JP2927014B2 - 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 an ultraviolet ray, a far ultraviolet ray, an X-ray, an electron beam, a molecular beam, a .gamma.
The present invention relates to a radiation-sensitive resin composition suitable as a resist for producing highly integrated circuits responsive to radiation such as synchrotron radiation and proton 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 using a positive resist, when a latent image formed by exposure is developed with a developing solution composed of an alkaline aqueous solution, the exposed portion contacts the wafer (the bottom of the pattern). It needs to be developed quickly.

[0003]

However, in the case of the conventional positive resist, if the distance between the resist patterns to be formed is 0.8 μm or less, development residue called scum tends to occur, and there is a problem in developability. Was. 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 effectively suppress the occurrence of scum during the formation of a resist pattern, while being excellent in developability, high sensitivity, and heat resistance, suitable as a positive resist excellent in residual film ratio. An object of the present invention is to provide a radiation-sensitive resin composition.

[0004]

According to the present invention SUMMARY OF], and shall achieve the above object, (A) an alkali-soluble resin, (B) a formula (1):

[0005]

Embedded image [Wherein, p is an integer of 0 or 1. And (C) a general formula (2):

[0006]

Embedded image Wherein p is an integer of 0 or 1, and D is independently hydrogen
An atom or an organic group having a 1,2-quinonediazide group
Yes, provided that part or all of D is 1,2-quinonedia
An organic group having a zide group].
A radiation-sensitive resin composition containing a diazide compound is provided. The radiation-sensitive resin composition of the present invention can be suitably used as a positive resist having high sensitivity, excellent heat resistance, and excellent residual film properties, while effectively suppressing the occurrence of scum and having excellent developability.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION (A) Alkali-Soluble Resin
Examples of the “resin (A)” include a novolak resin, a resole resin, polyvinyl phenol or a derivative thereof, a styrene-maleic anhydride copolymer, polyvinyl hydroxybenzoate, and a carboxyl group-containing methacrylic acid-based resin. In particular, a novolak resin is preferably used. Among the novolak resins, the following general formula (3):

[0008]

Embedded image (Wherein, n represents an integer of 1 to 3) is particularly preferably obtained by polycondensing a phenol and an aldehyde represented by the following formula:

The preferred 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 can be mentioned, among which o-cresol, m-cresol, p-cresol, 2,5-xylenol, 3,5-xylenol and 2,3,5-trimethylphenol are preferable. .
These phenols are used alone or in combination of two or more.

The aldehydes to be polycondensed with the phenols include, for example, formaldehyde, trioxane, balaformaldehyde, 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 0.7 to 1 mol of the phenol.
It is preferably 3 mol, more preferably 0.8 to 1.5 mol.

For the polycondensation of phenols and aldehydes, an acidic catalyst is usually used. Examples of the acidic catalyst include inorganic acids such as hydrochloric acid, nitric acid, and sulfuric acid, and organic acids such as formic acid, oxalic acid, and acetic acid. The use amount of these acidic catalysts is usually 1 × 10
^{−5 to} 5 × 10 ⁻¹ mol. In the polycondensation reaction, water is usually used as a reaction medium, but when the phenol used for the polycondensation does not dissolve in the aqueous solution of the aldehyde and becomes a heterogeneous system from the beginning of the reaction, hydrophilicity is used as the reaction medium. 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 these reaction media used is usually 10
20 to 1000 parts by weight per 0 parts by weight. The temperature of the polycondensation can be appropriately adjusted according to the reactivity of the reaction raw materials, but is usually 10 to 200 ° C., preferably 70 ° C.
~ 130 ° C. As the method of the polycondensation reaction, 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, should be adopted. Can be. After the completion of the polycondensation reaction, 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,
Volatile components are distilled off under reduced pressure, for example, at about 20 to 50 mmHg, and the obtained resin (A) is recovered.

The resin (A) used in the present invention preferably has a weight average molecular weight in terms of polystyrene (hereinafter referred to as "Mw") of 2,000 to 20,000, and 3,000 to 15,000. It is more preferred that there be. When Mw exceeds 20,000, it may be difficult to uniformly apply the composition of the present invention to a wafer,
Further, the developability and sensitivity tend to decrease, and when Mw is less than 2,000, the heat resistance tends 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 dissolved in water, n-hexane, and n-hexane. What is necessary is just to mix a poor solvent such as heptane, and then separate the resin solution layer to be deposited, and recover the high molecular weight resin (A).

(B) Polyhydroxy Compound The composition of the present invention contains, as a component (B), a polyhydroxy compound represented by the general formula (1) (hereinafter, referred to as “polyhydroxy compound (B)”). Be blended.

Specific examples of the polyhydroxy compound (B) represented by the general formula (1) include the following. 1,1-bis (4-hydroxyphenyl) -1-phenylethane

[0015]

Embedded image

1,1,1-tris (4-hydroxyphenyl) ethane

Embedded image

The above-mentioned polyhydroxy compound (B) represented by the general formula (1) is exemplified by, for example, West German Patent No. 1,
As disclosed in US Pat. No. 930,333, it is obtained by condensing a substituted or unsubstituted phenol with a substituted or unsubstituted acetophenone in the presence of an acidic catalyst. The reaction product is generally obtained as an oily mixture, but can also be purified by means such as recrystallization.

In the present invention, the polyhydroxy compound (B) is used in an amount of 0.1 to 100 parts by weight of the resin (A).
It is preferable to use 5 to 90 parts by weight, particularly 2 to 50 parts by weight.

(C) 1,2-quinonediazide compound 1,2-quinonediazide used in the composition of the present invention
The compound has the general formula (2):

[0020]

Embedded image [In the formula, p is an integer of 0 or 1, D is independently a hydrogen atom or an organic group having a 1,2-quinonediazide group, provided that part or all of D has a 1,2-quinonediazide group. An organic group) (hereinafter, referred to as an organic group).
"Quinonediazide compound (C) "). here,
Examples of the organic group having a 1,2-quinonediazide group include a 1,2-benzoquinonediazide-4-sulfonyl group, a 1,2-naphthoquinonediazide-5-sulfonyl group, and a 1,2-naphthoquinonediazide-4-sulfonyl group. , 2,1-naphthoquinonediazide-5-sulfonyl group, 2,1-naphthoquinonediazide-4-sulfonyl group and the like, among which a 1,2-benzoquinonediazide-4-sulfonyl group and 1,2-naphthoquinonediazide −
A 5-sulfonyl group is preferred.

The quinonediazide compound (C) is a polyhydroxy compound (B) represented by the above-mentioned general formula (1) in which some or all of the hydroxyl hydrogen atoms are an organic group containing a 1,2-quinonediazide group. Is a compound substituted with
For example, the polyhydroxy compound (B) and 1,2-naphthoquinonediazide-4-sulfonyl chloride, 1,2-
It can be obtained by an esterification reaction with 1,2-quinonediazidosulfonyl halide such as naphthoquinonediazide-5-sulfonyl chloride. Here, in the present invention, in order to sufficiently exhibit the function for improving the developability of the quinonediazide compound (C) , the average condensation rate of the esterification reaction [(the number of esterified phenolic hydroxyl groups / reaction Number of phenolic hydroxyl groups before) x 100]
(Hereinafter, referred to as “average condensation rate”) is usually 100% or less, preferably 50% or less, and more preferably 30% or less.

In the present invention, the quinonediazide compound (C) is used in an amount of 0.5 to 0.5 parts by weight per 100 parts by weight of the resin (A).
It is preferred to use 90 parts by weight, especially 2 to 50 parts by weight. The composition of the present invention contains the quinonediazide compound (C) as an essential component.
Including a 2-quinonediazide compound as an optional component
it can. Examples of quinone diazide compound other than the quinonediazide compound (C), -1,2- 2,3,4- trihydroxy benzophenone-naphthoquinonediazide-4-
Sulfonate, 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate, 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-
Sulfonic acid ester, 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-
5-sulfonic acid ester, 3'-methoxy-2,3,
4,4'-tetrahydroxybenzophenone-1,2-
Naphthoquinonediazide-4-sulfonic acid ester, 3 '
Polyhydroxybenzophenone such as methoxy-2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester
1,2-naphthoquinonediazidosulfonic acid ester, and a hydrogen atom of a hydroxyl group of a novolak resin or a resol resin (hereinafter, these are simply referred to as “resin (B)”),
For example, 1,2-quinonediazide such as 1,2-naphthoquinonediazido-4-sulfonyl group, 1,2-naphthoquinonediazide-5-sulfonyl group at a ratio of 20 to 100 mol%, preferably 40 to 100 mol% per hydrogen atom. Examples thereof include 1,2-quinonediazidosulfonic acid esters substituted with a sulfonyl group.

The resin (B) is obtained by condensation 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-phenol. Naphthol, 2-naphthol and the like can be used. As the aldehydes, those used in the formation of the resin (A) can be used. The amount of the aldehyde used is preferably 0.1 to 3 mol, more preferably 0.2 to 1.5 mol, per 1 mol of the phenol. In this condensation, an alkaline catalyst can be used in addition to the acidic catalyst used for the synthesis of the resin (A). The Mw of the resin (B) is usually preferably 10,000 or less, more preferably 200 to 2,000, from the viewpoint of ease of esterification reaction and solubility in a solvent. Particularly preferably, it is 300 to 1,000. Examples of the 1,2-quinonediazidosulfonic acid ester of the resin (B) include phenol / formaldehyde condensed novolak resin, m-cresol / formaldehyde condensed novolak resin, p-cresol / formaldehyde condensed novolak resin, o-cresol /
1,2-benzoquinonediazide-4-sulfonic acid ester, 1,2-naphthoquinonediazide-4-sulfonic acid ester or 1,2-naphtho, such as formaldehyde condensed novolak resin, m-cresol / p-cresol / formaldehyde condensed novolak resin Quinonediazide-5
-Sulfonic acid esters.

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).
Although it is parts by weight, the total amount of the 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.

The sensitizer is compounded for improving the sensitivity of the composition.
For example, 2H-pyridone (3,2-b) -1,4-oxazin-3 (4H) -ones and 10H-pyridone (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 is usually 50 parts by weight or less based on 100 parts by weight of the resin (A).

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, EFTOP EF301, EF303, EF352 (trade names,
Shin-Akita Chemical Co., Ltd.), Megafax F171, F17
2, F173 (trade name, manufactured by Dainippon Ink), Florado FC430, FC431 (trade name, manufactured by Sumitomo 3M Limited), Asahi Guard AG710, Surflon S-38
2, 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. 9
5 (trade name, manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.).
The content of these surfactants is 100% of the solid content of the composition.
It is usually 2 parts by weight or less per part by weight.

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), polyhydroxy compound (B), quinonediazide compound (C) and, if necessary, various compounding agents, Concentration 20
Dissolved in a solvent so as to have a pore size of 0.2 to 40% by weight.
It is prepared by filtering through a filter of about 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, ethyl acetate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3- Ethyl ethoxypropionate,
Methyl 3-ethoxypropionate can be used. These organic solvents are used alone or in combination of two or more. Further, N-methylformamide,
N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, benzylethylether, dihexylether, acetonylacetone, isophorone, caproic acid, caprylic Add a high boiling point solvent such as 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. Can also.

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 photosensitive layer, and a predetermined mask pattern is formed. The pattern is formed by irradiating the photosensitive layer with radiation 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 exposed, and then heated at 70 to 140 ° C., and thereafter, The effect of the present invention can be further improved by developing.

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)-
7-undecene, 1,5-diazabicyclo- (4,3,
0) An alkaline aqueous solution obtained by dissolving an alkaline compound such as 5-nonane at a concentration of usually 1 to 10% by weight, preferably 2 to 5% 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, G
The measurement was carried out by Kelper permeation chromatography using monodisperse polystyrene as a standard under the analysis conditions of 1.5 Hg / min, elution solvent of tetrahydrofuran and column temperature of 40 ° C. using one 3000H _{6 and} one G4000H ₆ ).

Sensitivity: The exposure time is changed with a Nikon-NSR-1505G4D reduction projection exposure machine (numerical aperture of lens: 0.45).
Exposure is performed using g-line having a wavelength of 436 nm, or the exposure time is changed using a Nikon-NSR-1505i6A reduction projection exposure machine (numerical aperture of lens: 0.45), and i-line having a wavelength of 365 nm is used. Exposure is performed, and then development is performed using a 2.4% by weight aqueous solution of tetramethylammonium hydroxide as a developing solution at 25 ° C. for 60 seconds, rinsing with water, and drying to form a resist pattern on a wafer. Exposure time for forming a line and space pattern (1LIS) with a width of 1: 1
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 after development of a 0.6 μm resist pattern were measured.
When 0.85 ≦ B / A ≦ 1, the pattern shape was determined to be good. However, in the case where the pattern shape has a skirt or a reverse tapered shape, it is determined that the pattern is defective even if B / A is within the above range.

<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 (0,0) of 2,3,5-trimethylphenol. 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⁾ ), The flask was immersed in an oil bath, polycondensation was performed for 30 minutes with stirring while maintaining the internal temperature at 100 ° C., and then 17.5 g (0.16 mol) of m-cresol and 2,3 , 5-trimethylphenol (40.0 g, 0.29 mol) was added, and polycondensation was further carried out for 40 minutes. Then, the oil bath temperature was raised to 180 ° C., and simultaneously the pressure in the flask was reduced to 30 to 50 mmHg. Water, oxalic acid, unreacted formaldehyde, m-cresol, p-cresol and 2,3,5-trimethylphenol Was removed.
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 this resin solution were added and stirred. And left. 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 converted into a resin (A
2).

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), water (52.6 g) and dioxane (182 g) were charged, and the autoclave was immersed in an oil bath.
The mixture was condensed for 6 hours while stirring at a temperature of ℃ C. After the reaction, the temperature was returned to room temperature, and the contents were taken out into a beaker. After separating into two layers in this beaker, take out the lower layer,
Concentrated, dehydrated and dried to recover 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 wt% aqueous formaldehyde solution 56.9 g (formaldehyde: 0.70 mol) and oxalic acid dihydrate 0.083 g (6.59 × 10 ⁻⁴ mol) were charged, and the flask was placed in an oil bath. After stirring for polycondensation for 30 minutes while maintaining the internal temperature at 100 ° C., 51.9 g (0.48 mol) of m-cresol and 9.77 g (0.08 mol) of 3,5-dimethylphenol were further added. ) Is continuously charged into the flask as the reaction proceeds.
The polycondensation was performed for 5 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, 26.0 g (0.24 mol) of m-cresol 78.2 g (0.64 mol) of 3,5-xylenol 37% by weight aqueous solution of formaldehyde 14.6 g (formaldehyde: 1.80 mol) and oxalic acid dihydrate 0.164 g (1.30 × 10 ⁻³ mol) were charged, the flask was immersed in an oil bath, and the internal temperature was maintained at 100 ° C. After performing polycondensation for 30 minutes while stirring, 104 g (0.96 mol) of m-cresol and 20.0 g (0.16 mol) of 3,5-xylenol were further added, and the mixture was further reacted for 70 minutes. Then, the oil bath temperature was increased to 180 ° C., and at the same time, the pressure in the flask was increased to 30 ° C.
The pressure was reduced to ４０40 mmHg to remove water, oxalic acid, unreacted formaldehyde, m-cresol and 3,5-xylenol. Next, the resin was recovered in the same manner as in Synthesis Example 1. This resin is referred to as resin (A5).

Synthesis Example 6 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 weight 154 g (formaldehyde: 1.90 mol) and 1.82 g (0.014 mol) of oxalic acid dihydrate were charged into the flask, and the flask was immersed in an oil bath and stirred while maintaining the internal temperature at 100 ° C. Polycondensation was performed for 90 minutes, and then 23.8 g (0.22 mol) of m-cresol and 97.6 g (0.72 mol) of 2,3,5-trimethylphenol were further added, and polycondensation was further performed for 60 minutes. Then, the oil bath temperature was raised to 180 ° C., and simultaneously the pressure in the flask was reduced to 30 to 40 mmHg, and water, oxalic acid, unreacted formaldehyde, m-cresol and 2,3,5
-The trimethylphenol was removed. Next, Synthesis Example 1
The resin was recovered in the same manner as described above. This resin is converted into a resin (A
6).

Synthesis Example 7 Resin (A6) was dissolved in ethyl cellosolve acetate so as to have a solid content of 20% by weight, and 1.8 times methanol and an equal amount of water were added to the weight of the resin solution. And left to stir. After being separated into two layers by leaving to stand, the resin solution layer (lower layer) is taken out, concentrated,
After dehydration and drying, the resin was recovered. This resin is referred to as resin (A7).

<Abbreviation of polyhydroxy compound (B)> Hereinafter, 1,1,1-tris (4-hydroxyphenyl) ethane is referred to as compound (B1) and 1,1-bis (4-hydroxyphenyl). ) -1-Phenylethane is abbreviated as compound (B2).

<Synthesis of quinonediazide compound (C) > Synthesis Example 8 30.6 g (0.10 mol) of 1,2-naphtho compound (B1) was placed in a flask equipped with a stirrer, a dropping funnel and a thermometer under light shielding. 80.6 g (0.30 mol) of quinonediazide-4-sulfonic acid chloride and 100 g of dioxane were charged and dissolved with stirring. Next, the flask was immersed in a water bath controlled at 30 ° C.
When the temperature became constant at 3 ° C., 33.3 g (0.33 mol) of triethylamine was slowly dropped into the 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 dilute hydrochloric acid to cause precipitation, and then the precipitate was collected by filtration at 40 ° C.
The product was dried all day and night with a heating vacuum dryer controlled by the above-mentioned method to obtain a compound. The obtained compound is called compound ( C1 ).

Synthesis Example 9 Compound (B1) 30.6 g (0.10 mol) 1,2-naphthoquinonediazido-5-sulfonic acid chloride 67.1 g (0.25 mol) and triethylamine 27.8 g (0. Compound ( C2 ) was obtained in the same manner as in Synthesis Example 8 except that 275 mol) was used.

Synthesis Example 10 29.0 g (0.10 mol) of compound (B2) 53.7 g (0.20 mol) of 1,2-naphthoquinonediazide-5-sulfonic acid chloride and 20.7 g (0.20 mol) of triethylamine ) Was used in the same manner as in Synthesis Example 8 to obtain a compound ( C3 ).

Examples 1 to 3 and Comparative Example 1 A resin (A), a polyhydroxy compound (B), a quinonediazide compound (C) and a solvent were mixed to form a uniform solution, which was then passed through a membrane filter having a pore size of 0.2 μm. After filtration, a solution of the composition of the present invention was prepared. The obtained solution is applied on a silicon wafer having a silicon oxide film using a spinner, and then applied on a hot plate.
Pre-baked at 2 ° C. for 2 minutes to form a resist film having a thickness of 1.2 μm, and a wavelength of 436 as described above via a reticle.
Exposure using nm (g-line) or 365 nm (i-line), development, rinsing, and drying, and evaluation of the resist film for sensitivity, resolution, residual film ratio, developability, heat resistance, and pattern shape Was done. The results are shown in Table 1 together with the used resins and the like. In addition, Examples 1 and 2 irradiated g-line, and Example 3 and Comparative Example 1 irradiated i-line.

[0053]

[Table 1]

[0054]

[Table 2]

Note: Each addition amount is shown in parts by weight. Note: The quinonediazide compounds (I) to (II)
The following: (I) ; 1 mol of 2,3,4,4'-tetrahydroxybenzophenone and 1,2-naphthoquinonediazide-5
Condensate with 3.6 mol of sulfonic chloride. (II) ; 1 mol of 2,3,4,4'-tetrahydroxybenzophenone and 1,2-naphthoquinonediazide-5
-Condensates with 4.0 moles of sulfonic chloride. Note: The types of solvents are as follows. (Α); ethyl cellosolve acetate. (Β); ethyl 2-hydroxypropionate.

[0056]

EFFECT OF THE INVENTION The radiation-sensitive resin composition of the present invention can be used as a positive resist which is highly sensitive, excellent in heat resistance and excellent in residual film properties, while effectively suppressing the occurrence of scum and having excellent developability. It can be suitably used.

Continuation of front page (72) Inventor Chozo Okuda 2-11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd. (56) References JP-A-3-200254 (JP, A) JP-A-3-158856 (JP, A) JP-A-4-174438 (JP, A) JP-A-3-228059 (JP, A) JP-A-3-142468 (JP, A) JP-A-1-189644 (JP, A) ( 58) Fields surveyed (Int.Cl. ⁶ , DB name) G03F ^7/ 00-7/42

Claims (1)

(57) [Claims] 1. A (A) an alkali-soluble resin, (B) a formula (1): ## STR1 ## [Wherein, p is an integer of 0 or 1. And (C) a general formula (2): [In the formula, p is an integer of 0 or 1, D is independently a hydrogen atom or an organic group having a 1,2-quinonediazide group, provided that part or all of D has a 1,2-quinonediazide group. A radiation-sensitive resin composition containing a 1,2-quinonediazide compound represented by the following formula: