JPH0756331A - Radiation sensitive resin composition - Google Patents

Abstract

PURPOSE:To obtain a radiation sensitive resin compsn. excellent in developability and pattern shape and having high sensitivity, especially improved dimensional faithfulness and focus latitude of a resist pattern by incorporating an alkali-soluble resin and a specified quinonediazido compd. CONSTITUTION:This radiation sensitive resin compsn. contains an alkali-soluble resin and a 1,2-quinonediazido compd. represented by the general formula, wherein each of X1-X14 is H, alkyl, alkoxy or a group represented by -OD, each of R1-R4 is H, alkyl or aryl, at least one of X1-X9 and at, least one of X10-X14 are groups represented by -OD and at least one of 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]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a radiation sensitive resin composition which is useful as a positive resist for producing highly integrated circuits. More specifically, ultraviolet rays such as g rays and i rays,
The present invention relates to a radiation-sensitive resin composition suitable as a resist for producing a highly integrated circuit, which is sensitive to radiation such as far ultraviolet rays such as excimer laser, X-rays such as synchrotron radiation, and charged particle beams such as electron beams.

[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. That is, when a fine resist pattern is formed with a positive resist, when the latent image formed by irradiation with radiation is developed with a developer composed of an alkaline aqueous solution, the portion where the radiation irradiation portion is in contact with the wafer (pattern It is necessary to develop quickly to the hem.

However, in the case of the conventional positive type resist, when the distance between the resist patterns to be formed is 0.8 μm or less, the developability and the pattern shape of a fine pattern are insufficient.

Further, in order to manufacture an integrated circuit having a high degree of integration, the difference between the design size of the mask and the size of the actual resist pattern is small, and the resist that faithfully reproduces the design size of the mask, that is, the size fidelity A resist of high degree is required, but generally, the narrower the line width of the pattern, the larger the difference between the design size of the mask and the size of the actual resist pattern tends to be.
It was not always possible to achieve satisfactory dimensional fidelity. Moreover, in the case of the conventional positive resist, when the focus shifts during the exposure by the stepper, the pattern shape is deformed, the developability is deteriorated, the difference between the obtained resist pattern and the design dimension becomes remarkable, and the focus tolerance is also increased. It wasn't enough.

[0005]

Therefore, an object of the present invention is to provide a novel radiation-sensitive resin composition, and more specifically, it is excellent in developability and pattern shape, highly sensitive, and particularly resist. It is an object of the present invention to provide a radiation-sensitive resin composition useful as a positive resist, which is excellent in pattern dimensional fidelity and focus tolerance.

[0006]

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

[0007]

[Chemical 2]

[In the general formula (1), X _{1 to} X ₁₄ are
The same or different, a hydrogen atom, an alkyl group, an alkoxy group or a group represented by -OD (provided that D is a hydrogen atom or an organic group containing a 1,2-quinonediazide group), and R _{1 to} R ₄ are the same or different and each is a hydrogen atom, an alkyl group or an aryl group, provided that in each combination of X _{1 to} X ₉ and X _{10 to} X ₁₄ , at least one is a group represented by -OD. And
At least one of a plurality of D of the groups represented by these -OD
One 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 described in detail below, but the purpose, constitution and effect of the present invention will become clearer.

Examples of the alkali-soluble resin (hereinafter referred to as "resin (A)") used in the present invention include novolac resin, polyvinyl phenol or its derivatives, styrene-maleic anhydride copolymer, polyvinyl hydroxybenzoate, Examples thereof include carboxyl group-containing methacrylic acid resin.

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

The preferred resin (A) is a novolac resin. Particularly preferred novolac resin is represented by the following general formula (2)

[0013]

[Chemical 3]

It is obtained by polycondensing phenols and aldehydes represented by (where n is an integer of 1 to 3).

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 m-cresol, p-cresol, 2,3-xylenol, 2,5-xylenol, 3,
4-xylenol, 3,5-xylenol and 2,3,
5-trimethylphenol is preferred. These phenols may be used alone or in combination of two or more, and for example, m-cresol / 2,3-xylenol / 3,
4-xylenol = 20-95 / 5-80 / 0-75
(Weight ratio), and m-cresol / 2,3,5-trimethylphenol / p-cresol = 30 to 95/5 to 7
A combination of 0/0 to 65 (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 1 mol of phenols.
It is 5 × 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. Examples of these hydrophilic solvents include alcohols such as methanol, ethanol, propanol and butanol, and cyclic ethers such as tetrahydrofuran and dioxane. The amount of these reaction media used is usually 20 to 1,000 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 reaction raw materials, but is usually 10 to 200 ° C. As the method of polycondensation reaction, adopt the method of charging phenols, aldehydes, acidic catalyst, etc. all at once, and the method of adding phenols, aldehydes, etc. in the presence of acidic catalyst as the reaction progresses. You can After completion of the polycondensation reaction, in order to remove unreacted raw materials, acidic catalyst, reaction medium and the like existing in the system, generally, the temperature of the reaction system is raised to 130 to 230 ° C. and volatilized under reduced pressure. The fraction is distilled off and the novolak resin is recovered.

The novolak resin used in the present invention has a polystyrene-reduced weight average molecular weight (hereinafter referred to as "Mw").
Called. ), From the viewpoint of workability when applying the composition of the present invention to a substrate, developability of the composition, sensitivity and heat resistance,
It is preferably 2,000 to 20,000 and preferably 3.0
It is particularly preferably from 0 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 ethyl cellosolve acetate, dioxane, methanol and ethyl acetate, and then water and n are added.
-A poor solvent such as hexane or n-heptane may be mixed, and then the resin solution layer that precipitates may be separated to recover the high molecular weight novolak resin.

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 a number of 0 to 3 (excluding the case where each is 0), x, y and z are each a number of 0 to 3, and a + x ≦ 5, b + y ≦ 5, c + z ≦ 5 (however, , Compounds (3-4) to (3-6) satisfy b + y ≦ 4). ]

The amount of the low molecular weight phenol compound to be blended is usually 50 parts by weight or less based on 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, referred to as "resin (B)") which 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, phenols other than those exemplified as the phenols used in the synthesis of the novolak resin can be used.
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 in addition to the acidic catalyst used for producing the novolac resin.

The Mw of the resin (B) is 200 to 2,000.
Is preferable, and 300 to 1,000 is particularly preferable. Examples of such a resin (B) include phenol / formaldehyde condensed novolak resin, m-cresol / formaldebito condensed novolac resin, p-
Cresol / formaldehyde condensed novolak resin, o
-Cresol / formaldehyde condensed novolak resin,
Examples include m-cresol / p-cresol / formaldehyde condensed novolac resin. 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 a compound represented by the above formula (1).

In equation (1), X₁~ X₁₄Is the hydrogen source
Child, alkyl group, alkoxy group and -OD
Group (however, D is a hydrogen atom or 1,2-quinonediazide
It is an organic group containing a group. In the group selected from
Yes, and X₁~ X₉And X _Ten~ X₁₄Each set of
In the combination, at least one group represented by OD (hereinafter
Below, it is called "OD group". ) Must be included
Yes, especially X₁~ X_Four, X_Five~ X₉And X_Ten~ X₁₄Noso
Contain at least one OD group in each combination
Preferably.

Here, the alkyl group has 1 to 1 carbon atoms.
The alkyl group of 4 is preferable, 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. The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, and specific examples thereof include a methoxy group, an ethoxy group, a propoxy group and a butoxy group.

In the formula (1), R _{1 to} R ₄ represent a hydrogen atom, an alkyl group or an aryl group. Here, as the alkyl group, the same groups as in the case of X _{1 to} X ₁₄ can be exemplified. Specific examples of the aryl group include a phenyl group, a toluyl group and a naphthyl group.

Examples of the organic group containing a quinonediazide group in the above D include, for example, 1,2-benzoquinonediazide-4-sulfonyl group, 1,2-naphthoquinonediazide-5-sulfonyl group and 1,2-naphthoquinonediazide-group.
6-sulfonyl group, 1,2-naphthoquinonediazide-4
A 1,2-quinonediazidesulfonyl group such as a -sulfonyl group may be mentioned as a preferable example. Among them, the 1,2-naphthoquinonediazide-4-sulfonyl group and the 1,2-naphthoquinonediazide-5-sulfonyl group are particularly preferable.

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 -OD group is a hydroxyl group is a precursor of the compound represented by the formula (1). (Hereinafter, this precursor is referred to as "compound (a)"). Specific examples of the compound (a) include:
Examples thereof include compounds represented by the following formulas (4-1) to (4-19).

[0036]

[Chemical 5]

[0037]

[Chemical 6]

[0038]

[Chemical 7]

[0039]

[Chemical 8]

[0040]

[Chemical 9]

The compounds represented by the above formulas (4-1) to (4-19) can be synthesized, for example, by condensing phenols and hydroxybenzalacetones using an acidic catalyst. For this phenol,
Resorcinol, hydroquinone, 2-methylresorcinol, methylhydroquinone, phloroglucinol,
Pyrogallol, hydroxyhydroquinone, etc. are preferable, and as hydroxybenzalacetones, p-hydroxybenzalacetone, m-hydroxybenzalacetone, o-hydroxybenzalacetone, 3-methoxy-4-hydroxybenzalacetone, 2, 4-dihydroxybenzalacetone etc. can be mentioned as a preferable thing.

A compound represented by the formula (1) (hereinafter,
It is referred to as "compound (b)". ) Is (4-1).
1,2-naphthoquinonediazide-4-sulfonic acid ester of a compound represented by (4-19) -1,2-naphthoquinonediazide-5-sulfonic acid ester, 1,2-
Benzoquinonediazide-4-sulfonic acid ester, 1,
2-naphthoquinone diazide-6-sulfonic acid ester etc. can be mentioned. Among them, the preferred one is
2-naphthoquinonediazide-4-sulfonic acid ester,
1,2-naphthoquinonediazide-5-sulfonic acid ester and the like.

The compound (b) is, for example, an ester of the compound (a) with 1,2-quinonediazidesulfonyl halide such as 1,2-naphthoquinonediazide-4-sulfonyl chloride and 1,2-naphthoquinonediazide-5-sulfonyl chloride. It can be obtained by a chemical reaction. In the esterification reaction, the reaction ratio of the compound (a) and 1,2-quinonediazidesulfonyl halide is such that 1,2-quinonediazidesulfonylhalide is preferably 0.2 to 1 mol per 1 mol equivalent of the phenolic hydroxyl group. Yes,
It is particularly preferably 0.4 to 1.0 mol, and can be obtained by reacting these in the presence of a basic catalyst.

In the present invention, the compound represented by the above formula (1) is added in an amount of 5 to 5 per 100 parts by weight of the resin (A).
It is preferable to use 0 parts by weight, particularly 10 to 40 parts by weight. Further, the compound represented by the formula (1) 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 a 2,2-naphthoquinonediazide-5-sulfonic acid ester can be added. Examples of such 1,2-quinonediazide compounds include, for example, 2,
1,2-Quinonediazide compound of 3,4-trihydroxybenzophenone, 1,2-quinonediazide compound of 2,3,4,4'-tetrahydroxybenzophenone, 1,1,1
-Tris (4-hydroxyphenyl) methane 1,2-
A quinonediazide compound etc. can be mentioned.

In the composition of the present invention, the content of the 1,2-quinonediazide compound other than the compound (b) is preferably 100 parts by weight or less based on 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, the composition of the present invention may contain 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-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 50 parts by weight or less with respect to 100 parts by weight of the resin (A).

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 Shin-Akita Kasei Co., Ltd.), Megafac 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 and reduce the influence of halation during radiation irradiation, and improve the adhesiveness. In order to do so, an adhesion aid can be added. Further, if necessary, a storage stabilizer, a defoaming agent and the like can be added.

The composition of the present invention contains the above-mentioned resin (A) and compound (b) and, if necessary, the above-mentioned various compounding agents, for example, a solid content concentration of 20 to 40% by weight.
It is prepared by dissolving it in a solvent so that it becomes 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, methyl cellosolve acetate, ethyl cellosolve 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, 2
-Ethyl hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, acetic acid Examples thereof include ethyl 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, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, etc. A high boiling point solvent can also be added. These solvents may be 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 at this time is g-ray,
Ultraviolet rays such as i rays are preferably used, but far ultraviolet rays such as excimer laser and X rays such as synchrotron radiation.
It is also possible to use each radiation such as a charged particle beam such as a beam or an electron beam.

In addition, the composition of the present invention forms a resist film, prebakes and irradiates it, and then 70-
The effect of the present invention can be further improved by performing an operation of heating at 140 ° C. and then performing development.

The developer used for the resist film is, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate,
Ammonia water, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, diethylmethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, Alkaline compounds such as 1,8-diazabicyclo- [5.4.0] -7-undecene and 1,5-diazabicyclo- [4.3.0] -5-nonene at a concentration of, for example, 1 to 10% by weight. An alkaline aqueous solution dissolved so that 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.

[0058]

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

Mw: Tosoh GPC column (G200
0H _6: 2 This, G3000H _6: 1 this, G4000H _6:
1 column), a flow rate of 1.5 ml / min, an elution solvent of tetrahydrofuran, and a column temperature of 40 ° C. were used for analysis by gel permeation chromatography using monodisperse polystyrene as a standard.

Sensitivity: A resist film of the composition was formed on a silicon wafer having a silicon oxide film, and a NSR-1755i7A reduction projection exposure machine (lens numerical aperture: 0.50) manufactured by Nikon Corporation was used. The i-line having a wavelength of 365 nm is exposed by changing the exposure time, and then a 2.4 wt% tetramethylammonium hydroxide aqueous solution is used to
After developing at 5 ° C. for 60 seconds, it was washed with water and dried to form a resist pattern. At that time, the exposure time for forming a 0.5 μm line-and-space pattern in a width of 1: 1 was determined.

Focus range (focus tolerance):
Using a scanning electron microscope, in a 0.45 μm line-and-space pattern, when the resolved pattern size is within ± 10% of the mask design size, the focus fluctuation 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: forming a resist film of the composition,
The scum after pattern formation and the degree 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 keep the internal temperature at
Polycondensation was carried out for 8 hours while maintaining the temperature at 0 ° C. with stirring. After the reaction, the temperature 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). Mw of resin A1
Was 8,000.

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 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 autoclave was immersed in an oil bath. Temperature 130
Polycondensation was carried out for 8 hours while maintaining the temperature at 0 ° C. with stirring. After the reaction, the temperature 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 (A2). Mw of resin A2
Was 7,800.

<Synthesis of Compound (b)> In the following, the compound represented by the formula (4-2) is referred to as (a-2) and the compound represented by the formula (4-6) is referred to as (a-6). Abbreviated.

Synthesis Example 3 36.4 g (0.1 mol) of compound (a-2) 1,2-naphthoquinonediazide-5-sulfonic acid chloride was placed in a flask equipped with a stirrer, a dropping funnel, and a thermometer under light shielding. 80.6 g (0.3 mol) and dioxane 450 g were charged and dissolved while stirring. Then, the flask was immersed in a water bath at 30 ° C, and when the internal temperature reached 30 ° C, 33.3 g (0.33 mol) of triethylamine was added dropwise to this solution so that the internal temperature did not exceed 35 ° C. Was slowly added dropwise. 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 at 40 ° C. to give compound (b-2). Got

Synthesis Example 4 Compound (a-6) 36.4 g (0.1 mol) 1,2-naphthoquinonediazide-5-sulfonic acid chloride 80.6 g (0.3 mol) triethylamine 33.3 g (0.33) Mol) and dioxane (450 g) were used and in the same manner as in Synthesis example 3, a compound (b-6) was obtained.

<Synthesis of 1,2-quinonediazide compound other than compound (b)> Synthesis example 5 2,3,4,4'-tetrahydroxybenzophenone 24.6 g (0.10 mol) 1,2-naphthoquinonediazide- 5-Sulfonic acid chloride 107.5 g (0.40 mol) Triethylamine 44.5 g (0.44 mol) and dioxane 450 g were used in the same manner as in Synthesis Example 3 to obtain a quinonediazide compound (a).

Synthesis Example 6 1,1,1-Tris (4-hydroxyphenyl) methane 29.2 g (0.1 mol) 1,2-naphthoquinonediazide-5-sulfonic acid chloride 67.2 g (0.25 mol) Using 25.3 g (0.28 mol) of triethylamine and 450 g of dioxane, a quinonediazide compound (ii) was obtained in the same manner as in Synthesis Example 3.

Examples 1 to 3 and Comparative Examples 1 to 3 In 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 were mixed. , After making a uniform solution, the pore size is 0.2μm
The solution of the composition was prepared by filtering with a membrane filter of. 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 have a thickness of 1.
After forming a 2 μm resist film, exposing it through a reticle using a wavelength of 365 nm (i-line) as described above, developing, rinsing and drying, the performance of the composition was examined. The results are shown in Table 2.

[0071]

[Table 1]

In Table 1, the types of dissolution promoter 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- Methyl methoxypropionate

[0073]

[Table 2]

[0074]

The radiation-sensitive resin composition of the present invention has excellent developability and pattern shape and high sensitivity, and in particular, the dimensional fidelity of resist patterns and focus tolerance are remarkably improved. 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.

Front page continuation (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 general formula (1): [In the general formula (1), X _{1 to} X ₁₄ are the same or different and each is a hydrogen atom, an alkyl group, an alkoxy group or -O.
A group represented by D (provided that D is a hydrogen atom or an organic group containing a 1,2-quinonediazide group).
And R _{1 to} R ₄ are the same or different and are a hydrogen atom, an alkyl group or an aryl group, provided that X ₁ to
In each combination of X ₉ and X _{10 to} X ₁₄ ,
At least one is a group represented by -OD, and these-
At least one of a plurality of D of the groups represented by OD is 1,
It is an organic group containing a 2-quinonediazide group. ] The radiation sensitive resin composition containing the 1,2-quinonediazide compound represented by these.