JP2002244285A - Radiation sensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a radiation sensitive resin composition ensuring good resolution and a good pattern section shape and suitable for use as a positive type resist having a good margin for exposure. SOLUTION: The radiation sensitive resin composition contains (A) an alkali- soluble novolak resin, (B) a naphthoquinonediazido compound of a phenol compound of formula (1) (where X1 and X2 are each H or alkyl and (p) and (q) are each 1 or 2) and (C) a low molecular weight compound containing 2 or 3 benzene rings and having at least one hydroxyl group on each of the benzene rings. The margin (Eop/Ec) of the composition for exposure is >=1.20.

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.
Radiation-sensitive resin composition suitable as a resist for fabricating highly integrated circuits that is sensitive to various types of radiation such as X-rays such as rF excimer lasers, X-rays such as synchrotron radiation, and charged particle beams such as electron beams, especially ultraviolet rays and far-ultraviolet rays About things.

[0002]

2. Description of the Related Art Positive resists are widely used in the production of integrated circuits. However, with the increasing integration of integrated circuits, positive resists capable of forming a scum-free resist pattern having excellent resolution and depth of focus have been developed. Is desired.
In general, to improve the resolution of a positive resist, there is a method of reducing the molecular weight of an alkali-soluble resin used in the resist, but in this case, there is a problem that the heat resistance of the resist is reduced. Occurs. On the other hand, as a resolution improvement by process improvement, recently, it is characterized by components such as a novolak resin, a naphthoquinonediazide compound, and a low-molecular-weight phenol compound which have been developed with the aim of responding to miniaturization due to such high integration. Many positive resist compositions have been proposed (JP-A-6-167805, JP-A-9-114).
093, JP-A-11-236367, etc.). For example, JP-A-6-167805 and JP-A-9-114093 disclose an alkali-soluble resin and a specific molecular structure for the purpose of improving the balance of resolution, pattern cross-sectional shape (profile) and depth of focus. A positive resist composition containing a quinonediazide-based photosensitizer is described. However, these compositions are not intended to improve the exposure margin, and no mention is made of the relationship between the composition and the exposure margin.

[0003]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned circumstances, and provides a radiation-sensitive material which can obtain a good resolution and a pattern cross-sectional shape and has a favorable exposure margin as a positive resist. An object is to provide a resin composition.

[0004]

The radiation-sensitive resin composition of the present invention comprises (A) an alkali-soluble novolak resin,
(B) a naphthoquinonediazidesulfonic acid ester compound of a phenol compound represented by the following general formula (1):
(C) a low-molecular weight compound having 2 or 3 benzene rings and having at least one hydroxyl group in each benzene ring, and a radiation-sensitive resin composition comprising: Exposure margin (Eop / Ec) is 1.
20 or more.

[0005]

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[In the formula (1), X ₁ and X ₂ are each independently a hydrogen atom or an alkyl group, and p and q are each independently 1 or 2. ]

(A) Alkali-soluble novolak resin The above-mentioned "(A) Alkali-soluble novolak resin" used in the present invention (hereinafter referred to as "resin (A)").
Is not particularly limited as long as it is a resin obtained by condensing phenols and aldehydes in the presence of an acidic catalyst.

Examples of phenols include phenol, o-cresol, m-cresol, p-cresol, 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5-dimethylphenol and 3,4-dimethylphenol , 3,5-dimethylphenol, 2,
3,5-trimethylphenol, 3,4,5-trimethylphenol, resorcinol, 2-methylresorcinol, 4-ethylresorcinol, hydroquinone, methylhydroquinone, catechol, 4-methyl-catechol, pyrogallol, phloroglucinol, thymol and isothymol And the like. Of these, phenol, m-cresol, p-cresol,
2,3-dimethylphenol, 2,4-dimethylphenol, 2,5-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol and 2,3
5-Trimethylphenol is preferred. These phenols can be used alone or in combination of two or more.

A preferred combination when two or more kinds are used in combination is, for example, m-cresol /
2,3-dimethylphenol, m-cresol / 2,4
-Dimethylphenol, m-cresol / 2,5-dimethylphenol, m-cresol / 2,3,5-trimethylphenol, m-cresol / 2,3-dimethylphenol / 2,4-dimethylphenol, m-cresol / 2,3-dimethylphenol / 3,4-dimethylphenol, m-cresol / 2,4-dimethylphenol / 2,5-dimethylphenol, m-cresol /
2,5-dimethylphenol / 3,4-dimethylphenol, m-cresol / 2,3-dimethylphenol /
2,3,5-trimethylphenol, m-cresol /
p-cresol / 2,3-dimethylphenol, m-cresol / p-cresol / 2,4-dimethylphenol, m-cresol / p-cresol / 2,5-dimethylphenol, and m-cresol / p-cresol /
2,3,5-trimethylphenol and the like can be mentioned.

The aldehydes to be condensed include:
For example, formaldehyde, trioxane, paraformaldehyde, benzaldehyde, acetaldehyde, propylaldehyde, phenylacetaldehyde, α-phenylpropylaldehyde, β-phenylpropylaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-methylbenzaldehyde, Examples thereof include m-methylbenzaldehyde, p-methylbenzaldehyde, furfural, glyoxal, glutaraldehyde, terephthalaldehyde, and isophthalaldehyde. Among these, formaldehyde and o-hydroxybenzaldehyde can be suitably used. These aldehydes can be used alone or in combination of two or more. The amount of this aldehyde is
0.4-2.0 mol is preferable with respect to 1 mol of phenols, and 0.6-1.5 mol is more preferable.

Examples of the acidic catalyst used for the condensation reaction between phenols and aldehydes include hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, acetic acid, methanesulfonic acid and p-
Toluenesulfonic acid and the like can be mentioned. The compounding amount of these acidic catalysts is usually 1 × 10 ^{-5 to} 5 × 10 ^-1 mol per 1 mol of phenols.

The condensation reaction is carried out without a solvent or in a solvent. Examples of the solvent include (1) alcohols such as methanol, ethanol, propanol, and butanol;
(2) Ethers such as tetrahydrofuran, dioxane and propylene glycol monomethyl ether; and (3) Ketones such as ethyl methyl ketone, methyl isobutyl ketone and 2-heptanone. The amount of the reaction medium is usually 20 to 100 parts by weight of the reaction raw material.
It is 1,000 parts by weight, preferably 50 to 800 parts by weight. 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, (1) a method in which phenols, aldehydes, acidic catalysts, and the like are charged in a reaction vessel at once,
(2) A method in which an acidic catalyst is charged in a reaction vessel in advance, and phenols, aldehydes, and the like are added in the presence thereof as the reaction proceeds, or the like can be appropriately adopted.

After the completion of the condensation reaction, the novolak resin is recovered by increasing the reaction temperature to 130 to 230 ° C. and removing the pressure under reduced pressure in order to remove unreacted raw materials, acidic catalyst, reaction medium and the like existing in the reaction system. A method for removing the volatile matter and recovering the novolak resin, and producing the novolak resin with ethylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, ethyl 2-hydroxypropionate, propylene glycol monomethyl ether, methyl isobutyl ketone, and 2-heptanone , Dioxane, methanol and ethyl acetate after dissolving in a good solvent such as water, n
A method in which a poor solvent such as -hexane and n-heptane is mixed and precipitated, and then the precipitated resin solution layer is separated to recover a high molecular weight fraction of the novolak resin.

Further, the novolak resin used in the present invention may be subjected to gel permeation chromatography (GP).
The polystyrene-equivalent weight average molecular weight (hereinafter, referred to as “Mw”) measured in C) is workability when applying the composition of the present invention to a substrate, developability when used as a resist, sensitivity, and heat resistance. 2,000-20,000 from the point of sex
And more preferably 3,000 to 15,000.

(B) Naphthoquinonediazidesulfonic acid ester compound The naphthoquinonediazidesulfonic acid ester compound (hereinafter referred to as "naphthoquinonediazide compound (B)") used in the present invention is represented by the above-mentioned general formula (1). Phenol compounds of 1,2-naphthoquinonediazide-4-sulfonic acid ester and 1,2-naphthoquinonediazide-5-sulfonic acid ester are preferred. This naphthoquinonediazide compound (B) is, for example, a phenol compound represented by the general formula (1) and 1,2-naphthoquinonediazide-4-sulfonyl chloride or 1,2-naphthoquinonediazide-5-sulfonylchloride as a basic compound. It is obtained by reacting in the presence of a catalyst. In the obtained naphthoquinonediazide compound (B), the ratio of esterification of all hydroxyl groups (average esterification ratio) was 20%.
Or more and 100% or less, and preferably 40% or more and 95% or less. If this average esterification rate is too low,
It is difficult to form a pattern, and if it is too high, the sensitivity may decrease and the developability may deteriorate.

Here, the phenol compound represented by the general formula (1) used in the present invention is not particularly limited, but as shown in claim 3, the following formulas (4) to (4) The phenol compound shown in 6) is preferable.

[0017]

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[0018]

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[0019]

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In the present invention, a 1,2-naphthoquinonediazidesulfonic acid ester compound (hereinafter, referred to as "other naphthoquinonediazide compound") other than the naphthoquinonediazide compound (B) can be optionally used. This case is preferable because sensitivity and resolution can be improved. The other naphthoquinonediazide compound is not particularly limited, but specifically, the phenolic compound represented by the following formulas (7) to (11),
And naphthoquinonediazidesulfonic acid ester.

[0021]

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Wherein a _{1 to} a ₁₅ 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. However, a _{1 to} a ₅ , a _{6 to} a ₁₀ and a
At least one in each group of ₁₁ ~a _{1 5} is a hydroxyl group. ]

[0023]

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Wherein a _{16 to} a ₂₈ are as defined for a _{1 to} a ₁₅ above. However, a _{1 6} ~a ₂₀ and a ₂₁
At least one in each group of ~a ₂₃ is a hydroxyl group.
B _{1 to} b _{4 each} independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]

[0025]

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Wherein a _{29 to} a ₄₂ are independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a hydroxyl group. Where a ₂₉
At least one in ~a _32, each group of a ₃₃ ~a ₃₇ and a ₃₈ ~a ₄₂ is a hydroxyl group. ]

[0027]

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Wherein a _{43 to} a ₅₈ are as defined for a _{1 to} a ₁₅ above. _{However, a 4 3 ~a 47, a} 48 ~
at least one in each group of a _50, a ₅₁ ~a ₅₃ and a ₅₄ ~a ₅₈ is a hydroxyl group. B _{5 to} b ₈ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]

[0029]

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[Wherein a₅₉~ A₇₈Is a₂₉~ A₄₂To
As defined above. Where a ₅₉~ A₆₃, A₆₄~
a₆₈, A₆₉~ A₇₃And a₇₄~ A₇₈Less in each group of
One is a hydroxyl group. ]

In the composition of the present invention, the compounding amount of the naphthoquinonediazide compound (B) is preferably 5 to 60 parts by weight based on 100 parts by weight of the resin (A).
More preferably, it is 50 parts by weight. The amount of other naphthoquinone diazide compounds other than the naphthoquinone diazide compound (B) is not particularly limited as long as the effects of the present invention are not impaired.

(C) Low-Molecular-Weight Compound A low-molecular-weight compound (C) having 2 or 3 benzene rings and having at least one hydroxyl group on each benzene ring (hereinafter referred to as “low-molecular-weight compound”) used in the present invention. (C) is not particularly limited, but as shown in claim 2, compounds represented by the following general formulas (2) to (3) are preferable.

[0033]

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In the formula (2), a and b are each independently an integer of 1 to 3, x and y are each independently an integer of 0 to 3,
+ X ≦ 5 and b + y ≦ 5. ]

[0035]

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[In the formula (3), a, b and c independently represent 1 to
X, y, and z are each independently an integer of 0 to 3, and a + x ≦ 5, b + y ≦ 4, and c + z ≦ 5. ]

As the compound represented by the above formula (2),
1,1-bis (2,5-dimethyl-4-hydroxyphenyl) acetone, 1,1-bis (2,4-dihydroxyphenyl) acetone, and 1,1-bis (2,6-dimethyl-4-hydroxy) Phenyl) acetone is preferred.
Compounds represented by the above formula (3) include 4, 6
-Bis [1- (4-hydroxyphenyl) -1-methylethyl] -1,3-dihydroxybenzene and 4,6-
Bis [1- (4-hydroxyphenyl) -1-methylethyl] -1,3-dihydroxy-2-methylbenzene is preferred.

The amount of the low molecular weight compound (C) is preferably 5 to 50 parts by weight, more preferably 10 to 45 parts by weight, based on 100 parts by weight of the resin (A). If the amount is too small, the sensitivity, resolution and exposure margin may be reduced. If the amount is too large, it may be difficult to form a rectangular pattern cross section.

In the composition of the present invention, if necessary, in addition to the resin (A), the naphthoquinonediazide compound (B) and the low-molecular-weight compound (C), other naphthoquinonediazide compounds (shown above), A surfactant and a solvent may be blended.

Surfactants can be added to improve the coatability and developability of the composition. Examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, "Megafax F171, F17
2, F173, F471, R-07, R-08 "(manufactured by Dainippon Ink and Chemicals, Inc.)," Fluorard FC430, FC43
1 (manufactured by Sumitomo 3M Limited), Asahi Guard AG71
0, Surflon S-382, SC-101, SC-10
2, SC-103, SC-104, SC-105, SC
-106 "(made by Asahi Glass Co., Ltd.)," KP341 "(made by Shin-Etsu Chemical Co., Ltd.)," Polyflow No. 75, No. 95 "
(Manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.), "NBX-7, NBX-
8, NBX-15 "(manufactured by Neos) and the like. The amount of the surfactant is 2 parts by weight based on 100 parts by weight of the total of the resin (A) and the naphthoquinonediazide compound (B).
It is preferable that the amount is not more than part by weight.

Examples of the solvent 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, and 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, ethyl ethoxyacetate, ethyl hydroxyacetate Methyl 2-hydroxy-3-methylbutanoate, 3-methoate Methyl Shipuropion acid, ethyl 3-ethoxypropionate, 3-methoxy propionic acid ethyl, ethyl acetate, butyl acetate, methyl pyruvate and ethyl pyruvate. Furthermore, N-methylformamide, N, N-dimethylformamide, N
-Methylformanilide, N-methylacetamide,
N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, benzylethyl ether,
Dihexyl ether, acetonylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-
Nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate,
High boiling solvents such as γ-butyrolactone, ethylene carbonate, propylene carbonate and ethylene glycol monophenyl ether acetate can also be added. These solvents are used alone or in combination of two or more.

The composition of the present invention may contain a dye or a pigment to visualize the latent image of the radiation-irradiated portion of the resist and reduce the influence of halation during the radiation. Further, an adhesion aid may be blended to improve the adhesiveness, and a storage stabilizer, an antifoaming agent, etc. may be blended if necessary.

The radiation-sensitive resin composition of the present invention comprises, for example, the above-mentioned resin (A), naphthoquinonediazide compound (B), low-molecular-weight compound (C) and, if necessary, other components. It is prepared by dissolving in a solvent to a concentration of 15 to 40% by weight and filtering through a filter having a pore size of about 0.2 μm.

Using the radiation-sensitive resin composition, for example, a resist pattern can be formed as follows. The radiation-sensitive resin composition is applied to a substrate to form a coating film, and the coating film is pre-baked to form a resist film,
The resist film is selectively irradiated with radiation so as to form a desired resist pattern, and then the irradiated resist film is developed with a developer.

In this method, the radiation-sensitive resin composition of the present invention prepared as a solution is applied by spin coating,
It is applied to a substrate such as a silicon wafer or a wafer coated with aluminum or the like, for example, by casting coating and roll coating. 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.

Further, the radiation-sensitive resin composition of the present invention comprises
After forming a resist film and irradiating with radiation, if necessary, an operation of heating at 70 to 140 ° C. (hereinafter referred to as “post-exposure bake”) is performed, and then development is performed. Can be further improved.

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, di-n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, , 8-diazabicyclo- (5,4,0) -7-undecene, and 1,5
Using an alkaline compound such as -diazabicyclo- (4,3,0) -5-nonane at a concentration of, for example, 1 to 10% by weight.
An alkaline aqueous solution dissolved in water is used so that Further, for example, methanol,
An appropriate amount of a water-soluble organic solvent such as an alcohol such as ethanol or a surfactant can be used. When a developer composed of such an alkaline aqueous solution is used, it is generally washed with water after development.

The radiation-sensitive resin composition of the present invention has an exposure margin (Epo / Ec) of at least 1.20, preferably at least 1.23, more preferably at least 1.26, particularly preferably at least 1.27. is there. This exposure margin is
The exposure amount (appropriate exposure amount (Eop)) when resolving a 0.35 μm line-and-space (L / S) pattern in a one-to-one line and space width is 0.35 μm L / S.
It indicates a value obtained by dividing by the exposure amount (Ec) when the pattern starts to be resolved, and a large value indicates that the pattern has a good exposure margin. Further, the radiation-sensitive resin composition of the present invention preferably has a resolution of 0.32 or less in a measurement method described below.
More preferably, it is 30 or less. Further, it is preferable that the pattern cross section is rectangular in the measurement method described below.

[0049]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. The measurement of the weight average molecular weight (Mw) and the evaluation of the resist in the examples were performed by the following methods. (Method for measuring Mw) GPC column (G200 manufactured by Tosoh Corporation)
0HXL: 2 pieces, G3000HXL: 1 piece, G4000
Gel permeation chromatography using monodisperse polystyrene as a standard (detector: differential refraction) under the analysis conditions using HXL: 1 bottle), flow rate: 1.0 ml / min, elution solvent: tetrahydrofuran, column temperature: 40 ° C. Total). (Method of Measuring Sensitivity) The exposure amount (appropriate exposure amount) when a 0.35 μm line and space pattern was resolved one-to-one was measured, and this value was defined as the sensitivity. (Measurement method of resolution) Exposure amount (appropriate exposure amount) when resolving a line and space (L / S) pattern of 0.35 μm in a line-to-space width ratio of 1: 1. The minimum dimension of the line and space pattern separating the space and the space was measured with a scanning electron microscope. (Method of Measuring Exposure Margin) A value obtained by dividing an appropriate exposure amount (Eop) by an exposure amount (Ec) at which a 0.35 μm L / S pattern starts to be resolved is defined as an exposure margin (Eo).
p / Ec). (Method of measuring pattern cross-sectional shape) L / S of 0.35 μm
The cross-sectional shape in the depth direction of the pattern was observed.

(1) Synthesis of Resin (A) Synthesis Example 1 In a 2 L separable flask equipped with a condenser and a stirrer, 151.2 g (1.4 mol) of m-cresol, 2,
73.2 g (0.6 mol) of 4-dimethylphenol, 3
60.8 g of a 7% by weight aqueous solution of formaldehyde (formaldehyde: 0.75 mol), oxalic acid dihydrate 12.6
g (0.1 mol) and 561 g of propylene glycol monomethyl ether, and the mixture was condensed for 8 hours while stirring at an internal temperature of 90 to 100 ° C. This resin solution was washed twice with 500 g of ion-exchanged water. M of this resin
w was 4,600. 600 g of n-hexane was added to 500 g of the obtained novolak resin solution, stirred for 30 minutes, and allowed to stand for 1 hour. The supernatant of the precipitated resin layer was removed by decantation, and the lower resin layer was heated and reduced in pressure to remove residual methyl isobutyl ketone and n-hexane, thereby obtaining a novolak resin [Resin (A-1)].
Mw of this novolak resin (A-1) was 9,100.

Synthesis Example 2 In a material charged into a flask, oxalic acid dihydrate was added to p
-A novolak resin [Resin (A-2)] was obtained in the same manner as in Synthesis Example 1 except that the amount was changed to 9.5 g (0.05 mol) of toluenesulfonic acid monohydrate. Mw of the resin (A-2) was 9,600.

Synthesis Example 3 The material charged into the flask was m-cresol 12
9.6 g (1.2 mol), 68.9 g of a 37% by weight aqueous formaldehyde solution (formaldehyde: 0.85 mol)
And 2,3-dimethylphenol and oxalic acid dihydrate in 73.2 g (0.62 g)
Mol), 8.55 g of p-toluenesulfonic acid monohydrate
(0.045 mol) and 21.6 g of p-cresol
A novolak resin [Resin (A-3)] was obtained in the same manner as in Synthesis Example 1 except that (0.2 mol) was added. Resin (A-
Mw of 3) was 9,600.

Synthesis Example 4 In the material charged to the flask, m-cresol 86.
4 g (0.8 mol), 69.7 g (formaldehyde: 0.86 mol) of a 37% by weight aqueous formaldehyde solution and 568 g of propylene glycol monomethyl ether, and 2,4 dimethylphenol and oxalic acid dihydrate were further added in a few minutes. -Dimethylphenol 97.6 g (0.8 mol), p-toluenesulfonic acid monohydrate 8.55 g
(0.045 mol) and 43.2 g of p-cresol
A novolak resin [Resin (A-4)] was obtained in the same manner as in Synthesis Example 1 except that (0.4 mol) was added. Resin (A-
Mw of 4) was 8,900.

Synthesis Example 5 In the material charged to the flask, m-cresol 14 was used.
3.7 g (1.33 mol), 81.8 g (0.67 mol) of 2,4-dimethylphenol, 44.6 g of a 37% by weight aqueous solution of formaldehyde (formaldehyde: 0.55
Mol) and propylene glycol monomethyl ether 5
63.8 g, oxalic acid dihydrate was further changed to 8.55 g (0.045 mol) of p-toluenesulfonic acid monohydrate, and 24.4 g of o-hydroxybenzaldehyde was obtained.
A novolak resin [Resin (A-5)] was obtained in the same manner as in Synthesis Example 1 except that (0.2 mol) was added. Resin (A-
Mw of 5) was 7,900.

(2) Naphthoquinonediazide compound (B)
Synthesis Example 6 A phenol compound 4 represented by the formula (4) was placed in a flask equipped with a stirrer, a dropping funnel, and a thermometer under light shielding.
9.7 g (0.1 mol), 56.4 g (0.21 mol) of 1,2-naphthoquinonediazide-5-sulfonic acid chloride and 636.6 g of acetone were charged and dissolved with stirring. Next, the flask was immersed in a water bath controlled at 30 ° C., and when the internal temperature became constant at 30 ° C., 23.3 g of triethylamine was added to the solution in the flask.
(0.23 mol) was added using a dropping funnel such that the internal temperature did not exceed 35 ° C., and the mixture was reacted at the same temperature for 2 hours. Thereafter, the precipitated triethylamine hydrochloride was removed by filtration, and the filtrate was poured into a large amount of a dilute hydrochloric acid aqueous solution to precipitate a reaction product.Then, the precipitate was filtered, collected, and dried overnight at 40 ° C. in a vacuum dryer. A naphthoquinonediazide compound (B-1) was obtained.

Synthesis Example 7 In the charged materials, 49.7 g (0.1 mol) of the phenol compound [represented by the formula (4)] used in the synthesis example 6 was converted to the phenol compound represented by the formula (5). ) To obtain a naphthoquinonediazide compound (B-2) in the same manner as in Synthesis Example 6.

Synthesis Example 8 In the charged materials, the phenol compound [represented by the formula (4)] used in the synthesis example 6 was replaced with 46.9 g (0.1 mol) of the phenol compound represented by the formula (6). ) And 619.8 g of acetone, except that the naphthoquinonediazide compound (B-
3) was obtained.

(3) Synthesis of other naphthoquinonediazide compounds Synthesis Example 9 The phenolic compound [represented by the above formula (4)] used in the synthesis example 6 was prepared from the following materials (12)
42.4 g (0.1 mol) of the phenolic compound represented by
Was replaced by 592.8 g of acetone and triethylamine 2
Other naphthoquinonediazide compounds (b-1) were obtained in the same manner as in Synthesis Example 6 except that the amount was changed to 2.3 g (0.22 mol).

[0059]

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Synthesis Example 10 The phenolic compound [represented by the above formula (4)] used in the synthesis example 6 was prepared by using the following formula (13)
39.2 g (0.1 mol) of the phenolic compound represented by
And 52.4 g (0.195 mol) of 1,2-naphthoquinonediazide-5-sulfonic acid chloride and acetone 4
Other naphthoquinonediazide compounds (b-2) were obtained in the same manner as in Synthesis Example 6 except that 76 g and 22.3 g (0.22 mol) of triethylamine were used.

[0061]

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Synthesis Example 11 In the charged materials, the phenol compound [represented by the above formula (4)] used in the synthesis example 6 was converted to the following formula (14)
36.4 g (0.1 mol) of the phenolic compound represented by
80.6 g (0.3 mol) of 1,2-naphthoquinonediazide-5-sulfonic acid chloride, acetone 702
g and 33.4 g (0.33 mol) of triethylamine, and by the same operation as in Synthesis Example 6, another naphthoquinonediazide compound (b-3) was obtained.

[0063]

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Synthesis Example 12 The phenolic compound [represented by the above formula (4)] used in Synthesis Example 6 was charged into the charged material by the following formula (15).
64.7 g (0.1 mol) of the phenolic compound represented by
And 41.6 g (0.155 mol) of 1,2-naphthoquinonediazide-5-sulfonic acid chloride, acetone 6
37.8 g and triethylamine 17.2 g (0.17 g)
Mol), but following the same procedure as in Synthesis Example 6, except that
Other naphthoquinonediazide compounds (b-4) were obtained.

[0065]

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Synthesis Example 13 The phenolic compound [represented by the formula (4)] used in Synthesis Example 6 was charged into the charged material by the following formula (16).
56.1 g (0.1 mol) of the phenolic compound represented by
And 94.0 g (0.35 mol) of 1,2-naphthoquinonediazide-5-sulfonic acid chloride, acetone 90
Other naphthoquinonediazide compounds (b-5) were obtained in the same manner as in Synthesis Example 6, except that the amounts were changed to 0.6 g and 39.5 g (0.39 mol) of triethylamine.

[0067]

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(4) Formation of resist pattern Examples 1 to 13 Compositions shown in Table 1 (however, "parts" means "parts by weight").
And a resin (A), a naphthoquinonediazide compound (B),
Other naphthoquinonediazide compounds, low molecular weight compounds (C) and solvents were mixed to form a uniform solution, which was then filtered through a membrane filter having a pore size of 0.2 μm to prepare each solution of the composition. However, as the low molecular weight compound (C), the following phenol compounds α, β and γ [the following formulas (α), (β) and (γ)] were used. As the solvent, S-1, S-2 and S-3 shown below were used.

(Low molecular weight compound) α: 1,1-bis (2,5-dimethyl-4-hydroxyphenyl) acetone β: 4,6-bis [1- (4-hydroxyphenyl) -1
-Methylethyl] -1,3-dihydroxybenzene γ: 4,6-bis [1- (4-hydroxyphenyl) -1
-Methylethyl] -1,3-dihydroxy-2-methylbenzene (solvent) S-1: ethyl 2-hydroxypropionate S-2: ethyl 3-ethoxypropionate S-3: 2-heptanone

[0070]

Embedded image

Each of the solutions obtained above is applied to a silicon wafer having a silicon oxide film on the surface by using a spinner to form a coating film.
Pre-baking was performed at 2 ° C. for 2 minutes to form a resist film having a thickness of 0.86 μm. Next, through a reticle, a wavelength of 365 nm (i) was obtained with a “NSR-2205i12D reduction projection exposure machine” (lens numerical aperture: 0.57) manufactured by Nikon Corporation.
) And post-exposure bake at 110 ° C. for 1 minute on a hot plate, followed by 2.3.
Each resist pattern was formed by developing with an 8 wt% aqueous solution of tetramethylammonium hydroxide, rinsing with ultrapure water, and drying. The obtained resist pattern was examined, and the characteristics of the resist pattern of the composition of each example were evaluated. Table 2 shows the results.

Comparative Examples 1 to 4 Except that the naphthoquinonediazide compound (B) or the low molecular weight compound (C) was not used, a solution of the composition was prepared in the same manner as in the example with the composition shown in Table 1, A resist pattern was formed and the same evaluation was performed. The results are also shown in Table 2.

[0073]

[Table 1]

[0074]

[Table 2]

[0075]

According to the radiation-sensitive resin composition of the present invention, a good pattern cross-sectional shape is obtained, the resolution is excellent, and the exposure margin is improved. Therefore, the radiation-sensitive resin composition can be suitably used as a resist for producing an integrated circuit having a high degree of integration.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 61/06 C08L 61/06 G03F 7/004 501 G03F 7/004 501 H01L 21/027 H01L 21/30 502R (72) Inventor Tsutomu Shimokawa 2-11-24 Tsukiji, Chuo-ku, Tokyo F-term in JSR Corporation (Reference) 2H025 AA01 AA02 AA03 AA10 AB16 AC01 AC08 AD03 BE01 CB29 CC20 4H006 AA02 AC61 4J002 CC031 EJ047 EJ067 EV246 FD310 GP03 GP03

Claims (3)

[Claims] (A) an alkali-soluble novolak resin, (B) a naphthoquinonediazidosulfonic acid ester compound of a phenol compound represented by the following general formula (1), and (C) a benzene ring number of 2 or 3. And a low molecular weight compound having at least one hydroxyl group in each benzene ring, wherein the radiation-sensitive resin composition has an exposure margin (Eop / Ec) of 1.20 or more. A radiation-sensitive resin composition, characterized in that: Embedded image [In the formula (1), X ₁ and X ₂ are each independently a hydrogen atom or an alkyl group, and p and q are each independently 1 or 2. ] 2. The radiation-sensitive resin composition according to claim 1, wherein the component (C) is at least one selected from compounds represented by the following general formulas (2) and (3). Embedded image [In the formula (2), a and b are each independently an integer of 1 to 3,
x and y are each independently an integer of 0 to 3, and a + x ≦ 5, b
+ Y ≦ 5. ] [In Formula (3), a, b, and c are each independently an integer of 1 to 3, x, y, and z are each independently an integer of 0 to 3, and a + x
≦ 5, b + y ≦ 4, and c + z ≦ 5. ] 3. The method according to claim 1, wherein the phenol compound of the component (B) is at least one phenol compound selected from the compounds represented by the following formulas (4), (5) and (6). The radiation-sensitive resin composition described in the above. Embedded image Embedded image Embedded image