JPH08262712A - Radiation-sensitive resin composition - Google Patents

Abstract

(57) [Summary] [Structure] An alkali-soluble resin and, for example, the following formula (1) A radiation-sensitive resin composition comprising a 1,2-quinonediazide sulfonic acid ester compound represented by the formula: [Effect] The radiation-sensitive resin composition of the present invention is a positive-working resin composition in which generation of scum is effectively suppressed, developability is excellent, high resolution and heat resistance are excellent, and particularly good focus tolerance is provided. It is suitable as a resist. Therefore, the radiation-sensitive resin composition of the present invention can be suitably used as a resist for producing an integrated circuit having a high degree of integration.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a radiation-sensitive resin composition containing an alkali-soluble resin. More specifically, high integration sensitive to various kinds of radiation such as ultraviolet rays such as g rays and i rays, far ultraviolet rays such as KrF excimer laser, X rays such as synchrotron radiation, charged particle rays such as electron beams, and particularly ultraviolet rays and far ultraviolet rays. The present invention relates to a radiation-sensitive resin composition suitable as a resist for circuit production.

[0002]

2. Description of the Related Art Positive resists are often used in the manufacture of integrated circuits. With the recent trend toward higher integration of integrated circuits, positive resists capable of forming resist patterns with higher resolution are desired. ing. Generally, in order to improve the resolution of a positive resist, there is a method of improving the resist material, for example, by reducing the molecular weight of an alkali-soluble resin used in the resist, but in this case, the heat resistance of the resist is reduced. Occurs. On the other hand, there is a method of increasing the aperture coefficient (NA) of the stepper to improve the resolution by improving the process.
In this case, there arises a problem that the depth of focus (focus tolerance) becomes narrower, and therefore it is necessary to improve the resist material at the same time. There are two ways to deal with this. However, if the addition amount of the quinonediazide compound is increased, the developability will be deteriorated. As described above, since positive performance of one resist decreases when another performance is improved, a positive resist having high resolution, good focus tolerance, and good developability for fine patterns is desired. ing.

[0003]

An object of the present invention is to provide a novel radiation sensitive resin composition. Another object of the present invention is to effectively suppress the generation of scum, excellent in developability and excellent in heat resistance with high resolution, and particularly,
It is an object of the present invention to provide a radiation-sensitive resin composition suitable as a positive resist having good focus tolerance.

[0004]

According to the present invention, the above-mentioned objects of the present invention include an alkali-soluble resin and a compound represented by the following formula (1):

[0005]

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[In the formula (1), X _{1 to} X ₂₄ and Y _{1 to} Y ₄
Are each the same or different from each other and are a hydrogen atom, an alkyl group, an alkoxyl group or a group represented by -OD (wherein D is a hydrogen atom or an organic group containing a 1,2-quinonediazide group), A is a methylene group,
1,1-dimethylmethylene group, 1,1-bis (trifluoromethyl) methylene group, carbonyl group, sulfone group,
An ether group, a thioether group or a single bond, X ₁
To at least one of X ₅ to at least one of X _{6 to} X ₁₀ ,
At least one of X _{11 to} X ₁₅ , at least one of X _{16 to} X ₂₀ , at least one of Y _{1 to} Y ₂ and at least one of Y _{3 to} Y ₄ is a group represented by —OD, and these -OD
At least one of the plurality of D represented by is an organic group containing a 1,2-quinonediazide group. ] The radiation-sensitive resin composition containing the 1,2-quinonediazide compound represented by the following (hereinafter referred to as "compound (b)"). Hereinafter, the present invention will be specifically described, but the purpose, constitution and effect of the present invention will be clarified.

Alkali-Soluble Resin The alkali-soluble resin used in the present invention (hereinafter,
It is called "resin (A)". Examples of) include novolac resins, polyvinylphenol or its derivatives, styrene-maleic anhydride copolymers or its derivatives, polyvinylhydroxybenzoates, and carboxyl group-containing methacrylic acid resins. Resin (A)
Can be used alone or in combination of two or more. Preferred resin (A)
Examples of the resin include novolac resin. Such novolac resin has the following formula (2)

[0008]

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[In the formula (2), n is an integer of 0 to 3. ] It is obtained by polycondensing phenols and aldehydes represented by Examples of the phenols include phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,5-
Xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3,4
5-trimethylphenol etc. can be mentioned. In particular, m-cresol, p-cresol, 2,3-xylenol, 2,5-xylenol, 3,4-xylenol,
3,5-xylenol and 2,3,5-trimethylphenol are preferred. These phenols may be used alone or in combination of two or more. When two or more phenols are used in combination, for example, m-cresol / 2,3-xylenol / 3,4-xylenol = 20 to 95/5 to 80/0 to 75 (weight ratio), and m-cresol / 2,3,5-trimethylphenol /
2,3-xylenol = 20-95 / 5-80 / 0-7
A combination of 5 (parts by weight) is particularly preferable.

Examples of the aldehydes to be polycondensed with the phenols include formaldehyde, trioxane, paraformaldehyde, benzaldehyde, acetaldehyde, propylaldehyde, phenylacetaldehyde, α-phenylpropylaldehyde, β-phenylpropylaldehyde and o-hydroxy. Benzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-chlorobenzaldehyde,
m-chlorobenzaldehyde, p-chlorobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, p-nitrobenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-
Methylbenzaldehyde, p-ethylbenzaldehyde, pn-butylbenzaldehyde, furfural and the like can be mentioned. Of these, formaldehyde can be used particularly preferably. Further, as the aldehydes, bisaldehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and isophthalaldehyde can be used. As the aldehydes, for example, formalin, trioxane, formaldehyde such as paraformaldehyde, or hemiformal such as methyl hemiformal, ethyl hemiformal, propylhemiformal, butylhemiformal, phenylhemiformal, etc. should be used as the raw material. You can Of these, formalin and butyl hemiformal are particularly preferably used. These aldehydes may be used alone or in combination of two or more. The amount of the aldehydes used is preferably 0.7 to 3 mol, and more preferably 0.8 to 1.5 mol, based on 1 mol of the phenol.

An acidic catalyst is usually used in the polycondensation reaction of phenols and aldehydes. Examples of the acidic catalyst include hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid,
Acetic acid etc. can be mentioned. The amount of these acidic catalysts used is usually 1 × 10 ⁻⁵ to 1 mol of phenols.
It is 5 × 10 ^-1 mol. In the polycondensation reaction,
Although water is used as the reaction medium, a hydrophilic solvent can be used as the reaction medium when the phenols used in the reaction do not dissolve in the aqueous solution of aldehydes and become a heterogeneous system from the initial stage of the reaction. Examples of these hydrophilic solvents include alcohols such as methanol, ethanol, propanol and butanol; cyclic ethers such as tetrahydrofuran and dioxane. The amount of these reaction media used is usually 20 to 1,000 parts by weight per 100 parts by weight of the reaction raw material. The reaction temperature for polycondensation can be appropriately adjusted depending on the reactivity of the raw materials, but is usually 10 to 200 ° C. As the polycondensation reaction method, a method of collectively charging phenols, aldehydes, acidic catalysts, etc. and a method of adding phenols, aldehydes, etc. in the presence of an acidic catalyst as the reaction progresses are appropriately adopted. be able to. After completion of the polycondensation reaction, the reaction temperature is generally set to 130 to 2 in order to remove unreacted raw materials, acidic catalyst, reaction medium, etc. existing in the system.
The temperature is raised to 30 ° C., the volatile matter is distilled off under reduced pressure, and the novolak resin is recovered.

The polystyrene-equivalent weight average molecular weight of the novolak resin used in the present invention (hereinafter referred to as "Mw")
Say. ) Is preferably 2,000 to 20,000 from the viewpoint of workability when applying the composition of the present invention to a substrate, developability when used as a resist, sensitivity and heat resistance, and particularly, Particularly preferably, it is 3,000 to 15,000. In order to obtain a novolak resin having a particularly high Mw, the novolak resin obtained by the above method is used as a good solvent such as ethylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, dioxane, methanol, and ethyl acetate. After dissolution, a poor solvent such as water, n-hexane, or n-heptane is mixed, and then the resin solution layer that precipitates is separated to recover the high molecular weight novolak resin.

Dissolution accelerator In the present invention, a low molecular weight phenol compound (hereinafter,
It is called "dissolution accelerator". ) Can be added. As the dissolution promoter, a phenol compound having a benzene ring number of 2 to 6 is suitable, and for example, the following formula (3-1) to
The compound represented by (3-8) can be illustrated.

[0014]

[Chemical 4]

[0015]

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[In the formulas (3-1) to (3-8), a, b and c are each a number from 0 to 3 (provided that each is 0), and x and y. And z are 0 to
3 and a + b ≦ 5, b + y ≦ 5 (provided that
For formulas (3-3) and (3-4), b + y ≦ 4 and c + z ≦ 5. ). ] The amount of the dissolution accelerator compounded is usually 100 g of the resin (A).
It is 50 parts by weight or less, preferably 10 to 40 parts by weight per part by weight.

Other Alkali-Soluble Resin In the present invention, a part of the resin (A) is referred to as a low molecular weight alkali-soluble resin (hereinafter referred to as “resin (B)”) for the purpose of promoting alkali-solubility of the resin (A). ) Can be changed. Examples of the resin (B) include an alkali-soluble novolac resin and an alkali-soluble resole resin, which are obtained by a polycondensation reaction of the phenols and aldehydes. As the phenols, 1-naphthol, 2-naphthol and the like can be used in addition to those exemplified as the phenols used in the synthesis of the novolak resin.
Further, as the aldehydes, those used in the synthesis of the novolak resin can be used. In this case, the amount of aldehydes used is usually 0.2 to 0.8 mol per mol of phenols. In addition, in this polycondensation reaction, in addition to the acidic catalyst used for producing the novolak resin, an alkaline catalyst such as pyridine or triethylamine can be used when producing the resole resin. The Mw of the resin (B) is 200 to 2,000.
It is preferably less than 300, and more preferably 300 to 1,000. As such a resin (B),
Examples thereof include phenol / formaldehyde condensation resin, o-cresol / formaldehyde condensation resin, m-cresol / formaldehyde condensation resin, p-cresol / formaldehyde condensation resin, m-cresol / p-cresol / formaldehyde condensation resin. The amount of the resin (B) compounded is generally 50 parts by weight or less based on 100 parts by weight of the total of the resin (A) and the resin (B).

1,2-Quinonediazide Compound The composition of the present invention contains a compound (b) (1,2-quinonediazide compound represented by the above formula (1)) as a 1,2-quinonediazide compound. In formula (1), X ₁ ~
X ₂₄ and Y _{1 to} Y ₄ are the same or different from each other and represent a hydrogen atom, an alkyl group, an alkoxyl group or —O.
The group represented by D (provided that D is a hydrogen atom or an organic group containing a 1,2-quinonediazide group; hereinafter, "O"
D group ". ) And A is a methylene group, 1,1-
It is a dimethylmethylene group, a 1,1-bis (trifluoromethyl) methylene group, a carbonyl group, a sulfone group, an ether group, a thioether group or a single bond. Here, as the alkyl group, an alkyl group having 1 to 4 carbon atoms is preferable, and specifically, a methyl group, an ethyl group, an n-propyl group,
Examples include isopropyl group, n-butyl group, t-butyl group and the like. Further, as the alkoxyl group, an alkoxyl group having 1 to 4 carbon atoms is preferable, and specific examples thereof include a methoxy group, an ethoxy group, a propoxy group, a butoxy group and the like.

Examples of the organic group containing a 1,2-quinonediazide group in the above D include a 1,2-benzoquinonediazide-4-sulfonyl group, a 1,2-naphthoquinonediazide-4-sulfonyl group, a 1,2-naphtho group. A preferable example is a 1,2-quinonediazidesulfonyl group such as a quinonediazide-5-sulfonyl group or a 1,2-naphthoquinonediazide-6-sulfonyl group.
The 1,2-naphthoquinonediazide-4-sulfonyl group and the 1,2-naphthoquinonediazide-5-sulfonyl group are particularly preferred. Incidentally, at least one of X _{1 to} X ₅ , X
_At least one of _{6 to} X ₁₀ and at least 1 of X _{11 to} X ₁₅
At least one of X _{16 to} X ₂₀ , at least one of Y _{1 to} Y ₂ and at least one of Y _{3 to} Y ₄ is an OD group, and at least one of the plurality of OD groups has D 1,
It is an organic group containing a 2-quinonediazide group. The compound (b) corresponding to the case where all D of the OD group in the formula (1) are hydrogen atoms, that is, the compound (b) corresponding to the case where the OD group is a hydroxyl group is represented by the formula (1). It is a precursor of compound (b) (hereinafter, this precursor is referred to as "compound (a)"). Specific examples of the compound (a) include compounds represented by the following formulas (4-1) to (4-30).

[0020]

[Chemical 6]

[0021]

[Chemical 7]

[0022]

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[0023]

[Chemical 9]

[0024]

[Chemical 10]

[0025]

[Chemical 11]

[0026]

[Chemical 12]

[0027]

[Chemical 13]

[0028]

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[0029]

[Chemical 15]

[0030]

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[0031]

[Chemical 17]

[0032]

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[0033]

[Chemical 19]

[0034]

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Specific examples of the compound (b) include:
1,2-benzoquinonediazide-4-sulfonic acid ester, 1,2-naphthoquinonediazide-4-sulfonic acid ester of compound (a) represented by (4-1) to (4-30), 1,2- Examples thereof include naphthoquinone diazide-5-sulfonic acid ester and 1,2-naphthoquinone diazide-6-sulfonic acid ester. Especially 1,2-
Naphthoquinonediazide-4-sulfonate and 1,2-naphthoquinonediazide-5-sulfonate are preferred. The compound (b) can be produced, for example, by an esterification reaction of the compound (a) with a 1,2-quinonediazidesulfonyl halide such as 1,2-naphthoquinonediazide-4-sulfonyl chloride or 1,2-naphthoquinonediazide-5-sulfonylchloride. can get. In the esterification reaction, the reaction ratio of the compound (a) and the 1,2-quinonediazidesulfonyl halide is preferably 1,2-quinonediazidesulfonyl halide, based on 1 equivalent of the phenolic hydroxyl group of the compound (a). 25 to 1 equivalent, particularly preferably 0.4 to 1 equivalent. The desired compound (b) is obtained by reacting these with a basic catalyst such as triethylamine or pyridine in the presence of 0.3 to 1.3 equivalents.
Is obtained. In the composition of the present invention, the compound (b)
Is 5 to 50 parts by weight per 100 parts by weight of the resin (A),
It is particularly preferable to use it in a proportion of 10 to 40 parts by weight. The compound (b) can be used alone or in combination of two or more kinds.

Other quinonediazide compounds In the present invention, 1,2-benzoquinonediazide-4-sulfonic acid ester other than compound (b), 1,2-naphthoquinonediazide-4-, is used in combination with compound (b).
Sulfonic acid ester, 1,2-naphthoquinonediazide-
A 1,2-quinonediazide compound such as 5-sulfonic acid ester (hereinafter referred to as "other quinonediazide compound") can be added. Examples of such other quinonediazide compounds include 2,3,4-trihydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2,2 ′, 3,4,4′-
Pentahydroxybenzophenone, tris (4-hydroxyphenyl) methane, 1,3,5-tris (4-hydroxy-α, α-dimethylbenzyl) benzene, 1,1
-Bis (4-hydroxyphenyl) -1- [4- {1-
(4-Hydroxyphenyl) -1-methylethyl} phenyl] ethane, 2- (3,4-dihydroxyphenyl)
-2- (4-hydroxyphenyl) propane, 2,4
Mention may be made of 1,2-quinonediazide sulfonic acid esters such as 4-trimethyl-2- (2,4-dihydroxyphenyl) -7-hydroxychroman. As these 1,2-quinonediazide sulfonic acid esters, particularly 1,2-naphthoquinonediazide-4-sulfonic acid ester or 1,2-naphthoquinonediazide-5-
Sulfonic acid esters are preferred. In the composition of the present invention, the blending amount of the other quinonediazide compound is preferably 100 parts by weight or less with respect to 100 parts by weight of the resin (A). Further, 1,2-occupying in the composition of the present invention
The total weight of the quinonediazide residue is adjusted to be 5 to 50% by weight, particularly preferably 10 to 30% by weight, based on the total solid content in the composition.

Various Compounding Agents The composition of the present invention may be compounded with various compounding agents such as a sensitizer and a surfactant, if necessary. The sensitizer is added to improve the sensitivity of the resist. Examples of such a sensitizer include 2H-pyrido- [3,2-b] -1,4-oxazine-3 (4H).
-Ones, 10H-pyrido- [3,2-b]-(1,
4 ′)-benzothiazines, urazoles, hydantoins, parpituric acids, glycine anhydrides, 1-hydroxybenzotriazoles, alloxans, maleimides and the like can be mentioned. The blending amount of these sensitizers is preferably 50 parts by weight or less with respect to 100 parts by weight of the resin (A).

The surface active agent is added to improve the coatability and developability of the composition. Examples of such a surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate. Rate, Megafax F171, F172, F173 (trade name, manufactured by Dainippon Ink and Chemicals, Inc.), Florard FC4
30, FC431 (trade name, manufactured by Sumitomo 3M Limited), Asahi Guard AG710, Surflon S-382, SC-
101, SC-102, SC-103, SC-104,
SC-105, SC-106 (trade name, manufactured by Asahi Glass Co., Ltd.),
KP341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 75, no. 95 (trade name, manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.), F-top EF301, EF303, EF35
2 (trade name, manufactured by Tochem Products) and the like. These surfactants can be used alone or in admixture of two or more. The blending amount of these surfactants is preferably 2 parts by weight or less per 100 parts by weight of the solid content of the composition excluding various blending agents, and the active ingredient of the surfactants. Further, the composition of the present invention includes
Dyes and pigments can be added in order to visualize the latent image on the irradiated area of the resist and reduce the effect of halation during irradiation, and an adhesion aid is added to improve the adhesion. You can also Further, if necessary, a storage stabilizer, a defoaming agent, etc. may be added.

Solvent The composition of the present invention contains, for example, the above-mentioned resin (A) and compound (b), and optionally a dissolution accelerator, resin (B), other quinonediazide compound, various compounding agents and the like. It is prepared by dissolving in a solvent so that the solid content concentration becomes 20 to 40% by weight, and filtering with a filter having a pore size of about 0.2 μm. Examples of the solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol methyl ether acetate,
Propylene glycol propyl ether acetate, propylene glycol methyl ether propionate, toluene, xylene, methyl ethyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone, ethyl 2-hydroxypropionate, 2-hydroxy-2-methylpropionic acid Ethyl, 2-methoxy-2
-Methyl methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-methoxy-2 -Methyl methylpropionate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate and the like can be mentioned. Furthermore, N-methylformamide, N, N-dimethylformamide, N
-Methylformanilide, N-methylacetamide,
N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, benzyl ethyl ether,
Dihexyl ether, acetonylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-
Nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate,
γ-butyrolactone, ethylene carbonate, propylene carbonate,
A high boiling point solvent such as ethylene glycol monophenyl ether acetate can also be added. These solvents are used alone or in combination of two or more.

The composition of the present invention prepared as a resist film forming solution is applied to a substrate such as a silicon wafer or a wafer coated with aluminum by spin coating, cast coating, roll coating or the like. It Next, this is prebaked to form a resist coating, and the resist coating is irradiated with radiation so as to form a desired resist pattern (hereinafter, referred to as
It is called "exposure". Then, the pattern is formed by developing with a developing solution. Radiation used at this time is preferably ultraviolet rays such as g rays and i rays, but far ultraviolet rays such as excimer lasers, X rays such as synchrotron radiation,
Various kinds of radiation such as charged particle beams such as electron beams can also be used. Further, the composition of the present invention forms a resist film, prebakes and exposes it, and then 70 to 140 ° C.
The effect of the present invention can be further improved by performing a heating operation (hereinafter, referred to as “post-exposure bake”) and then developing.

The developer used for the resist film is, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate,
Ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1, An alkaline compound such as 8-diazabicyclo [5.4.0] -7-undecene or 1,5-diazabicyclo [4.3.0] -5-nonene is dissolved in a concentration of, for example, 1 to 10% by weight. An alkaline aqueous solution is used. In addition, 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. When a developer containing such an alkaline aqueous solution is used, it is generally washed with water after development.

[0042]

The present invention will be described in detail below with reference to examples. <Measurement and Evaluation> The Mw measurement and the resist evaluation in the examples were carried out by the following methods. Mw: Tosoh GPC column (G2000H _XL : 2
Gel, G3000H _XL : 1 bottle, G4000H _XL : 1 bottle), flow rate: 1.0 ml / min, elution solvent: tetrahydrofuran, column temperature: 40 ° C. It was measured by a solution chromatography method. Heat resistance: A wafer on which a resist pattern was formed was placed in a clean oven, and the temperature at which the pattern started to collapse was measured. Focus range (focus tolerance): Focusing when the resolution of a 0.4 μm line-and-space pattern is within ± 10% of the mask design dimension using a scanning electron microscope. The swing range was used as the focus range and was used as the evaluation index. A large focus range means that it has a good focus tolerance. Developability: The scum after resist pattern formation and the extent of residual development were examined using a scanning electron microscope.

<Synthesis of Resin (A)> Synthesis Example 1 m-cresol 69.2 g (0.64 mol) 2,3-xylenol 9.8 g (0.98 mol) 3,4-xylenol 9. 8 g (0.08 mol) 37% by weight aqueous formaldehyde solution 61.0 g (formaldehyde: 0.75 mol) oxalic acid dihydrate 6.3 g (0.05 mol) Water 52.6 g and dioxane 182 g were charged, and the autoclave was charged. Immerse in an oil bath and set the internal temperature to 130
Polycondensation was carried out for 8 hours while maintaining the temperature at 0 ° C. with stirring. After the reaction, the mixture was cooled to room temperature and the contents were taken out in a beaker.
After separating into two layers in this beaker, the lower layer was taken out, concentrated, dehydrated and dried to recover the novolak resin. This resin had an Mw of 8,600. This resin is referred to as resin (A1).

Synthesis Example 2 In an autoclave, m-cresol 64.9 g (0.6 mol) 2,3-xylenol 36.7 g (0.3 mol) 3,4-xylenol 12.2 g (0.1 mol) 37 Weight% formaldehyde aqueous solution 77.1 g (formaldehyde: 0.9 mol) Oxalic acid dihydrate 6.3 g (0.05 mol) Water 79.4 g and dioxane 383.9 g were charged, and the same operation as in Synthesis Example 1 was performed. The novolak resin was recovered. This resin had an Mw of 7,800. This resin is referred to as a resin (A2).

<Synthesis of Compound (b)> The above formula (4)
-5) is a compound represented by the formula (4-).
The compound represented by 7) is represented by the formula (4-1):
Let the compound represented by 5) be (a-15).

Synthesis Example 3 6.22 g (0.01 mol) of 1,2-naphthoquinonediazide-5-sulfonic acid chloride compound (a-5) was placed in a flask equipped with a stirrer, a dropping funnel and a thermometer in the dark. 10.74 g (0.04 mol) and 88 g of dioxane were charged and dissolved with stirring. Then, the flask was immersed in a water bath controlled at 30 ° C., and the internal temperature was adjusted to 3
When the temperature became constant at 0 ° C., 5.05 g (0.05 mol) of triethylamine was added to this solution using a dropping funnel so that the internal temperature did not exceed 35 ° C., and the reaction was carried out at the same temperature for 2 hours. Then, the precipitated triethylamine hydrochloride was removed by filtration, and the filtrate was poured into a large amount of dilute hydrochloric acid aqueous solution to precipitate a reaction product,
The precipitate is then filtered, recovered and dried in a vacuum oven at 40 ° C.
After that, it was dried for one day and night to obtain the compound (b-5).

Synthesis Example 4 Compound (a-7) 7.34 g (0.01 mol) 1,2-naphthoquinonediazide-5-sulfonic acid chloride 10.74 g (0.04 mol) dioxane 93 g and triethylamine 5.05 g ( 0.05 mol) was used in the same manner as in Synthesis Example 3 except that the compound (b-
7) was obtained.

Synthesis Example 5 Compound (a-15) 7.62 g (0.01 mol) 1,2-naphthoquinonediazide-5-sulfonic acid chloride 10.74 g (0.04 mol) dioxane 94 g and triethylamine 5.05 g ( Compound (b-1) was prepared in the same manner as in Synthesis Example 3 except that 0.05 mol) was used.
5) was obtained.

<Synthesis of other quinonediazide compounds> Synthesis example 6 2,3,4,4'-tetrahydroxybenzophenone 24.6 g (0.1 mol) 1,2-naphthoquinonediazide-5-sulfonic acid chloride 80.6 g (0.3 mol) A quinonediazide compound (i) was obtained in the same manner as in Synthesis Example 3 except that 552 g of dioxane and 33.3 g (0.33 mol) of triethylamine were used.

Synthesis Example 7 Tris (4-hydroxyphenyl) methane 14.6 g (0.05 mol) 1,2-naphthoquinonediazide-5-sulfonic acid chloride 40.3 g (0.15 mol) dioxane 222 g and triethylamine 18. A quinonediazide compound (II) was obtained in the same manner as in Synthesis Example 3 except that 2 g (0.18 mol) was used.

Examples 1 to 7 and Comparative Examples 1 to 3 In the composition ratios shown in Table 1 (where parts are parts by weight),
The resin (A), the compound (b), the dissolution promoter, the other quinonediazide compound and the solvent are mixed to form a uniform solution, which is then filtered through a membrane filter having a pore size of 0.2 μm.
A solution of the composition was prepared. The obtained solution was applied onto a silicon wafer having a silicon oxide film by using a spinner, and then prebaked on a hot plate at 90 ° C. for 2 minutes to form a resist film having a thickness of 1.1 μm. Then, through the reticle, NSR-17 manufactured by Nikon Corporation
55i7A reduction projection exposure machine (lens numerical aperture: 0.50)
Exposure with a wavelength of 365 nm (i-line), development with a 2.38 wt% aqueous solution of tetramethylammonium hydroxide, rinsing with ultrapure water, and drying to form a resist pattern. The obtained resist pattern was examined and the characteristics of the composition of each example as a resist were evaluated. Table 2 shows the results.

[0052]

[Table 1]

In Table 1, the types of dissolution accelerators and solvents are as follows. Dissolution accelerator α: 1,1,1-tris (4-hydroxyphenyl) ethane β: 1,1-bis (4-hydroxyphenyl)-
1-Phenylethane Solvent S1: Ethyl 2-hydroxypropionate S2: Ethyl 3-ethoxypropionate

[0054]

[Table 2]

[0055]

The radiation-sensitive resin composition of the present invention effectively suppresses the generation of scum, has excellent developability, high resolution and excellent heat resistance, and in particular has good focus tolerance. It is suitable as a positive resist. Therefore, the radiation-sensitive resin composition of the present invention can be suitably used as a resist for producing an integrated circuit having a high degree of integration.

 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Akira Tsuji 2-11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd.

Claims (1)

[Claims] 1. An alkali-soluble resin and the following formula (1): [In the formula (1), X _{1 to} X ₂₄ and Y _{1 to} Y ₄ are the same or different from each other and represent a hydrogen atom, an alkyl group, an alkoxyl group or a group represented by -OD (wherein D is a hydrogen atom or 1,2-quinonediazide group-containing organic group), and A is a methylene group, a 1,1-dimethylmethylene group, a 1,1-bis (trifluoromethyl) methylene group, a carbonyl group, a sulfone group. , An ether group, a thioether group or a single bond, and at least one of X _{1 to} X ₅ , at least one of X _{6 to} X ₁₀ , at least one of X _{11 to} X ₁₅ , and at least 1 of X _{16 to} X ₂₀ . One, Y _{1 to} Y ₂
And at least one of Y _{3 to} Y ₄ is-
A group represented by OD, and at least one of the plurality of D represented by -OD is an organic group containing a 1,2-quinonediazide group. ] The radiation-sensitive resin composition containing the 1,2-quinonediazide compound represented by