JPH02220056A - Radiation sensitive resin composition - Google Patents

Abstract

PURPOSE:To provide a radiation sensitive resin composition superior in each of resolution, sensitivity, and pattern profile after development, and yet, high in film remaining rate after development, also superior in antihalation effect, and suited as a positive type resist by incorporating an alkali-soluble novolak resin and a specified 1,2-quinonediazido compound. CONSTITUTION:The radiation sensitive resin composition composed of the alkali- soluble novolak resin and the 1,2-quinonediazido compound containing a mixture of a compound represented by formula I and a compound represented by formula II each in an amount of 2 - 30wt.%, and when as the radiation to be used for the composition, ultraviolet rays are used, a light absorber may be used.

Description

Detailed Description of the Invention a. Industrial Field of Application The present invention relates to a radiation-sensitive resin composition, and more particularly, it relates to a radiation-sensitive resin composition that is sensitive to ultraviolet rays (g-rays, i-rays), deep ultraviolet rays, X-rays, electron beams, molecular beams, γ-rays, etc. The present invention relates to a radiation-sensitive resin composition suitable for a positive photoresist for manufacturing highly integrated semiconductor integrated circuits that is sensitive to radiation such as radiation, synchrotron radiation, and proton beams.

b. Prior Art Conventionally, in order to manufacture highly integrated circuits, a positive photoresist comprising an alkali-soluble novolak resin and a 1,2-quinonediazide compound has been widely used.

When trying to achieve both a good pattern profile after development and high resolution, these positive photoresists usually suffer from a significant decrease in sensitivity.Especially when using materials such as aluminum, which have high reflectance and are prone to halley silane. A positive resist containing a light-absorbing material used on the substrate exhibits a significant decrease in sensitivity.

Problems to be solved by the C0 invention The purpose of the present invention is to solve the problems of the above-mentioned prior art and to improve the resolution and
Excellent accuracy, sensitivity, and pattern profile after development.
A radiation-sensitive resin composition suitable as a positive resist, which also has excellent heat resistance and storage stability, has a high residual film rate after development, and also has an excellent Halley silane prevention effect by incorporating a light absorbing agent. Our goal is to provide the following.

61 Means for Solving the Problems The present invention provides a radiation-sensitive resin composition comprising an alkali-soluble novolak resin and a 1.2-quinonediazide compound, wherein the 1.2-quinonediazide compound is a compound represented by the following general formula (I). (hereinafter referred to as "compound (I)") and the compound represented by (II) (hereinafter referred to as "compound (II)")
) J), and (n) O [wherein R1 and I? , are each a hydrogen atom or a 1,2-benzoquinonediazide-4-sulfonyl group, 1
, 2-naphthoquinonediazide-4-sulfonyl group, 1.
1 such as 2-naphthoquinonediazide-5-sulfonyl group
．． It is a 2-quinonediazide sulfonyl group, and the average composition is at least 2 or more of R1, preferably 2.2 to 3
, at least 3 or more of Rg, preferably 3 to 3.7
is a 1,2-quinonediazide sulfonyl group. ] 2 to 30 parts by weight of compound (1) and 2 parts by weight of compound (If) to 100 parts by weight of the above alkali-soluble novolak resin.
The object of the present invention is to provide a radiation-sensitive resin composition characterized in that it contains 30 parts by weight.

The alkali-soluble novolak resin (hereinafter simply referred to as "novolak resin") is obtained by condensing phenols and aldehydes.

Examples of phenols include phenol, O-cresol, m-cresol, p-cresol, 3°5-dimethylphenol, 2.5-dimethylphenol, 2.3
-dimethylphenol, 2,4-dimethylphenol,
2.6-dimethylphenol, 3゜4-dimethylphenol, 2,3.5-)dimethylphenol, 4-t-butylphenol, 2-t-butylphenol, 3-t-
Butylphenol, 2-methylresorcinol, 4-methylresorcinol, 5-methylresorcinol, 4-
t-Butylcatechol, 4-methoxyphenol, 3-
Methoxyphenol, 2-methoxyphenol, 2-methoxycatechol, 2-methoxyresorcinol, 3-
Methoxyresorcinol, 2,3-dimethoxyphenol, 2.5-dimethoxyphenol, 3.5-dimethoxyphenol, methyl gallate, ethyl gallate, 3-
Methoxy-4,5-dihydroxybenzoate, 3-
Ethyl methoxy-4,5-dihydroxybenzoate, 4-
Methoxy-3,5-dihydroxybenzoate, 4-
Ethyl methoxy-3,5-dihydroxybenzoate, 3.
Methyl 4-dimethoxy-5-hydroxybenzoate, 3.
Ethyl 4-dimethoxy-5-hydroxybenzoate, 3.
Methyl 5-dimethoxy-4-hydroxybenzoate, 3.
Ethyl 5-dimethoxy-4-hydroxybenzoate, 3-
Ethylphenol, 2-ethylphenol, 4-ethylphenol, 2,3.5-triethylphenol, 3.
Examples include 5-diethylphenol, 2.5-diethylphenol, 2.3-diethylphenol, resorcinol, catechol, and pyrogallol. These compounds may be used alone or in combination of two or more.

Among these, a combination of m-cresol and other phenols is particularly preferable. The ratio (mol%) of m-cresol and other phenols used is usually 6 to 94/94 to 6.
, preferably 30-90/70-10. When the proportion of m-cresol used is less than 6 mol % or more than 94 mol %, the balance between resolution, sensitivity, developability, residual film rate after development, and pattern profile deteriorates. Note that this usage ratio is the usage ratio of raw materials during novolac resin synthesis.

Here, preferred combinations of m-cresol and other phenols include m-cresol and 2.3゜5-trimethylphenol, m-cresol and 3゜5-dimethylphenol, and m-cresol and 3.5-dimethyl. Phenol and p-cresol, m-cresol and 2.3.5-)
Examples include combinations of dimethylphenol and p-cresol. In addition, when 3.5-dimethylphenol or 2,3.5-1-dimethylphenol and P-cresol are used together as other phenols, the usage ratio (mol%) thereof is preferably 40 to 60/60. ~40.

Examples of aldehydes include formaldehyde,
Paraformaldehyde, acetaldehyde, propylaldehyde, benzaldehyde, phenylacetaldehyde, α-phenylpropylaldehyde, β-phenylpropylaldehyde, O-hydroxybenzaldehyde,
m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, p-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, 0
-Nitrobenzaldehyde, m-nitrobenzaldehyde, p-nitrobenzaldehyde, 0-methylbenzaldehyde, p-methylbenzaldehyde, p-ethylbenzaldehyde, pn-butylbenzaldehyde, etc., formaldehyde and acetaldehyde are preferred, and formaldehyde is particularly preferred. Preferably, these aldehydes can be used alone or in combination of two or more.

The aldehyde is usually 0.0% per mole of phenol.
It is used in a proportion of 7 to 3 mol, preferably 0.7 to 2 mol.

Novolac resins are synthesized by condensing the above phenols with the above aldehydes in the presence of an acid catalyst, but they can also be synthesized without a catalyst.

As the acid catalyst, for example, inorganic acids such as hydrochloric acid, nitric acid, and sulfuric acid, and organic acids such as formic acid, oxalic acid, and acetic acid can be used.Normally, the amount of acid catalyst used is 0.1 mol per 1 mol of phenols. It is as follows.

In condensation, water is usually used as the reaction medium, but if the phenol used is not dissolved in the aldehyde aqueous solution and the reaction becomes a heterogeneous system from the early stage, a hydrophilic solvent may be used as the reaction medium. You can also do that. As the hydrophilic solvent, for example, alcohols such as methanol, ethanol, propatool, and butanol, and cyclic ethers such as tetrahydrofuran and dioxane can be used. The amount of these reaction media used is preferably 2 parts by weight per 100 parts by weight of the total amount of phenols and aldehydes.
It is 0 to 1000 parts by weight.

The reaction temperature for condensation can be adjusted as appropriate depending on the reactivity of the phenols and aldehydes, but is usually 10 to
200″C1 is preferably 70 to 130°C.

Reaction methods for obtaining novolak resin include, for example, a method in which phenols, aldehydes, and an acid catalyst used as necessary are charged all at once and reacted, and a method in which phenols are reacted with aldehydes and an acid catalyst used as necessary. A method of adding and reacting as the reaction progresses can be used. In the latter method, in which phenols are added as the reaction progresses, 20 to 70% by weight of the phenols used initially, aldehydes, and as necessary It is preferable to use a method in which an acid catalyst to be used is charged and condensation is carried out, and then the remaining phenols are added as the reaction progresses to carry out the reaction.

After the condensation is completed, unreacted substances, acid catalyst, reaction medium, etc. present in the system are removed, and the novolak resin is recovered.

The novolac resin obtained as described above preferably has a polystyrene equivalent weight average molecular weight of 2,000 to 5,000, as determined by gel vermiercigon chromatography using monodisperse polystyrene as a standard.

The 1,2-quinonediazide compound used in the present invention is a mixture of compound (I) and compound (II), and as compound (1), for example, 2.3.4-trihydroxybenzophenone-1,2-quinonediazide 1-10% by weight of sulfonic acid monoester, 2.3.4-1 lyhydroxybenzophenone-1,2-naphthoquinone diazide sulfonic acid diester 20-50% by weight and 2.3.4
-) dihydroxybenzophenone-1,2-naphthoquinonediazide sulfonic acid triester, a mixture consisting of 45 to 80% by weight, and the like.

Further, as the compound (n), for example, 2,3.4°4'
-tetrahydroxybenzophenone-1,2-quinonediazide sulfonic acid monoester 0-5% by weight, 2.3,
4.4'-tetrahydroxybenzophenone-1,
2-quinonediazide sulfonic acid diester 0-10% by weight, 2.3,4,4'-tetrahydroxybenzophenone-1,2-quinonediazide sulfonic acid triester 2-40% by weight and 2,3°4.4'-tetra Examples include a mixture consisting of 50 to 95% by weight of hydroxybenzophenone-1°2-quinonediazide sulfonic acid tetraester.

These compound (1) or compound (If) has a
．． 2-3 mol, preferably 2.2-3 mol of 4-trihydroxybenzophenone or 3-4 mol, preferably 3-3.
7 mol, 1,2-naphthoquinonediazide-5-sulfonic acid chloride, 1,2-naphthoquinonediazide-4-sulfonic acid chloride, 1,2-benzoquinonediazide-4
It can be obtained by condensing 1 mole of one or more 1,2-quinonediazide sulfonic acid halides such as -sulfonic acid chloride in the presence of a basic catalyst.

As the basic catalyst, for example, amines such as trimethylamine, triethylamine, tripropylamine, pyridine, and tetramethylammonium hydroxide, and inorganic alkalis such as sodium hydroxide, potassium hydroxide, and sodium carbonate are used.

The amount of these basic catalysts used is usually 1 mole of 1,2-quinonediazide sulfonic acid halide used.
The amount is 0.8 to 2 mol, preferably 1 to 1.5 mol. The condensation reaction is usually carried out in the presence of a solvent. Examples of solvents used at this time include water, dioxane,
Examples include diethyl ether, tetrahydrofuran, acetone, methyl ethyl ketone, T-butyrolactone, N-methylpyrrolidone, 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 based on 100 parts by weight of the reaction raw materials.

The temperature of the condensation reaction varies depending on the solvent used, but is usually -20 to 60°C, preferably 0 to 40°C.

Purification methods after the condensation reaction include filtering the hydrochloride produced as a by-product, or adding water to dissolve the hydrochloride, purifying it by reprecipitation with a large amount of acidic water such as a dilute aqueous hydrochloric acid solution, and then drying. An example of how to do this can be given.

The compounding amount of compound (1) and compound (II) is 2 to 30 parts by weight, preferably 5 to 25 parts by weight, respectively, per 100 parts by weight of the novolak resin.
Parts by weight, particularly preferably 5 to 15 parts by weight of compound (1)
Parts by weight, Compound (II) is 15 to 25 parts by weight, and optimally Compound (■)/Compound (1) (weight ratio) is 2 to 5 parts by weight.
and (R in the average composition of compound (1).

is a 1,2-quinonediazide sulfonyl group × amount of compound (1) (parts by weight)) + [compound (II
) is used so that the average number of R2 in the average composition of 1.2-quinonediazide sulfonyl group x blending amount (parts by weight) of compound (n) is 90 to 100.

If the amounts of compound ([) and compound (II) are too large or too small, the effects of the present invention cannot be obtained.

The composition of the present invention includes compound (1) and compound (n)
Other 1,2-naphthoquinonediazide compounds may also be blended. Such 1,2-naphthoquinonediazide compounds include 1,2-benzoquinonediazide-4-sulfonic acid esters of (poly)hydroxybenzenes such as p-cresol, resorcinol, pyrogallol, and phloroglycitur, and 1,2-naphthoquinonediazide compounds. Quinonediazide-4-
Sulfonic acid ester or 1.2-naphthoquinonediazide-5-sulfonic acid ester; 2,4-dihydroxyphenyl-propyl ketone, 2.4-dihydroxyphenyl-n-hexyl ketone, 2.4-dihydroxybenzophenone, 2.3. 4-) Lihydroxyphenyl n-
hexylketone, 2.4.6-)dihydroxybenzophenone, 2.3.4.3'-tetrahydroxybenzophenone, 2.3.4.4'-tetrahydroxy-3'-methoxybenzophenone, 2.2'4. 4'-
Tetrahydroxybenzophenone, 2°2', 3.4
．． 6'-pentahydroxybenzophenone, 2.3
．． 3', 4.4', 5'-hexahydroxybenzophenone, 2.3', 4.4', 5'-hexahydroxybenzophenone, etc. Ketone 1,2-benzoquinonediazide-4
-sulfonic acid ester, 1゜2-naphthoquinonediazide-4-sulfonic acid ester or 1,2-naphthoquinonediazide-5-sulfonic acid ester; bis(p-hydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)methane , bis(2,3,4-1-dihydroxyphenyl)methane, 2,2-bis(p-hydroxyphenyl)propane, 2,2-bis(2,4-dihydroxyphenyl)propane, 2,2-bis( 1,2-benzoquinonediazide-4-sulfonic acid ester, 1゜2-naphthoquinonediazide-4-sulfonic acid ester of bis[(poly)hydroxyphenyl coalkane such as 2,3,4-)dihydroxyphenyl)propane, .2-naphthoquinonediazide-5-sulfonic acid ester;

The composition of the present invention may include a light absorbing agent when ultraviolet radiation is used as a radiation source to cause nausea in the composition. As a light absorbing agent, 1,7-bis-(4-hydroxyphenyl)-1,6-heftashiene-3,5-dione,
1-(4-hydroxyphenyl)-7-(3-methoxy-4-hydroxyphenyl)-1,6-hebutadiene-
3,5-dione, l.

7-bis-(3-methoxy-4-hydroxyphenyl)
-1,6-hebutadiene-3,5-dione, 1゜7-bis-(2,4-dihydroxyphenyl)-16-hebutadiene-3,5-dione, 1,7-bis-(2,3 ,4
-)dihydroxyphenyl)-1゜6-hebutadiene-
β-diketone compounds with 3,5-dione, Methyl Violet 2B (CI N1142555), Malachite Green (CI Nct42000), Victoria Blue B (CI NcL44045), Neutral Red (CI No, 50040), Solvent Yellow 2 (CI Nat1020), Solvent Yellow 6
(C1 11390), Solvent Yellow 14 (C
INα12055), Solvent Yellow 15 (C1
CI Na 18820), Solvent Yellow 16 (CI Na
12700), Solvent Yellow 2HCI Sou 1869
0), Solvent Yellow D-33 (CIN11470
00), Solvent Yellow 56 (C1-11021
), Miketon Fast Yellow 7G, Miketon Fast Orange 5R (manufactured by Mitsui Toatsu Dye Co., Ltd.), Holon (
(manufactured by Santo), methine dyes such as Macrolex Yellow 6G (manufactured by Bayer), Yellow HM-1123
, Yellow HM-1134 (manufactured by Mitsui Toatsu Dye Co., Ltd.), 5-
Methyl-1-phenyl-4-phenylazohyrazole,
Pyrazole or imidazole dyes such as 1-phenyl-4-phenylazo-5-oxypyrazole, 1-phenyl-4-phenylazo-5-methylimidazole, 1-phenyl-4-phenylazo-5-oximidazole, stilbene, 4. Examples include 4-diaminostilbenesulfonic acid derivatives, fluorescent brighteners, such as coumarin derivatives, pyrazoline derivatives, and hydroxyazo dyes described in JP-A-59-142538. The amount of the light absorbing agent added is preferably 10 parts by weight or less, particularly preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the novolac resin. If the amount is too large, the sensitivity will decrease, and if the amount is too small, the antihalation effect cannot be exhibited. Two or more of these light absorbers may be used in combination.

A sensitizer may be added to the composition of the present invention to improve sensitivity. Examples of sensitizers include 2■-pyrido(3,2-b)-1,4-oxazine-3(4H)
ons, 1011-pyrido(3,2-b) (1,4
]-benzothiazines, urazoles, hydantoins, barbylic acids, glycine anhydrides, 1-hydroxybenzotriazoles, alloxanes, maleimides, and the like. The blending amount of these sensitizers is usually 100 parts by weight or less based on 100 parts by weight of the 1,2-quinonediazide compound.

In addition, a surfactant may be added to the composition of the present invention in order to improve the coating properties of striations and the like and the developability after dry coating film formation. Examples of surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether, and polyoxyethylene alkyl phenols such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether. Ethers, nonionic surfactants such as polyethylene glycol dialkyl ethers such as polyethylene glycol dilaurate and polyethylene glycol distearate, FTOP EF301, BP303, I! F352
(manufactured by Shinjuyo Kasei Co., Ltd.), Megafac F171, F17
2, F173 (manufactured by Dainippon Ink Co., Ltd.), Florado FC
430, FC431 (manufactured by Sumitomo 3M), Asahi Guard AG710, Surflon S-382, 5CIOI
, 5C102, 5C103, 5C104, 5C105
, 5C106 (manufactured by Asahi Glass Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), and acrylic acid- or methacrylic acid-based (co)polymers Polyflow-75 and Ibi-95 (Kyoeisha Yushi Kagaku Kogyo Co., Ltd.). (manufactured by a company). The blending amount of these surfactants is usually 2 parts by weight or less per 100 parts by weight of the total amount of novolak resin and 1,2-quinonediazide compound.

Furthermore, the composition of the present invention may contain an adhesion aid to improve adhesion, and if necessary, a storage stabilizer, an antifoaming agent, and the like.

The composition of the present invention can be prepared by dissolving the novolak resin, 1,2-quinone di, azide compound, and various compounding agents in a solvent, and filtering it through a filter with a pore size of, for example, about 0.2 μm to a solid content concentration of 10 to 35 μm. It is prepared to about % by weight and used by coating it on a silicon wafer or the like by spin coating, flow coating, roll coating, etc.

Examples of the solvent used at this time include glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethyl glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, etc. Cellosolve esters, monohydroxy monocarboxylic acid esters such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate, ketones such as methyl ethyl ketone and cyclohexane, or ethyl acetate,
Examples include esters such as butyl acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate.

These solvents may be used alone or in combination of two or more. In addition, benzyl ethyl ether, dihexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octatool, 1-nonanol, benzyl alcohol, benzyl acetate, benzoic acid. High-boiling solvents such as ethyl, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenylcellosolve acetate, or aromatic hydrocarbons such as toluene and xylene can be added.

Examples of the developer for the composition of the present invention include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia;
secondary amines such as diethylamine and di-n-propylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, and tetramethylammonium hydroxide. , quaternary ammonium salts such as tetraethylammonium hydroxide, or virol, piperidine, 1,8-diazabicyclo(5,4,0)-7-undecene, 1,5-diazabicyclo(4,3,0)-5- An alkaline aqueous solution containing a cyclic amine such as nonane is used. Further, an alkaline aqueous solution obtained by adding a suitable amount of a water-soluble organic solvent, for example, an alcohol such as methanol or ethanol, or a surfactant to the above-mentioned developer can also be used as the developer.

Furthermore, the composition of the present invention can be heated after radiation irradiation (post-exposure bake: hereinafter referred to as rp+a J), for example, by heating at 80 to 120"C for 60 to 90 seconds, to improve the apparent sensitivity and post-development It is possible to further improve the pattern profile and the like.

e. Examples Hereinafter, the present invention will be explained in detail with reference to Examples, but the present invention is not limited to these Examples.

Example 1 (1) Into a flask equipped with a stirrer, condenser and thermometer, 78.8 (0.73 mol) of m-cresol and 2.3
゜20.3 g (0.15 mol) of 5-trimethylphenol, 121.0 g of a 37% by weight formaldehyde aqueous solution, and 1.52 g of oxalic acid were charged, and the separable flask was immersed in an oil bath while maintaining the internal temperature at 100''C. After reacting for 70 minutes, 19.7 g of m-cresol (0
, 18 mol) and 81.1 g (0.60 mol) of 2,3°5-trimethylphenol were continuously charged into a separable flask as the reaction progressed and allowed to react for 30 minutes.

The oil bath temperature was then raised to 180'C, and at the same time the pressure inside the separable flask was reduced to remove water, unreacted formaldehyde, m-cresol and 3,5-dimethylphenol, and oxalic acid. The molten novolak resin was then returned to room temperature and collected.

The polystyrene equivalent weight average molecular weight distribution of this novolac resin was measured using a GPC column manufactured by Toyo Soda Co., Ltd. (G200OH&
Two bottles (G3000H*, G4000Hi) were used, and the flow rate was 1.5ml/win.

3300 as determined by gel permeation chromatography using monodisperse polystyrene as a standard under the analytical conditions of elution solvent tetrahydrofuran and column temperature 40°C.
Met.

(2) In a flask equipped with a stirrer, dropping funnel, and thermometer, 10.2 g of 2.3.4.4'-tetrahydroxybenzophenone and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (hereinafter referred to as NQD) were added. ) 3
6.7 g was charged at a molar ratio of 1:a, a, and 240 g of dioxane was added to this solution and dissolved with stirring. Separately, 3.8 g of triethylamine was charged into a dropping funnel.

The flask was then immersed in a water bath adjusted to 30°C, and when the internal temperature reached 30°C, triethylamine was slowly added dropwise to the solution so that the internal temperature did not exceed 35°C. After that, the precipitated triethylamine hydrochloride is removed by filtration, and the filtrate is poured into a large amount of diluted hydrochloric acid.
2. '3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester (hereinafter referred to as compound A) was precipitated. Compound A recovered by filtration was dried overnight in a vacuum drying dish adjusted to 40°C. Compound A was added at a flow rate of 0 using HPLC column Inertsil 0055 μ11 manufactured by Gascro Kogyo.
．． 5 d/sin elution solvent tetrahydrofuran/acetonitrile 10.1% by weight phosphoric acid aqueous solution = 27/27/4
6 (volume ratio), it was found that monoester 3
% by weight, 6% by weight of diester, 3% by weight of triester,
The tetraester content was 60% by weight.

(3) In the same manner as in (2), 1 mol of 2.3.4-trihydroxybenzophenone and 2.6 mol of NQD were condensed, and 2.3.4-)rihydroxybenzophenone-1
2-naphthoquinonediazide-5-sulfonic acid ester (hereinafter referred to as compound B) was obtained and dried. When the composition ratio of compound B was examined in the same manner as in (1), it was found to be 1% by weight of monoester, 23% by weight of diester, and 76% by weight of triester.

(4) 100 parts by weight of novolak resin obtained in (1), 20 parts by weight of compound A obtained in (2), compound 81
0 parts by weight and 1,7-bis-(3-methoxy-4-hydroxyphenyl)-1,6-hebutadiene-3. 5
- dione (2.5 parts by weight) was dissolved in 320 parts by weight of ethyl cellosolve acetate and filtered through a filter with a pore size of 0.2 μm to prepare a solution of the composition of the present invention.・
(5) Spread the solution of the composition obtained in (4) to a thickness of 0.
A 2 .mu.m aluminum layer was spin-coated onto a silicon wafer, which was then evaporated and then brebaked for 2 minutes on a hot plate kept at 80.degree. C. to obtain a resist film with a dry film thickness of 1.8 .mu.m.

This resist film has a line width equal to a space width (I
L/Is pattern) Using a test pattern reticle, 1
FEB was performed for 1 minute on a hot plate maintained at 100°C for 0.42 seconds using a 115 reduction projection exposure apparatus equipped with a 00OW ultra-high pressure mercury lamp, and tetramethylammonium hydroxide 2.4% % aqueous solution, developed at 25°C for 1 minute, rinsed with water,
It was dried to form a resist pattern. The residual film rate at this time was 98%.

When the formed resist pattern was observed with a scanning electron microscope, it was found to have a good pattern profile with steep sidewalls as shown in FIG.

Furthermore, the developability was good, with no development residue observed, and there were no disconnections or chipping at the bottom of the pattern due to the effects of halation, and resist patterns up to 0.55 μm could be accurately resolved.

Further, when a wafer with a resist pattern formed thereon was placed in an oven and the temperature at which the pattern began to collapse was determined, it was 150''C, indicating that the resist had good heat resistance.

Example 2 (1) In the same manner as in Example 1 (2), 2, 3, 4.
1 mol of 4'-tetrahydroxybenzophenone and NQDs
3.7 mol of 2.3.4.4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester (hereinafter referred to as compound C) was obtained and dried. When the composition ratio of compound C was investigated in the same manner as in Example 1 (2), it was found that 0% by weight of monoester, 4% by weight of diester, 15% by weight of triester, and 8% by weight of tetraester.
It was 1% by weight.

(2) A solution of the composition of the present invention was prepared in the same manner as in Example 1 (4) except that 20 parts by weight of Compound C was used instead of Compound A in Example 1 (4).

(3) In Example 1 (5), a resist pattern was formed in the same manner as in Example 1 (5) except that the solution of the composition obtained in (2) was used and the exposure time was 0.58 seconds. death,
Upon observation, as shown in FIG. 1, it was found to have a good pattern profile with steep sidewalls. In addition, the developability is good, with no development residue observed, and there are no disconnections or chips at the bottom of the pattern due to the effects of halation.
It was possible to accurately resolve resist patterns down to 0.55 μm.

Furthermore, when a wafer with a resist pattern formed thereon was placed in an oven and the temperature at which the pattern began to collapse was determined, it was 150° C., indicating that the resist had good heat resistance.

Example 3 (1) In the same manner as in Example 1 (2), 1 mole of 2.3.4-)trihydroxybenzophenone and 2.3 moles of NQDs were condensed to form 2.3.4-trihydroxybenzophenone. -1,2-naphthoquinonediazide-5-sulfonic acid ester (hereinafter referred to as compound) was obtained and dried.

When the composition ratio of the compound was examined in the same manner as in Example 1 (2), it was found to be 4% by weight of monoester, 34% by weight of diester, and 61% by weight of triester.

(2) A solution of the composition of the present invention was prepared in the same manner as in Example 1 (4) except that parts by weight of Compound DIO was used instead of Compound B in Example 1 (4).

(3) In Example 1 (5), a resist pattern was formed in the same manner as in Example 1 (5) except that the solution of the composition obtained in (2) was used and the exposure time was 0.38 seconds. death,
Upon observation, as shown in FIG. 1, it was found to have a good pattern profile with steep sidewalls. In addition, the developability is good, with no development residues, and there are no disconnections or chips at the bottom of the pattern due to halation.
, it was possible to accurately resolve resist patterns down to 0.55 μm.

Furthermore, when a wafer with a resist pattern formed thereon was placed in an oven and the temperature at which the pattern began to collapse was determined, it was 150° C., indicating that the resist had good heat resistance.

Comparative Example 1 (1) Example 1 (4) except that Compound A was not used in Example 1 (4) and 35 parts by weight of Compound B was used alone.
A solution of a composition for comparison was prepared in the same manner as above.

(2) In Example 1 (5), a resist pattern was formed in the same manner as in Example 1 (5) except that the solution of the composition obtained in (1) was used and the exposure time was 0.56 seconds. death,
When observed, the developability was good and no development residue was observed, but as shown in FIG. 2, the pattern profile became spindle-shaped due to the effect of halation.

Comparative Example 2 (1) Example 1 (4) except that Compound B was not used in Example 1 (4) and 25 parts by weight of Compound A was used alone.
A solution of a composition for comparison was prepared in the same manner as above.

(2) In Example 1 (5), a resist pattern was formed in the same manner as in Example 1 (5) except that the solution of the composition obtained in (1) was used and the exposure time was 0.42 seconds. When observed, the developability was good and no development residue was observed, but as shown in FIG. 3, the pattern profile became a rectangle with a constricted bottom due to the effect of halation.

Example 4 (1) In Example 1 (4), 1,7-bis-(3-
Example 1 (4-methoxy-4-hydroxyphenyl)-1,6-hebutadiene-3,5-dione was not added.
) A solution of the composition of the present invention was prepared in the same manner.

(2) After spin-coating the solution of the composition obtained in (1) onto a silicon wafer,
Pre-bake on a plate for 2 minutes to obtain a dry film thickness of 1.2
A μ- resist film was obtained. This resist film was exposed in the same manner as in Example 1 (5) except that the exposure time was 0.26 seconds.
FEB, development, rinsing and drying were performed to form a resist pattern. The residual film rate at this time was 98%. The developability was good, no development residue was observed, and even a 0.5 μm resist pattern could be accurately resolved.

Further, when a wafer with a resist pattern formed thereon was placed in an oven and the temperature at which the pattern began to collapse was determined, it was 150° C., indicating that the resist had good heat resistance.

f0 Effects of the Invention The composition of the present invention has excellent resolution, sensitivity, and pattern profile after development, as well as excellent heat resistance and storage stability, and has a high residual film rate after development. It is suitable as a positive resist that has an excellent halation prevention effect when molded.

[Brief explanation of the drawing]

FIG. 1 is a cross-sectional view of the resist pattern obtained in Examples 1 to 3, FIG. 2 is a cross-sectional view of the resist pattern obtained in Comparative Example 1, and FIG. 3 is a cross-sectional view of the resist pattern obtained in Comparative Example 2. FIG. 3 is a cross-sectional view of a resist pattern. 1... Resist pattern, 2... Base aluminum substrate. Figure 1 Figure 2

Claims (1)

[Scope of Claims] A radiation-sensitive resin composition comprising an alkali-soluble novolac resin and a 1,2-quinonediazide compound, wherein the 1,2-quinonediazide compound is a compound represented by the following general formula (I) and a compound represented by (II). (I) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R_1 and R_2 are hydrogen atoms or 1, 2- It is a quinonediazide sulfonyl group, and as an average composition, at least two or more of R_1 and at least three or more of R_2 are 1,2-quinonediazide sulfonyl groups. ] It is characterized by containing 2 to 30 parts by weight of the compound represented by the above general formula (I) and 2 to 30 parts by weight of the compound represented by the above general formula (II) based on 100 parts by weight of the above alkali-soluble novolak resin. A radiation-sensitive resin composition.