JPH11231521A - Radiation sensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a radiation sensitive resin composition suitable for a positive resist in which the occurrence of scum is effectively controlled and high in resolution and sensitivity without damaging heat resistance and a film endurance rate. SOLUTION: This radiation sensitive resin composition contains (i) an alkali- soluble resin and (ii) a phenol compound represented by formula in which each of R1 -R3 is, the same or independently, an H atom or a hydroxy, alkoxy or hydroxyalkoxy group and at least one of them is a hydroxy alkoxy group; and each of A1 -A4 is an alkyl group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a radiation-sensitive resin composition containing an alkali-soluble novolak resin. More specifically, the present invention relates to a radiation-sensitive resin composition as a positive resist composition particularly suitable as a resist for producing a highly integrated circuit which is sensitive to ultraviolet rays and far ultraviolet rays.

[0002]

2. Description of the Related Art Positive resists are widely used in the manufacture of integrated circuits because of their ability to provide high-resolution resist patterns. There is a demand for a resist composition having excellent properties such as acceptability) and developability.
Further, from the standpoint of improving the productivity in semiconductor manufacturing, it is desired to increase the sensitivity of the resist. As a method of increasing the sensitivity of a resist, for example, there is a method of reducing the molecular weight of an alkali-soluble novolak resin. However, in this case, the heat resistance of the resist is reduced, and the film loss in the non-exposed portion is increased (remaining film ratio is reduced), causing problems such as deterioration of the pattern shape.

As described above, in general, sensitivity, heat resistance, and residual film ratio tend to contradict each other, and when one of them is to be improved, the other is disadvantageously deteriorated. Therefore, the emergence of a positive resist excellent in various characteristics such as high resolution and developability, high in sensitivity, and excellent in heat resistance and residual film ratio is desired.

[0004]

An object of the present invention is to provide a novel radiation-sensitive resin composition. Another object of the present invention is to provide a radiation-sensitive resin composition which is suitable as a high-sensitivity positive resist with high resolution without impairing heat resistance and residual film ratio. Still other objects and advantages of the present invention will become apparent from the following description.

[0005]

According to the present invention, the above objects and advantages of the present invention are attained by an alkali-soluble novolak resin, a quinonediazide sulfonic acid ester-based photosensitizer and a compound represented by the following general formula (1):

[0006]

Embedded image [In the general formula (1), R _{1 to} R ₃ are the same or different and are a hydrogen atom, a hydroxyl group, an alkoxy group or a hydroxyalkoxy group, and at least one is a hydroxyalkoxy group. A _{1 to} A ₄ are alkyl groups. The radiation-sensitive resin composition is characterized by containing a phenol compound represented by the following formula:

Hereinafter, the present invention will be described in detail, which will clarify the purpose, structure and effect of the present invention.

Alkali-Soluble Resin The alkali-soluble novolak resin used in the present invention is a resin obtained by condensing a phenol and an aldehyde in the presence of an acidic catalyst (hereinafter referred to as "resin (A)"). . Examples of the phenol used in the resin (A) include phenol, o-cresol, m-cresol, p-cresol, 2,3-dimethylphenol, 2,4-dimethylphenol, 3,4-dimethylphenol, , 5-dimethylphenol, 3,5-dimethylphenol, 2,3,5-trimethylphenol, 3,4,
Examples thereof include 5-trimethylphenol, resorcinol, 2-methylresorcinol, 4-ethylresorcinol, hydroquinone, methylhydroquinone, catechol, 4-methyl-catechol, pyrogallol, phloroglucinol, thymol, and isothymol.
Among them, phenol, m-cresol, p-cresol, 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5-dimethylphenol, 3,4-dimethylphenol and 2,3,5-trimethylphenol preferable. These phenols can be used alone or in combination of two or more. The combination of the phenols is not particularly limited, and can be arbitrarily selected from the above specific examples.

The aldehydes to be condensed include
For example, formaldehyde, paraformaldehyde, benzaldehyde, acetaldehyde, propylaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde,
Examples thereof include o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, furfural, glyoxal, glutaraldehyde, terephthalaldehyde, and isophthalaldehyde.
Among these, formaldehyde and o-hydroxybenzaldehyde can be particularly preferably used.

[0010] These aldehydes can be used alone or in combination of two or more. The amount of the aldehyde used is 0.4 to 1 mol per phenol.
It is preferably 2 mol, more preferably 0.6 to 1.5 mol. In the condensation reaction between phenols and aldehydes,
Usually, an acidic catalyst is used. Examples of the acidic catalyst include hydrochloric acid, sulfuric acid, formic acid, oxalic acid, methanesulfonic acid, p
-Toluenesulfonic acid and the like. The use amount of these acidic catalysts is usually 1 × 10 ^{-5 to} 5 × 10 ^-1 mol per 1 mol of phenols.

In the condensation reaction, for example, methanol,
It is desirable to use alcohols such as ethanol, propanol, butanol and propylene glycol monomethyl ether; cyclic ethers such as tetrahydrofuran and dioxane; and ketones such as ethyl methyl ketone, methyl isobutyl ketone and 2-heptanone as the reaction medium. The amount of these reaction media used is usually 20 to 1,000 parts by weight per 100 parts by weight of phenol as a reaction raw material. Although the temperature of the condensation reaction can be appropriately adjusted according to the reactivity of the raw materials, it is usually 10 to 200 ° C.

As the reaction method, there are a method in which phenols, aldehydes, an acidic catalyst, a reaction medium, and the like are charged at once, and a method in which phenols, aldehydes, and the like are added as the reaction proceeds in the presence of the acidic catalyst. It can be adopted as appropriate. After completion of the condensation reaction, the reaction temperature is increased to 130 ° C. to 230 ° C. to remove unreacted raw materials, acidic catalyst, reaction medium and the like present in the system, and volatile components are removed under reduced pressure to remove the novolak resin. It is preferable to carry out a recovery method. The novolak resin obtained after the completion of the condensation reaction was treated with ethylene glycol monomethyl ether acetate, methyl 3-methoxypropionate,
-Heptanone, methyl isobutyl ketone, dioxane,
After dissolving in a good solvent such as methanol and ethyl acetate,
Mixing a poor solvent such as water, n-hexane and n-heptane,
Next, a method of separating the resin solution layer to be precipitated and recovering a high-molecular-weight novolak resin can also be performed.

The novolak resin used in the present invention has a polystyrene reduced weight average molecular weight (hereinafter referred to as “M”).
w ". ) Is preferably from 2,000 to 20,000 from the viewpoint of workability when applying the composition of the present invention to a substrate, developability when used as a resist, sensitivity and heat resistance. It is particularly preferred that the molecular weight is from 5,000 to 15,000.

Phenol compound The composition of the present invention contains the phenol compound represented by the above formula (1).

[0015]

Embedded image

In the formula (1), R _{1 to} R ₃ are the same or different and are a hydrogen atom, a hydroxyl group, an alkoxy group or a hydroxyalkoxy group, at least one of which is a hydroxyalkoxy group. Here, as the alkoxy group, an alkoxy group having 1 to 4 carbon atoms is preferable, and specifically, a methoxy group, an ethoxy group, an n-propoxy group,
-Butoxy, sec-butoxy, iso-butoxy, t
-Butoxy group and the like, and a methoxy group is particularly preferable. Further, as the hydroxyalkoxy group,
Hydroxyalkoxy groups having 2 to 6 carbon atoms are preferred,
Specific examples include a 2-hydroxyethoxy group, a 3-hydroxypropoxy group, and a 4-hydroxybutoxy group, and a 2-hydroxyethoxy group is particularly preferable.

A _{1 to} A _{4 each} represent an alkyl group. Here, the alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, an n-propyl group, and an n-butyl group. Groups are preferred. The phenol compound represented by the formula (1) is, for example, represented by the following formula (5)

[0018]

Embedded image (Where the definitions of R ^{1 to} R ³ are the same as in the formula (1)) and a benzene derivative represented by the following formula (6)

[0019]

Embedded image (Where the definitions of A ₁ and A ₂ are the same as in formula (1)) or an alcohol represented by the following formula (7)

[0020]

Embedded image (Wherein the definition of A ₁ is the same as that of the formula (1), and B ₁ represents a hydrogen atom or an alkyl group) and a phenol compound represented by an acidic catalyst such as hydrochloric acid, sulfuric acid, p-toluenesulfonic acid and the like. By reacting in the presence of

In the reaction, the compound of the formula (6) or the compound of the formula (7) is usually used in an amount of 2 mol or more to the compound of the formula (5). The reaction temperature and the reaction time can be appropriately adjusted depending on the reactivity of the raw materials, but are usually 20 to 100 ° C.
4 hours to 10 hours.

As a specific example of the equation (1), the following equation (4-
Compounds represented by 1) to (4-4) (hereinafter, referred to as “compound (a)”) can be mentioned as preferable examples.

[0023]

Embedded image

The compounding amount of the phenol compound represented by the formula (1) is 2 to 50 per 100 parts by weight of the resin (A).
It is preferably used in a proportion of 5 parts by weight , especially 5 to 40 parts by weight . The above formula (1) can be used alone or in combination of two or more.

Quinone Diazide Sulfonate Compound The quinone diazide compound used in the present invention is not particularly limited, but 1,2-benzoquinonediazide-4-sulfonic acid ester of a polyhydroxy compound, 1,2-naphthoquinonediazide-4-sulfonic acid Ester 1,2-
Naphthoquinonediazide-5-sulfonic acid ester, 1,
Examples thereof include 2-naphthoquinonediazide-6-sulfonic acid ester. Among them, preferred are 1,2
-Naphthoquinonediazide-4-sulfonic acid ester,
1,2-naphthoquinonediazide-5-sulfonic acid ester.

The quinonediazide compound (hereinafter referred to as "photosensitizer (B)") includes, for example, a polyhydroxy compound and 1,2-naphthoquinonediazide-4-sulfonyl chloride, 1,2-naphthoquinonediazide-5-sulfonyl. It can be obtained by subjecting 1,2-quinonediazidosulfonyl halide such as chloride to an esterification reaction. In the esterification reaction, the use ratio of the polyhydroxy compound and 1,2-quinonediazidosulfonyl halide is based on 1 molar equivalent of the phenolic hydroxyl group.
The proportion of 1,2-quinonediazidosulfonyl halide is preferably from 0.2 to 1.0 mol, particularly preferably from 0.4 to 1.0 mol. These are reacted in the presence of a basic catalyst. Here, the polyhydroxy compound used is not particularly limited, but specific examples thereof include a compound represented by the following formula.

[0027]

Embedded image [Wherein, X _{1 to} X _{15 each} independently represent a hydrogen atom, a carbon number of 1 to
4 is an alkyl group or a hydroxyl group. However, X _{1 to} X ₅ ,
At least one of the groups X _{6 to} X ₁₀ and X _{11 to} X ₁₅ is a hydroxyl group. ]

[0028]

Embedded image [In the formula, X _{16 to} X ₂₅ represent the same atoms or groups as those of X _{1 to} X ₁₅ above. However, at least one of X _{16 to} X ₂₀ is a hydroxyl group. X _{26 to} X ₂₈ are independently
A hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or a hydroxyl group, at least one of which is a hydroxyl group. Y _{1 to} Y ₄ are independently a hydrogen atom or a carbon atom
To 4 alkyl groups. ]

[0029]

Embedded image [Wherein X _{29 to} X ₄₂ represent the same atoms or groups as X _{1 to} X ₁₅ above] Provided that at least one in each group of _{X 29 ~X 32, X 33 ~X} 37 and X ₃₈ to X ₄₂ is a hydroxyl group. Y ₅ is an alkyl group having 1 to 4 carbon atoms. ]

[0030]

Embedded image Wherein, X ₄₃ to X ₄₈ mean the same atom or group as the X ₂₆ to X _28. However, X _{43 to} X ₄₅ and X _{46 to} X ₄₈
In each group, at least one is a hydroxyl group. Also,
Y _{6 to} Y ₉ represent the same atoms or groups as Y _{1 to} Y ₄ . ]

[0031]

Embedded image [In the formula, X _{49 to} X ₆₈ represent the same atoms or groups as those of X _{26 to} X ₂₈ above. However, X _{49 to} X ₅₃ , X _{54 to} X ₅₈ , X
At least one in ₅₉ in each group to X ₆₃ and X ₆₄ ~ ₆₈ is a hydroxyl group. Y ₁₀ is an alkyl group having 1 to 4 carbon atoms. ]

The amount of the photosensitive agent (B) is based on the resin (A)
It is preferable to use 5 to 50 parts by weight, particularly 10 to 40 parts by weight, per 100 parts by weight. The photosensitive agent (B) can be used alone or in combination of two or more.

Various Compounding Agents The composition of the present invention may optionally contain additives such as a dissolution promoter and a surfactant. The dissolution promoter used herein has a molecular weight of 1000 other than the above formula (1).
The following phenol compounds are exemplified, and the compounding amount is 40 parts by weight or less per 100 parts by weight of the resin (A).
The surfactant is compounded for improving the coating property and the developability of the composition, and the compounding amount is preferably 2 parts by weight or less per 100 parts by weight of the solid content of the composition. Further, in the composition of the present invention, in order to visualize the latent image of the radiation-irradiated portion of the resist, and to reduce the influence of halation upon irradiation, a dye or pigment can be added, and the adhesiveness is improved. For this purpose, an adhesion aid may be added. Further, a storage stabilizer, an antifoaming agent and the like can be added as required.

Solvent The composition of the present invention comprises the solid component such as the resin (A) described above,
For example, it is prepared by dissolving in a solvent so that the solid content concentration becomes 20 to 40% by weight, and filtering through a filter having a pore size of about 0.2 μm. As the solvent used at this time, for example, 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, propylene glycol monomethyl ether acetate, propylene glycol monopropyl ether acetate, xylene, methyl ethyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone, ethyl lactate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-
Examples thereof include methyl methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, ethyl acetate, butyl acetate, methyl pyruvate, and ethyl pyruvate. Further, N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, benzylethyl ether, dihexyl ether, 1-octanol , 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, ethylene glycol monophenyl ether acetate, and other high-boiling solvents can also be added. . These solvents can be used alone or
More than one species can be used in combination.

The composition of the present invention prepared as a solution for forming a resist film is applied to a silicon wafer or a wafer coated with aluminum or the like by spin coating, casting coating, roll coating or the like. Next, a resist film is formed by pre-baking the resist film, and the resist film is irradiated with radiation so as to form a desired resist pattern, and is developed with a developer to form a pattern. As the radiation used at this time, ultraviolet rays such as g-rays and i-rays are preferably used, and various radiations such as charged ultraviolet rays such as far ultraviolet rays such as excimer laser, X-rays such as synchrotron radiation, and electron beams are used. You can also.

The composition of the present invention forms a resist film, and after pre-baking and irradiation,
The effect of the present invention can be further improved by performing an operation of heating at 140 ° C. (hereinafter, referred to as “post-bake”) and then performing development. Examples of the developer used for the resist film include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, and di-n-propyl. Amine, 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 in water at a concentration of, for example, 1 to 10% by weight is used.

Further, a water-soluble organic solvent,
For example, an appropriate amount of an alcohol such as methanol or ethanol or a surfactant may be used. When a developer composed of such an alkaline aqueous solution is used, it is generally preferable to wash with water after development.

[0038]

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: Tosoh GPC column (G200
0H _XL : 2 pieces, G3000H _XL : 1 piece, G4000
H _XL : 1 bottle), the flow rate was 1.0 ml / min, the elution solvent was tetrahydrofuran, and the column temperature was 40 ° C. The analysis was carried out by gel permeation chromatography using monodisperse polystyrene as a standard. Sensitivity: 0.35 μm line and space (L / S)
The exposure amount (appropriate exposure amount) when the pattern was resolved one-to-one was defined as the sensitivity. Resolution: The minimum dimension of the L / S pattern separated without film thinning when exposed at an appropriate exposure amount was measured with a scanning electron microscope. Heat resistance: The wafer on which the resist pattern was formed was placed in a clean oven for 2 minutes, and the temperature at which the pattern shape began to be deformed was measured. Developability: A resist film of the composition was formed, and the scum after pattern formation and the extent of undeveloped portions were examined using a scanning electron microscope. Remaining film ratio: The film thickness of the resist pattern obtained by irradiating with an optimal exposure amount at the α-step manufactured by Tencor Co., Ltd. and developing is divided by the film thickness of the resist film before development, and this value is expressed in%. did.

<Synthesis of Resin (A)> Synthesis Example 1 172.8 g (1.6 mol) of m-cresol was placed in a 2 L separable flask equipped with a cooling tube and a stirrer.
-Dimethylphenol 36.6 g (0.3 mol), 3,
4-dimethylphenol 12.2 g (0.1 mol), 3
121.6 g of a 7% by weight aqueous solution of formaldehyde (formaldehyde: 1.5 mol), oxalic acid dihydrate 12.
6 g (0.1 mol) and methyl isobutyl ketone 5
54 g were charged, and condensation was carried out for 8 hours while stirring and maintaining the internal temperature at 90 to 100 ° C. This reaction solution was washed twice with 500 g of ion-exchanged water, 554 g of n-heptane was added, and the mixture was stirred for 30 minutes, and then allowed to stand for 1 hour. The upper layer separated into two layers was removed by decantation, ethyl lactate was added, residual methyl isobutyl ketone, n-heptane and water were removed by concentration under reduced pressure, and the novolak resin (A
-1) An ethyl lactate solution was obtained. Mw of this resin (A-1) was 8,600.

Synthesis Example 2 In a 2 L separable flask equipped with a cooling tube and a stirrer, 48.8 g (0.4 mol) of 2,5-dimethylphenol, 151.2 g (1.4 mol) of m-cresol, p
-Cresol 21.6 g (0.2 mol), 37% by weight aqueous formaldehyde solution 120.0 g (formaldehyde: 1.4 mol), oxalic acid dihydrate 12.6 g (0.2 mol)
1 mol) and 554 g of methyl isobutyl ketone, and the same operation as in Synthesis Example 1 was carried out to obtain an ethyl lactate solution of the novolak resin (A-2). Mw of the resin (A-2) was 8,300.

Synthesis Example 3 64.9 g of m-cresol was placed in a 1 L autoclave.
(0.6 mol) 2,3-dimethylphenol 36.6 g
(0.3 mol) 2,3,5-trimethylphenol 1
3.6 g (0.1 mol), 64.9 g of 37% by weight aqueous solution of formaldehyde (formaldehyde: 0.80 mol),
6.3 g (0.05 mol) of oxalic acid dihydrate and 384 g of dioxane were charged, immersed in an oil bath, stirred while maintaining the temperature of the reaction solution at 130 ° C., and subjected to condensation for 8 hours.
Thereafter, the mixture was cooled to room temperature, the contents were taken out into a beaker, and the separated lower layer (resin layer) was separated. This resin layer is concentrated, dehydrated, dissolved in ethyl lactate and dissolved in a novolak resin (A
-3) was obtained. Mw of resin (A-3) is 7,10
It was 0.

Synthesis Example 4 In a 1 L autoclave, 64.9 g of m-cresol was added.
(0.6 mol) 12.2 g of 2,3-dimethylphenol
(0.1 mol) 3,6.6 g of 2,4-dimethylphenol
(0.3 mol), 37% by weight aqueous formaldehyde solution 6
0.0 g (formaldehyde: 0.74 mol), 5.7 g (0.03 mol) of p-toluenesulfonic acid monohydrate and 285 g of methyl isobutyl ketone were charged, immersed in an oil bath, and the temperature of the reaction solution was 130 ° C. And stirred for 6 hours for condensation. Thereafter, the mixture was cooled to room temperature, washed three times with 500 mL of ion-exchanged water, and washed with 400 m of n-heptane.
L was added and stirred for 30 minutes. After allowing to stand for 1 hour, the separated upper layer was removed by decantation, and ethyl lactate was added thereto to remove residual methyl isobutyl ketone, n-heptane,
The water was removed by concentration under reduced pressure to obtain a novolak resin (A-4) solution of ethyl lactate. Mw of resin (A-4) is 7.6
00.

<Synthesis of Compound (a)> Synthesis Example 5 In a 1000 ml separable flask, 89.6 g of 1,3-bis (2-hydroxyethoxy) benzene and p-
53.7 g of isopropenylphenol, 466. 6 toluene.
After charging 6 g and stirring at 50 ° C., 0.38 g of p-toluenesulfonic acid was added and reacted at the same temperature for 6 hours. Thereafter, the mixture was cooled to 20 ° C., and the precipitated crystals were filtered. The obtained filtrate was dissolved in 500 ml of ethyl acetate, and the organic layer was washed with 300 ml of pure water three times, and then concentrated by adding 500 ml of toluene, and the precipitated crystals were collected by filtration. The obtained crystals were dried under reduced pressure at 50 ° C. for 24 hours, and 1,3-bis (2-hydroxyethoxy) -4,6.
As a result, 77.3 g (purity by liquid chromatography, 99%) of -bis {1- (4-hydroxyphenyl) -1-methylethyl} benzene [the compound represented by the compound (4-1)] was obtained.

<Synthesis of Quinone Diazide Sulfonate Compound> Synthesis Example 6 18.2 g (0.05 mol) of a compound represented by the following formula:
40.3 g (0.15 mol) of 1,2-naphthoquinonediazide-5-sulfonic acid chloride and 346 g of acetone
And dissolved with stirring. Then, the flask was immersed in a water bath controlled at 30 ° C.
When the temperature became constant at 0 ° C., a solution prepared by dissolving 16.2 g (0.16 mol) of triethylamine in 40 g of acetone was added to the solution using a dropping funnel so that the internal temperature did not exceed 35 ° C. The reaction was performed for 2 hours. Thereafter, the precipitated hydrochloride was removed by filtration, and the filtrate was diluted with 4 L of 0.1%.
The reaction product was precipitated by pouring into an aqueous hydrochloric acid solution, filtered, washed with water, and dried in a vacuum dryer at 40 ° C. overnight to obtain a quinonediazidesulfonic acid ester compound (B-1).

[0046]

Embedded image

Synthesis Example 7 19.6 g (0.05 mol) of a compound represented by the following formula:
A quinonediazidesulfonic acid ester compound (B-2) was prepared in the same manner as in Synthesis Example 6 except that 24.2 g (0.09 mol) of 1,2-naphthoquinonediazide-5-sulfonic acid chloride and 262 g of acetone were charged. Obtained.

[0048]

Embedded image

Synthesis Example 8 32.3 g (0.05 mol) of a compound represented by the following formula:
A quinonediazide sulfonic acid ester compound (B-3) was prepared in the same manner as in Synthesis Example 6 except that 21.5 g (0.08 mol) of 1,2-naphthoquinonediazide-5-sulfonic acid chloride and 345 g of acetone were charged. Obtained.

[0050]

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Example A resin (A), a dissolution promoter, a quinonediazide sulfonic acid ester compound and a solvent were mixed at the composition ratios shown in Table 1 (parts are parts by weight) to form a uniform solution. Filtration through a membrane filter with a pore size of 0.2 μm,
A solution of the composition was prepared. The obtained solution was applied on a silicon wafer having a silicon oxide film by 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 0.86 μm. Then, through a reticle, NS made by Nikon Corporation
R-2005i9C reduction projection exposure machine (lens numerical aperture =
0.57) using a wavelength of 365 nm (i-line),
After post-baking at 110 ° C. for 1 minute on a hot plate, developing with a 2.38% by weight aqueous solution of tetramethylammonium hydroxide for 1 minute, rinsing with ultrapure water,
After drying, a positive resist pattern was formed. The obtained resist pattern was examined, and the characteristics of the composition of each example as a resist pattern were evaluated. Table 2 shows the results.

In Table 1, the types of the phenol compound and the solvent are as follows. Phenol compound a-1: Compound represented by the above formula (4-1) a-2: Compound represented by the above formula (4-2) Solvent S1: Ethyl 2-hydroxypropionate S2: 3-Ethoxypropionic acid Ethyl S3: 2-heptanone

[0053]

[Table 1]

[0054]

[Table 2]

[0055]

According to the radiation-sensitive resin composition of the present invention, the generation of scum is effectively controlled, the resolution is high, and the sensitivity is high without impairing the heat resistance and the residual film ratio. Therefore, the radiation-sensitive resin composition can be suitably used as a resist for producing an integrated circuit having a high degree of integration.

Claims (1)

[Claims] 1. An alkali-soluble novolak resin, a quinonediazidesulfonic acid ester-based photosensitizer, and the following general formula (1): ## STR1 ## [In the general formula (1), R _{1 to} R ₃ are the same or different and are a hydrogen atom, a hydroxyl group, an alkoxy group or a hydroxyalkoxy group, and at least one is a hydroxyalkoxy group. A _{1 to} A ₄ are alkyl groups. ] The radiation sensitive resin composition characterized by containing the phenolic compound represented by these.