JP3367087B2 - Radiation-sensitive resin composition - Google Patents

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, it relates to a radiation-sensitive resin composition suitable as a resist for producing highly integrated circuits, which is sensitive to radiation such as ultraviolet rays, far ultraviolet rays, X-rays, charged particle beams and the like.

[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 irradiation portion is in contact with the wafer (the bottom of the pattern) It is necessary that the image is rapidly developed. Further, in order to realize high resolution, it is necessary to drastically change the solubility of the resist in the developing solution at a certain radiation dose. That is, it is necessary that it is not dissolved in a developing solution below a certain radiation irradiation amount, and that it is rapidly dissolved in the developing solution above the radiation irradiation amount (having a solubility contrast).

[0003]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a novel radiation sensitive resin composition. Another object of the present invention is excellent in developability and high resolution,
It is an object of the present invention to provide a radiation-sensitive resin composition suitable as a positive resist having a particularly good solubility contrast (hereinafter referred to as γ value).

[0004]

According to the present invention, the above objects and advantages are an alkali-soluble resin and a dissolution accelerator.
Low molecular weight phenol compound and the following formula (1)

[0005]

[Chemical 2]

[In the formula (1), X _{1 to} X ₁₀ are the same or different and each is 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). Is an organic group containing.)
And R _{1 to} R ₃ are the same or different and are alkyl groups. However, the combination of each of X ₁ to X ₅ and X ₆ to X _10, at least one is a group represented by -OD, a plurality of D groups represented by these -OD
Is at least one organic group containing a 1,2-quinonediazide group. Contain represented by 1,2-quinonediazide compound, said alkali-soluble resin is Porisuchi
Ren equivalent weight average molecular weight of 7,800 to 20,000
It is achieved by the radiation-sensitive resin composition, wherein the novolak resin der Rukoto.

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

Alkali-Soluble Resin The alkali-soluble resin used in the present invention (hereinafter,
It is referred to as "resin (A)". ) Is, novolac tree Aburadea
It

[0009] The resin (A), also in alone can be used in combination of two or more.

[0010] Japanese Preferred novolak resins, the following formula (2)

[0011]

[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. Especially, m-cresol / 2,3-xylenol / 3,4-xylenol = 20 to 95/5
80 / 0-75 (weight ratio) and m-cresol / 2,
3,5-Trimethylphenol / 2,3-xylenol =
A combination of 20 to 95/5 to 80/0 to 75 (weight ratio) is particularly preferable.

Examples of the 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 as preferable ones. Of these, formaldehyde can be used particularly preferably.

Examples of the formaldehyde generating source include formalin, trioxane, paraformaldehyde, methyl hemiformal, ethyl hemiformal, propyl hemiformal, butyl hemiformal,
Examples thereof include phenyl hemiformal. 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 between 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 a heterogeneous system is formed 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; 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, a method in which phenols, aldehydes, acidic catalysts and the like are charged all at once and phenols in the presence of an acidic catalyst,
A method of adding aldehydes and the like as the reaction proceeds can be adopted. 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,
Ru 7,800 20,000 der. 7,800 ～15,00
It is particularly preferably 0.

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, ethyl acetate, and then water, n −
It is advisable to mix a poor solvent such as hexane or n-heptane, and then separate the resin solution layer that precipitates to recover the high molecular weight novolak resin.

[0021] In the dissolution promoter present invention, for the purpose of promoting the alkali solubility of the resin (A), the you added phenol compound having a low molecular weight as a dissolution accelerator. 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). Among them, the compound represented by the formula (3-8) is preferable, and particularly 1,1,
1-Tris (4-hydroxyphenyl) ethane and 1,1-bis (4-hydroxyphenyl) -1-phenylethane are preferred.

[0022]

[Chemical 4]

[In formulas (3-1) to (3-8),
a, b and c are each a number from 0 to 3 (provided that
(Except for 0), x, y, and z are numbers 0 to 3, and a + x ≦ 5, b + y ≦ 5, and c + z ≦
5 (however, b + y in the case of formulas (3-4) to (3-6))
≦ 4) is satisfied. ]

The amount of the low molecular weight phenolic compound to be added 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.

Here, the resin (B) is obtained by polycondensation of phenols and aldehydes. As the phenols, phenol, 1-, other than those exemplified as the phenols used in the synthesis of the novolak resin can be used. 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 or more and 2,000
It is preferably less than 0, particularly preferably 300 to 1,000. Examples of such resin (B) include phenol / formaldehyde condensed novolac resin, m-cresol / formaldebito condensed novolac resin, p-cresol / formaldehyde condensed novolac resin, o-cresol / formaldehyde condensed novolac resin, m-cresol / p. -Cresol / formaldehyde condensed novolac resin and the like can be mentioned. The amount of the resin (B) compounded is generally the resin (A).
It is 50 parts by weight or less in 100 parts by weight.

1,2-quinonediazide compound The composition of the present invention contains a 1,2-quinonediazide compound represented by the above formula (1) as a 1,2-quinonediazide compound.

In equation (1), X₁~ X_TenIs 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~ X_FiveAnd X ₆~ X_TenEach set of
In the combination, at least one group represented by OD (hereinafter
Below, it is called "OD group". ).

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. 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 the formula (1), R _{1 to} R ₃ are the same or different and each represents an alkyl group. Here, as the alkyl group, the same groups as in the case of X _{1 to} X ₁₀ can be exemplified. A methyl group is particularly preferable.

Examples of the organic group containing a 1,2-quinonediazide group in D of the formula (1) include 1,2-benzoquinonediazide-4-sulfonyl group, 1,2-naphthoquinonediazide-4-sulfonyl group, 1 A 1,2-quinonediazidesulfonyl group such as a 2,2-naphthoquinonediazide-5-sulfonyl group and a 1,2-naphthoquinonediazide-6-sulfonyl group can be mentioned as a preferable example. Among them, 1,2-naphthoquinonediazide-4-
Sulfonyl group and 1,2-naphthoquinonediazide-5
The -sulfonyl group is 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 -OD group is a hydroxyl group is a 1,2-quinonediazide compound represented by the formula (1). (Hereinafter, this precursor is referred to as “compound (a)”). Specific examples of the compound (a) include the following formulas (4-1) to (4-1).
The compound represented by 7) can be mentioned.

[0034]

[Chemical 5]

[0035]

[Chemical 6]

[0036]

[Chemical 7]

[0037]

[Chemical 8]

The compounds represented by the above formulas (4-1) to (4-17) can be synthesized, for example, by condensing phenols and isopropenylcyclohexenes using an acidic catalyst. The phenols include phenol, o-cresol, p-cresol and o.
-Methoxyphenol, 2,4-xylenol, 2,5-
Preferred examples include xylenol, 2,6-xylenol, 3,4-xylenol, resorcinol, 2-methylresorcinol, catechol, homocatechol, hydroquinone, methylhydroquinone, pyrogallol, phloroglucinol, and hydroxyhydroquinone. As the isopropenyl cyclohexenes, dipentene, limonene and the like can be mentioned as preferable ones.

Specific examples of the 1,2-quinonediazide compound represented by the formula (1) include (4-1) to (4)
-17) 1,2-benzoquinonediazide-4-sulfonic acid ester, 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, preferred is 1,2-naphthoquinonediazide-4-sulfonic acid ester, 1,2-
Naphthoquinone diazide-5-sulfonic acid ester and the like.

The 1,2-quinonediazide compound represented by the formula (1) includes, for example, the compound (a) and 1,2-naphthoquinonediazide-4-sulfonyl chloride, 1,2-naphthoquinonediazide-5-sulfonyl chloride and the like. , 2
-Can be obtained by an esterification reaction with a quinonediazide sulfonyl halide. In the esterification reaction,
The reaction ratio between the compound (a) and 1,2-quinonediazidesulfonyl halide is such that 1,2-quinonediazidesulfonyl halide is preferably 0.2 to 1 mol with respect to 1 mol equivalent of the phenolic hydroxyl group of the compound (a). And particularly preferably 0.4 to 1.0 mol, and can be obtained by reacting these in the presence of a basic catalyst such as triethylamine or pyridine.

In the present invention, the 1,2-quinonediazide compound represented by the above formula (1) is added to the resin (A) 1
It is preferable to use 5 to 50 parts by weight, particularly 10 to 40 parts by weight, per 00 parts by weight. The 1,2-quinonediazide compound represented by the formula (1) can be used alone or in combination of two or more kinds.

In the present invention, the 1,2-quinonediazide compound represented by the formula (1) is used in combination with another 1,2-quinonediazide compound.
Benzoquinonediazide-4-sulfonic acid ester, 1,
2-naphthoquinonediazide-4-sulfonic acid ester,
A 1,2-quinonediazide compound such as 1,2-naphthoquinonediazide-5-sulfonic acid ester can be blended. As such a 1,2-quinonediazide compound, for example, a 1,2-quinonediazide compound of 2,3,4-trihydroxybenzophenone, a 1,2-quinonediazide compound of 2,3,4,4'-tetrahydroxybenzophenone, 1,1,1-tris (4-hydroxyphenyl)
Examples thereof include 1,2-quinonediazide compounds of ethane.

In the composition of the present invention, the content of the other 1,2-quinonediazide compound is preferably 100 parts by weight or less based on 100 parts by weight of the resin (A).

In the composition of the present invention, 1,2-
The total amount of quinonediazidesulfonyl residues 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.

Various Additives 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 50 parts by weight or less with respect to 100 parts by weight of the resin (A).

The surfactant is added to improve the coating property and developability of the composition. Examples of such a surfactant include polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, Ftop EF301, EF303,
EF352 (trade name, manufactured by Shin-Akita Kasei Co., Ltd.), Megafac F171, F172, F173 (trade name, manufactured by Dainippon Ink and Chemicals Co., Ltd.), Florard FC430, FC431
(Product name, Sumitomo 3M), Asahi Guard AG
710, Surflon S-382, SC-101, SC
-102, SC-103, SC-104, SC-10
5, SC-106 (trade name, manufactured by Asahi Glass Co., Ltd.), KP341
(Trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 7
5, No. 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 effect 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 compositions of the solvent present invention, the above-mentioned resin (A), 1,2-quinonediazide compound represented by the dissolution accelerator Contact <br/> and formula (1), and that used as needed each For example, the seed additive is dissolved in a solvent so that the solid content concentration becomes 20 to 40% by weight, and then filtered with a filter having a pore size of about 0.2 μm.

Examples of the solvent used at this time 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, 3 -Methyl ethoxypropionate, ethyl acetate, butyl acetate 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, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate. It is also possible to add a high-boiling solvent such as γ-butyrolactone, ethylene carbonate, propylene carbonate or phenyl cellosolve acetate. These solvents may be used alone or in combination of two or more.

Method of Use as Resist The composition of the present invention prepared as a solution is applied by spin coating, cast coating, roll coating or the like to a silicon wafer or a wafer coated with aluminum or the like and prebaked. Thus, a resist film is formed, the resist film is irradiated with radiation so as to form a desired resist pattern, and the resist film is developed with a developing solution to form the pattern.

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 particle rays such as electron beam can also be used.

Further, the composition of the present invention, after forming a resist film, prebaking and irradiating,
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.

[0055]

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) and a flow rate of 1.0 ml / min, an elution solvent of tetrahydrofuran, and a column temperature of 40 ° C. were analyzed by gel permeation chromatography using monodisperse polystyrene as a standard.

Sensitivity and resolution: Nikon NSR-15
05i7A reduction projection exposure machine (lens numerical aperture: 0.50)
Exposure is performed using i-line with wavelength of 365nm, and 0.4μ
The exposure time when the line-and-space pattern of m was resolved one-to-one was used as the sensitivity, and the exposure time was measured. At that time, a line that separates without reducing the film
The smallest dimension of the and space pattern was taken as the resolution and measured with a scanning electron microscope.

Developability: A resist film was formed, and scum after pattern formation by development and the extent of residual development were examined using a scanning electron microscope.

Γ value: The normalized film thickness (= remaining film thickness / initial film thickness) was plotted with respect to the logarithm of the exposure amount, and the slope was taken as the γ value. The larger this value, the higher the solubility contrast during development.

<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
The polycondensation reaction was carried out for 8 hours while maintaining the temperature at 0 ° C. with stirring.
After the reaction was completed, it was cooled to room temperature and the contents were taken out into 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). Resin A1
Had a Mw of 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 77.1 g of a weight% 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 autoclave was immersed in an oil bath. Temperature 130
The polycondensation reaction was carried out for 8 hours while maintaining the temperature at 0 ° C. with stirring.
After the reaction was completed, it was cooled to room temperature and the contents were taken out into 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). Resin A2
Had a Mw of 7,800.

Synthesis Example 3 67.6 g of m-cresol was placed in a flask equipped with a stirrer, a condenser and a thermometer.
(0.63 mol) 2,3,5-trimethylphenol 10.0 g
(0.073 mol) p-cresol 31.8 g
(0.29 mol) 37% by weight aqueous formaldehyde solution 107.1 g (formaldehyde: 1.32 mol) and oxalic acid dihydrate 1.33 g (1.06 × 10 ^-2)
Mol) was added, the flask was immersed in an oil bath, the internal temperature was kept at 100 ° C., and the polycondensation reaction was carried out for 30 minutes while stirring. After the reaction was completed, the oil bath temperature was raised to 180 ° C., the pressure inside the flask was simultaneously reduced to 30 to 50 mmHg, water, oxalic acid, unreacted raw materials, etc. were removed, and the molten resin was returned to room temperature and recovered. . This resin is referred to as (A3). Resin (A
The Mw of 3) was 7,200. <Synthesis of 1,2-quinonediazide compound represented by the formula (1)> In the following, the compound represented by the formula (4-1) is represented by (a-
1), the compound represented by the formula (4-2) is (a-
2) is abbreviated.

Synthesis Example 4 36.4 g (0.1 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 under light shielding. 24.2 g (0.09 mol) and 202 g of dioxane were charged and dissolved with stirring. Then, the flask was immersed in a water bath at 30 ° C, and when the internal temperature became constant at 30 ° C, 10.0 g (0.10 mol) of triethylamine was added dropwise to this solution so that the internal temperature did not exceed 35 ° C. It dripped slowly using the funnel. Then, 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 in a heating vacuum dryer controlled at 40 ° C. for one day and then 1,2. A quinonediazide compound was obtained. This compound (b
-1).

Synthesis Example 5 Compound (a-2) 17.4 g (0.05 mol) 1,2-naphthoquinonediazide-5-sulfonic acid chloride 21.5 g (0.08 mol) triethylamine 9.1 g (0.09) Mol) and dioxane 156 g were used, and a 1,2-quinonediazide compound was obtained in the same manner as in Synthesis Example 4. This compound is called (b-1).

<Synthesis of other 1,2-quinonediazide compounds> Synthesis example 6 2,3,4,4'-tetrahydroxybenzophenone 24.
6 g (0.10 mol) 1,2-naphthoquinonediazide-5-sulfonic acid chloride 80.6 g (0.30 mol) and triethylamine 44.5 g (0.30 mol).
A quinonediazide compound (a) was obtained in the same manner as in Synthesis Example 4 except that 44 mol) was used.

Synthesis Example 7 1,1,1-Tris (4-hydroxyphenyl) ethane 3
0.6 g (0.1 mol) 1,2-naphthoquinonediazide-5-sulfonic acid chloride 67.2 g (0.25 mol) and triethylamine 25.3 g (0.2 mol).
28 mol) was used, and a quinonediazide compound (ii) was obtained in the same manner as in Synthesis Example 4.

Examples 1 to 4 and Comparative Examples 1 to 4 At the composition ratios shown in Table 1 (however, parts are parts by weight), the alkali-soluble resin, the 1,2-quinonediazide compound and, if necessary, the dissolution accelerator. Then, a solvent was mixed to form a uniform solution, which was then filtered through a membrane filter having a pore size of 0.2 μm to prepare a solution of the composition. The obtained solution is applied on a silicon wafer having a silicon oxide film by using a spinner, and then 90 ° C. on a hot plate.
Was prebaked for 2 minutes to form a resist film having a thickness of 1.1 μm. Through reticle wavelength 365 as described above
After exposure using nm (i-line), it was baked at 110 ° C. for 1 minute. Then, using a 2.38 wt% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 1 minute,
A resist pattern was formed by developing by a dipping method, rinsed with running water for 30 seconds, and then dried. The performance of the obtained resist pattern was investigated. The results are shown in Table 1. The actual
Example 4 is a reference example.

[0068]

[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: 3- Ethyl ethoxypropionate

[0070]

Industrial Applicability The radiation-sensitive resin composition of the present invention has excellent developability and high resolution, and is particularly suitable for use as a positive resist having a good solubility contrast (γ value). .

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Akira Tsuji 2-11-24 Tsukiji, Chuo-ku, Tokyo Within Japan Synthetic Rubber Co., Ltd. (56) Reference JP-A-7-209861 (JP, A) JP-A 7-134405 (JP, A) JP-A-6-83048 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03F ^7/ 00-7/42

Claims (3)

(57) [Claims] 1. An alkali-soluble resin and a dissolution accelerator.
Low molecular weight phenol compound and the following general formula (1) [In the formula (1), X _{1 to} X ₁₀ are the same or different and each is a hydrogen atom, an alkyl group, an alkoxy group or -OD.
(Wherein D is a hydrogen atom or an organic group containing a 1,2-quinonediazide group), and R _{1 to} R ₃ are the same or different and are alkyl groups.
However, in each combination of X _{1 to} X ₅ and X _{6 to} X ₁₀ , at least one is a group represented by —OD, and at least one of a plurality of D of the groups represented by —OD is 1 It is an organic group containing a 2,2-quinonediazide group. Contain represented by 1,2-quinonediazide compound, said alkali-soluble resin is polystyrene equivalent weight
Novolac with a weight average molecular weight of 7,800-20,000
The radiation-sensitive resin composition, wherein the resin der Rukoto. 2. The dissolution promoter is a flux having a benzene ring number of 2 to 6.
The radiation-sensitive resin according to claim 1, which is an enol compound.
Composition. 3. The 1,2-quinonediazide compound has the following formula:
(4-1) or (4-2): At least one of the compounds represented by
The hydrogen atom of the hydroxyl group of contains a 1,2-quinonediazide group
The compound according to claim 1, which is a compound converted into an organic group
The radiation-sensitive resin composition of.