JP2921519B2 - 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 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 type resist, when the interval between the resist patterns to be formed becomes 0.8 μm or less, a development residue called a scum tends to occur, which causes a problem in developability. there were. 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]

[Means for Solving the Problems] According to the present invention,
(A) The weight average molecular weight in terms of polystyrene is 2,000
(B) General formula (1):

[0005]

Embedded image

Wherein p is an integer of 0 or 1, and D is
A hydrogen atom or an organic group having a 1,2-quinonediazide group, provided that part or all of D is an organic group having a 1,2-quinonediazide group] , and ( C) General formula (3):

Embedded image [Where p is an integer of 0 or 1]
A radiation-sensitive resin composition containing a hydroxy compound is provided.

[0007] The radiation-sensitive resin composition of the present invention effectively suppresses the generation of scum and has excellent developability.
It can be suitably used as a positive resist having high sensitivity and excellent heat resistance and residual film properties.

(A) Alkali-soluble resin The alkali-soluble resin used in the present invention (hereinafter referred to as “the 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 (2):

[0009]

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, baraformaldehyde, 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 the phenols used for the polycondensation do not dissolve in the aqueous solution of the aldehyde,
When a heterogeneous system is obtained from the beginning of the reaction, a hydrophilic solvent can be used as a reaction medium. Examples of these hydrophilic solvents include alcohols such as methanol, ethanol, propanol, and butanol; and cyclic ethers such as tetrahydrofuran and dioxane. The use amount of these reaction media is usually 20 to 1000 parts by weight per 100 parts by weight of the reaction raw materials.

[0013] The temperature of the polycondensation can be appropriately adjusted according to the reactivity of the reaction raw materials.
° C, preferably 70 to 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 existing in the system, the temperature of the reaction system is generally set to 130 to 2
The temperature is raised to 30 ° C., and 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 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 3,000.
It is preferably from 15,000 to 15,000. Mw is 20,0
If it exceeds 00, it may be difficult to uniformly apply the composition of the present invention to a wafer, and furthermore, the developability and sensitivity tend to decrease. There is a tendency for the properties to decrease. Note that M
In order to obtain a resin (A) having a high w, the resin obtained above is dissolved in a good solvent such as ethyl cellosolve acetate, dioxane, methanol, or ethyl acetate, and then dissolved in water, n
A poor solvent such as hexane and n-heptane may be mixed, and then a resin solution layer to be separated may be separated to recover a high molecular weight resin (A).

(B) 1,2-quinonediazide compound The composition of the present invention contains, as the component (B), the compound represented by the above-mentioned general formula (1):

[0016]

Embedded image 1,2-quinonediazide compound represented by
At least one of “quinonediazide compounds (B)”).

In the general formula (1), D in the group OD represents a hydrogen atom or an organic group having a 1,2-quinonediazide group (provided that part or all of D is an organic group having a 1,2-quinonediazide group). But examples of such organic groups include 1,2-benzoquinonediazide-4
-Sulfonyl group, 1,2-naphthoquinonediazide-5
A sulfonyl group, a 1,2-naphthoquinonediazido-4-sulfonyl group, a 2,1-naphthoquinonediazide-5-sulfonyl group, a 2,1-naphthoquinonediazide-4-sulfonyl group, and the like. A naphthoquinonediazide-4-sulfonyl group, a 1,2-naphthoquinonediazide-5-sulfonyl group and the like are preferable. The quinonediazide compound (B) has the general formula (3):

[0018]

Embedded image

[Where p is an integer of 0 or 1], wherein some or all of the hydrogen atoms of the hydroxyl groups in the polyhydroxy compound are substituted with an organic group containing a 1,2-quinonediazide group. A compound obtained by an esterification reaction of the polyhydroxy compound with a 1,2-quinonediazidosulfonyl halide such as 1,2-naphthoquinonediazide-4-sulfonyl chloride and 1,2-naphthoquinonediazide-5-sulfonylchloride. Can be. Here, in the present invention, in order to sufficiently exhibit the function for improving the developability of the quinonediazide compound (B), the average condensation rate of the esterification reaction [(the number of esterified phenolic hydroxyl groups / reaction (The number of previous phenolic hydroxyl groups) × 100] (hereinafter referred to as “average condensation rate”) is usually 100% or less, preferably 50% or less, and more preferably 30% or less. Specific examples of the polyhydroxy compound used in the above esterification reaction include:
The following can be mentioned. 1,1-bis (4-
(Hydroxyphenyl) -1-phenylethane

[0020]

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

[0021]

Embedded image As disclosed in, for example, West German Patent No. 1,930,333, a polyhydroxy compound represented by the above-mentioned general formula (3) may be substituted or unsubstituted phenols and substituted or unsubstituted acetophenones. Is condensed 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. The composition of the present invention includes the quinonediazide compound (B) described above.
Is preferably used at a ratio of 0.5 to 90 parts by weight, particularly 2 to 50 parts by weight, per 100 parts by weight of the resin (A).

[0022] (C) a polyhydroxy compound composition of the present invention, prior Symbol polyhydroxy compound represented by the general formula (3) (hereinafter, "polyhydroxy compound (C)" hereinafter) containing. The compounding amount of the polyhydroxy compound (C) is 0.5 to 100 parts by weight of the resin (A).
The proportion is preferably from 90 to 90 parts by weight, particularly preferably from 2 to 50 parts by weight.

Another 1,2-quinonediazide compound In the present invention, a 1,2-quinonediazide compound other than the quinonediazide compound (B) of the general formula (1) can be blended. Examples of such a 1,2-quinonediazide compound include 1,2-benzoquinonediazide-4-sulfonic acid ester, 1,2-naphthoquinonediazide-4-sulfonic acid ester, and 1,2-naphthoquinonediazide-5-sulfonic acid. Esters and the like.

Specifically, 2,3,4-trihydroxybenzophenone-1,2-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,
1,1,1-tris (4-hydroxyphenyl) ethane-1,2-naphthoquinonediazide-4-sulfonic acid ester, 1,1,1-tris (4-hydroxyphenyl)
Hydrogen atoms of hydroxyl groups of ethane-1,2-naphthoquinonediazide-5-sulfonic acid ester and a novolak resin or a resol resin (hereinafter simply referred to as “resin (B)”), for example, 20 to 100 mol% per hydrogen atom 1,2-naphthoquinonediazide-4-sulfonyl group, preferably 1,2-naphthoquinonediazido-5-sulfonyl group, etc. Quinonediazidesulfonic acid esters.

The resin (B) is obtained by condensation of a phenol and an aldehyde. Examples of the phenol include phenol, 1-phenol and phenol used in the synthesis of the resin (A). Naphthol, 2-naphthol and the like can be used. As the aldehydes, those used in the synthesis 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 10,000, in view of the easiness of the esterification reaction and the solubility in a solvent.
It is preferably 0 or less, more preferably 200 to 2,000. 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 / formaldehyde condensed novolak resin,
1,2-benzoquinonediazide such as m-cresol / p-cresol / formaldehyde condensed novolak resin
Examples thereof include 4-sulfonic acid ester, 1,2-naphthoquinonediazide-4-sulfonic acid ester and 1,2-naphthoquinonediazide-5-sulfonic 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).
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 a sensitizer, a surfactant and a dissolution promoter can be compounded. The sensitizer is compounded for improving the sensitivity of the composition. Examples of such a sensitizer include 2H-pyrido- (3,2-b) -1,4-oxazine-3. (4H)-
Ons, 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 depends on the resin (A)
It is usually 50 parts by weight or less for 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, 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) polymer polyflow No. 75 , No.95
(Trade name, manufactured by Kyoeisha Yushi Kagaku Kogyo KK). 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 a latent image in a radiation-irradiated portion and reducing the influence of halation at the time of radiation, 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.

The compositions of the preparation of the composition and patterning the present invention, the above-mentioned resin (A), the key Nonjiaji <br/> de compound (B) and the polyhydroxy compound (C), and blended as required other 1,2-being
It is prepared by dissolving the quinonediazide compound and various compounding agents in a solvent, for example, so that the solid content concentration is 20 to 40% by weight, and filtering the solution with a filter having a pore size of about 0.2 μm.

The solvent used at this time includes, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol methyl ether acetate, propylene glycol propyl Ether acetate, toluene, xylene, methyl ethyl ketone, cyclohexanone, ethyl 2-hydroxypropionate, 2
Ethyl-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 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 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.

[0035]

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.

Mw: Toyo Soda GPC column (G2
000H ₆ 2 pieces, G3000H ₆ 1 piece, G4000H ₆
The measurement was carried out by gel permeation chromatography using monodispersed polystyrene as a standard under the analysis conditions of a flow rate of 1.5 ml / min, an elution solvent of tetrahydrofuran, and a column temperature of 40 ° C.

Sensitivity: Nikon-NSR-1505G4
The exposure time is changed using a D reduction projection exposure machine (numerical aperture of the lens; 0.45) and exposure is performed using g-line having a wavelength of 436 nm, or a Nikon-NSR-1505i6A reduction projection exposure machine (lens Exposure time is changed at a numerical aperture of 0.45), exposure is performed using i-ray having a wavelength of 365 nm, and then development is performed at 25 ° C. for 60 seconds using a 2.4% by weight aqueous solution of tetramethylammonium hydroxide as a developing solution. Then, rinse with water and dry to form a resist pattern on the wafer, and an exposure time for forming a 0.6 μm line-and-space pattern (1 LIS) in a one-to-one width (hereinafter referred to as “optimum”). Exposure time ").

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

Residual film ratio: The thickness of the pattern after development at the optimal 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 the rectangular cross section of the 0.6 μm resist pattern after development were measured, and 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 an inverted taper 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 In a flask equipped with a stirrer, a cooling tube and a thermometer, 67.6 g (0.63 mol) of m-cresol 10.0 g of 2,3,5-trimethylphenol (0.073 mol) p-cresol 31.8 g (0.29 mol) 37 wt% aqueous formaldehyde solution 107.1 g (formaldehyde: 1.32 mol) and oxalic acid dihydrate 1.33 g (1.06 × 10 3) ^-2 mol), the flask was immersed in an oil bath, polycondensation was carried out for 30 minutes while maintaining the internal temperature at 100 ° C. and stirring, 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 carried out for further 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, and water, oxalic acid, unreacted formaldehyde, m-cresol, p-
Cresol and 2,3,5-trimethylphenol were 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 the 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, m-cresol 26.0 g (0.24 mol) 3,5-xylenol 78.2 g (0.64 mol) 37% by weight aqueous formaldehyde solution 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 polymerization for 30 minutes with stirring, 104 g (0.96 mol) of m-cresol and 20.0 g (0.16 mol) of 5-xylenol were further added and reacted for 70 minutes. Next, the oil bath temperature was raised to 180 ° C., and simultaneously the pressure in the flask was reduced to 30 to 40 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. Resin (A5)
That.

Synthesis Example 6 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 3,5-xylenol 37% by weight aqueous solution of formaldehyde 154 g (formaldehyde: 1.90 mol) and oxalic acid dihydrate 1.82 g (0.014 mol) were charged, the flask was immersed in an oil bath, and the mixture was stirred for 90 minutes while maintaining the internal temperature at 100 ° C. After polycondensation, 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 to remove water, oxalic acid, unreacted formaldehyde, m-cresol and 2,3,5-trimethylphenol. Next, the resin was recovered in the same manner as in Synthesis Example 1. This resin is referred to as resin (A6).

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).

<Synthesis of Resin B> Synthesis Example 8 In a flask similar to that used in Synthesis Example 1, 108.0 g (1.00 mol) of m-cresol 24.3 g of a 37% by weight aqueous solution of formaldehyde (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 performed for 40 minutes while maintaining the internal temperature at 100 ° C. Next, the resin was recovered in the same manner as in the synthesis of the resin (A1). This resin is referred to as resin (B1).

Synthesis Example 9 In a flask similar to that used in Synthesis Example 1, m-cresol 64.9 g (0.06 mol) p-cresol 43.3 g (0.40 mol) 37% by weight aqueous formaldehyde solution 3 g (formaldehyde: 0.25 mol) and oxalic acid dihydrate 0.30 g (2.40 × 10 ⁻³ mol) were charged, the flask was immersed in an oil bath, and the internal temperature was kept at 100 ° C. for 30 minutes. Polycondensation was performed. Next, Synthesis Example 1
The resin was recovered in the same manner as described above. The resin (B)
2).

<Abbreviation of polyhydroxy compound (C)> Hereinafter, 1,1-tris (4-hydroxyphenyl) ethane is referred to as compound (C1) and 1,1-bis (4-hydroxyphenyl) -1 -Phenylethane is abbreviated as compound (C2).

<Synthesis of Quinonediazide Compound (B)> Synthesis Example 10 Under a light shielding condition, 30.6 g (0.10 mol) of 1,2-naphtho compound (C1) was placed in a flask equipped with a stirrer, a dropping funnel and a thermometer. 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., and when the internal temperature became constant at 30 ° C., 33.3 g (0.33 mol) of triethylamine was added to the solution.
Was slowly dropped using a dropping funnel such 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 (B1).

Synthesis Example 11 Compound (C1) 30.6 g (0.10 mol) 1,2-naphthoquinonediazide-5-sulfonic acid chloride 67.1 g (0.25 mol) and triethylamine 27.8 g (0.275 mol) ) Was used in the same manner as in Synthesis Example 10 to obtain a compound (B2).

Synthesis Example 12 29.0 g (0.10 mol) of compound (C2) 53.7 g (0.20 mol) of 1,2-naphthoquinonediazide-5-sulfonic acid chloride and 20.7 g (0.20 mol) of triethylamine Compound (B3) was obtained in the same manner as in Synthesis Example 10 except that) was used.

<Synthesis of Another 1,2-Quinone Diazide Compound> Synthesis Example 13 Resin (B1) 10.0 g 1 , 2-naphthoquinone diazide-4-sulfonic acid chloride 13.9 g and triethylamine 5.75 g were used. A quinonediazide compound (I) was obtained in the same manner as in Synthesis Example 10.

Synthesis Example 14 The procedure of Synthesis Example 10 was repeated except that 10.0 g (0.10 mol) of compound (B2), 16.6 g of 1,2-naphthoquinonediazide-5-sulfonic acid chloride and 6.86 g of triethylamine were used. As a result, a quinonediazide compound (II) was obtained.

[0058] Examples 1-3, Comparative Examples 1-3 resin (A), the quinonediazide compound (B), Po polyhydroxy compound (C) and other 1,2-quinonediazide compound, and a solvent as shown in Table 1 To give a homogeneous solution, which 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 obtained solution is applied on a silicon wafer having a silicon oxide film using a spinner, and then applied on a hot plate.
Pre-baking was performed at 0 ° C. for 2 minutes to form a resist film having a thickness of 1.2 μm.
After exposure using 6 nm (g-line) or 365 nm (i-line), development, rinsing and drying, evaluation of the resist film for sensitivity, resolution, residual film ratio, developability, heat resistance and pattern shape Was done. Table 2 shows the results. In addition, Examples 1 and 2 and Comparative Examples 1 and 2 irradiated g-line, and Example 3 and Comparative Example 3 irradiated i-line.

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[Table 1]

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[Table 2]Note: Each addition amount is shown in parts by weight. Note: Quinonediazide compound (III) ~(V)
Is: (III); 2,3,4-trihydroxybenzopheno
1 mole of 1,2-naphthoquinonediazide-5-sul
Condensate with 3.0 mol of phonic chloride. (IV); 2,3,4,4'-tetrahydroxybenzo
1 mol of phenone and 1,2-naphthoquinonediazide-5
-Condensates with 3.6 mol of sulfonic chloride. (V); 2,3,4,4'-tetrahydroxybenzofu
1 mol of enone and 1,2-naphthoquinonediazide-5
Condensate with 4.0 mol of sulfonic acid chloride. Note: The types of solvents are as follows. (Α); ethyl cellosolve acetate. (Β); ethyl 2-hydroxypropionate.note : Compound (*); m-cresol 108.0 g
(1.00 mol), 37% by weight aqueous formaldehyde solution
20.3 g (formaldehyde: 0.25 mol) and
Oxalic acid dihydrate 0.30 g (2.40 × 10^-3Mo
), Keep the internal temperature at 100 ° C, and condense for 30 minutes.
Otherwise, an alkali-soluble novola synthesized in the same manner as in Synthesis Example 1
Resin (Mw = 520).

[0061]

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 the front page (72) Inventor Chozo Okuda 2--11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd. (56) References JP-A-4-211255 (JP, A) JP-A-4-29242 (JP, A) JP-A-3-158856 (JP, A) JP-A-1-189644 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) G03F 7/00-7 / 42

Claims (2)

(57) [Claims] (A) an alkali-soluble resin having a weight average molecular weight of 2,000 to 20,000 in terms of polystyrene; (B) a general formula (1): [In the formula, p is an integer of 0 or 1, D is a hydrogen atom or an organic group having a 1,2-quinonediazide group, provided that part or all of D is 1,2 - quinonediazide. 1,2-quinonediazide compound represented by an organic group] with a group, and (C) the general formula (3): ## STR2 ## [Where p is an integer of 0 or 1]
A radiation-sensitive resin composition containing a hydroxy compound . 2. A novolak resin obtained by subjecting the alkali-soluble resin (A) to polycondensation of phenols and aldehydes in an amount of 0.7 to 3 moles of aldehydes per mole of phenols. The radiation-sensitive resin composition according to claim 1, wherein