultraviolet rays for the number of exposure seconds shown in Table 1, developed with an aqueous TMA solution having each concentration shown in Table 1, rinsed with water, and dried.
Table 1 shows the resolution of the obtained resist pattern.

Comparative Examples 1 to 4 1,2-quinonediazide sulfonic acid was prepared by substituting 14.3 g of triethylamine with the basic catalysts shown by A to D in Table 1 and otherwise treating as in Example 1 (1). The ester was obtained. Table 1 shows the amount of raw material charged and the compositional analysis results of the obtained 1,2-quinonediazide sulfonic acid ester by GPC. Next, the novolak resin obtained in Example 1 (2) and the 1,2-quinonediazide sulfonic acid ester were used, and the other treatments were performed in the same manner as in Example 1 (3), and a positive type radiation sensitive resin composition was obtained. A solution of the product was prepared. Then
A resist layer was formed on a silicon wafer in the same manner as in Example 1 (3), and a stepper was used to interpose a pattern mask,
It was irradiated with ultraviolet rays for the number of exposure seconds shown in Table 1, developed with an aqueous TMA solution having each concentration shown in Table 1, rinsed with water, and dried.
The resolution of the obtained resist pattern is shown in Table 1.

[0029]

[Table 1] A: 20 wt% sodium carbonate aqueous solution 95 ml B: Saturated sodium hydrogen carbonate aqueous solution 296 ml + 10 wt% sodium carbonate aqueous solution 42 ml C: 25 wt% sodium carbonate aqueous solution 20.4 g D: Saturated sodium hydrogen carbonate aqueous solution 198 ml + 10 wt% sodium carbonate 28 ml (Note) * THBP: 2,3,4,4'-tetrahydroxybenzophenone-** NQD: 1,2-naphthoquinonediazide-5-sulfonic acid chloride

Examples 5 to 8 Instead of the novolac resin obtained in Example 1 (2),
A novolak resin obtained by polycondensation using mixed cresols having a mixing ratio shown in Table 2, 66 ml of a 37% by weight aqueous formaldehyde solution and 0.04 g of oxalic acid was used, and otherwise the same as in Example 1 (3). To prepare a solution of the composition of the present invention. Then, a resist layer was formed on a silicon wafer in the same manner as in Example 1 (3), and was irradiated with ultraviolet rays through the pattern mask using a stepper for the exposure time shown in Table 2 and developed with a 2.4% by weight TMA aqueous solution. Then rinsed with water and dried. The resolution of the obtained resist pattern was high, and no development residue was observed. The results are shown in Table 1.

[0031]

[Table 2]

[0032]

INDUSTRIAL APPLICABILITY According to the present invention, by using a 1,2-quinonediazide compound added to an alkali-soluble resin, which is produced by using amines as a basic catalyst in a condensation reaction, other basic catalysts, for example, Positive-type radiation-sensitive resin that gives a resist pattern with excellent developability and high resolution, with a higher proportion of tetraester in the condensation reaction product than when using inorganic alkalis such as sodium carbonate and sodium hydrogen carbonate. A composition can be provided. Further, it is possible to provide a positive-type radiation-sensitive resin composition in which a metal based on an extremely small amount of an inorganic alkali catalyst which is extremely difficult to purify and which affects the performance of an integrated circuit does not remain. The positive-type radiation-sensitive resin composition of the present invention is sensitive to radiation such as ultraviolet rays, far ultraviolet rays, X-rays, electron beams, molecular beams, γ-rays, synchrotron radiation, and proton beams, and is a resist for manufacturing integrated circuits. In particular, it is suitable as a positive resist for producing an integrated circuit having a high degree of integration.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yoshiyuki Haruta 2-11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd.

Claims (1)

[Claims] 1. A positive-type radiation-sensitive resin composition comprising an alkali-soluble resin and a 1,2-quinonediazide compound, wherein the 1,2-quinonediazide compound is tetrahydroxybenzophenone and 1,2-quinonediazidesulfonic acid halide. Is a 1,2-quinonediazide sulfonic acid ester obtained by condensation reaction of the above in the presence of amines.