JP3209754B2 - Radiation-sensitive resin composition - Google Patents

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 containing an alkali-soluble resin, and more particularly to ultraviolet rays, far ultraviolet rays, X-rays, electron beams, molecular beams, gamma rays, synchrotron radiation, protons, and the like. The present invention relates to a radiation-sensitive resin composition suitable as a resist for producing a highly integrated circuit responsive to radiation such as a beam.

[0002]

2. Description of the Related Art Positive resists are widely used in the manufacture of integrated circuits because they provide high-resolution resist patterns. However, with the recent increase in the degree of integration of integrated circuits, resists with higher resolution have been developed. A positive resist capable of forming a pattern is desired. That is, when a fine resist pattern is formed by a positive resist, when a latent image formed by irradiation with radiation is developed with a developing solution composed of an alkaline aqueous solution, a portion where the radiation irradiation portion is in contact with the wafer (the bottom of the pattern). ) Must be developed promptly.

[0003]

However, in the case of the conventional positive type resist, when the interval between the resist patterns to be formed is 0.8 μm or less, a development residue called a scum tends to occur, and there is a problem in developability. . Further, with the improvement in the degree of integration of integrated circuits, the method of etching a wafer has shifted from conventional wet etching with large side etching to dry etching with small side etching. In this dry etching, it is necessary that the resist pattern does not change at the time of etching, and thus it is necessary that the heat resistance is good. Therefore, an object of the present invention is to suppress the occurrence of scum effectively, while being excellent in developability, high sensitivity, high resolution, heat resistance, suitable as a positive resist excellent in residual film ratio and the like. An object of the present invention is to provide a conductive resin composition.

[0004]

According to the present invention ,

[0005] A alkali-soluble resin, the following formula (A2) or
At least one of the hydroxyl compounds represented by (A3)
Species, and as a radiation-sensitive component, a radiation-sensitive resin composition characterized by containing a 1,2-quinonediazide compound,

[0006]

Embedded image Is provided.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION

The radiation-sensitive resin composition of the present invention effectively suppresses the generation of scum, has excellent developability,
It can be suitably used as a positive resist having high sensitivity, high resolution, and excellent heat resistance and residual film ratio.

Alkali-soluble resin The alkali-soluble resin used in the present invention (hereinafter referred to as “the alkali-soluble resin”)
It is called “resin (A)”. Examples of the) include novolak resin, resol resin, polyvinylphenol or a derivative thereof, styrene-maleic anhydride copolymer, polyvinylhydroxybenzoate, and carboxyl group-containing (meth) acrylic acid resin. Is preferably used. Among the novolak resins, the following general formula (1):

[0010]

Embedded image In the formula, n represents an integer of 1 to 3, and is preferably obtained by polycondensing a phenol and an aldehyde represented by the following formula.

The phenols include, for example, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4- Xylenol, 3,5-
Xylenol, 2,3,4-trimethylphenol, 2,3,5
-Trimethylphenol, 3,4,5-trimethylphenol and the like, among which o-cresol, m-
Cresol, p-cresol, 2,5-xylenol,
3,5-xylenol and 2,3,5-trimethylphenol are preferred, more preferably m-cresol /
3,5-xylenol / p-cresol = 95/5/0
20/80/25 (molar ratio), m-cresol / 2,3,5
-Trimethylphenol / p-cresol = 95/5 /
It is a combined system of 0 to 30/70/65 (molar ratio).

The aldehydes to be polycondensed with the phenols include, for example, formaldehyde, trioxane, paraformaldehyde, benzaldehyde, acetaldehyde, propylaldehyde, phenylacetaldehyde, α-phenylpropylaldehyde, β-phenylpropylaldehyde, o-hydroxybenzaldehyde , M-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-chlorobenzaldehyde, m
-Chlorobenzaldehyde, p-chlorobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, p-nitrobenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, p-ethylbenzaldehyde,
Examples thereof include pn-butylbenzaldehyde and furfural, and formaldehyde is particularly preferably used. These aldehydes may be used alone or
It can be used in combination of more than one kind.

The amount of the aldehyde used is preferably 0.7 to 3 mol, more preferably 0.8 to 1.5 mol, per 1 mol of the phenol. For the polycondensation of phenols and aldehydes, an acidic catalyst is usually used. Examples of the acidic catalyst include hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, and acetic acid. The use amount of these acidic catalysts is usually 1 × 10 ⁻⁵ to 1 mol of phenols.
5 × 10 ^-1 mol.

In the polycondensation, water is usually used as a reaction medium. However, when the phenol used in the polycondensation does not dissolve in the aqueous solution of the aldehyde and becomes a heterogeneous system from the beginning of the reaction, it is used as the reaction medium. Hydrophilic solvents can also be used. 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 the reaction medium is usually 20 to 1000 parts by weight per 100 parts by weight of the reaction raw material.

The temperature of the polycondensation can be appropriately adjusted according to the reactivity of the reaction raw materials.
Preferably it is 70-130 ° C. As a method of polycondensation,
A method in which phenols, aldehydes, acidic catalysts, and the like are charged at once, and a method in which phenols, aldehydes, and the like are added in the presence of the acidic catalyst as the reaction proceeds, can be adopted. After completion of the polycondensation, in order to remove unreacted raw materials, acidic catalyst, reaction medium, and the like present in the system, generally, the temperature of the reaction system is increased to 130 to 230 ° C., and the pressure is reduced, for example, to 20 to 230 ° C. The volatiles are distilled off at about 50 mmHg, and the obtained resin (A) is recovered.

The resin (A) used in the present invention has a weight average molecular weight in terms of polystyrene (hereinafter referred to as "Mw").
Is preferably 2,000 to 20,000, and 3,000 to 1
More preferably, it is 5,000. When Mw exceeds 20,000, it may be difficult to uniformly apply the composition of the present invention to a wafer, and furthermore, there is a tendency that developability and sensitivity tend to decrease, and when Mw is less than 2,000, heat resistance is reduced. Properties tend to decrease. In order to obtain a resin (A) having a high Mw, the resin obtained above was dissolved in a good solvent such as ethyl cellosolve acetate, dioxane, methanol and ethyl acetate, and then water, n-hexane and n-hexane were dissolved. What is necessary is to mix a poor solvent such as heptane and the like, then separate the resin solution layer to be precipitated, and recover the resin (A).

In the present invention, a phenol compound having a low molecular weight may be used as a dissolution promoter for the purpose of promoting the alkali solubility of the resin (A).
As the low-molecular-weight phenol compound, a phenol compound having about 2 to 6 benzene rings is suitable, and is not particularly limited, and examples thereof include compounds represented by the following formula.

[0018]

Embedded image

[0019]

Embedded image

[0020]

Embedded image In the above formula, a, b and c are each a number from 0 to 3 (however, excluding the case where all are 0), x, y and z
Is a number from 0 to 3. The amount of the low-molecular-weight phenol compound to be blended is usually preferably 50 parts by weight or less, particularly preferably 32 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 novolak resin or alkali-soluble resol resin (hereinafter simply referred to as "resin (B)") may be used as a dissolution accelerator. Here, the resin (B) is
The phenols are obtained by polycondensation of phenols and aldehydes. Examples of the phenols include phenols, 1-naphthol, 2-naphthol and the like, in addition to those exemplified as the phenols used in the synthesis of the resin (A). be able to. As the aldehydes, those used in the synthesis of the resin (A) can be used. The amount of the aldehyde used is 0.1 to 1 mol per phenol.
It is preferably 3 moles, more preferably 0.2 to 1.5 moles. In this polycondensation, an alkaline catalyst can be used in addition to the acidic catalyst used for the polycondensation of the resin (A). Mw of the resin (B) is usually preferably 10,000 or less, more preferably 200 to 2,000, and 3
It is particularly preferred that it is from 00 to 1,000. Such resin
(B) includes phenol / formaldehyde condensed novolak resin, m-cresol / formaldehyde condensed novolak resin, p-cresol / formaldehyde condensed novolak resin, o-cresol / formaldehyde condensed novolak resin, m-cresol / p-cresol /
Formaldehyde condensed novolak resins and the like can be mentioned. The amount of such a resin (B) is usually
The amount is preferably not more than 60 parts by weight, particularly preferably not more than 40 parts by weight, per 100 parts by weight.

[0022] In the inventions of hydroxyl compounds present,

[0023] at least one hydroxyl compound selected from hydroxyl compounds represented by the following Symbol formula (A 2) or (A3) is used.

Embedded image

The hydroxyl compound represented by the formula (A2 ) or (A3) is, for example, an acid-catalyzed condensation reaction between a dicarbonyl compound and a phenol, or an acid reaction between an α, β-unsaturated carbonyl compound and a phenol. It can be synthesized by a condensation addition reaction using a catalyst.

In the present invention, the above-mentioned hydroxyl compound is used in an amount of 0.5 to 90 parts by weight per 100 parts by weight of the resin (A),
In particular, it is preferable to use 2 to 50 parts by weight.

1,2-quinonediazide compound In the present invention, in addition to the resin (A) and the hydroxyl compound, a 1,2-quinonediazide compound is blended. this
1,2-quinonediazide compound is a radiation-sensitive component,
This is for imparting radiation sensitivity to the composition of the present invention. Such 1,2-quinonediazide compounds include, for example, 1,2-benzoquinonediazide-4-sulfonic acid ester, 1,2-naphthoquinonediazide-4-sulfonic acid ester, 1,2-naphthoquinonediazide-5-sulfonic acid Examples thereof include 1,2-quinonediazidesulfonic acid esters such as esters, and the following can be exemplified.

2,3,4-trihydroxybenzophenone,
3,4,4'-tetrahydroxybenzophenone, 3'-methoxy-2,3,4,4'-tetrahydroxybenzophenone, 2,
2 ', 5,5'-tetramethyl-2 ", 4,4'-trihydroxytriphenylmethane, 1,1,1-tris (4-hydroxyphenyl)
Ethane, 1,1-bis (4-hydroxyphenyl) -4- [1- (4-hydroxyphenyl) -1-methylethyl] -1-phenylethane, 2,4,4-trimethyl-2 ', 4' 1,7-trihydroxy-2-phenylflavan, 1,1,3-tris (4-hydroxyphenyl) butane, 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) propane, etc. 2-benzoquinonediazide
4-sulfonic acid ester, 1,2-naphthoquinonediazide-
4-sulfonic acid ester, 1,2-naphthoquinonediazide-
5-sulfonic acid ester. Further, the hydrogen atom of the hydroxyl group of the resin (B) described as the dissolution promoter in the section of the alkali-soluble resin is, for example, 0.2 to 1 mol%, preferably 0.4 to 1 mol, of 1,2-naphtho per one hydrogen atom. 1,2-quinonediazidesulfonic acid ester substituted with a 1,2-quinonediazidosulfonyl group such as quinonediazide-5-sulfonyl group.

In the composition of the present invention, the amount of the 1,2-quinonediazide compound is based on 100 parts by weight of the resin (A).
Usually, it is 3 to 100 parts by weight, preferably 5 to 50 parts by weight.

Various Compounding Agents In the composition of the present invention, various compounding agents such as sensitizers and surfactants can be compounded. A sensitizer is compounded to improve the sensitivity of the composition. Examples of such a sensitizer include 2H-pyrido- (3,2-b) -1,4-
Oxazine-3 (4H) -ones, 10H-pyrido- (3,2-b)-(1,4)
-Benzothiazines, urazoles, hydantoins,
Examples include parbituric acids, glycine anhydrides, 1-hydroxybenzotriazoles, alloxanes, and maleimides. The compounding amount of these sensitizers is as follows.
It is usually 50 parts by weight or less based on parts by weight.

Surfactants are incorporated to improve the coating properties and developability of the composition. Examples of such surfactants include polyoxyethylene lauryl ether and polyoxyethylene stearyl ether. ,
Polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, F-top EF301, EF303, EF352 (trade name, manufactured by Shin-Akita Kasei), Megafax F171, F172, F173 (trade name, manufactured by Dainippon Ink), Florard FC430, FC431 (trade name, manufactured by Sumitomo 3M Limited), Asahi Guard AG710, Surflon S-382, SC-101, SC-102, SC-103 , SC- 104, SC-
105, SC-106 (trade name, manufactured by Asahi Glass Co., Ltd.), organosiloxane polymer KP341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), acrylic acid or methacrylic acid (co) weight polyflow No.75, No.95 ( (Product name, manufactured by Kyoeisha Yushi Kagaku Kogyo)
And the like. The amount of these surfactants is usually 2 parts by weight or less per 100 parts by weight of the solid content of the composition.

Further, the composition of the present invention may contain a dye or a pigment for visualizing the latent image in the irradiated area and reducing the influence of halation at the time of irradiation, and improving the adhesiveness. For this purpose, an adhesion aid may be added. Further, if necessary, a storage stabilizer, an antifoaming agent and the like can be added.

Preparation of Composition and Pattern Formation The composition of the present invention comprises the above-mentioned resin (A), a hydroxyl compound and a 1,2-quinonediazide compound and the above-mentioned various compounding agents, for example, having a solid content of 20 to 40. It is prepared by dissolving in a solvent so as to give a weight% and filtering through 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, and 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-methoxypropionate, ethyl 3-ethoxypropionate, 3 -Methyl ethoxypropionate, ethyl acetate, butyl acetate and the like can be used. Further, N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, benzylethyl ether, dihexyl ether, acetonylacetone ,
Isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, etc. Boiling solvents can also be added.

The composition of the present invention is applied to, for example, a silicon wafer or a wafer coated with aluminum or the like by spin coating, flow coating, roll coating or the like to form a radiation-sensitive layer, and a predetermined mask is formed. The pattern is formed by irradiating the radiation-sensitive layer with radiation through the pattern and developing with a developer. When the composition of the present invention is used as a positive resist, the composition is coated on a wafer or the like, prebaked and irradiated, and then heated at 70 to 140 ° C. By performing the development, the effect of the present invention can be further improved.

Developer The developer of the composition of the present invention includes, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, diamine, and the like. -N-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- (5,4,0)- An alkaline aqueous solution obtained by dissolving an alkaline compound such as 7-undecene and 1,5-diazabicyclo- (4,3,0) -5-nonane at a concentration of, for example, 1 to 10% by weight is used. . Further, a suitable amount of a water-soluble organic solvent, for example, an alcohol such as methanol or ethanol or a surfactant may be added to the developer. When development is performed using a developing solution composed of such an alkaline aqueous solution, rinsing is generally continued with water.

[0036]

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

[0037] Mw: Toyo Soda Co., Ltd. GPC column (G2000H ₆ 2 this, G3000H ₆
One, using G4000H ₆ one), flow rate 1.5 ml / min, eluent tetrahydrofuran, analytical conditions of column temperature 40 ° C.,
The measurement was performed by gel permeation chromatography using monodisperse polystyrene as a standard.

Sensitivity: Nikon-NSR-1505G4D Exposure is performed using a gamma ray having a wavelength of 436 nm while changing the exposure time with a reduction projection exposure machine (lens numerical aperture; 0.45), or Nikon-NSR -1505i6A
The exposure time was changed using a reduction projection exposure machine (lens numerical aperture; 0.45), exposure was performed using i-rays having a wavelength of 365 nm, and then 2.4% by weight of tetramethyl ammonium hydroxide
Using an aqueous solution as a developer, develop at 25 ° C. for 60 seconds, rinse with water, dry to form a resist pattern on the wafer, and form a 0.6 μm line-and-space pattern (1 LIS) on a one-to-one basis. The exposure time for forming the width (hereinafter referred to as “optimal exposure time”) was determined.

Resolution: The dimension of the minimum resist pattern resolved when exposed for the optimal exposure time was measured.

Residual film ratio: The thickness of the pattern after development at the optimum exposure time was divided by the thickness of the resist film before development, and this value was multiplied by 100 to give a unit of%.

Developability: The degree of scum and residual development was examined.

Heat resistance: The wafer on which the resist pattern was formed was placed in a clean oven, and the temperature at which the pattern began to collapse was measured.

<Synthesis of Resin A> Synthesis Example 1 A flask equipped with a stirrer, a condenser and a thermometer was charged with 67.6 g (0.63 mol) of m-cresol 10.0 g (0.073 mol) of 2,3,5-trimethylphenol p -Cresol 31.8 g (0.29 mol) 37 wt% formaldehyde aqueous solution 107.1 g (formaldehyde: 1.32 mol) and oxalic acid dihydrate 1.33 g (1.06 × 10 ^-2 mol) were charged, and the flask was immersed in an oil bath and heated at an internal temperature. Was maintained at 100 ° C., and polycondensation was carried out for 30 minutes while stirring. Then, 17.5 g (0.16 mol) of m-cresol and 40.0 g (0.29 mol) of 2,3,5-trimethylphenol were added, and the mixture was further added for 40 minutes. Polycondensation was performed. Next, the oil bath temperature was raised to 180 ° C, and at the same time, the pressure in the flask was increased to 30 to
The pressure was reduced to 50 mmHg to remove water, oxalic acid, unreacted raw materials and the like. Then, the molten resin was returned to room temperature and collected.
This resin is referred to as resin (A1).

Synthesis Example 2 Resin (A1) was dissolved in ethyl cellosolve acetate so as to have a solid content of 20% by weight, and twice the amount of methanol and an equal amount of water with respect to the weight of the resin solution were added and stirred. And left. After being separated into two layers by standing, the resin solution layer (lower layer) is taken out, concentrated, dehydrated,
After drying, the resin was recovered. This resin is referred to as resin (A2).

Synthesis Example 3 In an autoclave, 69.2 g (0.64 mol) of m-cresol 21.8 g (0.16 mol) of 2,3,5-trimethylphenol 61.0 g of a 37% by weight aqueous solution of formaldehyde (formaldehyde: 0.75 mol) oxalic acid dihydrate 6.3 g (0.05 mol), 52.6 g of water and 182 g of dioxane were charged, and the autoclave was immersed in an oil bath.
The mixture is condensed for 6 hours with stirring and after the reaction,
After returning to room temperature, 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 collect the resin. This resin is referred to as resin (A3).

Synthesis Example 4 In a flask similar to that used in Synthesis Example 1, m-cresol 13.0 g (0.12 mol) p-cresol 32.4 g (0.3 mol) 3,5-xylenol 39.0 g (0.32 mol) 37 weight 56.9 g (formaldehyde: 0.70 mol) and 0.083 g (6.59 × 10 ^-4 mol) of oxalic acid dihydrate were placed in the flask, and the flask was immersed in an oil bath and stirred while maintaining the internal temperature at 100 ° C. After 30 minutes of polycondensation, 51.9 g (0.48 mol) of m-cresol and 9.77 g (0.08 mol) of 3,5-dimethylphenol were continuously charged into the flask as the reaction proceeded.
The polycondensation was performed for minutes. Thereafter, the resin was recovered in the same manner as in Synthesis Example 1. This resin is referred to as resin (A4).

Synthesis Example 5 In a flask similar to that used in Synthesis Example 1, 95.2 g (0.88 mol) of m-cresol 24.4 g (0.18 mol) of 2,3,5-trimethylphenol 154 g of a 37% by weight aqueous solution of formaldehyde (formaldehyde) : 1.90 mol) and 1.82 g (0.014 mol) of oxalic acid dihydrate, the flask was immersed in an oil bath, and the mixture was stirred for 90 minutes while maintaining the internal temperature at 100 ° C. -23.8 g (0.22 mol) of cresol and 97.6 g (0.72 mol) of 2,3,5-trimethylphenol were added, and polycondensation was further conducted for 60 minutes. Next, the resin was recovered in the same manner as in Synthesis Example 1. This resin was dissolved in ethyl cellosolve acetate so as to have a solid content of 20% by weight. Then, 1.8 times methanol and an equal amount of water with respect to the weight of the resin solution were added, and the mixture was stirred and allowed to stand. After being separated into two layers by standing, the resin solution layer (lower layer) was taken out, concentrated, dehydrated, and dried to collect the resin. This resin is referred to as resin (A5).

<Synthesis of Resin B> Synthesis Example 6 In a flask similar to that used in Synthesis Example 1, m-cresol 108.0 g (1.00 mol) 24.3 g (formaldehyde: 0.30 mol) of 37% by weight aqueous formaldehyde solution and oxalic acid 0.30 g (2.40 × 10 ⁻³ mol) of dihydrate was charged, the flask was immersed in an oil bath, and polycondensation was performed for 40 minutes while maintaining the internal temperature at 100 ° C. Next, the resin was recovered in the same manner as in Synthesis Example 1. This resin is referred to as resin (B1).

Synthesis Example 7 In a flask similar to that used in Synthesis Example 1, m-cresol 64.9 g (0.60 mol) p-cresol 43.3 g (0.40 mol) 37% by weight formaldehyde aqueous solution 20.3 g (formaldehyde: 0.25 mol) Then, 0.30 g (2.40 × 10 ⁻³ mol) of oxalic acid dihydrate was charged, the flask was immersed in an oil bath, and polycondensation was performed for 30 minutes while maintaining the internal temperature at 100 ° C. Next, the resin was recovered in the same manner as in Synthesis Example 1. This resin is referred to as resin (B2).

<Abbreviated names of hydroxyl compounds> The following abbreviated names of the hydroxyl compounds used in the examples are shown below .

[0051] The lower following formula (A2):

[0052]

Embedded image 1,1,4-tris (2,5-dimethyl-4-hydroxyphenyl) pentane represented by the following formula is abbreviated as compound (A2). The following formula (A3):

[0053]

Embedded image The in represented by 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) propane you abbreviated as compound (A3).

<Synthesis of 1,2-quinonediazide compound> Synthesis Example 8 10.0 g of 1,2-naphthoquinonediazide-5-sulfonic acid in a flask equipped with a stirrer, a dropping funnel and a thermometer under light shielding. Chloride
13.9 g and 100 g of dioxane were charged and dissolved with stirring. Then remove the flask
Immersion in a water bath controlled at 30 ° C, and when the internal temperature became constant at 30 ° C, 5.75 g of triethylamine was slowly dropped into 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, and the filtrate was poured into a large amount of diluted hydrochloric acid to cause precipitation.Then the precipitate was collected by filtration, and dried all day and night in a vacuum dryer controlled at 40 ° C. for 1,2 hours. -A quinonediazide compound (C1) was obtained.

Synthesis Example 9 10.0 g of resin (B2) 1,2-naphthoquinonediazide-5-sulfonic acid chloride
A 1,2-quinonediazide compound (C2) was obtained in the same manner as in Synthesis Example 8 except that 16.6 g and 6.86 g of triethylamine were used.

Synthesis Example 10 2,3,4-Trihydroxybenzophenone 23.0 g (0.10 g)
Mol) 1,2-naphthoquinonediazide-5-sulfonic acid chloride (69.9 g, 0.26 mol) and triethylamine, 28.9 g (0.286 mol), except that 1,2-quinonediazide compound (C3) was prepared in the same manner as in Synthesis Example 8. Obtained.

Synthesis Example 11 24.6 g of 2,3,4,4'-tetrahydroxybenzophenone
(0.10 mol) 1,2-naphthoquinonediazide-5-sulfonic acid chloride 10
A 1,2-quinonediazide compound (C4) was obtained in the same manner as in Synthesis Example 8 except that 7.5 g (0.40 mol) and 44.5 g (0.44 mol) of triethylamine were used.

Synthesis Example 12 1,1-bis (4-hydroxyphenyl) -4- [1- (4-hydroxyphenyl) -1-methylethyl] -1-phenylethane 42.4
g (0.10 mol) 1,2-naphthoquinonediazide-5-sulfonic acid chloride 6
A 1,2-quinonediazide compound (C5) was obtained in the same manner as in Synthesis Example 8 except that 7.2 g (0.25 mol) and 27.8 g (0.275 mol) of triethylamine were used.

Examples 1 to 5, Comparative Examples 1 to 3 Resin (A), a 1,2-quinonediazide compound, a hydroxyl compound and a solvent were mixed as shown in Table 1 to form a uniform solution. The solution of the composition of the present invention was prepared by filtration through a membrane filter. The resulting solution is applied on a silicon wafer having a silicon oxide film using a spinner, and then heated to 90 ° C. on a hot plate.
For 2 minutes to form a resist film having a thickness of 1.2 μm, and a wavelength of 436 nm (g)
Line) or 365 nm (i-line), developed, rinsed and dried, then the sensitivity, resolution,
The remaining film ratio, developability and heat resistance were evaluated.
Table 2 shows the results. Examples 1 to 3 and Comparative Examples 1 and 2 were irradiated with g-rays, and Examples 4 and 5 and Comparative Example 3 were irradiated with i-rays.

[0060]

[Table 1]

Note: The dissolution enhancers are : alpha; 1,1,1-tris (4-hydroxyphenyl) ethanone emissions B 2; resin obtained in Synthesis Example 7 (B2) Note: The type of the solvent is as follows. S1; ethyl cellosolve acetate tape preparative S 3; 3- methyl methoxypropionate

[0062]

[Table 2]

[0063]

According to the radiation-sensitive resin composition of the present invention, the development of scum is effectively suppressed and the developability is excellent, and the radiation-sensitive resin composition has high sensitivity, high resolution, and excellent heat resistance and residual film ratio. It can be suitably used as a positive resist.

 ──────────────────────────────────────────────────の Continuing on the front page (72) Inventor Koji Yumoto 2--11-24 Tsukiji, Chuo-ku, Tokyo Inside Synthetic Rubber Co., Ltd. (72) Takao Miura 2--11-24 Tsukiji, Chuo-ku, Tokyo No. Japan Synthetic Rubber Co., Ltd. (56) Reference JP-A-4-12357 (JP, A) JP-A-4-50851 (JP, A) JP-A-4-101147 (JP, A) JP-A-3- 200254 (JP, A) JP-A-4-1650 (JP, A) JP-A-4-12356 (JP, A) JP-A-4-251,849 (JP, A) JP-A-4-37571 (JP, A) JP-A-3-179353 (JP, A) JP-A-3-200252 (JP, A) JP-A-4-211254 (JP, A) JP-A-4-211256 (JP, A) JP-A-4-122938 (JP, A)

Claims (1)

(57) [Claims] 1. An alkali-soluble resin, a hydroxyl compound represented by the following formula (A2) or (A3):
And 1,2-quino as a radiation-sensitive component
Sensitization characterized by containing a diazide compound
Radiating resin composition. Embedded image