JPH06138654A - Radiation sensitive resin composition - Google Patents

Abstract

PURPOSE:To improve developability and to enhance the dimensional fidelity and the focal allowance of an obtained pattern by incorporating an alkali-soluble resin and a specified compound. CONSTITUTION:This resin composition contains the alkali-soluble resin and the compound represented by formula I in which each of X<1>-X<5> is H, alkyl, alkoxy, or -OD; D is H or a group having a quinonediazido group; each of Y<1>-Y<4> is H, alkyl, or -OZ; Z is a group having an alkyl aryl group: and at least one of X<1>-X<5> and at least one of X<6>-X<10> are each a -OD group, and at least one of D is a group having a quinonediazido group, and at least one of Y<1>-Y<4> is a -OZ group.

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 useful as a highly integrated resist for producing integrated circuits.

[0002]

2. Description of the Related Art Conventionally, positive resists have been widely used in the manufacture of integrated circuits because a resist pattern of high resolution can be obtained. However, with the progress of high integration in recent years, resists with higher resolution have been obtained. A positive resist capable of forming a pattern is desired. That is, in order to form a fine resist pattern using a positive resist, when a latent image formed by irradiation with radiation is developed with a developer composed of an alkaline aqueous solution, the portion irradiated with radiation is a substrate such as a wafer. It is necessary to develop quickly up to the part in contact with the material (the hem of the pattern),
In the case of the conventional positive resist, the developability was not sufficient when the line width of the resist pattern to be formed was as fine as 0.8 μm or less. Further, in order to manufacture an integrated circuit having a high degree of integration, the difference between the design dimension of the mask and the dimension of the actual resist pattern is small, and the resist that faithfully reproduces the design dimension of the mask, that is, the dimension fidelity is high. Although a resist is required, in general, the smaller the line width of the pattern, the larger the difference between the mask design dimension and the actual resist pattern dimension tends to be. Fidelity could not be achieved. Moreover, in the case of the conventional positive type resist, when the focus is deviated when the stepper irradiates the radiation, the pattern shape is deformed, the developability is deteriorated, the difference between the obtained resist pattern and the design dimension becomes remarkable, and the focus tolerance is deteriorated. But it wasn't enough.

[0003]

Therefore, an object of the present invention is to provide a novel radiation-sensitive resin composition, and more specifically, it has good developability and the dimensions of the resulting resist pattern. It is an object of the present invention to provide a radiation-sensitive resin composition which is useful as a positive resist having excellent fidelity and particularly excellent focus tolerance.

[0004]

According to the present invention, the above-mentioned problems are solved by an alkali-soluble resin and the following general formula (1):

[0005]

[In the general formula (1), X ^{1 to} X ¹⁰ may be the same or different and each represents a hydrogen atom, an alkyl group, an alkoxy group or an -OD group (wherein D is a hydrogen atom or a quinonediazide group). Is an organic group having
Y ¹ to Y ⁴ may be the same or different, a hydrogen atom, an alkyl group or an -OZ group (wherein, Z is an organic group having one or aryl group which is an alkyl group.) Shows a.
R ^{1 to} R ⁴ may be the same or different and each represents a hydrogen atom or an alkyl group. However, at least one of X ^{1 to} X ⁵ and at least one of X ^{6 to} X ¹⁰ are —OD groups, and at least one of D is an organic group having a quinonediazide group. In addition, at least one of Y ^{1 to} Y ⁴ is an —OZ group. ] A radiation-sensitive resin composition characterized by containing a compound represented by the following.

The present invention will be specifically described below, but the purpose, constitution and effect of the present invention will be clarified by this. Examples of the alkali-soluble resin used in the present invention include novolac resin, poly (vinylphenol) or its derivatives, styrene-maleic anhydride copolymer, poly (vinylhydroxybenzoate), carboxyl group-containing acrylic acid resin, and carboxyl group. Examples thereof include group-containing methacrylic acid-based resins. A preferred alkali-soluble resin is novolac resin. A particularly preferred novolac resin is represented by the following formula (2)

[0007]

[Chemical 2] [Here, n is an integer of 1 to 3. ] It is obtained by polycondensing phenols and aldehydes represented by

Examples of the phenols include o-cresol, m-cresol, p-cresol and 2,3-
Examples thereof include xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol and 3,4,5-trimethylphenol. Of these, o-cresol,
m-cresol, p-cresol, 2,3-xylenol, 2,5-xylenol, 3,4-xylenol,
3,5-xylenol and 2,3,5-trimethylphenol are preferred. These phenols may be used alone or in combination of two or more. A particularly preferable combination is a weight ratio of m-cresol / 2,3-xylenol / p-cresol = 95 to 20/5 to 60 /.
0-75, m-cresol / 3,5-xylenol / p
-Cresol = 95-30 / 5-70 / 0-65, m-
Cresol / 2,3,5-trimethylphenol / p-
Cresol = 95-35 / 5-5 / 60-60, m-cresol / 2,3-xylenol / 3,4-xylenol = 95-35 / 5-65 / 0-60, m-cresol / 2,5- Xylenol / 3,5-xylenol = 95
~ 25/5 to 70/0 to 70, m-cresol / 2,3
-Xylenol / 2,3,5-trimethylphenol =
95-35 / 5-65 / 0-60, m-cresol /
2,5-xylenol / 2,3,5-trimethylphenol = 95 to 35/5 to 65/0 to 60, m-cresol / 3,4-xylenol / 2,3,5-trimethylphenol = 95 to 35 / 5-50 / 0-60, m-cresol / 3,5-xylenol / 2,3,5-trimethylphenol = 95-35 / 5-65 / 0-60, m-
Cresol / p-cresol = 90-30 / 10-70
Etc.

Examples of the aldehydes to be polycondensed with the phenols include formaldehyde, trioxane, paraformaldehyde, benzaldehyde, acetaldehyde, propylaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde,
P-hydroxybenzaldehyde, furfural and the like are preferable, and of these, formaldehyde is particularly preferable. When formaldehyde is used as the aldehyde, examples of the formaldehyde generation source include formalin, trioxane, and paraformaldehyde, as well as methyl hemiformal and butyl hemiformal. Of these, formalin and butyl hemiformal are particularly preferred. The aldehydes may be used alone or in combination of two or more. The amount of the aldehyde used is preferably 0.7 to 3 mol, and more preferably 0.1 to 3 mol, relative to 1 mol of the phenol.
It is 8 to 1.5 mol.

An acid catalyst is usually used for the polycondensation of the phenols and the aldehydes. Examples of the acidic catalyst include hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, acetic acid and the like. The amount of these acidic catalysts used is usually 1 × 10 ^{−5 to} 5 per mol of phenols.
× 10 ^-1 mol. In the polycondensation of phenols and aldehydes, water is usually used as the reaction medium, but if the phenols used do not dissolve in the aqueous solution of aldehydes and become a heterogeneous system from the beginning of the reaction, hydrophilic It is also possible to use a protic solvent as the reaction medium. Examples of the hydrophilic solvent 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 20 to 1,000 parts by weight per 100 parts by weight of the reaction raw material. The polycondensation temperature of the phenols and the aldehydes is appropriately adjusted according to the reactivity of the reaction raw material, but is usually 10 to 20.
It is 0 ° C. The polycondensation method of phenols and aldehydes includes a method of charging phenols, aldehydes, acidic catalysts, etc. all at once and reacting by gradually adding phenols, aldehydes, etc. in the presence of acidic catalysts. It is possible to adopt a method of making it possible. After completion of the polycondensation, in order to remove the unreacted raw materials, the acid catalyst, the reaction medium and the like existing in the reaction system, the reaction system is generally set to 130
The temperature is raised to 230 ° C., and under reduced pressure, for example, 20 to 50 mmHg
The volatiles are removed under moderate pressure to recover the novolac resin produced.

The polystyrene-reduced weight average molecular weight (hereinafter referred to as "Mw") of the novolak resin can be appropriately selected from the range of the molecular weight of the novolak resin conventionally used in the radiation sensitive resin composition. 2,000
It is preferably 0 to 20,000, and more preferably 3,000 to 15,000 (hereinafter, the novolac resin having Mw in the range of 2,000 to 20,000 is referred to as "resin (A)"). . If the Mw exceeds 20,000, it may be difficult to uniformly apply the composition of the present invention onto a substrate, and the developability and sensitivity tend to be lowered. On the other hand, when Mw is less than 2,000,
Heat resistance tends to decrease. Particularly when a high molecular weight novolak resin is desired, the novolak resin obtained by the polycondensation is treated with ethylene glycol monomethyl ether acetate, methyl 3-methoxypropionate,
It was fractionated by dissolving it in a good solvent such as dioxane, methanol, ethyl acetate, and then mixing a poor solvent such as water, n-hexane, n-heptane, etc., and separating the precipitated novolak resin from the solution layer. The high molecular weight novolak resin may be recovered. Further, in the present invention, a low molecular weight phenolic compound may be used in combination with the alkali-soluble resin, which improves the alkali solubility of the alkali-soluble resin. The low molecular weight phenol compound is not particularly limited,
The number of benzene rings is preferably about 2 to 6. Specific examples thereof include compounds represented by the following formula.

[0012]

[Chemical 3]

[0013]

[Chemical 4]

[0014]

[Chemical 5]

[0015]

[Chemical 6]

[0016]

[Chemical 7]

[0017]

[Chemical 8]

[0018]

[Chemical 9]

[0019]

[Chemical 10] [Here, a, b, and c are each an integer of 0 to 3 (provided that all are 0), and x, y, and z
Are integers of 0 to 3, respectively. The compounding amount of these low molecular weight phenol compounds is usually 50 parts by weight or less per 100 parts by weight of the alkali-soluble resin.

In the present invention, as the low molecular weight phenol compound, a low molecular weight alkali-soluble novolac resin and / or an alkali-soluble resole resin (hereinafter referred to as "resin (B)") can be used. The resin (B) is obtained by polycondensation of phenols and aldehydes. Examples of the phenols include phenols, 1-naphthol, 2-naphthol and the like, in addition to those listed for the novolac resin. Other phenols can also be used. Further, as the aldehydes, those mentioned for the novolak resin can be used. The amount of aldehydes used is usually 0.2 per mol of phenols.
~ 0.8 mol. In the polycondensation reaction, a basic catalyst can be used in addition to the acidic catalyst used in the production of the novolak resin. Mw of resin (B)
Is usually 200 to 2,000, preferably 30.
It is 0 to 1,000. The compounding amount of the resin (B) is usually
It is 50 parts by weight or less with respect to 100 parts by weight of the resin (A).

Next, in the compound represented by the general formula (1) (hereinafter referred to as "compound (a)"), X ^{1 to} X ¹⁰
May be the same or different and each is a hydrogen atom, an alkyl group, an alkoxy group or an -OD group (provided that D is a hydrogen atom or an organic group having a quinonediazide group).
Provided that at least one of X ^{1 to} X ⁵ and at least one of X ^{6 to} X ¹⁰ is an —OD group, and at least one of D is an organic group having a quinonediazide group. . Of X ^{1 to} X ¹⁰ , the alkyl group preferably has 4 or less carbon atoms, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n- group.
Examples thereof include a butyl group and a t-butyl group. The alkoxy group preferably has 4 or less carbon atoms, and examples thereof include a methoxy group, an ethoxy group, an n-propoxy group, and an n-butoxy group. Y ^{1 ~} Y
⁴ may be the same or different and each represents a hydrogen atom, an alkyl group or an -OZ group (provided that Z is an alkyl group or an organic group having an aryl group), but at least one is an -OZ group. Must. As the alkyl group of Y ¹ to Y ^4, wherein X ¹ can be mentioned as preferred the same groups as in the case of to X ^10, the alkyl group of Z in the -OZ group, wherein X ¹ to X ^Ten
The same groups as in the case of can be mentioned. As the aryl group, a phenyl group, a toluyl group, a naphthyl group,
Examples thereof include a benzyl group and a phenethyl group. Further, R ^{1 to} R ⁴ may be the same or different and each represents a hydrogen atom or an alkyl group. Examples of the alkyl group include the same groups as in the case of X ^{1 to} X ¹⁰ . −
Among D in the OD group, the organic group having a quinonediazide group is, for example, 1,2-benzoquinonediazide-
4-sulfonyl group, 1,2-naphthoquinonediazide-4
-Sulfonyl group, 1,2-naphthoquinonediazide-5-
Examples thereof include a sulfonyl group, a 1,2-quinonediazide-6-sulfonyl group, a 2,1-naphthoquinonediazide-4-sulfonyl group, and a 2,1-naphthoquinonediazide-5-sulfonyl group. Of these, a 1,2-naphthoquinonediazide-4-sulfonyl group and a 1,2-naphthoquinonediazide-5-sulfonyl group are particularly preferable.

The compound (a) includes, for example, a compound (a) in which all D are hydrogen atoms, that is, the -OD group is a hydroxyl group (hereinafter referred to as "compound (b)") and 1,2-naphthoquinonediazide-4. -Sulfonyl chloride, 1,2
It can be obtained by an esterification reaction with 1,2-quinonediazidesulfonyl halide such as naphthoquinonediazide-5-sulfonyl chloride in the presence of a basic catalyst. Specific examples of the compound (b) include compounds represented by the following formulas (3) to (14).

[0023]

[Chemical 11]

[0024]

[Chemical 12]

[0025]

[Chemical 13]

[0026]

[Chemical 14]

[0027]

[Chemical 15]

[0028]

[Chemical 16]

[0029]

[Chemical 17]

[0030]

[Chemical 18]

[0031]

[Chemical 19]

[0032]

[Chemical 20]

[0033]

[Chemical 21]

[0034]

[Chemical formula 22] The compound (b) is, for example, a phenol and a dimethylol compound represented by the following formula.

[0035]

[Chemical formula 23] [In the formula, Z represents an organic group having an alkyl group or an aryl group, Y ^{11 to} Y ¹⁵ may be the same or different and each represents a hydrogen atom, an alkyl group or a methylol group. However, at least two of Y ^{11 to} Y ¹⁵ are methylol groups. ] Can be manufactured by making it react with the presence of an acidic catalyst. Examples of the phenols here include phenol, o-cresol, m-cresol, p-cresol, 2,5-xylenol, 3,4-xylenol, resorcinol,
Catechol, hydroquinone, methylhydroquinone,
Phloroglucinol, pyrogallol and the like are preferable. In addition, specific examples of the dimethylol compound represented by the above formula include compounds represented by the following formula.

[0036]

[Chemical formula 24]

[0037]

[Chemical 25]

[0038]

[Chemical formula 26]

[0039]

[Chemical 27]

The reaction ratio between the compound (b) and 1,2-quinonediazidesulfonyl halide is 0.2 to 1 mol of 1,2-quinonediazidesulfonyl halide per 1 gram equivalent of the phenolic hydroxyl group of the compound (b). Is preferable, and particularly preferably 0.4 to 1 mol. In the present invention, the compound (a) is used alone or in combination of two or more kinds. The amount used is usually 5 to 50 parts by weight, and particularly preferably 10 to 30 parts by weight, relative to 100 parts by weight of the alkali-soluble resin. By compounding the compound (a) in this way, in addition to developability, dimensional fidelity and focus tolerance are improved.

In the radiation-sensitive resin composition of the present invention,
A quinonediazide compound (hereinafter referred to as "compound (c)") other than the compound (a) can be added. As the compound (c), 1,2-naphthoquinonediazide-4-sulfonic acid ester other than the compound (a), 1,2-naphthoquinonediazide-5-sulfonic acid ester, 1,2
-Naphthoquinonediazide-6-sulfonic acid ester,
Examples thereof include 1,2-benzoquinonediazide-4-sulfonic acid ester, and 1,2-naphthoquinonediazide-4-sulfonic acid ester and 1,2-naphthoquinonediazide-5-sulfonic acid ester are preferable. Specific examples of the compound (c) include 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) -4'- [1- (4-hydroxyphenyl)
-1-Methylethyl] -1-phenylethane, 2,4
4-trimethyl-2 ', 4', 7-trihydroxy-2
A 1,2-naphthoquinonediazide-4-sulfonic acid ester, a 1,2-naphthoquinonediazide-5-sulfonic acid ester of a phenolic hydroxyl group-containing compound such as phenylflavan, and a hydrogen atom of the hydroxyl group of the resin (B). , 1,2-naphthoquinonediazide-4-sulfonyl group or 1,2-naphthoquinonediazide-5-sulfonyl at a ratio of 0.2 to 1 mol, preferably 0.4 to 1 mol, per gram equivalent of the hydrogen atom. 1, substituted with a group
2-quinone diazide sulfonic acid ester can be mentioned.

The compounding amount of the compound (c) in the radiation-sensitive resin composition of the present invention is preferably 100 parts by weight or less, more preferably 50 parts by weight or less with respect to 100 parts by weight of the alkali-soluble resin. As described above, the composition of the present invention contains the compound (a) and, if necessary, the compound (c). However, the component having a quinonediazide group in the composition, that is, the compound (a) and the compound ( The total content of c) is appropriately selected in consideration of the development characteristics of the composition, the characteristics of the resist pattern, etc., but the total content of the quinonediazide group in the solid content of the composition is preferably 5 to 35% by weight. %, More preferably 10 to 20% by weight
Is.

Furthermore, various additives such as a sensitizer and a surfactant can be added to the composition of the present invention, if necessary. The sensitizer improves the sensitivity of the resist to radiation, and examples thereof include 2H-pyrido- (3,2-b) -1,4-oxazine-3 (4H)-.
Ons, 10H-pyrido- (3,2-b)-(1,4)
-Benzothiazines, urazoles, hydantoins,
Examples thereof include 1-hydroxybenzotriazoles. The content of these sensitizers is preferably 50 parts by weight or less with respect to 100 parts by weight of the alkali-soluble resin. Further, the surfactant has an effect of improving the coating property, the developability and the like, and examples thereof include nonionic surfactants such as polyoxyethylene lauryl ether, polyoxyethylene octyl phenyl ether and polyethylene glycol distearate. In addition to KP341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) which is an organosiloxane polymer, Polyflow No. which is an acrylic acid-based or methacrylic acid-based polymer. 75, no. 95 (trade name, manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.), and Megafax F171, F17
2, F173 (trade name, manufactured by Dainippon Ink and Chemicals, Inc.), Florard FC430, FC431 (trade name, manufactured by Sumitomo 3M Limited), Asahi Guard AG710, Surflon S-38.
2, SC-101, SC-102, SC-103, SC
Examples thereof include fluorine-containing surfactants such as -104, SC-105, SC-106 (trade name, manufactured by Asahi Glass Co., Ltd.). The content of these surfactants is preferably 2 parts by weight or less with respect to 100 parts by weight of the solid content of the composition.

Further, the composition of the present invention may be mixed with a dye or pigment or an adhesion aid. In the former case, the latent image on the radiation irradiation portion is visualized to suppress the effect of halation during radiation irradiation. In the latter case, the adhesion to the substrate can be improved. Further, if necessary, a storage stabilizer, a defoaming agent, etc. may be added. When forming a resist pattern using the radiation-sensitive resin composition of the present invention, an alkali-soluble resin, a compound (a), a compound (c) optionally blended, the above various additives, For example, it is prepared as a solution by dissolving it in a solvent so that the solid content concentration becomes 20 to 40% by weight and filtering it with a filter having a pore size of about 0.2 μm.

Examples of the solvent used for preparing this solution include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol. Monomethyl ether acetate, propylene glycol monopropyl ether acetate, toluene, xylene, methyl ethyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethoxy Ethyl acetate, ethyl hydroxyacetate, 2-
Examples thereof include methyl hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate and the like. Further, these solvents are N, N-
Dimethylformamide, N-methylformanilide,
N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, benzyl ethyl ether,
Dihexyl ether, acetonylacetone, isophorone, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, ethylene glycol monophenyl ether. It can also be used in combination with a high boiling point solvent such as acetate.

The radiation-sensitive resin composition of the present invention prepared as a solution is applied onto a substrate such as a silicon wafer or an aluminum-coated wafer by a coating method such as spin coating, cast coating or roll coating. A radiation-sensitive layer is formed by coating, radiation is applied (hereinafter referred to as “exposure”) through a predetermined mask pattern, and the layer is developed with a developing solution to form a pattern. When the radiation-sensitive resin composition of the present invention is used as a positive resist, it is applied on a substrate, prebaked and exposed,
The effect of the present invention can be further improved by performing a heat treatment operation at 140 ° C. and then developing. Examples of the developer for the radiation-sensitive resin composition of the present invention include sodium hydroxide, potassium hydroxide, ammonia water, ethylamine, n-propylamine, diethylamine, triethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxy. , Tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- (5,4,0) -7-undecene, 1,5-diazabicyclo- (4,3,0) -5-nonane and the like. An alkaline aqueous solution in which an alkaline compound is dissolved to have a concentration of, for example, 1 to 10% by weight is used. Further, an appropriate amount of a water-soluble organic solvent, for example, alcohols such as methanol and ethanol and a surfactant can be added to the developer. When a developer containing such an alkaline aqueous solution is used, it is generally washed with water after development.

[0047]

The present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. Here, Mw measurement and various performance evaluations of the resist were performed by the following methods. Mw: GPC column manufactured by Tosoh Corporation (G2000H6:
2 pieces, G3000H6: 1 piece, G4000H6: 1 piece)
Was measured by a gel permeation chromatographic method using monodisperse 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. Dimensional fidelity: Using Nikon NSR-1505i6A reduction projection exposure machine (numerical aperture of lens; 0.50),
I-line with a wavelength of 365 nm is exposed by changing the exposure time,
Then, the resist film was developed with a 2.4 wt% tetramethylammonium hydroxide aqueous solution at 25 ° C. for 60 seconds, washed with water, and dried to form a positive resist pattern on a silicon wafer having a silicon oxide film. . At that time, the resist when exposed with an exposure time for forming a line-and-space pattern of 0.5 μm in a width of 1: 1 while reducing the mask dimension of the line-and-space pattern at intervals of 0.02 μm The difference between the line-and-space pattern dimension and the mask design dimension was measured by a scanning electron microscope, and the difference between the pattern dimension and the mask design dimension was obtained. The minimum design dimension of the mask when the formed pattern dimension is within ± 10% of the design dimension of the mask is defined as the dimension fidelity. Focus tolerance: A resist pattern is formed on a silicon wafer having a silicon oxide film in the same manner as in the case of dimensional fidelity, measured using a scanning electron microscope, and a line and space with a line width of 0.5 μm. For the pattern, the resolved pattern size is ± 1 of the mask design size.
The range of focus deviation when it was within 0% was defined as focus tolerance.

<Synthesis of Resin (A)> Synthesis Example 1 In a flask equipped with a stirrer, a condenser and a thermometer, m-
Cresol 69.2 g (0.64 mol), 2,3-xylenol 9.8 g (0.08 mol), 3,4-xylenol 9.8 g (0.08 mol), 37 wt% formaldehyde aqueous solution 38.5 g ( Formaldehyde: 0.47
5 mol), and 0.19 g of oxalic acid dihydrate (0.0
015 mol) and then soak the flask in an oil bath,
The temperature of the reaction solution was maintained at 100 ° C., and polycondensation was performed for 60 minutes while stirring. Then, 17.3 g of m-cresol
(0.16 mol), 2,3-xylenol 2.5 g
(0.02 mol), 2.5 g of 3,4-xylenol
(0.02 mol), 37 wt% formaldehyde aqueous solution 38.5 g (formaldehyde: 0.475 mol), and oxalic acid dihydrate 1.69 g (0.0135 mol).
Was added, and polycondensation was further performed for 150 minutes. Then
The oil bath temperature was raised to 180 ° C., and at the same time, the pressure inside the flask was reduced to 30 to 50 mmHg to remove water, oxalic acid, unreacted raw materials and the like. Then, the molten resin was cooled to room temperature and collected. This resin was dissolved in methyl 3-methoxypropionate at a solid content of 30% by weight, and half the amount of toluene and 0.4 times the amount of n-hexane were added to the weight of the resin solution and stirred. After that, left. The lower layer (resin solution) separated into two layers by standing was taken out, concentrated, dehydrated and dried to recover the resin (A). This resin (A) is called resin (A1).

Synthesis Example 2 69.2 g (0.6%) of m-cresol was placed in an autoclave.
4 mol), 2,3-xylenol 9.8 g (0.08 mol), 3,4-xylenol 9.8 g (0.08 mol), 37 wt% formaldehyde aqueous solution 61.0 g
(Formaldehyde: 0.75 mol), oxalic acid dihydrate 6.3 g (0.05 mol), water 52.6 g, and dioxane 182 g were charged, the autoclave was immersed in an oil bath, and the temperature of the reaction solution was 130 ° C. Hold at 8 while stirring
After time condensation, the reaction was cooled to room temperature and the contents were taken out into a beaker. The lower layer separated into two layers in the beaker was taken out, concentrated, dehydrated and dried to recover the resin (A). This resin (A) is called resin (A2).

Synthesis Example 3 64.9 g (0.6 g) of m-cresol was placed in an autoclave.
Mol) 2,3-xylenol 36.7 g (0.3 mol), 3,4-xylenol 12.2 g (0.1 mol), 37 wt% formaldehyde aqueous solution 77.1 g
(Formaldehyde: 0.9 mol), oxalic acid dihydrate 6.3 g (0.05 mol), water 79.4 g, and dioxane 383.9 g were charged, and then the autoclave was immersed in an oil bath to prepare a reaction solution. While maintaining the temperature at 130 ° C., polycondensation was carried out for 8 hours under stirring. After the reaction, the mixture was cooled to room temperature and the contents were taken out in a beaker. The lower layer separated into two layers in the beaker was taken out, concentrated, dehydrated and dried to recover the resin (A). This resin (A) is referred to as resin (A3).

<Synthesis of Resin B> Synthesis Example 4 In a flask similar to that used in Synthesis Example 1, 64.8 g (0.60 mol) of m-cresol and 43.
2 g (0.40 mol), 37% by weight aqueous formaldehyde solution 24.3 g (formaldehyde: 0.30 mol),
And 0.30 g of oxalic acid dihydrate (2.40 × 10 ⁻³
Mol) was charged, the flask was immersed in an oil bath, and polycondensation was performed for 40 minutes while maintaining the temperature of the reaction solution at 100 ° C. After the reaction, water, oxalic acid, unreacted raw materials and the like were removed in the same manner as in Synthesis Example 1, and the resin (B) was recovered by cooling. This resin (B) is referred to as resin (B1). Mw of resin (B1)
Was 800.

<Synthesis of Compound (a)> Synthesis Example 5 A compound 23.5 represented by the above formula (11) was placed in a flask equipped with a stirrer, a dropping funnel and a thermometer under light shielding.
g (0.05 mol), 1,2-naphthoquinonediazide-
4-sulfonic acid chloride 40.2 g (0.15 mol),
And 250 g of dioxane were charged and dissolved with stirring. Then, the flask was immersed in a water bath controlled at a temperature of 30 ° C., and when the temperature of the reaction solution became constant at 30 ° C., 17.2 g of triethylamine was added to the solution.
(0.17 mol) was slowly added dropwise using a dropping funnel so that the temperature of the reaction liquid did not exceed 35 ° C. Then
The precipitated triethylamine hydrochloride was filtered off and the filtrate was poured into a large amount of dilute hydrochloric acid to precipitate the product. The precipitated product was collected by filtration and dried overnight with a heating vacuum dryer controlled at 40 ° C. to obtain a quinonediazide compound (a1). Synthesis Example 6 23.5 g (0.05) of the compound represented by the formula (14)
Mol), 1,2-naphthoquinonediazide-5-sulfonic acid chloride 40.2 g (0.15 mol), triethylamine 17.2 g (0.17 mol), and dioxane 2
A quinonediazide compound (a2) was obtained in the same manner as in Synthesis Example 5 except that 50 g was used.

<Synthesis of Compound (c)> Synthesis Example 7 2,3,4,4′-tetrahydroxybenzophenone 2
4.6 g (0.10 mol), 1,2-naphthoquinonediazide-5-sulfonyl chloride 67.2 g (0.25 mol), triethylamine 27.3 g (0.27 mol),
A quinonediazide compound (c1) was obtained in the same manner as in Synthesis Example 5, except that 350 g of dioxane was used. Synthesis example 8 1,1,1-tris (4-hydroxyphenyl) ethane 30.6 g (0.1 mol), 1,2-naphthoquinonediazide-5-sulfonyl chloride 53.8 g (0.2 mol), triethylamine 22 0.2 g (0.22 mol),
A quinonediazide compound (c2) was obtained in the same manner as in Synthesis Example 5, except that 300 g of dioxane was used.

Examples 1 to 3 and Comparative Examples 1 to 3 Compositions shown in Table 1 (however, parts are parts by weight) were mixed to prepare a uniform solution, which was then filtered through a membrane filter having a pore size of 0.2 μm. Then, the composition solution was prepared. The obtained solution was applied onto 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 resist film having a thickness of 1.2 μm. Various performance evaluations were performed. The evaluation results are shown in Table 2.

[0055]

[Table 1] In Table 1, the types of low molecular weight phenolic compounds and solvents are as follows. α: 1,1,1-tris (4-hydroxyphenyl)
Ethane β: 1,1-bis (4-hydroxyphenyl) -1-
Phenylethane S1: Ethyl 2-hydroxypropionate S2: Methyl 3-methoxypropionate

[0056]

[Table 2] As is clear from Table 2, the composition of the present invention, which contains the compound represented by the general formula (1), has extremely excellent dimensional fidelity and focus tolerance as a positive resist.

[0057]

As described above in detail, the radiation-sensitive resin composition of the present invention has a good developability, is excellent in dimensional fidelity of the obtained resist pattern, and is particularly excellent in focus tolerance. It is useful as a mold resist.

Claims (1)

[Claims] 1. An alkali-soluble resin and the following general formula (1): [In the general formula (1), X ^{1 to} X ¹⁰ may be the same or different, and are a hydrogen atom, an alkyl group, an alkoxy group or an -OD group (wherein D is a hydrogen atom or an organic group having a quinonediazide group). , And Y ^{1 to} Y
⁴ may be the same or different and represents a hydrogen atom, an alkyl group or an -OZ group (provided that Z is an alkyl group or an organic group having an aryl group). Also, R
¹ to R ⁴ may be the same or different, represent a hydrogen atom or an alkyl group. However, at least one of X ^{1 to} X ⁵ and at least one of X ^{6 to} X ¹⁰ is an —OD group, and D
At least one of them is an organic group having a quinonediazide group. In addition, at least one of Y ^{1 to} Y ⁴ is an —OZ group. ] The radiation-sensitive resin composition containing the compound represented by these.