JP3063197B2 - 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. Further, as the degree of integration is improved, it is required to improve the throughput during the production of integrated circuits, and a highly sensitive resist is required.
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, there is provided a radiation-sensitive resin composition containing an alkali-soluble resin (hereinafter, referred to as "resin (A)"), which is represented by the following general formula (1):

Embedded image Or the following general formula (2);

Embedded image Wherein, X ¹ to X ²⁰ is a hydrogen atom, an alkyl group, an alkoxy group or an OD group (where, D is an organic group containing a hydrogen atom or a 1,2-quinonediazide group) one of and X ^{1 ~X 5, X 6 ~X 10,} X 11 ~X 15 and X ¹⁶ to X
^At least one O in each combination of ²⁰
R is a compound represented by a hydrogen atom, an alkyl group or an aryl group (hereinafter, a compound in which D is a hydrogen atom is referred to as “compound (A)”; Wherein the compound is an organic group containing a 1,2-quinonediazide group (hereinafter referred to as "compound (B)").

Alkali-soluble resin As the resin (A) used in the present invention, for example, novolak resin, resol resin, polyvinyl phenol or its derivative, styrene-maleic anhydride copolymer, polyvinyl hydroxybenzoate, carboxyl group-containing methacrylic acid Novolak resin is particularly preferably used. Among the novolak resins, those obtained by polycondensing phenols and aldehydes represented by the following formula (3) are particularly preferable.

[0006]

Embedded image In the formula, n represents an integer of 1 to 3.

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
20/80/75 (molar ratio) and m-cresol /
2,3,5-trimethylphenol // p-cresol = 9
It is a combined system of 5/5/0 to 30/70/65 (molar ratio).

The aldehydes to be polycondensed with the above 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. In this case, as a formaldehyde generating source, hemifomals such as trioxane, paraformaldehyde, methylhemiformal, ethylhemiformal, propylhemiformal, butylhemiformal, and phenylhemiformal can be used. These aldehydes can be used alone or in combination of two or more. 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} 5 × 10 ^-1 mol per 1 mol of phenols. 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 heterogeneous from the beginning of the reaction, a hydrophilic solvent is used as the reaction medium. 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 depends on the reactivity of the reactants,
Although it can be adjusted as appropriate, it is usually 10 to 200 ° C, preferably 70 to 130 ° C. As the polycondensation method, there may be adopted a method in which phenols, aldehydes, acidic catalysts, etc. are charged at once, and a method in which phenols, aldehydes, etc. are added as the reaction proceeds in the presence of an acidic catalyst. it can. 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. Volatiles are distilled off at about 50 mmHg, and the obtained resin (A) is recovered.

The weight average molecular weight in terms of polystyrene of the resin (A) used in the present invention (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. There is a tendency for the properties to decrease. In addition, resin with high Mw (A)
In order to obtain, the resin obtained above, ethyl cellosolve acetate, dioxane, methanol, dissolved in a good solvent such as ethyl acetate, water, n- hexane, mixed with a poor solvent such as n-heptane, Next, the resin solution layer to be deposited may be separated, and the resin (A) may be recovered.

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 preferable.
Although not particularly limited, a compound represented by the following formula (4) can be exemplified.

Embedded image In the 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 is usually 5 parts by weight per 100 parts by weight of the resin (A).
0 parts by weight or less.

For the same purpose as described above, a low molecular weight alkali-soluble novolak resin or an alkali-soluble resol resin (hereinafter simply referred to as "resin (B)") may be used as a dissolution accelerator. Here, the resin (B) is obtained by polycondensation of a phenol and an aldehyde. Examples of the phenol include those exemplified as the phenol used in the synthesis of the resin (A), and phenol and 1-naphthol. , 2-naphthol and the like can be used. Also as aldehydes,
Those used for the synthesis of the resin (A) can be used. The amount of the aldehyde used is preferably 0.1 to 3 mol, more preferably 1 mol of the phenol.
0.2 to 1.5 mol. 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 resin (B) is usually 1
It is preferably at most 0,000, more preferably from 200 to 2,000, particularly preferably from 300 to 1,000. Examples of such resin (B) include phenol / formaldehyde condensed novolak resin, m-cresol / formaldehyde condensed novolak resin, p-cresol / formaldehyde condensed novolak resin, o-cresol / formaldehyde condensed novolak resin, and m-cresol / p- Cresol / formaldehyde condensed novolak resin and the like can be mentioned. The amount of the resin (B) is generally 50 parts by weight per 100 parts by weight of the resin (A).

Compounds (A) and (B) In the composition of the present invention, the above-mentioned general formula (1), ie,

Embedded image Or the general formula (2):

Embedded image At least one of the compound (A) or the compound (B) represented by

In these general formulas, X ^{1 to} X ²⁰ are selected from a hydrogen atom, an alkyl group, an alkoxy group and an OD group (where D is a hydrogen atom or an organic group containing a 1,2-quinonediazide group). And X ^{1 to} X
⁵ , at least one in each combination of X ^{6 to} X ¹⁰ , X ^{11 to} X ¹⁵ and X ^{16 to} X ²⁰ is an OD group. That is, at least one OD group is substituted for each benzene ring. Here, as the alkyl group, those having 4 or less carbon atoms are preferable, and specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-
Examples thereof include a butyl group and a t-butyl group. As the alkoxy group, those having 4 or less carbon atoms are preferable, and specific examples include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Further, in connection with the OD group, the organic group containing a 1,2-quinonediazide group includes a 1,2-benzoquinonediazide-4-sulfonyl group,
1,2-naphthoquinonediazide-5-sulfonyl group and 1,2-quinonediazidosulfonyl group such as 1,2-naphthoquinonediazide-4-sulfonyl group, among which 1,2-naphthoquinonediazide-4- Sulfonyl or 1,2-naphthoquinonediazide-5-sulfonyl are preferred.

In the general formula (2), R represents a hydrogen atom, an alkyl group or an aryl group, and the alkyl group preferably has 4 or less carbon atoms as in the case of X ^{1 to} X ^20. It is. As the aryl group, those having 6 to 10 carbon atoms such as a phenyl group, a toluyl group, a xylyl group, and a naphthyl group are preferable.

Specific examples of the compound (A) represented by the general formula (1) include a compound represented by the following formula (5).

[0017]

Embedded image

Compound (A) represented by the above formula (5)
Can be synthesized, for example, by condensing pentaerythritol and hydroxybenzaldehydes using an acid catalyst.

The compound (A) represented by the general formula (2)
As a specific example, a compound represented by the following formula (6) can be given.

[0020]

Embedded image

Embedded image

Embedded image

Compound (A) represented by the above formula (6)
Can be synthesized, for example, by condensing phenols with glyoxal or ketoaldehydes using an acid catalyst.

The compound (B) represented by the general formula (1) or the general formula (2) can be obtained by substituting a part or all of the hydroxyl atoms of the above-mentioned compound (A) with a 1,2-quinonediazide group. A compound substituted with an organic group, for example, the compound (A) described above and 1,2-quinonediazidosulfonyl such as 1,2-naphthoquinonediazide-5-sulfonyl chloride and 1,2-naphthoquinonediazide-4-sulfonylchloride. It can be synthesized by an esterification reaction with chloride. Average condensation rate of this esterification reaction [(number of esterified phenolic hydroxyl groups / number of phenolic hydroxyl groups before reaction) × 100] (hereinafter referred to as “average condensation rate”)
Is usually 100% or less, preferably 40 to 100%.

In the present invention, the above-mentioned compound (A)
Alternatively, the compound (B) is used per 100 parts by weight of the resin (A),
It is preferred to use 0.5 to 90 parts by weight, especially 2 to 50 parts by weight.

1,2-quinonediazide compound In the present invention, when the compound (B) is not used,
It is necessary to mix a 1,2-quinonediazide compound other than the compound (B), and when the compound (B) is used, a 1,2-quinonediazide compound other than the compound (B) can be mixed. . 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 esters and the like, and specific examples thereof include the following. 2,3,4-trihydroxybenzophenone, 2,3,4,4'-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) -1-phenylethane, 1,1-bis (4-hydroxyphenyl) -4- [1- (4-hydroxyphenyl) -1-methylethyl] -1-
1,2-benzoquinonediazide-4-sulfonic acid ester such as phenylethane, 2,4,4-trimethyl-2 ', 4', 7-trihydroxy-2-phenylflavan, 1,2-naphthoquinonediazide-4- Sulfonates, 1,2-naphthoquinonediazido-5-sulfonates. The hydrogen atom of the hydroxyl group of the resin (B) is, for example,
1,2-substituted by 1,2-naphthoquinonediazido-5-sulfonyl group in a ratio of 0.2 to 1 mol, preferably 0.4 to 1 mol
Quinonediazidesulfonic acid ester.

In the composition of the present invention, the amount of the 1,2-quinonediazide compound is usually 3 to 100 parts by weight, preferably 5 to 50 parts by weight, per 100 parts by weight of the resin (A). The total amount of 1,2-quinonediazidosulfonyl groups in the composition is usually adjusted to 5 to 25% by weight, preferably 10 to 20% 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 for improving the sensitivity of the resist. Examples of such a sensitizer include 2H-pyrido- (3,2-b) -1,4
-Oxazine-3 (4H) -ones, 10H-pyrido- (3,2-b)-(1,
4) -Benzothiazines, urazoles, hydantoins, parbituric acids, glycine anhydrides, 1-hydroxybenzotriazoles, alloxanes, maleimides and the like. The compounding amount of these sensitizers depends on the resin (A)
It is usually 50 parts by weight or less based on 100 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-1
05, 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 (trade 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 upon irradiation, and improve 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) and compound (A) or compound (B) 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.

[0033]

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.

[0034] 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: The exposure time is changed using a Nikon-NSR-1505i6A reduction projection exposure machine (lens numerical aperture; 0.45), exposure is performed using i-ray having a wavelength of 365 nm, and then tetramethylammonium hydroxide 2.4. 25% by weight aqueous solution
Exposure time for forming a 0.6 μm line-and-space pattern (1 LIS) in a one-to-one width (hereinafter, referred to as a resist pattern) was formed by developing at 60 ° C. for 60 seconds, rinsing with water, and drying to form a resist pattern on the wafer. This is referred to as “optimal exposure time”).

Resolution: The dimension of the smallest resist pattern that was 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.

Pattern shape: Using a scanning electron microscope, the lower side A and the upper side B of a rectangular cross section of a 0.6 μm resist pattern after development were measured to obtain 0.85 μm.
When ≦ B / A ≦ 1, the pattern shape was determined to be good. However, the pattern shape is pulling the hem,
If the tapered shape is reversed, it is determined to be defective even if B / A is within the above range.

<Synthesis of Resin A> Synthesis Example 1 In a flask equipped with a stirrer, a cooling pipe and a thermometer, m
-Cresol 67.6 g (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) were charged, and the flask was immersed in an oil bath. After condensation, m-cresol
17.5 g (0.16 mol) and 2,3,5-trimethylphenol
40.0 g (0.29 mol) was added and polycondensation was carried out for another 40 minutes. Next, the oil bath temperature was raised to 180 ° C., and simultaneously the pressure in the flask was reduced to 30 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 69.2 g (0.64 g) of m-cresol was placed in an autoclave.
Mol) 2,3,5-trimethylphenol 21.8 g (0.16 mol) 37% by weight aqueous formaldehyde solution 61.0 g (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, the autoclave was immersed in an oil bath, condensation was carried out for 6 hours with stirring while maintaining the internal temperature at 130 ° C., after the reaction, the temperature was returned to room temperature, and the contents were placed in a beaker. I took it out. 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, 13.0 g (0.12 mol) of m-cresol p-cresol 32.4
g (0.3 mol) 3,5-xylenol 39.0 g (0.32 mol) 37 wt% formaldehyde aqueous solution 56.9 g (formaldehyde: 0.70 mol) and oxalic acid dihydrate 0.083
g (6.59 × 10 ^-4 mol), the flask was immersed in an oil bath, and the mixture was stirred and polycondensed for 30 minutes while maintaining the internal temperature at 100 ° C., and then 51.9 g of m-cresol (0.
48 mol) and 9.77 g of 3,5-dimethylphenol (0.08
Mol) was continuously charged into the flask as the reaction proceeded, and polycondensation was carried out for 45 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, m-cresol 95.2 g (0.88 mol) 2,3,5-trimethylphenol 24.4 g (0.18 mol) 37% by weight formaldehyde aqueous solution 154 g (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 while maintaining the internal temperature at 100 ° C.
After 90 minutes of polycondensation, m-cresol 2
3.8 g (0.22 mol) and 2,3,5-trimethylphenol
97.6 g (0.72 mol) was added and polycondensation was carried out for another 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, stirred, and allowed to stand. 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 (A5).

<Synthesis of Resin B> Synthesis Example 6 A flask similar to that used in Synthesis Example 1 was charged with 64.8 g (0.60 mol) of m-cresol and 43.2 g of p-cresol.
(0.40 mol) 24.3 g of 37% by weight aqueous formaldehyde solution
(Formaldehyde: 0.30 mol) and oxalic acid dihydrate 0.30 g (2.40 × 10 ⁻³ mol) were charged, the flask was immersed in an oil bath, and polycondensation was carried out 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).

<Abbreviation and Synthesis of Compound (A)> In the following, 3,9-bis (2-hydroxyphenyl) -2,4,8,10 which is the compound (A) represented by the general formula (1) -Tetraoxaspiro [5,5] undecane (Structural formula 5 in the formula (5)
-3) with compound (A1), 3,9-bis (4-hydroxyphenyl) -2,4,8,10-tetraoxaspiro [5,5] undecane (the structural formula 5-1 in the formula (5)) ) With compound (A2), 3,9-bis
(3-Methoxy-4-hydroxyphenyl) -2,4,8,10-tetraoxaspiro [5,5] undecane (Structural Formula 5-8 in Formula (5)) was converted to Compound (A3), 3,9 -Bis (3,4-dihydroxyphenyl) -2,4,8,10-tetraoxaspiro [5,5] undecane (Structural Formula 5-4 in Formula (5)) is abbreviated as Compound (A4). In addition, 1,1- which is the compound (A) represented by the general formula (2)
Bis (4-hydroxyphenyl) -acetone (Structural Formula 6-12 in Formula (6)) was converted to Compound (A5), 1,1-bis (2,5-dimethyl).
-4-Hydroxyphenyl) acetone (Structural Formula 6-18 in Formula (6)) is converted to Compound (A6) and 1,1-bis (3,5-dimethyl).
-4-Hydroxyphenyl) acetaldehyde (formula (6)
The structural formula 6-10) in abbreviated as compound (A7).

Synthesis Example 7 In a flask equipped with a stirrer, a dropping funnel and a thermometer, 33.7 g (0.10 mol) of 1,2-naphthoquinonediazide-5-sulfonic acid chloride (53.7 g) was added to a flask equipped with a stirrer, a dropping funnel and a thermometer.
20 mol) and 250 g of dioxane were charged and dissolved with stirring. Next, the flask was immersed in a water bath controlled at 30 ° C, and when the internal temperature became constant at 30 ° C,
22.2 g (0.22 mol) of triethylamine was added to this solution,
The solution was slowly dropped 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 dilute 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. to obtain a compound ( B) was obtained. The obtained compound (B) is referred to as compound (B1).

Synthesis Example 8 Synthesis Example 7 was conducted except that 40.4 g (0.10 mol) of compound (A3) 53.7 g (0.2 mol) of 1,2-naphthoquinonediazide-5-sulfonic acid chloride and 22.2 g (0.22 mol) of triethylamine were used. Compound (B2) was obtained in the same manner as described above.

Synthesis Example 9 Synthesis Example 7 except that 37.6 g (0.10 mol) of compound (A4) 80.4 g (0.3 mol) of 1,2-naphthoquinonediazide-5-sulfonic acid chloride and 33.4 g (0.33 mol) of triethylamine were used. Compound (B3) was obtained in the same manner as described above.

<Synthesis of 1,2-quinonediazide compound> Synthesis Example 10 10.0 g of resin (B1) 1,2-naphthoquinonediazide-5
A 1,2-quinonediazide compound (a) was obtained in the same manner as in Synthesis Example 7, except that 13.9 g of sulfonic acid chloride and 5.75 g of triethylamine were used.

Synthesis Example 11 23.0 g (0.10 mol) of 2,3,4-trihydroxybenzophenone 69.9 g (0.26 mol) of 1,2-naphthoquinonediazide-5-sulfonic acid chloride and 28.9 g of triethylamine
g (0.286 mol), except that 1,2 was used in the same manner as in Synthesis Example 7.
-Quinonediazide compound (II) was obtained.

Synthesis Example 12 2,3,4,4'-Tetrahydroxybenzophenone 24.6 g
(0.10 mol) 1,2-naphthoquinonediazide-5-sulfonic acid chloride 107.5 g (0.40 mol) and triethylamine
A 1,2-quinonediazide compound (c) was obtained in the same manner as in Synthesis Example 7 except that 44.5 g (0.44 mol) was used.

Synthesis Example 13 42.4 g of 1,1-bis (4-hydroxyphenyl) -4- [1- (4-hydroxyphenyl) -1-methylethyl] -1-phenylethane
(0.10 mol) 1,2-naphthoquinonediazide-5-sulfonic acid chloride 67.2 g (0.25 mol) and triethylamine 27.8 g (0.275 mol) were used in the same manner as in Synthesis Example 7 except that 1,2-quinonediazide compound (d ).

[0055] [Examples 1-10 and Comparative Examples 1-2] Resin A, 1,2-quinonediazide compound, compound (A), compound (B) and solvent were mixed as shown in Table 1, and the homogeneous solution Thereafter, the solution was filtered through a membrane filter having a pore size of 0.2 μm to prepare a solution of the composition of the present invention. 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 365 nm (i.
After exposure, development, rinsing, and drying, the resist film was evaluated for sensitivity, resolution, residual film ratio, developability, heat resistance, and pattern shape. result
Are shown in Table 2 .

[0056]

[Table 1]

[Table 2]

Note 1: The types of dissolution accelerators are as follows. α; 1,1,1-tris (4-hydroxyphenyl) ethane β; 1,1-bis (4-hydroxyphenyl) -1-phenylethane Note 2: The types of solvents are as follows. S1: ethyl cellosolve acetate. S2: ethyl lactate.

[0058]

According to the radiation-sensitive resin composition of the present invention, the generation of scum during the formation of a resist pattern is effectively suppressed and the developability is excellent, and at the same time, the sensitivity, the resolution, the heat resistance and the residual film are high. It can be suitably used as a positive resist excellent in efficiency and the like.

──────────────────────────────────────────────────続 き Continuation of front page (72) Inventor Takao Miura 2--11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd. (56) References JP-A-1-309052 (JP, A) JP-A Sho 57-63526 (JP, A) JP-A-55-6397 (JP, A) JP-A-2-191248 (JP, A) JP-A-50-76156 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03F ^7/ 00-7/42

Claims (4)

(57) [Claims] 1. A radiation-sensitive resin composition containing an alkali-soluble resin, which is represented by the following general formula (1): Wherein, X ¹ to X ²⁰ is a hydrogen atom, an alkyl group, an alkoxy group or an OD group (where, D is an organic group containing a hydrogen atom or a 1,2-quinonediazide group) one of and X ^{1 ~X 5, X 6 ~X 10,} X 11 ~X 15 and X ¹⁶ to X
^At least one O in each combination of ²⁰
A radiation-sensitive resin composition comprising at least one compound represented by the following formula: wherein the group D is contained and R represents a hydrogen atom, an alkyl group or an aryl group. (2) In the definition of the general formula (2), D is water
The composition according to claim 1, which is an elemental atom. (3) In the definition of the general formula (2), R is
3. The composition according to claim 1, which is a tyl group. Wherein said compound represented by the general formula (2) is,
Formula: 2] A compound represented by the formula:
A composition according to claim 1.