JP3052960B2 - 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, since it is important that the resist pattern does not change during the etching, it is necessary to have good heat resistance. Further, as the degree of integration increases, it is required to improve the throughput at the time of fabricating an integrated circuit, 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, an alkali-soluble resin (hereinafter referred to as "resin A") having the following general formula (1):

[0005]

Embedded image Wherein, X ¹ to X ¹³ is a hydrogen atom, an alkyl group, either alkoxy groups or hydroxyl groups, and X ¹
Shall contain at least one hydroxyl group in each combination of ~X ^5, X ⁶ ~X ⁸ and ^{X 9 ~X 13, Y 1 ~Y} 4 represents a hydrogen atom or an alkyl radical, R ¹ represents a group represented by —COOR ² (R ² represents a hydrogen atom, an alkyl group, or an aryl group) (hereinafter, referred to as compound (A)); A radiation-sensitive resin composition comprising a 1,2-quinonediazide compound is provided.

Alkali-soluble resin The "resin (A)" used in the present invention includes, for example, a novolak resin, a resol resin, polyvinyl phenol or a derivative thereof, a styrene-maleic anhydride copolymer, polyvinyl hydroxybenzoate, and a carboxyl group-containing ( A (meth) acrylic acid-based resin can be used, and a novolak resin is particularly preferably used. Among the novolak resins, those obtained by polycondensing phenols and aldehydes represented by the following formula (2) are particularly preferable.

[0007]

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, m-cresol / 2,3,5-trimethylphenol / p-cresol = 95/5/0 to 30/70/65 (molar ratio).

The aldehydes to be polycondensed with the phenols include, for example, formaldehyde, trioxane, paraformaldehyde, benzaldehyde, acetaldehyde, propylaldehyde, phenylacetaldehyde, α-phenylpropylaldehyde, β-phenylpropylaldehyde, o-hydroxybenzaldehyde , M-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-chlorobenzaldehyde, m
-Chlorobenzaldehyde, p-chlorobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, p-nitrobenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, p-ethylbenzaldehyde,
Examples thereof include pn-butylbenzaldehyde and furfural, and formaldehyde is particularly preferably used. 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 amount of these acidic catalysts used is usually
It is 1 × 10 ^{-5 to} 5 × 10 ^-1 mol per 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 a heterogeneous system from the beginning of the reaction, the reaction medium is used as the reaction medium. Hydrophilic solvents can also be used. Examples of these hydrophilic solvents include alcohols such as methanol, ethanol, propanol and butanol, and cyclic ethers such as tetrahydrofuran and dioxane. The amount of the reaction medium is usually 20 to 1000 parts by weight per 100 parts by weight of the reaction raw material. The temperature of the polycondensation can be appropriately adjusted according to the reactivity of the reaction raw materials, but is usually 10 to 200 ° C.
Preferably it is 70-130 ° C. As a method of polycondensation,
A method in which phenols, aldehydes, acidic catalysts, and the like are charged at once, and a method in which phenols, aldehydes, and the like are added in the presence of the acidic catalyst as the reaction proceeds, can be adopted. After completion of the polycondensation, in order to remove unreacted raw materials, acidic catalyst, reaction medium, and the like present in the system, generally, the temperature of the reaction system is increased to 130 to 230 ° C., and the pressure is reduced, for example, to 20 to 230 ° C. Volatiles are distilled off at about 50 mmHg, and the obtained resin (A) is recovered.

The resin (A) used in the present invention has a weight average molecular weight in terms of polystyrene (hereinafter referred to as "Mw").
Is preferably 2,000 to 20,000, and 3,000 to 1
More preferably, it is 5,000. When Mw exceeds 20,000, it may be difficult to uniformly apply the composition of the present invention to a wafer, and furthermore, there is a tendency that developability and sensitivity tend to decrease, and when Mw is less than 2,000, heat resistance is reduced. 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 low-molecular-weight phenol compound 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 can be exemplified.

[0014]

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[0015]

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[0016]

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 compounding amount of such a low molecular weight phenol compound is usually 50 parts by weight or less per 100 parts by weight of the resin (A).

For the same purpose as described above, a low molecular weight alkali-soluble novolak resin or an alkali-soluble resol resin (hereinafter, these are 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 not more than 60 parts by weight per 100 parts by weight of the resin (A).

Compound (A) In the composition of the present invention, the above-mentioned general formula (1), namely,

[0019]

Embedded image And at least one compound (A) represented by the formula:

In the general formula (1), X ^{1 to} X
¹³ is a group selected from a hydrogen atom, an alkyl group, an alkoxy group and a hydroxyl group, and X ^{1 to} X
It is necessary that at least one hydroxyl group be contained in each combination of ⁵ , X ^{6 to} X ⁸ and X ^{9 to} X ¹³ . That is, at least one hydroxyl 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-butyl group, a t-butyl group Can be exemplified. As the alkoxy group, those having 4 or less carbon atoms are preferable, and specifically,
Examples thereof include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.

In the general formula (1), Y ^{1 to} Y ⁴
Represents a hydrogen atom or an alkyl group. As the alkyl group, a lower alkyl group having 4 or less carbon atoms is preferable as in the case of X ^{1 to} X ¹³ .

Further, R¹ Is -COOR^Two (R^Two Is the water
Represented by an atom, an alkyl group, or an aryl group)
Is shown. This R^Two In connection with the alkyl group,
Note X ¹ ~ X¹³Alkyl group having 4 or less carbon atoms as in
Are preferable, and as the aryl group, a phenyl group,
Groups having 6 to 10 carbon atoms, such as
Is preferred.

Specific examples of the compound (A) represented by the general formula (1) include the compounds represented by the following formulas (a) to (c1).

[0025]

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[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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The compounds (A) represented by the above formulas (a) to (c1) can be synthesized, for example, by condensing hydroxybenzyl alcohols and phenol compounds using an acid catalyst.

In the present invention, the compound (A) described above
Is preferably 0.5 to 100 parts by weight, particularly 2 to 50 parts by weight, per 100 parts by weight of the resin (A).

1,2-quinonediazide compound In the present invention, a 1,2-quinonediazide compound is blended in addition to the resin (A) and the compound (A). Such 1,2-quinonediazide compounds include, for example, 1,2-
Benzoquinonediazide-4-sulfonic acid ester, 1,2
-Naphthoquinonediazide-4-sulfonic acid ester,
Examples include 1,2-quinonediazidesulfonic acid esters such as 1,2-naphthoquinonediazide-5-sulfonic acid ester, and the following can be exemplified. Of 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-phenylethane, 2,4,4-trimethyl-
2 ', 4', 7-Trihydroxy-2-phenylflavan, 1,1,3
1,2-benzoquinonediazide-4-sulfonic acid ester such as -tris (4-hydroxyphenyl) butane, 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) propane, 1,2-naphtho The quinonediazide-4-sulfonic acid ester, the 1,2-naphthoquinonediazide-5-sulfonic acid ester, and the above-mentioned hydroxyl group of the resin (B) may have a hydrogen atom of, for example, 0.20 to 1 mol, preferably 0.40 to 1 mol per hydrogen atom.
1,2-quinonediazidosulfonic acid ester substituted with 1,2-naphthoquinonediazido-5-sulfonyl group or the like at a mole ratio.

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

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

The surfactant is blended 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), Mega Fax F171, F172, F173 (trade name, manufactured by Dainippon Ink), Florard FC430, FC431 (trade name, manufactured by Sumitomo 3M), 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 at the time of irradiation, and improving the adhesiveness. For this purpose, an adhesion aid may be added. Further, if necessary, a storage stabilizer, an antifoaming agent and the like can be added.

Preparation of Composition and Pattern Formation The composition of the present invention comprises the above-mentioned resin (A), compound (A) and 1,2-quinonediazide compound and the above-mentioned various compounding agents, for example, having a solid content of 20%. It is prepared by dissolving in a solvent so as to have a concentration of about 40% by 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. Aromatic hydrocarbons such as ether acetate, toluene and xylene, methyl ethyl ketone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy-3- Methyl methylbutanoate, 3
-Methyl-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl acetate, and butyl acetate can be used. Furthermore, N−
Methylformamide, N, N-dimethylformamide, N
-Methylformanilide, N-methylacetamide,
N, N-dimethylacetamide, N-methylpyrrolidone,
Dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetonylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ- High-boiling solvents such as butyrolactone, ethylene carbonate, propylene carbonate, and phenyl cellosolve acetate can also be added.

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 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 effect of the present invention can be further improved by applying the composition on a wafer or the like, performing pre-baking and irradiation, heating at 70 to 140 ° C., and then 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)- 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. You. Further, the developer includes a water-soluble organic solvent such as methanol,
An appropriate amount of an alcohol such as ethanol or a surfactant may be added for use. When development is performed using a developing solution composed of such an alkaline aqueous solution, rinsing is generally continued with water.

[0047]

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: GPC column (G2000H manufactured by Toyo Soda Co., Ltd.)
₆ 2, G3000H ₆ 1 present, the G4000H ₆ 1 present) using a flow rate 1.
5 ml / min, elution solvent tetrahydrofuran, column temperature 40
The measurement was performed by gel permeation chromatography using monodisperse polystyrene as a standard under the analysis conditions of ° C.

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

Resolution: The dimension of the smallest 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 judged to be good. However, if the pattern shape has a skirt or has a reverse tapered shape, it is determined to be defective even if B / A is within the above range.

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

Synthesis Example 2 Resin (A1) was dissolved in ethyl cellosolve acetate so as to have a solid content of 20% by weight, and twice the amount of methanol and an equal amount of water with respect to the weight of this 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 m-cresol 69.2 g (0.64 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, and the internal temperature was lowered to 130 ° C.
The mixture is condensed for 6 hours with stirring and after the reaction,
After returning to room temperature, the contents were taken out into a beaker. After separating into two layers in this beaker, the lower layer was taken out, concentrated, dehydrated, and dried to collect the resin. This resin is referred to as resin (A3).

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

Synthesis Example 5 In a flask similar to that used in Synthesis Example 1, 95.2 g (0.88 mol) of m-cresol 24.4 g (0.18 mol) of 2,3,5-trimethylphenol 154 g of a 37% by weight aqueous solution of formaldehyde (formaldehyde) : 1.90 mol) and 1.82 g (0.014 mol) of oxalic acid dihydrate, the flask was immersed in an oil bath, polycondensation was performed for 90 minutes while stirring at an internal temperature of 100 ° C, and then m -Cresol (23.8 g, 0.22 mol) and 2,3,5-trimethylphenol (97.6 g, 0.72 mol) were added to carry out polycondensation for further 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) was taken out, concentrated, dehydrated, and dried to collect the resin. This resin is referred to as resin (A5).

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

<Abbreviations and Synthesis of Compound (A)> In the following, 2,6-bis (4-hydroxy-3,5-
Methyl (dimethylbenzyl) -3,4,5-trihydroxybenzoate is abbreviated as compound (A2) (formula (e)).

<Synthesis of 1,2-quinonediazide compound> Synthesis Example 7 10.0 g of resin (B1) 1,2-naphthoquinonediazide-5-sulfonic acid chloride 1
3.9 g and 250 g of dioxane were charged and dissolved with stirring. Then remove the flask
It was immersed in a water bath controlled at 30 ° C., and when the internal temperature became constant at 30 ° C., 5.75 g of triethylamine was slowly dropped into this solution using a dropping funnel so that the internal temperature did not exceed 35 ° C. Thereafter, the precipitated triethylamine hydrochloride was removed by filtration, and the filtrate was poured into a large amount of dilute hydrochloric acid to precipitate.Then, the precipitate was collected by filtration, and dried overnight in a vacuum dryer controlled at 40 ° C. A 2-quinonediazide compound (a) was obtained.

Synthesis Example 8 2,3,4-trihydroxybenzophenone 23.0 g (0.10 mol) 1,2-naphthoquinonediazide-5-sulfonic acid chloride 6
A 1,2-quinonediazide compound (b) was obtained in the same manner as in Synthesis Example 7 except that 9.9 g (0.26 mol) and 28.9 g (0.286 mol) of triethylamine were used.

Synthesis Example 9 2,3,4,4'-tetrahydroxybenzophenone 24.6 g
(0.10 mol) 1,2-naphthoquinonediazide-5-sulfonic acid chloride 10
A 1,2-quinonediazide compound (c) was obtained in the same manner as in Synthesis Example 7 except that 7.5 g (0.40 mol) and 44.5 g (0.44 mol) of triethylamine were used.

Synthesis Example 10 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 6
A 1,2-quinonediazide compound (d) was obtained in the same manner as in Synthesis Example 7 except that 7.2 g (0.25 mol) and 27.8 g (0.275 mol) of triethylamine were used.

Examples 1 and 2 and Comparative Examples 1 and 2 Resin A, quinonediazide compound, compound (A) and a solvent were mixed as shown in Table 1 to form a uniform solution.
The solution was filtered through a 0.2 μm membrane filter 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 prebaked on a hot plate at 90 ° C. for 2 minutes to form a 1.2 μm-thick resist film. After exposure using a wavelength of 365 nm (i-line) as described above, development, rinsing, and drying, evaluation of the sensitivity, resolution, residual film ratio, developability, heat resistance and pattern shape of the resist film Was done. Table 2 shows the results.

[0067]

[Table 1]

Note 1: Each addition amount is shown in parts by weight. Note 2: The types of dissolution accelerators are as follows. α; 1,1,1-tris (4-hydroxyphenyl) ethane Note 3: The types of solvents are as follows. S1; Ethyl cellosolve acetate S2; Ethyl lactate S3; Methyl-3-methoxypropionate

[0069]

[Table 2]

[0070]

According to the radiation-sensitive resin composition of the present invention, the generation of scum during the formation of a resist is effectively suppressed, the developing property is excellent, the sensitivity is high, the resolution is high, the heat resistance is high, and the residual film ratio is high. It can be used favorably as a positive resist excellent in odor.

──────────────────────────────────────────────────続 き Continuation of front page (72) Inventor Takao Miura 2-11-24 Tsukiji, Chuo-ku, Tokyo Inside JSR Corporation (56) References JP-A-3-259149 (JP, A) JP-A JP-A-3-200251 (JP, A) JP-A-4-122938 (JP, A) JP-A-3-200253 (JP, A) JP-A-2-2560 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03F ^7/ 00-7/42

Claims (1)

(57) [Claims] An alkali-soluble resin represented by the following general formula (1): Wherein, X ¹ to X ¹³ is a hydrogen atom, an alkyl group, either alkoxy groups or hydroxyl groups, and X ¹
X 1 to X ⁵ , X ^{6 to} X ⁸ and X ^{9 to} X ¹³ each include at least one hydroxyl group; Y ¹ to Y ^{4 each} represent a hydrogen atom or an alkyl group; ¹ represents a group represented by —COOR ² (R ² represents a hydrogen atom, an alkyl group or an aryl group), and at least one compound represented by the formula: and a 1,2-quinonediazide compound A radiation-sensitive resin composition.