JPH07219227A - Negative radiation sensitive resist composition and forming method for fine pattern using the same - Google Patents

Abstract

PURPOSE:To obtain a negative radiation sensitive resist compsn. excellent in dry etching durability, resolution, and sensitivity which can be developed with an alkali soln. with high safety by incorporating a specified alkali-soluble resin and quinonediazide compd. CONSTITUTION:This negative radiation sensitive resist compsn. contains an alkali-soluble resin having <=300nm/30sec dissolving rate to 2.38% aq. soln. of tetramethylammonium hydroxide and one or more kinds of quinonediazide compds. The quinonediazide compd. is selected from among 1,2-naphthoquinone diazide-4-sulfonate, 1,2-naphthoquinone diazide-5-sulfonate and 1,2-naphthoquinone diazide-6-sulfonate of monohydroxy compds., monoamino compds., polyhydroxy compds. and polyamino compds. The alkali-soluble resin used for the compsn. is a novolac resin, poly p-hydroxystyrene or the like.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a negative-working radiation sensitive resist composition for use in the production of masks for photolithography, semiconductor integrated circuits and the like using radiation such as electron beams, molecular beams and X-rays. And a fine pattern forming method using the same.

[0002]

2. Description of the Related Art Conventionally, polyglycidyl methacrylate, chloromethylated polystyrene and the like have been used as a negative type electron beam resist, but they are poor in resolution due to swelling during development using an organic solvent. Further, recently, a chemically amplified resist which uses a novolac resin and is developed using an alkaline aqueous solution has been commercialized, but there is a problem that the process is unstable.

It is also known that a positive photoresist containing a novolac resin and a quinonediazide compound may act as a negative electron beam resist, but the sensitivity is extremely low and not at a practical level.

That is, there is known an example in which a positive pattern photoresist AZ-1350 manufactured by Hoechst Co., Ltd. is used to obtain a negative pattern by electron beam exposure, followed by overall exposure with ultraviolet light (WG Oldham, E .; Hieeke, IEEE
Electron Device Letters,
EDL-1, No. 10, Oct. , 217 (198
0). ). When this experiment was repeated, the sensitivity obtained was extremely low. The present inventors analyzed the quinonediazide compound used in this resist, and found that 1,3,2,3,4-trihydroxybenzophenone
It was found to be an ester of 2-naphthoquinonediazide-5-sulfonic acid and the esterification rate was 50%.

Further, a method is known in which a negative pattern is obtained by subjecting an i-ray photoresist AZ-2415 manufactured by Hoechst Co., Ltd. to electron beam exposure and then exposing the whole surface to ultraviolet light (TD Be).
rker, D.R. D. Casey, IEEE Journal
al of Solid-State Circuit
s, SC-17, 155 (1982). ). The sensitivity of this resist to electron beams is 80 to 120 μC / cm.
It was as low as ² (20 kV). The quinonediazide compound used in this resist is known to be 1,2-naphthoquinonediazide-4-sulfonic acid ester of cumylphenol (DW Johnson).
n, SPIE. , 469, (1984). ). The present inventors separated the novolak component of this resist and examined the dissolution rate in a 2.38% aqueous solution of tetramethylammonium hydroxide, and found that it was 2519.8 nm / 30 seconds.

[0006]

An object of the present invention is to use an alkali-soluble resin and a quinonediazide compound as main components,
It is an object of the present invention to provide a negative radiation sensitive resist composition which has excellent dry etching resistance, resolution and sensitivity and can be developed with a highly safe alkaline aqueous solution, and a fine pattern forming method using the same.

[0007]

Means for Solving the Problems As a result of studying a resist composition and a process containing an alkali-soluble resin and a quinonediazide compound as main components, the present inventors have found that
It was found that a highly accurate negative pattern can be obtained by using a specific process for a resist whose material and composition are optimized.

The negative radiation-sensitive resist composition of the present invention comprises (1) tetramethylammonium hydroxide.2.
Alkali-soluble resin having a dissolution rate in a 38% aqueous solution of 300 nm / 30 seconds or less, and (2) 1,2-naphthoquinonediazide of monohydroxy compound, monoamino compound, polyhydroxy compound and polyamino compound
4-sulfonic acid ester, 1,2-naphthoquinonediazide-5-sulfonic acid ester and 1,2-naphthoquinonediazide-6-sulfonic acid ester (provided that the esterification rate is 70% in the case of an ester of polyhydroxy compound and polyamino compound) Above), one or more quinonediazide compounds selected from the group consisting of

The alkali-soluble resin used in the negative radiation-sensitive resist composition of the present invention includes novolac resin, poly-p-hydroxystyrene and its copolymers,
There are polyacrylic acid and its copolymers, polymethacrylic acid and its copolymers, poly p-hydroxyphenyl acrylate and its copolymers, poly p-hydroxyphenyl methacrylate and its copolymers.

The dissolution rate of these alkali-soluble resins in a 2.38% aqueous solution of tetramethylammonium hydroxide needs to be 300 nm / 30 seconds or less, preferably in the range of 300 to 1 nm / 30 seconds. 200 to 5 nm / 30 seconds is preferable. If the dissolution rate is too high, the development time becomes short and the process becomes unstable. On the other hand, if it is too low, the developing time becomes long and the productivity becomes low. Here, the “dissolution rate in a 2.38% aqueous solution of tetramethylammonium hydroxide” means that a coating film of an alkali-soluble resin is formed so that the film thickness after drying is 2 μm, and the coating film is tetramethylammonium hydroxyde. After being immersed in a 2.38% aqueous solution at 23 ° C for 30 seconds and rinsed with pure water, the amount of film reduction (= [film thickness before immersion]-[ Film thickness after immersion])
(Nm). That is, the unit is [nm / 30 seconds]
Is.

The novolak resin used in the present invention is obtained by condensing cresol, for example, a mixture of p-cresol and m-cresol, with formaldehyde or its polymer, paraformaldehyde or 1,3,5-trioxane. .

The condensation reaction is carried out without solvent or in an organic solvent. As the organic solvent, alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, methyl cellosolve, ethyl cellosolve, cellosolves such as butyl cellosolve, methyl cellosolve acetate, cellosolve esters such as ethyl cellosolve acetate, Tetrahydrofuran,
Ethers such as 1,4-dioxane are preferably used.

As a catalyst for the condensation reaction, oxalic acid, formic acid, hydrochloric acid, sulfuric acid, perchloric acid, phosphoric acid, acids such as p-toluenesulfonic acid, and metal salts such as zinc acetate and magnesium acetate are preferably used.

The novolac resin thus obtained generally contains a low molecular weight component such as a binuclear compound in which two phenol units are condensed and a trinuclear compound in which three phenol units are condensed.
Among such low molecular weight components, there are components that cause scum and deteriorate the pattern shape. When the synthesized novolak contains a large amount of these low molecular weight components, it is preferably removed by an appropriate operation so that the total content of the binuclear body and the trinuclear body is 10% by weight or less.

As the treatment for removing the low molecular weight component from the novolac resin, for example, the following method can be used.

(1) Extraction method The novolac resin is finely pulverized and benzene, toluene,
A low molecular weight component is extracted by stirring at a constant temperature with an organic solvent such as xylene, chlorobenzene, dichlorobenzene, or a mixed solution of water or an organic solvent such as methanol or ethanol and water.

(2) Reprecipitation method Novolak resin is treated with methanol, ethanol, acetone,
It is soluble in organic solvents such as ethyl cellosolve. Then,
A poor solvent such as water, petroleum ether or hexane is dropped into this novolak solution, or conversely, the novolak solution is dropped into the poor solvent to precipitate a novolak resin, which is separated and dried.

(3) Separation method The novolak resin is treated with methanol, ethanol, acetone,
Dissolve in a mixed solvent of water-miscible organic solvent such as ethyl cellosolve and water-immiscible organic solvent such as ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, and drop water to separate the two layers. Separate and concentrate.

As the poly-p-hydroxystyrene and the copolymer thereof used in the present invention, a copolymer of p-hydroxystyrene and other vinyl monomer is preferably used. Preferable comonomers are, for example, methyl methacrylate and styrene. Further, a polymer obtained by partially hydrogenating the benzene ring of poly-p-vinylphenol and a polymer obtained by nitrating, halogenating, alkylating or acetylating the benzene ring are also used.

A compound having a phenolic hydroxyl group is preferably used as a monohydroxy compound or a polyhydroxy compound as a raw material compound of the quinonediazide compound used in the present invention.

Phenol, naphthol, hydroxyanthracene and the like are used as the monohydroxy compound. These monohydroxy compounds are alkyl groups, allyl groups, aryl groups, aralkyl groups, acyl groups, alkyloxycarbonyl groups, aryloxycarbonyl groups, allyloxycarbonyl groups, carboxyl groups, carbamoyl groups, nitro groups, fluorine, chloro groups. It may have a substituent such as a halogen group such as bromo, iodo, or a cyano group.

The polyhydroxy compound is preferably an aromatic compound having 2 to 8 phenolic hydroxyl groups,
You may have the said substituent. Polymers having a phenolic hydroxyl group such as novolac and polyvinylphenol are also preferably used.

1,2-naphthoquinonediazide-4-sulfonyl chloride and 1,2-naphthoquinonediazide-5 are added to these monohydroxy compounds and polyhydroxy compounds.
By reacting -sulfonyl chloride and 1,2-naphthoquinonediazide-6-sulfonyl chloride, a quinonediazide compound used in the present invention can be obtained.

In the case of a polyhydroxy compound having two or more hydroxyl groups in the same molecule, it is not necessary that all the hydroxyl groups are esterified, but on average 70% or more of the hydroxyl groups are not esterified. I won't. If the esterification rate is low, the sensitivity will be low, so the esterification rate will be 8
It is more preferably 0% or more.

An aliphatic or aromatic monoamine or polyamine is used as the monoamino compound or polyamino compound as the raw material compound of the quinonediazide compound used in the present invention.

As the monoamino compound, aliphatic or aromatic monoamines are used. These monoamines include alkyl groups, allyl acids, aryl groups, aralkyl groups, acyl groups, alkyloxycarbonyl groups and aryloxy. It may have a substituent such as a carbonyl group, a carboxyl group, an allyloxycarbonyl group, a carbamoyl group, a nitro group, a halogen group such as fluorine, chloro, promo and iodo, and a cyano group.

The polyamino compound is preferably an aliphatic or aromatic compound having 2 to 8 amino groups, and may have the above-mentioned substituents. Polymers having an amino group such as polyethyleneimine and polyaniline are also preferably used.

Reacting these monoamino compounds and polyamino compounds with 1,2-naphthoquinonediazide-4-sulfonyl chloride, 1,2-naphthoquinonediazide-5-sulfonyl chloride, and 1,2-naphthoquinonediazide-6-sulfonyl chloride. Thus, the quinonediazide compound used in the present invention can be obtained.

In the case of a polyamino compound having two or more amino groups in the same molecule, 70% or more of all amino groups must be esterified. It is preferably 90% or more. When the esterification rate is low, the quinonediazide compound becomes unstable and the storage stability of the resist becomes poor.

The quinonediazide compound used in the present invention may have different quinonediazide groups in the same molecule, or two or more kinds thereof may be mixed and used.

The content of the quinonediazide compound in the solid resist component is preferably 5 to 50% by weight, more preferably 10 to 30% by weight. If the content is too small, the sensitivity will be low, and if it is too high, problems such as crystal precipitation from the resist solution and phase separation in the resist film will occur. here,
The resist solid content refers to a resist composition obtained by removing a solvent.

To the resist composition of the present invention, a low molecular weight phenolic compound, a dye, a surfactant, a storage stabilizer and the like can be added as additives.

As the low molecular weight phenol compound, for example, the compounds described in JP-A-5-127375 can be used. As the dye, a dye that absorbs visible light and ultraviolet light can be added in order to improve stability to light after the resist coating film.

To increase the sensitivity, a compound or polymer having an epoxy group, a chloromethyl group, an allyl group, a cinnamoyl group, a halogenated phenyl group, a vinyl group or a vinylsilyl group can be added.

Further, a chemically amplified resist can be obtained by adding a compound which generates an acid by an electron beam and a compound which is crosslinked by the acid.

The resist composition of the present invention can be obtained by dissolving the above components in a solvent. Although the amount of the solvent used is not particularly limited, it is adjusted so that the resist solid content is 10 to 35% by weight in the resist composition.
As the solvent preferably used, ethyl acetate, butyl acetate, amyl acetate, methyl propionate, ethyl propionate, methyl butyrate, ethyl butyrate, methyl benzoate, methyl lactate, ethyl lactate, esters such as gamma butyrolactone, methyl cellosolve, Cellosolves such as ethyl cellosolve and butyl cellosolve, methyl cellosolve acetate, cellosolve esters such as ethyl cellosolve acetate and butyl cellosolve acetate, propylene glycol ether ethers such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate, 1,2-dimethoxy Ethers such as ethane, 1,2-diethoxyethane, tetrahydrofuran, 1,4-dioxane, anisole, methyl ethyl Ketone, methyl isobutyl ketone,
Cyclohexanone, ketones such as isophorone, dimethylformamide, dimethylacetamide, amides such as N-methylpyrrolidone, dimethylsulfoxide, a solvent selected from aprotic polar solvents such as sulfolane,
Alternatively, a solvent obtained by mixing a plurality of these solvents can be used.

The negative-working radiation-sensitive resist composition of the present invention is coated on a substrate using a spinner, dried, pattern-exposed using radiation such as an electron beam, and exposed on the whole surface using ultraviolet light, and then unexposed. A fine pattern is formed by developing and removing the portion.

The coating, drying, and pattern exposure by radiation may be performed by a conventionally known method for forming a pattern of an electron beam resist. For example, using a spinner or the like, the coating is applied so that the film thickness after drying is about 0.5 to 2.0 μm, and dried at about 90 to 120 ° C. for about 1 to 30 minutes. Examples of the radiation used for the exposure include electron beams, X-rays, ion beams, and the like. Exposure is
A normal electron beam exposure apparatus may be used.

The wavelength of the ultraviolet light used for the whole surface exposure of the present invention is preferably between 436 and 250 nm. Further preferably 10 to 2000 mJ / cm ² as an exposure amount, and more preferably from 30~1000mJ / cm ^2.

The exposure amount of the ultraviolet light used for the whole surface exposure varies depending on the resist composition and the film thickness, and it is preferable to set the unexposed portion at the time of the pattern exposure by the electron beam to dissolve in 30 seconds to 4 minutes. If the total exposure is too large,
The development time becomes short, the process becomes unstable, and if the exposure amount is too small, scum easily occurs in the resist pattern.

Further, in the method of the present invention, a resist composition containing two or more quinonediazide compounds having different absorption spectra for ultraviolet light is used, and the light absorption intensity of at least one quinonediazide compound is at least one of the other compounds. A pattern with higher resolution can be obtained by exposing the entire surface with ultraviolet light having a wavelength that is twice or more different from the light absorption intensity.

For example, 1,2-naphthoquinonediazide-4
-When a sulfonyl compound and a 1,2-naphthoquinonediazide-5-sulfonyl compound are mixed and exposed to light at 436 nm on the entire surface, the 1,2-naphthoquinonediazide-5-sulfonyl compound is selectively decomposed to increase the contrast. You can

In the method of the present invention, a higher resolution can be obtained by pretreating the resist film with an alkaline aqueous solution before the whole surface exposure with ultraviolet light.

A method of treating the surface of a positive photoresist with an alkaline aqueous solution before pattern exposure is well known (for example, JP-A-2-84656). However, this method clearly has a positive pattern as described in the claims, "after the surface treatment layer is formed, the resist is selectively exposed and developed to selectively remove the resist". It is intended for formation.

The alkaline aqueous solution for pretreatment used in the present invention includes inorganic alkalis such as hydroxides, carbonates, phosphates, silicates and borates of alkali metals, 2-diethylaminoethanol, monoethanolamine, An aqueous solution containing one or more kinds of amines such as diethanolamine, quaternary ammonium hydroxide such as tetramethylammonium hydroxide, and choline is used.

A surfactant may be added to the pretreatment liquid in order to improve the wettability with respect to the resist.

The alkali normality is preferably 0.05 to 2.00 N, more preferably 0.10 to 1.00 N. The treatment time is preferably 0.5 to 10 minutes. The alkali normality and the treatment time are preferably selected so that the film thickness of the resist film is 0.1 μm.

The pretreatment with the alkaline aqueous solution may be performed at any stage between the drying and the whole surface exposure with ultraviolet light.

After performing pattern exposure with radiation using an electron beam or the like, pretreatment with an alkaline aqueous solution, and overall exposure with ultraviolet light, the resist film is developed.

For the development, it is preferable to use a highly safe aqueous alkali solution, such as an inorganic alkali such as an alkali metal hydroxide, carbonate, phosphate, silicate or borate, 2-diethylaminoethanol or monoalkaline. An aqueous solution containing one or more amines such as ethanolamine and diethanolamine, and quaternary ammonium hydroxide such as tetramethylammonium hydroxide and choline is used.

The development time is preferably set to 1.1 to 2.0 times the time taken for the unexposed portion to dissolve in pattern exposure. If the development time is short, a development residue may remain or the resist size may become larger than the designed value. If the developing time is too long, the sensitivity may be lowered and the resist size may be smaller than the designed value.

[0052]

EXAMPLES The present invention will be described in more detail below with reference to examples.

Example 1 (1) Preparation of Novolac A novolak resin was obtained from 40 parts of m-cresol, 60 parts of p-cresol, 0.5 part of oxalic acid and 46 parts of 37% formalin by a usual method.

The weight average molecular weight (converted to polyethylene oxide) of this novolak determined by gel permeation chromatography was 7250, and the number average molecular weight was 1210.
Met.

This novolak was dissolved in ethyl cellosolve acetate, and a silicon wafer was coated with a spinner. Bake in an oven at 100 ° C for 10 minutes,
A 2 μm novolak film was obtained. This was immersed in a 2.38% aqueous solution of tetramethylammonium hydroxide (TMAH) at 23 ° C. for 30 seconds and rinsed with pure water. The film thickness reduction amount was determined by measuring the film thickness of the novolak film before and after the immersion, and it was 1517.5 nm. That is,
The dissolution rate in a 2.38% TMAH aqueous solution is 151.
It was 7.5 nm / 30 seconds.

This novolak is referred to as novolak (I).

1.00 parts of novolak (I) was taken, dissolved in 4.00 parts of methanol, and 2.45 parts of water was added dropwise with stirring to precipitate novolak. The supernatant was removed, the precipitated novolak was dissolved in acetone and taken out, and the acetone was removed by an evaporator. The obtained powder is 2 at 50 ℃
It was vacuum dried for 4 hours.

0.75 parts of novolak was obtained, and the weight average molecular weight of this novolak was 7523 and the number average molecular weight was 1890.

When the dissolution rate in a 2.38% TMAH aqueous solution was determined by the above method, it was 125.9 nm /
It was 30 seconds. This novolak is novolak (II)
And

1.00 part of novolak (I) was taken, dissolved in 4.00 parts of methanol, and 1.71 parts of water was added dropwise with stirring to precipitate novolak. The supernatant was removed, the precipitated novolak was dissolved in acetone and taken out, and the acetone was removed by an evaporator. The obtained powder is 2 at 50 ℃
It was vacuum dried for 4 hours.

0.65 parts of novolak was obtained, and the weight average molecular weight of this novolak was 8034 and the number average molecular weight was 2553.

When the dissolution rate in a 2.38% TMAH aqueous solution was determined by the above method, it was 63.8 nm / 3.
It was 0 seconds. This novolak is novolak (III)
And

In addition to Novolac, CST50, a copolymer of p-hydroxystyrene and styrene (monomer ratio 50:50), obtained from Maruzen Petrochemical was used as an alkali-soluble resin.

When the dissolution rate in a 2.38% TMAH aqueous solution was determined by the above-mentioned method, it was 5.7 nm / 30.
It was seconds.

(2) Synthesis of quinonediazide compound Low molecular weight novolak consisting of p-cresol having a weight average molecular weight of 596 and a number average molecular weight of 191 10.0 g, 1, 2
-Naphthoquinonediazide-5-sulfonyl chloride 2
2.18 g was dissolved in 80 g of dioxane, and the temperature was raised to 40 ° C. 8.34 g of triethylamine in 30 of dioxane
The solution dissolved in g was added dropwise with stirring for 30 minutes. 40
After stirring at ℃ for 5.5 hours, the reaction mixture was poured into water, and the precipitate was collected by filtration and washed with water. After washing with methanol and vacuum drying,
22.7 g of a yellow powder was obtained.

The esterification rate determined from the ultraviolet absorption spectrum was 81%.

This compound was converted to a quinonediazide compound (1)
And

The following quinonediazide compounds were synthesized by the same method.

[0069]

[Table 1] (3) Preparation of developer The following developer was used.

Developer A: TMAH 2.38% aqueous solution Developer B: TMAH 1.50%, 2-diethylaminoethanol 6.50% aqueous solution Developer C: TMAH 1.35%, 2-diethylaminoethanol 5.85% Aqueous solution Developer D: caustic potash 0.27 mol / kg, boric acid 0.
50 ppm of surfactant Surfynol 104 (manufactured by Air Products) added to 094 mol / kg aqueous solution.

(4) Preparation of resist composition The following raw materials were mixed to prepare a resist solution.

Novolak (III) 10.72 parts Quinonediazide compound (1) 2.68 parts Propylene glycol monomethyl ether acetate (PGMA) 66.60 parts γ-butyrolactone (GBL) 20.00 parts “Troysol” 366 (Troy Chemical). 0.03 parts (5) Resist process and evaluation The resist prepared in (4) was coated on a chrome blank using a spinner, baked in an oven at 100 ° C. for 10 minutes, and coated to a thickness of 0.5 μm. Membrane samples were prepared.

Elionix electron beam exposure apparatus ERE-3
01, acceleration voltage 20 kV, beam diameter 0.2 μm,
A rectangular area of 0.18 mm × 0.24 mm was subjected to scanning exposure while sequentially changing the exposure time. At the same time, the exposure time was changed to expose the line and space of 1: 1 to 10:10.

Next, the entire surface was exposed for 7 seconds using Canon PLA-501F. The illuminance is 13.4 mW / cm ² with g line,
It is 7.4 mW / cm ² for the i-line.

It was immersed in the developer A for 1 minute and 51 seconds with stirring, rinsed with pure water, and dried.

(6) Evaluation of characteristics The resist film thickness in a rectangular area was measured, and the vertical axis represents the residual film ratio when the film thickness before exposure was 1.00, and the horizontal axis represents the exposure dose. Created. From this sensitivity curve, the residual film rate is 0.5
When reading the exposure amount (D ₅₀ ) giving 0, it is 11μ
It was C / cm ² .

The line-and-space pattern exposed with an exposure amount equal to D ₅₀ was observed with an electron microscope, and the resolution was determined. As a result, a 0.4 μm pattern was resolved.

Examples 2 to 21 The resist sensitivity (D ₅₀ ) and resolution were evaluated in the same manner as in Example 1. The results are shown in Table 2.

In Examples 7 and 15, before the whole surface exposure,
A pretreatment of dipping in the developing solution B for 4 minutes is performed.

In Example 16, a g-line filter was used for whole surface exposure. The g-line illuminance after passing through the filter is 7.4.
It was mW / cm ² .

Comparative Examples 1 to 4 In Comparative Example 1, novolak (I) having a dissolution rate in a 2.38% TMAH aqueous solution of 1517.5 nm / 30 seconds was used.

In Comparative Example 2, a quinonediazide compound having an esterification rate of 50% was used.

In Comparative Examples 3 and 4, positive type photoresist AZ1350 (esterification rate: 50%) manufactured by Hoechst Co. was evaluated at film thicknesses of 1.5 μm and 0.5 μm, respectively. The results are shown in Table 2.

[0084]

[Table 2]

[0085]

According to the present invention, a negative radiation sensitive resist composition containing an alkali-soluble resin and a quinonediazide compound as main components and excellent in dry etching resistance and resolution can be obtained. A fine pattern is obtained.

Continuation of front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display area H01L 21/027

Claims (8)

[Claims] 1. A dissolution rate of (1) tetramethylammonium hydroxide in a 2.38% aqueous solution of 300 nm /
Alkali-soluble resin for 30 seconds or less, and (2) 1,2-naphthoquinonediazide-4-sulfonic acid ester of monohydroxy compound, monoamino compound, polyhydroxy compound and polyamino compound, 1,2-naphthoquinonediazide-5-sulfone Acid ester and 1,2-naphthoquinonediazide-6-sulfonic acid ester (provided that the esterification rate is 70% or more in the case of an ester of a polyhydroxy compound and a polyamino compound), or one or more kinds selected from the group consisting of A negative radiation-sensitive resist composition comprising a quinonediazide compound. 2. The quinonediazide compound is a 1,2-naphthoquinonediazide-4-sulfonic acid ester, a 1,2-naphthoquinonediazide-5-sulfonic acid ester or a 1,2-naphthoquinonediazide-6 of a monophenol compound or a polyphenol compound. -The negative-working radiation-sensitive resist composition according to claim 1, which is a sulfonic acid ester. 3. The quinonediazide compound is a 1,2-naphthoquinonediazide-4-sulfonic acid ester, 1,2-naphthoquinonediazide-5-sulfonic acid ester or 1,2-naphthoquinonediazide-6-, which is a monoamino compound or a polyamino compound. The negative radiation-sensitive resist composition according to claim 1, which is a sulfonic acid ester. 4. The negative radiation-sensitive resist composition according to claim 1, containing two or more kinds of quinonediazide compounds having different absorption spectra for ultraviolet light. 5. The negative-type radiation-sensitive resist composition according to claim 1 is applied to a substrate, dried, pattern-exposed with radiation, and exposed to ultraviolet light over the entire surface, and then exposed. A method for forming a fine pattern, which comprises removing by development. 6. The method for forming a fine pattern according to claim 5, wherein the unexposed portion is developed and removed with an alkaline aqueous solution. 7. The negative radiation-sensitive resist composition according to claim 4, wherein the light absorption intensity of at least one quinonediazide compound is twice or more different from the light absorption intensity of at least one other quinonediazide compound. The fine pattern forming method according to claim 5, wherein the entire surface is exposed using light. 8. The method for forming a fine pattern according to claim 5, wherein the resist surface is treated with an alkaline aqueous solution after the drying and before the whole surface exposure with ultraviolet light.