JPH0827535B2 - Positive type radiation sensitive resin composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a positive-type radiation-sensitive resin composition, more specifically, an alkali-soluble resin and a 1,2-quinonediazide compound to which a compound having a specific structure is added. Ultraviolet rays, far ultraviolet rays, X-rays, electron beams, molecular beams, γ rays,
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 is particularly suitable as a resist for producing integrated circuits.

(Prior Art) Conventionally, as a resist used 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 used. A resist is 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 cyclized rubber solvent is high. However, cross-linking does not completely cure the UV-irradiated area, so the resist pattern swells significantly in the developer and the resist pattern resolution is poor. There is.

On the other hand, the positive type resist contains an alkali-insoluble 1,2-quinonediazide compound in an alkali-soluble resin, and thus is difficult to dissolve in a developer composed of an alkaline aqueous solution.
Almost no swelling. That is, in the positive resist, the 1,2-quinonediazide compound in the ultraviolet irradiation area changes to indenecarboxylic acid, and even when developed with a developing solution composed of an alkaline aqueous solution, the change in the unirradiated area forming the resist pattern is extremely small, Faithful to the mask pattern,
In addition, a resist pattern having a high resolution can be obtained. For this reason, in recent years, when high integration of integrated circuits is required, positive resists having excellent resolution are often used.

However, in the case of a positive resist formed by dissolving an alkali-soluble resin and a 1,2-quinonediazide compound in a solvent, if stored for a long time, deterioration of the alkali-soluble resin and deterioration of the 1,2-quinonediazide compound gradually proceed,
There is a problem that the sensitivity changes and the viscosity of the resist solution changes.

(Problems to be Solved by the Invention) An object of the present invention is to solve the above-mentioned problems of the prior art and to provide a positive radiation-sensitive resin composition excellent in storage stability against changes in sensitivity and changes in viscosity. To provide.

(Means for Solving the Problems) The present invention provides a positive-type radiation-sensitive resin composition containing an alkali-soluble resin and a 1,2-quinonediazide compound, which has structural formulas (I) to (IV) Of at least one selected from the group consisting of dimethyl sulfone, diethyl sulfone and diphenyl sulfone in the molecule, and the content of these compounds is 0.001 to 100 parts by weight based on 100 parts by weight of the alkali-soluble resin. It is characterized by being 10 parts by weight.

Examples of the compound having at least one of structural formulas (I) to (IV) in the molecule (hereinafter sometimes referred to as compound (A)) used in the present invention include compounds having structural formula (I). Examples include thiocarbanilide, di-o-tolylthiourea, N, N'-diethylthiourea, 1,3-bis (dimethylaminopropyl) -2-thiourea, trimethylthiourea, tetramethylthiourea, 2-mercaptobenzimidazole, 2- Examples of thioureas such as mercaptomethylbenzimidazole and 2-mercaptoimidazoline, and compounds having the structural formula (II) include mercaptobenzothiazole, Nt-butyl-2-benzothiazolylsulfenamide, N, N'- Dicyclohexyl-2-benzothiazolyl sulfenamide, dibenzothiazolyl disulfide , 2- (4-morpholinodithio) benzothiazole, 2- (2,4-dinitro-phenyl) mercaptobenzothiazole, cyclohexylamine salt of mercaptobenzothiazole, N, N'-diethylthiocarbamoyl-2-benzothiazolyl Sulfide,
Thiazoles such as N, N′-diisopropyl-2-benzothiazole sulfenamide, N-cyclohexyl-2-benzothiazolyl sulfenamide, N-oxydiethylene-2-benzothiazolyl sulfenamide, structural formula (III ), Dithiocarbamines such as piperidinium pentamethylene dithiocarbamate and pipecoline pipecolyl dimethyldithiocarbamate, and compounds having the structural formula (IV) are represented by the following general formula (VII) (Wherein R represents an alkyl group having 1 to 18 carbon atoms or a phenyl group, and 4 ≧ n ≧ 1), for example, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, tetra Examples thereof include thiurams such as methyl thiuram monosulfide, tetraethyl thiuram monosulfide, tetrabutyl thiuram monosulfide and dipentamethylene thiuram tetrasulfide. In the present invention,
In addition to these compounds (A), dimethyl sulfone, diethyl sulfone and diphenyl sulfone (hereinafter sometimes referred to as compound (B)) can be used. Of these compounds (A) and (B), the compound (A) is preferable, and the compound having the structural formula (IV) is particularly preferable.

These compounds can be used alone or in combination of two or more.

The amount of the compounds (A) and (B) used is 0.001 to 10 parts by weight, preferably 0.01 to 5 parts by weight, based on 100 parts by weight of the alkali-soluble resin. When the usage ratio is less than 0.001 part by weight, the storage stability with respect to sensitivity and viscosity is deteriorated, and when the usage ratio exceeds 10 parts by weight, the resist performance such as sensitivity, residual film rate and resolution is deteriorated, which is preferable. Absent.

Examples of the alkali-soluble resin used in the present invention include an alkali-soluble novolac resin (hereinafter, simply referred to as “novolac resin”). The novolak resin is obtained by condensing phenols and aldehydes in the presence of an acid catalyst.

Examples of the phenols used at this time 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, hydroxynon, catechol, resorcinol, 2-methylresorcinol, pyrogallol, α-naphthol, bisphenol A, dihydroxybenzoate, gallic Acid esters and the like can be mentioned. 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 combination of two or more.

Examples of aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, propylaldehyde, benzaldehyde, phenylacetaldehyde, 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-methylbenzaldehyde, p-ethylbenzaldehyde,
Examples thereof include pn-butylbenzaldehyde, and formaldehyde, acetaldehyde and benzaldehyde are preferable among these aldehydes. These aldehydes can be used alone or in combination of two or more. The amount of aldehydes used is 1 phenol
It is preferably 0.7 to 3 mol per mol.

As the acid catalyst, 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 usually 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, a hydrophilic solvent is used as the reaction medium. Can also be used. Examples of the hydrophilic solvent used at this time 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.
It is 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 is usually 10 to 200 ° C.

After the completion of the condensation reaction, the unreacted raw materials, the acid catalyst and the reaction medium existing in the system are removed to recover the novolak resin.

As the alkali-soluble resin other than the novolac resin used in the present invention, for example, polyhydroxystyrene or its derivative, styrene-maleic anhydride copolymer, polyvinyl hydroxybenzoate, carboxyl group-containing methacrylic resin, etc. are used.

These novolac resins can be used alone or in combination of two or more.

The 1,2-quinonediazide compound used in the present invention is
Although not particularly limited, examples thereof include 1,2-benzoquinonediazide-4-sulfonic acid ester, 1,2-naphthoquinonediazide-4-sulfonic acid ester, and 1,2-naphthoquinonediazide-5-sulfonic acid ester. Specifically, p-cresol-1,2-benzoquinonediazide-
1,2-quinonediazidesulfonic acid of (poly) hydroxybenzene such as 4-sulfonic acid ester, resorcinol-1,2-naphthoquinonediazide-4-sulfonic acid ester, pyrogallol-1,2-naphthoquinonediazide-5-sulfonic acid ester Esters, 2,4-dihydroxyphenyl-propyl ketone-1,2-benzoquinonediazide-4-sulfonic acid ester, 2,4-dihydroxyphenyl-n-hexylketone-1,2-naphthoquinonediazide-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-sulfone Acid ester, 2,3,4-trihydroxybenzophenone-1,2-naphthoquinone diazide-5-sulfonic acid ester, 2,4,
6-trihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,4,6-trihydroxybenzophenone-1,2-naphthoquinonediazide-
5-sulfonic acid ester, 2,2 ', 4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5
-Sulfonic acid ester, 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,2 ', 4,4'-tetrahydroxybenzophenone-1,2-naphtho Quinonediazide-4-sulfonic acid ester, 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,2 ', 3,4,6'-pentahydroxybenzophenone- 1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,2 ', 3,4,6'-pentahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,3,3', 4 ′, 5′-Hexahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,3 ′, 4,4 ′, 5′-hexahydroxybenzophenone-1,2-naphthoquinonediazide-5 Sulfone Ester, 2,3 ', 4,4', 5 ', 1,2-6-hexahydroxybenzophenone naphthoquinonediazide -4
-(Poly) hydroxyphenylalkylketone or (poly) hydroxy such as sulfonic acid ester, 2,3 ', 4,4', 5 ', 6-hexahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester Phenylaryl ketone 1,2-quinonediazide sulfonates, bis (p-hydroxyphenyl) methane-1,2
-Naphthoquinone diazide-4-sulfonic acid ester, bis (2,4-dihydroxyphenyl) methane-1,2-naphthoquinone diazide-5-sulfonic acid 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 (2,4-
Dihydroxyphenyl) propane-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,2-bis (2,3,4
-Trihydroxyphenyl) propane-1,2-naphthoquinonediazide-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-trihydroxybenzoic acid propyl- 1,2-
Naphthoquinonediazide-5-sulfonate, 3,4,
5-trihydroxybenzoic acid phenyl-1,2-naphthoquinonediazide-5-sulfonic acid ester (poly) hydroxybenzoic acid alkyl ester or (poly) hydroxybenzoic acid aryl ester 1,2-quinonediazide sulfonic acid esters, Bis (2,5-dihydroxybenzoyl) methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (2,3,4-trihydroxybenzoyl) methane-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 (2,3,4-trihydroxybenzoyl) benzene-1,2-naphthoquinonediazide-5-sulfonic acid ester, p-bis (2,4,6-trihydroxybenzoyl) benzene-1 1,2-naphthoquinonediazide-5-sulfonic acid ester and other bis [(poly) hydroxybenzoyl] alkanes or bis [(poly) hydroxybenzoyl] benzene 1,2-quinonediazidesulfonic acid esters, ethylene glycol-di (3, Five
-Dihydroxybenzoate) -1,2-naphthoquinonediazide-5-sulfonate, polyethylene glycol-di (3,4,5-trihydroxybenzoate) -1,2
-1,2-quinonediazide sulfonic acid esters of (poly) ethylene glycol-di [(poly) hydroxybenzoate] such as naphthoquinonediazide-5-sulfonic acid ester, and α-pyrone natural dye having a hydroxyl group, 1,2-
Quinonediazide sulfonates, γ-pyrone natural dyes having hydroxyl groups 1,2-quinonediazide sulfonates, diazine natural dyes having hydroxyl groups 1,
Examples thereof include 2-quinonediazide sulfonic acid esters. Besides these compounds, “Light-Sensiti” by J. Kosar
ve Systems "339-352 (1965), John Wiley & Sons (New York) and WSDe Forest" Photoresist "50 (197
5), published in McGraw-Hill, Inc., (New York)
A 1,2-quinonediazide compound can also be used.

These 1,2-quinonediazide compounds may be used alone or in admixture of two or more.

The content of these 1,2-quinonediazide compounds is usually 5 to 1 with respect to 100 parts by weight of the alkali-soluble resin.
It is used in an amount of 00 parts by weight, preferably 10 to 50 parts by weight. If this blending amount is too small, the amount of carboxylic acid generated by the 1,2-quinonediazide compound absorbing the radiation is small, and thus patterning becomes difficult.On the other hand, if the blending amount is too large, the amount of carboxylic acid added by short-time irradiation is 1, All of the 2-quinonediazide compound cannot be decomposed, making it difficult to develop with a developer containing an alkaline aqueous solution.

In the present invention, the compounds (A) and (B) may be used in combination with general phenol-based and amine-based antioxidants. Examples of the fireproofing agent include p-phenylphenol, 4,4'-dihydroxyphenyl, 2,5-di-t-amylhydroquinone, 4,4'-dihydroxydiphenylcyclohexane,
2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,6-di-t-butyl-p-cresol,
4,4'-butylidene-bis (6-t-butyl-m-cresol), octadecyl-3- (3 ', 5'-di-t-butyl-4-hydroxyphenyl) -propionate, 2,
4-bis (n-octylthio) -6- (4-hydroxy-3,5-t-butylanilide) -1,3,5-triazine and other phenolic antioxidants, and phenylenediamine,
Diphenylamine, aldol-α-naphthylamine,
Phenyl-α-naphthylamine, phenyl-β-naphthylamine, p, p'-dimethoxydiphenylamine, octylated diphenylamine, N, N'-diphenyl-
p-phenylenediamine, N, N'-di-β-naphthylmethyl-p-phenylenediamine, N- (1,3-dimethyl-butyl) -N'-phenyl-p-phenylenediamine, N, N'-bis (1,4-Dimethyl-pentyl) -p-phenylenediamine, N-phenyl-N'-cyclohexyl-p-phenylenediamine, N-phenyl-N'-isopropyl-p-phenylenediamine, N, N'-bis ( 1-methylheptyl) -p-phenylenediamine, N,
Examples include amine anti-aging agents such as N'-diallyl-p-phenylenediamine.

The proportion of these antiaging agents used is usually 0.01 to 10 parts by weight, preferably 0.01 to 5 parts by weight, based on 100 parts by weight of the alkali-soluble resin.

The composition of the present invention may contain a sensitizer in order to improve the sensitivity as a resist. Examples of these sensitizers include 2H-pyrido [3,2-b] -1,4-
Oxazin-3 [4H] ones, 10H-pyrido [3,2-b]
[1,4] -Benzothiazines, urazoles, hydantoins, barbituric acids, glycine anhydrides, 1-hydroxybenzotriazoles, alloxans, maleimides, and JP-B-48-12242 and JP-B-48- 35402
Examples thereof include sensitizers described in JP-A Nos. 58-37641 and 58-149042. The compounding amount of these sensitizers is usually 100 parts by weight or less, preferably 4 to 60 parts by weight with respect to 100 parts by weight of the 1,2-quinonediazide compound.
Parts by weight.

A surfactant may be added to the composition of the present invention in order to improve coatability, for example, striation or developability of a radiation-irradiated portion after 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 octylphenol ether, polyoxyethylene nonylphenol ether and other polyoxyethylene alkylphenols. Nonionic surfactants of polyethylene glycol dialkyl ethers such as ethers, polyethylene glycol dilaurate, polyethylene glycol distearate,
F-top EF301, EF303, EF352 (manufactured by Shin-Akita Kasei Co., Ltd.),
Megafac F171, F173 (manufactured by Dainippon Ink and Chemicals, Inc.)
57-178242, a linear fluorine-containing surfactant having a fluorinated alkyl group or a perfluoroalkyl group, Fluorard FC430, FC431 (manufactured by Sumitomo 3M Limited), Asahi Guard AG710, Surflon S-382, SC101, S
Fluorine-based surfactants such as C102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.), organosiloxane polymer KP34
1 (manufactured by Shin-Etsu Chemical Co., Ltd.), acrylic acid-based or methacrylic acid-based (co) polymers Polyflow No. 75, No. 95 (manufactured by Kyoeisha Yushi-Kagaku Kogyo Co., Ltd.) and the like. The amount of these surfactants to be added depends on the amount of alkali-soluble resin and 1,2 in the composition.
The amount is usually 2 parts by weight or less, preferably 1 part by weight or less, per 100 parts by weight of the total amount of the quinonediazide compound.

Further, the composition of the present invention, to visualize the latent image of the radiation irradiated portion, a colorant to reduce the effect of halation during irradiation, an adhesion aid to improve the adhesion, Further, if necessary, an antifoaming agent or the like can be added.

When applying the composition of the present invention to a substrate, the alkali-soluble resin, the 1,2-quinonediazide compound,
At least one selected from the compound (A) and the compound (B) and various compounding agents are dissolved in a predetermined amount in a suitable solvent so that the concentration becomes 5 to 50% by weight, for example, a pore diameter of about 0.2 μm. A composition solution is prepared by filtering with a filter No. 1, and is applied to a silicon wafer or the like by spin coating, flow coating, roll coating, or the like. Examples of the solvent used in this case include ethylene glycol monomethyl ether, glycol ethers such as ethylene glycol monoethyl ether, methyl cellosolve acetate, cellosolve esters such as 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, and esters such as ethyl acetate and butyl acetate.
These solvents may be used alone or in combination of two or more. If necessary, benzyl ethyl ether, dihexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, acetonylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, A high boiling point solvent such as diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate and phenyl cellosolve acetate can also be added.

The developer of the composition of the present invention includes, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, inorganic alkalis such as aqueous ammonia, primary amines such as ethylamine and n-propylamine. , Secondary amines such as diethylamine and di-n-propylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethyl Quaternary ammonium salts such as ammonium hydroxide and choline, or pyrrole, piperidine, 1,8-diazabicyclo (5,4,0) -7-undecene, 1,5-diazabicyclo (4,3,0) -5- An alkaline aqueous solution prepared by dissolving cyclic amines such as nonane is used. It

Further, 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.

(Examples) Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples.

Example 1 In a flask, 324 g of m-cresol (3 mol), 3,5-
After charging 244 g (2 mol) of dimethylphenol, 770 g of 37% by weight aqueous formaldehyde solution and 0.8 g of oxalic acid,
The separable flask was immersed in an oil bath and reacted for 1 hour while maintaining the internal temperature at 100 ° C., and then 324 g (3 mol) of m-cresol and 244 g of 3,5-dimethylphenol.
(2 mol) was continuously charged into the flask as the reaction proceeded and reacted for 2 hours. Next, the oil bath temperature was raised to 180 ° C., and at the same time, the pressure inside the flask was reduced to remove water, unreacted formaldehyde, m-cresol, 3,5-dimethylphenol, oxalic acid, etc., and recover the novolak resin (hereinafter , This resin is referred to as "Novolak Resin A").

100 parts by weight of the obtained novolak resin A, (2,3,4,4'-
29 parts by weight of compound (C) obtained by condensing tetrahydroxybenzophenone with 1,2-naphthoquinonediazide-5-sulfonic acid chloride on an average of 2.5 mol, and tetramethylthiuram monosulfide having structural formula (IV) in the molecule.
1 part by weight was dissolved in 301 parts by weight of ethyl cellosolve acetate to prepare a solution of the positive type radiation sensitive resin composition.

The composition solution was filtered through a filter having a pore size of 0.2 μm, and then the viscosity and the sensitivity were measured. Further, a part of this composition solution was sealed in a bottle and stored at 25 ° C. for 3 months, and then the viscosity and the sensitivity were measured and the rate of change thereof was determined.

The above viscosity was measured using an ELD viscometer manufactured by Tokyo Keiki Co., Ltd. For sensitivity, spin coating on a silicon wafer with a spinner by a conventional method, prebaking at 90 ° C for 2 minutes on a hot plate to form a 1.2 µm thick resist film, and then exposing with a reduction projection exposure machine. Then, using a 2.4% by weight tetramethylammonium hydroxide aqueous solution as a developing solution for development at 25 ° C for 60 seconds, rinsing with water and drying, and observing the resulting resist pattern with a scanning electron microscope, 2 μm pattern lines and spaces Is 1
It was measured by determining the exposure amount to be 1: 1. The results are shown in Table 1.

Example 2 162 g (1.5 mol) of m-cresol, p-
Cresol 468 g (6 mol), 37 wt% formaldehyde aqueous solution 770 g and oxalic acid 0.45 g were charged, the flask was immersed in an oil bath and reacted for 1 hour while keeping the internal temperature at 100 ° C., and then m-cresol 270 g (2.5 (Mol) was continuously charged into the flask as the reaction proceeded, and the reaction was carried out for 2 hours. Next, the oil bath temperature was raised to 180 ° C., and at the same time, the pressure inside the flask was reduced to remove water, unreacted formaldehyde, m-cresol and p-cresol, oxalic acid, etc., and recover the novolak resin (hereinafter, this The resin is referred to as "Novolak Resin B").

Example 1 except that the obtained novolak resin B was used.
A positive-type radiation-sensitive resin composition solution was prepared in the same manner as in Example 1 and, similarly to Example 1, the rate of change in viscosity and sensitivity immediately after preparation and after storage at 25 ° C. for 3 months were determined. The results are shown in Table 1.

Comparative Example 1 A positive radiation-sensitive resin composition solution was prepared in the same manner as in Example 1 except that tetramethylthiuram monosulfide was not used. The rate of change in viscosity and sensitivity after storage for 3 months was determined. The results are shown in Table 1.

Comparative Example 2 A positive radiation-sensitive resin composition solution was prepared in the same manner as in Example 2 except that tetramethylthiuram monosulfide was not used. The rate of change in viscosity and sensitivity after storage for 3 months was determined. The results are shown in Table 1.

Examples 3 to 6 As Example 1, except that a compound containing structural formula (I), (II) or (III) in the molecule and dimethyl sulfone were used instead of tetramethylthiuram monosulfide. Similarly, a positive-type radiation-sensitive resin composition solution was prepared, and as in Example 1, immediately after preparation and at 25 ° C.
The rate of change in viscosity and sensitivity after storage for 3 months was determined. The results are shown in Table 1.

Example 7 In Example 2, tetramethylthiuram monosulfide was used instead of tetramethylthiuram monosulfide.
Same as Example 2 except that 05 parts by weight and 0.05 parts by weight of a phenolic anti-aging agent, octadecyl-3- (3 ', 5'-di-t-butyl-4-hydroxyphenyl) -propionate, were used. A positive-type radiation-sensitive resin composition solution was prepared, and the rate of change in viscosity and sensitivity immediately after preparation and after storage at 25 ° C. for 3 months were determined in the same manner as in Example 1. The results are shown in Table 1.

Example 8 In Example 2, tetramethylthiuram monosulfide was used instead of tetramethylthiuram monosulfide.
05 parts by weight and N-N'-bis (1,4-dimethylpentyl) -p-phenylenediamine, an amine anti-aging agent
A positive-type radiation-sensitive resin composition solution was prepared in the same manner as in Example 2 except that 0.05 part by weight was used, and the viscosity and sensitivity of the solution immediately after preparation and after storage at 25 ° C. for 3 months were measured in the same manner as in Example 1. The rate of change was calculated. The results are shown in Table 1.

Example 9 In Example 1, the compound (C) was replaced with a compound (D) obtained by condensing 2,3,4-trihydroxybenzophenoin with 1,2-naphthoquinonediazide-5-sulfonic acid chloride on average 2.2 mol. A positive type radiation sensitive resin composition solution was prepared in the same manner as in Example 1 except that the viscosity and the rate of change in sensitivity were determined immediately after preparation and after storage at 25 ° C. for 3 months in the same manner as in Example 1. . The results are shown in Table 1, but the rate of change was small.

Comparative Example 3 A positive radiation-sensitive resin composition solution was prepared in the same manner as in Example 9 except that tetramethylthiuram monosulfide was not used. Immediately after preparation and at 25 ° C. The rate of change in viscosity and sensitivity after storage for 3 months was determined. The results are shown in Table 1.

(Effect of the invention) According to the present invention, by adding a compound having a specific structure to a positive-type radiation-sensitive resin composition containing an alkali-soluble resin and a 1,2-quinonediazide compound, sensitivity change and viscosity change A composition having excellent storage stability can be obtained.

 ─────────────────────────────────────────────────── --- Continuation of the front page (56) References JP-A-48-100202 (JP, A) JP-A-55-133030 (JP, A) JP-A-56-75643 (JP, A) JP-A 61- 260239 (JP, A) JP 60-237439 (JP, A) JP 61-210064 (JP, A) Special table 58-502169 (JP, A)

Claims (1)

[Claims] 1. A positive-type radiation-sensitive resin composition containing an alkali-soluble resin and a 1,2-quinonediazide compound, wherein structural formulas (I) to (IV) Of at least one selected from the group consisting of dimethyl sulfone, diethyl sulfone and diphenyl sulfone in the molecule, and the content of these compounds is 0.001 to 100 parts by weight based on 100 parts by weight of the alkali-soluble resin. A positive-type radiation-sensitive resin composition, which is 10 parts by weight.