JPH07120917A - Radiation sensitive resin composition - Google Patents

Abstract

PURPOSE:To ensure superior developability and high resolution and to improve focus latitude by incorporating an alkali-soluble resin and a specified 1,2- quinonediazido compd. CONSTITUTION:An alkali-soluble resin and a 1,2-quinonediazido compd. represented by the formula are incorporated. In the formula, each of X1-X12, Y1 and Y2 is H, an alkyl, alkoxy or a group represented by -OD (where D is H or an org. group contg. a 1,2-quinonediazido group), each of R1-R4 is an alkyl, at least one of X1-X5, at least one of X8-X12 and at least one of Y1 and Y2 are groups represented by -OD and at least one of the plural D's of the groups represented by -OD is an org. group contg. a 1,2-quinonediazido group.

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, ultraviolet rays, far ultraviolet rays, X-rays, electron beams, molecular beams, γ rays,
The present invention relates to a radiation-sensitive resin composition suitable as a positive resist sensitive to radiation such as synchrotron radiation and proton beam.

[0002]

2. Description of the Related Art Positive resists are often used in the manufacture of integrated circuits because a resist pattern of high resolution can be obtained. However, with the high integration of integrated circuits in recent years, resists with higher resolution have been obtained. A positive resist capable of forming a pattern is desired.

Generally, as a method of improving the resolution of the resist, there is a method of reducing the molecular weight of the alkali-soluble resin, but there is a problem that the heat resistance of the resist is reduced. Further, there is a method of increasing the aperture coefficient (NA) of the stepper, but in this case, there arises a problem that the depth of focus (focus tolerance) becomes narrow.

Therefore, it is conceivable to increase the amount of the quinonediazide compound added in order to improve the focus tolerance. However, when the addition amount of the quinonediazide compound is increased, the developability is deteriorated. When one performance is improved, the other performance is deteriorated. Therefore, a positive resist having high resolution, good focus tolerance, and good developability with a fine pattern is desired.

[0005]

An object of the present invention is to provide a novel radiation sensitive resin composition. Another object of the present invention is a radiation-sensitive resin composition suitable for use as a positive resist, in which generation of scum is effectively suppressed, developability is excellent, and resolution is high, and particularly good focus tolerance is provided. To provide things.

[0006]

According to the present invention, the above objects and advantages of the present invention are achieved by using an alkali-soluble resin and the following formula (1):

[0007]

[Chemical 2]

[In the formula (1), X _{1 to} X ₁₂ , Y ₁ and Y ₂ are the same or different from each other and are a hydrogen atom, an alkyl group, an alkoxy group or a group represented by --OD (here, D Is an organic group containing a hydrogen atom or a 1,2-quinonediazide group), and R _{1 to} R ₄ are alkyl groups. However, in each combination of X _{1 to} X ₅ and X _{8 to} X ₁₂ , at least one is a group represented by —OD, and at least one of Y ₁ and Y ₂ is —OD.
And at least one of a plurality of D of the groups represented by -OD is an organic group containing a 1,2-quinonediazide group. ] The radiation-sensitive resin composition is characterized by containing a 1,2-quinonediazide compound represented by

The present invention will be specifically described below, but the purpose, constitution and effect of the present invention will be more apparent.

The alkali-soluble resin used in the present invention (hereinafter referred to as "resin (A)") is, for example, novolac resin, polyvinylphenol or its derivative, styrene-maleic anhydride copolymer, polyvinylhydroxybenzoate, carboxyl. Examples thereof include a group-containing methacrylic acid resin.

As the resin (A), the resins represented by the above examples can be used alone or in combination of two or more kinds.

As a preferable resin (A), a novolac resin can be mentioned. Such novolac resin has the following formula (2)

[0013]

[Chemical 3]

It is obtained by polycondensing phenols represented by the formula (2) with n being an integer of 1 to 3 and aldehydes.

Examples of the above-mentioned phenols include o-cresol, m-cresol, p-cresol and 2,3-
Examples thereof include xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol and 3,4,5-trimethylphenol. In particular o-cresol, 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. In this case, m-cresol / 2,3-xylenol / 3,4-xylenol = 20 to 95/5 to 80
/ 0-75 (weight ratio), or m-cresol / 2,3.5
-Trimethylphenol / 2,3-xylenol = 20
A combination of ˜95 / 5 to 80/0 to 75 (weight ratio) is particularly preferable.

Examples of aldehydes to be polycondensed with the above phenols include formaldehyde, trioxane, paraformaldehyde, benzaldehyde, acetaldehyde, propylaldehyde, phenylacetaldehyde, α-phenylpropylaldehyde, β-phenylpropylaldehyde, 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.

As a formaldehyde source,
For example, formalin, trioxane, paraformaldehyde, methyl hemiformal, ethyl hemiformal, propyl hemiformal, butyl hemiformal, phenyl hemiformal, etc. can be mentioned. Of these, formalin and butyl hemiformal can be particularly preferably used.

These aldehydes may be used alone or in combination of two or more. The amount of the aldehyde used is preferably 0.7 to 3 mol, and more preferably 0.8 to 1.5 mol, per 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 and the like. The amount of these acidic catalysts used is usually 1 × 10 ^{−5 to} 5 per mol of phenols.
× 10 ^-1 mol.

In the polycondensation reaction, water is usually used as the reaction medium, but when the phenols used in the polycondensation reaction do not dissolve in the aqueous solution of aldehydes and become a heterogeneous system from the beginning of the reaction, It is also possible to use hydrophilic solvents as reaction medium. As these hydrophilic solvents,
Examples thereof include alcohols such as methanol, ethanol, propanol and butanol; and cyclic ethers such as tetrahydrofuran and dioxane. The amount of these reaction media used is usually 20 per 100 parts by weight of the reaction raw material.
-1,000 parts by weight. The temperature of the polycondensation reaction can be appropriately adjusted depending on the reactivity of the reaction raw materials,
It is usually 10 to 200 ° C. As the polycondensation reaction method, for example, a method in which phenols, aldehydes, acidic catalysts, etc. are collectively charged, and a method in which phenols, aldehydes, etc. are added in the presence of an acidic catalyst as the reaction progresses are adopted. be able to. After completion of the polycondensation reaction, in order to remove unreacted raw materials, acidic catalyst, reaction medium and the like existing in the system, the temperature of the reaction system is generally set to 130 to 230.
The temperature is raised to ℃, the volatile matter is distilled off under reduced pressure, and the novolak resin is recovered.

The polystyrene-equivalent weight average molecular weight (hereinafter referred to as "Mw") of the novolac resin is the workability when the composition of the present invention is applied to a substrate, the developability of the composition,
From the viewpoint of sensitivity and heat resistance, it is preferably 2,000 to 20,000, particularly preferably 3,000 to 15,000.

In order to obtain a novolak resin having a high Mw, the novolak resin obtained by the above method is dissolved in a good solvent such as ethylene glycol monomethyl ether acetate, dioxane, methanol, ethyl acetate and then water. , A poor solvent such as n-hexane or n-heptane may be mixed, and then the high molecular weight novolac resin may be recovered from the separated resin solution layer.

Further, in the present invention, the above resin (A)
A low molecular weight phenolic compound may be added as a dissolution accelerator for the purpose of promoting the alkali solubility of the above.
As the low molecular weight phenol compound, a phenol compound having a benzene ring number of 2 to 6 is suitable, and examples thereof include compounds represented by the following formulas (3-1) to (3-8).

[0024]

[Chemical 4]

[In the above general formula, a, b and c are
Each is a number from 0 to 3 (except when both are 0), x, y, and z are each a number from 0 to 3,
Then, a + x ≦ 5, b + y ≦ 5 (provided that the compound (3-
4) to (3-6), b + y ≦ 4) and c + z ≦
5 is satisfied. ]

The amount of the low molecular weight phenolic compound to be added is usually 50 parts by weight or less per 100 parts by weight of the resin (A).

For the same purpose as described above, a low molecular weight alkali-soluble novolac resin or alkali-soluble resole resin (hereinafter, these are referred to as "resin (B)") that acts as a dissolution accelerator for a part of the resin (A). .) Can be replaced.

The resin (B) is obtained by a polycondensation reaction of phenols and aldehydes. As the phenols, other than the phenols used for the synthesis of the novolak resin, phenol,
1-naphthol, 2-naphthol and the like can be used. 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. Further, in this polycondensation reaction, an alkaline catalyst can be used when producing the resole resin, in addition to the acidic catalyst used for producing the novolak 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),
Phenol / formaldehyde condensed novolak resin, m
-Cresol / formaldebito condensation novolak resin,
p-cresol / formaldehyde condensed novolac resin, o-cresol / formaldehyde condensed novolac resin, m-cresol / p-cresol / formaldehyde condensed novolac resin, phenol / formaldehyde condensed resol resin, m-cresol / formaldehyde condensed resol resin, p-cresol / Formaldehyde condensed resol resin, o-cresol / formaldehyde condensed resol resin, m-cresol / p-cresol / formaldehyde condensed resol resin, and the like. The amount of the resin (B) compounded is generally 50 parts by weight or less based on 100 parts by weight of the resin (A).

The composition of the present invention contains the compound represented by the above formula (1). In the formula (1), X _{1 to} X
₁₂ is the same or different from each other and is a hydrogen atom, an alkyl group, an alkoxy group or a group represented by -OD (wherein D is a hydrogen atom or an organic group containing a 1,2-quinonediazide group). Yes, and X _{1 to} X ₅ and X ₈ to
In each combination of X ₁₂ , at least one O
The group represented by D is included.

Here, the alkyl group has 1 to 4 carbon atoms.
Are preferred, and specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and a t-butyl group. As the alkoxy group, alkoxy 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.

In equation (1), R₁~ R_FourIs an alkyl group
Indicates. As the alkyl group, the above X ₁~ X₁₂Same as
Such things can be illustrated. Among them, the methyl group
preferable.

In the formula (1), Y ₁ and Y ₂ are the same or different from each other and are a hydrogen atom, an alkyl group, an alkoxy group or a group represented by —OD, and Y ₁ and Y ₂
At least one of the groups is a group represented by OD. Here, as the alkyl group and the alkoxy group, the same groups as in the case of the above X _{1 to} X ₁₂ can be exemplified. The group represented by -OD is synonymous with X _{1 to} X ₁₂ .

Examples of the organic group containing a 1,2-quinonediazide group in the above D include, for example, a 1,2-benzoquinonediazide-4-sulfonyl group, a 1,2-naphthoquinonediazide-4-sulfonyl group and a 1,2-naphthogroup. A preferable example is a 1,2-quinonediazidesulfonyl group such as a quinonediazide-5-sulfonyl group and 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.

In the formula (1), the compound corresponding to the case where all D are hydrogen atoms, that is, the compound corresponding to the case where the group represented by -OD is a hydroxyl group is the compound represented by the formula (1) Is a precursor of. (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 (4-10).

[0036]

[Chemical 5]

[0037]

[Chemical 6]

The compounds represented by the above formulas (4-1) to (4-10) can be synthesized, for example, by condensing phenols and isopropenylphenols using an acidic catalyst. For this phenol,
Resorcinol, 2-methylresorcinol, methylhydroquinone, pyrogallol, m-methoxyphenol, o-methoxyphenol, m-cresol, o-cresol and the like are preferable, and isopropenylphenols include p-isopropenylphenol and m-isopropenyl. Phenol and the like can be mentioned as preferable ones.

A compound represented by the formula (1) (hereinafter,
It is called "compound (b)". Specific examples of () are (4-1) to
1,2-benzoquinonediazide-4-sulfonic acid ester of compound represented by (4-10), 1,2-naphthoquinonediazide-4-sulfonic acid ester, 1,2-naphthoquinonediazide-5-sulfonic acid ester, 1 , 2
-Naphthoquinonediazide-6-sulfonic acid ester and the like can be mentioned. Among them, 1,2-naphthoquinonediazide-4-sulfonic acid ester and 1,2-naphthoquinonediazide-5-sulfonic acid ester are particularly preferable.

The compound (b) is, for example, an ester of the compound (a) with 1,2-quinonediazidesulfonyl chloride such as 1,2-naphthoquinonediazide-4-sulfonyl chloride and 1,2-naphthoquinonediazide-5-sulfonyl chloride. It is obtained by a chemical reaction. In the esterification reaction, the reaction ratio between the compound (a) and 1,2-naphthoquinonediazidesulfonyl halide is preferably 1,2-naphthoquinonediazidesulfonyl halide with respect to 1 equivalent of the phenolic hydroxyl group of the compound (a). 2 to 1 equivalent, particularly preferably 0.4 to 1 equivalent,
They are obtained by reacting these in the presence of a basic catalyst such as triethylamine or pyridine in an amount of 0.2 to 1.4 equivalents.

In the composition of the present invention, the compound (b)
Is preferably used in an amount of 5 to 50 parts by weight, particularly 10 to 40 parts by weight, per 100 parts by weight of the resin (A). Further, the compound (b) can be used alone or in combination of two or more kinds.

In the present invention, 1,2-benzoquinonediazide-4-sulfonic acid ester, 1,2-naphthoquinonediazide-4-sulfonic acid ester other than compound (b) is used in combination with compound (b). A 1,2-quinonediazide compound such as 2,2-naphthoquinonediazide-5-sulfonic acid ester can be added. Examples of such 1,2-quinonediazide compounds include, for example, 2,
1,2-Quinonediazidesulfonic acid ester of 3,4-trihydroxybenzophenone, 1,2-quinonediazidesulfonic acid ester of 2,3,4,4'-tetrahydroxybenzophenone, 1,1-bis (4-hydroxyphenyl) -1- [4- {1- (4-hydroxyphenyl)-
Examples include 1,2-quinonediazide sulfonic acid ester of 1-methylethyl}] phenylethane.

In the composition of the present invention, the compounding amount of the 1,2-quinonediazide compound other than the compound (b) 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 sulfonyl residue is adjusted to be 5 to 50% by weight, more preferably 10 to 30% by weight, based on the total solid content in the composition.

Further, various additives such as a sensitizer and a surfactant can be added to the composition of the present invention, 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-oxazin-3 (4H) -ones and 10H-pyrido- [3,
2-b] -1,4-benzothiazines, urazoles,
Hydantoins, parbituric acids, glycine anhydrides, 1-hydroxybenzotriazoles, alloxans, maleimides and the like can be mentioned. The blending amount of these sensitizers is preferably 5 with respect to 100 parts by weight of the resin (A).
It is 0 parts by weight or less.

The surfactant is added to improve the coatability and developability of the composition. Examples of such a surfactant include polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, F-top EF301, EF303, EF35
2 (trade name, manufactured by Mitsubishi Metals), Megafax F17
1, F172, F173 (trade name, manufactured by Dainippon Ink and Chemicals, Inc.), Florard FC430, FC431 (trade name, manufactured by Sumitomo 3M Limited), Asahi Guard AG71
0, Surflon S-382, SC-101, SC-1
02, SC-103, SC-104, SC-105, S
C-106 (trade name, manufactured by Asahi Glass Co., Ltd.), KP341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 75, N
o. 95 (trade name, manufactured by Kyoeisha Oil and Fat Chemical Co., Ltd.) and the like. The content of these surfactants is preferably 2 parts by weight or less per 100 parts by weight of the solid content of the composition.

Further, in the composition of the present invention, a dye or a pigment can be blended in order to visualize the latent image in the radiation-irradiated portion of the resist and reduce the influence of halation at the time of radiation irradiation. In order to improve the above, an adhesion aid can be added. Further, if necessary, a storage stabilizer, a defoaming agent and the like can be added.

In the composition of the present invention, the above-mentioned resin (A) and compound (b) and the above-mentioned various compounding agents, which are optionally used, are mixed in a solvent so that the solid content concentration becomes 20 to 40% by weight. It is prepared as a solution by dissolving and filtering with a filter having a pore size of about 0.2 μm.

Examples of the solvent used in this case 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, toluene, xylene, methyl ethyl ketone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate,
Examples thereof include ethyl acetate and butyl acetate. Furthermore, N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, benzylethylether, dihexylether, acetonylacetone , Isophorone, caproic acid, caprylic acid, 1-octanol,
1-nonanol, benzyl alcohol, benzyl acetate,
A high boiling point solvent such as ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate or phenyl cellosolve 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 solution is
By spin coating, casting coating, roll coating, etc.,
For example, a resist film is formed by applying and pre-baking a silicon wafer or a wafer coated with aluminum or the like, irradiating the resist film with radiation so as to form a desired resist pattern, and developing with a developing solution to form a pattern. The formation takes place.

The radiation used in this case is g-ray,
Ultraviolet rays such as i rays are preferably used, but far ultraviolet rays such as excimer laser, X rays such as synchrotron radiation, and charged rays such as electron beam can also be used.

In addition, the composition of the present invention, after forming a resist film, prebaking and irradiating, 70 to 1
The effect of the present invention can be further improved by performing an operation of heating at 40 ° C. and then performing development.

Examples of the developing solution used for the resist film include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate,
Ammonia water, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1 Alkaline compounds such as, 8-diazabicyclo- (5.4.0) -7-undecene and 1,5-diazabicyclo- (4.3.0) -5-nonene are contained at a concentration of, for example, 1 to 10% by weight. An alkaline aqueous solution dissolved so that is used is used. Further, an appropriate amount of a water-soluble organic solvent, for example, alcohols such as methanol and ethanol and a surfactant can be added to the developer. When a developer containing such an alkaline aqueous solution is used, it is generally washed with water after development.

[0055]

The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. The measurement of Mw and the evaluation of the resist in the examples were carried out by the following methods.

Mw: Tosoh GPC column (G200
0H _XL : 2 pieces, G3000H _XL : 1 piece, G4000
H _XL (1 bottle), the flow rate was 1.0 ml / min, the elution solvent was tetrahydrofuran, and the column temperature was 40 ° C. The analysis conditions were gel permeation chromatography using monodisperse polystyrene as a standard.

Resolution: 0.5 μm line-and-space pattern is resolved by one-to-one by the exposure amount, and the minimum dimension of the line-and-space pattern is separated without reducing the film thickness. It was measured with a microscope.

Focus range (focus tolerance):
Using a scanning electron microscope, in a 0.5 μm line-and-space pattern, when the resolved pattern size is within ± 10% of the mask design size, the focus swing range is taken as the focus range and evaluated. It was used as an index. A large focus range means that it has a good focus tolerance.

Developability: The scum after 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 (0.08 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 novolac resin. This resin is called resin (A1). The Mw of the resin (A1) was 8,600.

Synthesis Example 2 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 in an autoclave By weight 7% of formaldehyde aqueous solution (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 procedure as in Synthesis Example 1 was performed. The resin was synthesized and recovered. This resin is called resin (A2). The Mw of the resin (A2) was 7,800.

<Synthesis of Compound (b)> In the following, the compound represented by the formula (4-1) is referred to as (a-1), and the compound represented by the formula (4-7) is referred to as (a-7). Abbreviated.

Synthetic Example 3 15.1 g (0.04 mol) of compound (a-1) 1,2-naphthoquinonediazide-5-sulfonic acid chloride was placed in a flask equipped with a stirrer, a dropping funnel and a thermometer in the dark. 21.5 g (0.08 mol) of dioxane (148 g) and N, N-dimethylformamide (37 g) 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., 9.7 g (0.096 mol) of triethylamine was slowly added dropwise to this solution using a dropping funnel so that the internal temperature did not exceed 35 ° C. Thereafter, the precipitated triethylamine hydrochloride was removed by filtration, the filtrate was poured into a large amount of dilute hydrochloric acid to cause precipitation, and then the precipitate was collected by filtration and dried overnight in a heating vacuum dryer controlled at 40 ° C. to give the compound (b -1) was obtained.

Synthesis Example 4 Compound (a-7) 11.8 g (0.03 mol) 1,2-naphthoquinonediazide-5-sulfonic acid chloride 24.2 g (0.09 mol) triethylamine 10.1 g (0.1) Mol) and dioxane 184 g were used in the same manner as in Synthesis Example 3 except for using compound (b-2).
Got

Synthesis Example 5 15.1 g (0.04 mol) of compound (a-1) 1,2-naphthoquinonediazide-5-sulfonic acid chloride 16.1 g (0.06 mol) triethylamine 7.3 g (0.07) Mol) dioxane 123 g and N, N-dimethylformamide 31 g were used in the same manner as in Synthesis Example 3 except that Compound (b-3) was used.
Got

<Synthesis of 1,2-quinonediazide compound other than compound (b)> Synthesis example 6 2,3,4,4'-tetrahydroxybenzophenone 24.6 g (0.10 mol) 1,2-naphthoquinonediazide- A quinonediazide compound (a) was obtained in the same manner as in Synthesis Example 3 except that 80.6 g (0.30 mol) of 5-sulfonic acid chloride and 33.3 g (0.33 mol) of triethylamine were used.

Synthesis Example 7 1,1-bis (4-hydroxyphenyl) -1- [4- {1- (4-hydroxyphenyl) -1-methylethyl}] phenylethane 42.4 g (0.1 mol) A quinonediazide compound (b) was prepared in the same manner as in Synthesis Example 3 except that 67.2 g (0.25 mol) of 1,2-naphthoquinonediazide-5-sulfonic acid chloride and 25.3 g (0.28 mol) of triethylamine were used. Obtained.

Synthesis Example 8 Bisphenol-M (commercially available product, manufactured by Mitsui Petrochemical Co., Ltd.) 17.3 g (0.05 mol) 1,2-naphthoquinonediazide-5-sulfonic acid chloride 26.8 g (0.1 mol) A quinonediazide compound (c) was obtained in the same manner as in Synthesis Example 3 except that 11.1 g (0.11 mol) of triethylamine and 220 g of dioxane were used.

Examples 1 to 6 and Comparative Examples 1 to 4 At the composition ratios shown in Table 1 (however, parts are parts by weight), the resin (A), the dissolution accelerator, the quinonediazide compound and the solvent are mixed. After preparing a uniform solution, it was filtered with a membrane filter having a pore size of 0.2 μm to prepare a solution of the composition. The obtained solution was applied onto a silicon wafer having a silicon oxide film using a spinner, and then prebaked at 90 ° C. for 2 minutes on a hot plate to a thickness of 1.1.
A resist film of μm is formed, exposed through a reticle using a wavelength of 365 nm (i-line) as described above, and developed.
After rinsing and drying, the performance of the composition was investigated. The results are shown in Table 2.

[0070]

[Table 1]

In Table 1, the types of dissolution accelerator and solvent 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; 3- Ethyl ethoxypropionate

[0072]

[Table 2]

[0073]

The radiation-sensitive resin composition of the present invention is excellent in developability, has high resolution, and remarkably improves focus tolerance. Therefore, the radiation-sensitive resin composition of the present invention can be suitably used as a positive resist for producing a highly integrated integrated circuit.

[Procedure amendment]

[Submission date] October 29, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0004

[Correction method] Change

[Correction content]

Therefore, it is conceivable to increase the amount of the quinonediazide compound added in order to improve the focus tolerance. However, generally, when the addition amount of the quinonediazide compound is increased, the developability is deteriorated, and when the performance of one is improved, the performance of the other is decreased , and both are satisfied.
No resist has been obtained so far. Therefore , there is a demand for a positive resist having a high level of high resolution, good focus tolerance, and good developability for fine patterns.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0033

[Correction method] Change

[Correction content]

In the formula (1), Y ₁ and Y ₂ are the same or different from each other and are a hydrogen atom, an alkyl group, an alkoxy group or a group represented by —OD, and Y ₁ and Y ₂
At least one of, - a group represented by OD. Here, as the alkyl group and the alkoxy group, the same groups as in the case of the above X _{1 to} X ₁₂ can be exemplified. The group represented by -OD is the same as in the case of X ₁ to X _12.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0040

[Correction method] Change

[Correction content]

The compound (b) includes, for example, the compound (a) and 1,2-quinonediazidesulfonyl halide such as 1,2-naphthoquinonediazide-4-sulfonyl chloride and 1,2-naphthoquinonediazide-5-sulfonylchloride. It is obtained by the esterification reaction with>. In the esterification reaction, the reaction ratio of the compound (a) and the 1,2-naphthoquinonediazidesulfonyl halide is preferably 1,2-naphthoquinonediazidesulfonyl halide with respect to 1 equivalent of the phenolic hydroxyl group of the compound (a). 2 to 1 equivalent, particularly preferably 0.4 to 1 equivalent,
They are obtained by reacting these in the presence of a basic catalyst such as triethylamine or pyridine in an amount of 0.2 to 1.4 equivalents.

 ─────────────────────────────────────────────────── ─── 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 ₁₂ , Y ₁ and Y ₂ are the same or different from each other and are a hydrogen atom, an alkyl group, an alkoxy group or a group represented by —OD (wherein D is a hydrogen atom). Or a 1,2-quinonediazide group-containing organic group), and R _{1 to} R ₄ are alkyl groups. However,
In each combination of X _{1 to} X ₅ and X _{8 to} X ₁₂ , at least one is a group represented by —OD, and Y ₁
And at least one of Y ₂ is a group represented by —OD, and at least one of a plurality of D of the groups 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 these.