JPH06202317A - Positive type radiation sensitive resin composition - Google Patents

Abstract

PURPOSE:To provide a positive type radiation sensitive resin compsn. useful as a resist especially excellent in focus latitude and also excellent in sensitivity, resolution, residual film rate, developability, pattern shape and heat resistance. CONSTITUTION:This positive type radiation sensitive resin compsn. contains alkali-soluble novolak resin and quinonediazidosulfonic ester of a copolymer of phenols with dicyclopntadiene.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive-type radiation-sensitive resin composition which is particularly useful as a resist for producing highly integrated circuits.

[0002]

2. Description of the Related Art Conventionally, positive resists have been widely used in the field of fine processing such as manufacturing of integrated circuits because a high-resolution resist pattern can be obtained. Along with this, the development of positive resists capable of forming resist patterns with higher resolution has been strongly promoted. On the other hand, during fine processing, a reduction projection exposure apparatus (stepper) is usually used to irradiate the positive resist with radiation through a predetermined mask pattern (hereinafter, referred to as “exposure”), and then develop the resist pattern. And a method of increasing the numerical aperture (N) of the stepper is one of means for improving the resolution. In general, in an optical system for fine processing as described above, the depth of focus (DO
There is a relationship between F) and the numerical aperture (N) expressed by the following Rayleigh equation. DOF = k × λ / N ² (k: constant, λ: wavelength of radiation) The depth of focus (DOF) is a focus tolerance that can form a dimension-controlled resist pattern even if the focus is slightly shifted in the optical axis direction. As is clear from the above equation, when the numerical aperture (N) is increased, the depth of focus (DOF), that is, the focus allowance is sharply reduced. Therefore, in order to cope with a stepper having a high numerical aperture, a positive resist having excellent focus tolerance is required. However, since the conventional positive resist is practically used near the resolution limit,
When the focus is deviated, the pattern shape is deformed, the difference from the designed line width, the developability is significantly deteriorated, and the focus cannot be said to be sufficient.

[0003]

Therefore, the present invention is particularly excellent in focus allowance, as well as in sensitivity, resolution,
It is an object of the present invention to provide a positive type radiation sensitive resin composition which is useful as a resist excellent in the residual film rate, developability, pattern shape and heat resistance.

[0004]

According to the present invention, the above-mentioned problems include (a) an alkali-soluble novolac resin and (b) a quinonediazide sulfonate ester of a copolymer of phenols and dicyclopentadiene. And a positive radiation-sensitive resin composition.

The present invention will be specifically described below, but the purpose, constitution and effect of the present invention will be clarified. First, the alkali-soluble novolac resin used in the present invention (hereinafter referred to as "novolac resin") is a novolac resin obtained by polycondensing phenols and aldehydes using an acidic catalyst.

Examples of the phenols include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p.
-Ethylphenol, on-propylphenol, m
-N-propylphenol, p-n-propylphenol, o-isopropylphenol, m-isopropylphenol, p-isopropylphenol, o-n-butylphenol, m-n-butylphenol, p-n-butylphenol, o-t- Butylphenol, mt-
Butylphenol, pt-butylphenol, pn
-Pentylphenol, pt-pentylphenol,
pn-hexylphenol, pt-hexylphenol, pn-heptylphenol, pt-heptylphenol, pn-octylphenol, pt-octylphenol, pn-nonylphenol, pt
-Nonylphenol, o-allylphenol, m-allylphenol, p-allylphenol, o-propenylphenol, m-propenylphenol, p-propenylphenol, o-cyclopentylphenol, m-cyclopentylphenol, p-cyclopentylphenol, o- Cyclohexylphenol, m-cyclohexylphenol, p-cyclohexylphenol, o-phenylphenol, m-phenylphenol, p-phenylphenol, p-cumylphenol, o-methoxyphenol, m-methoxyphenol, p-methoxyphenol, o -Ethoxyphenol, m-ethoxyphenol, p-ethoxyphenol, on-propoxyphenol, mn-propoxyphenol, pn-
Propoxyphenol, o-isopropoxyphenol, m-isopropoxyphenol, p-isopropoxyphenol, on-butoxyphenol, mn-
Butoxyphenol, pn-butoxyphenol, o
-T-butoxyphenol, m-t-butoxyphenol, pt-butoxyphenol, on-pentyloxyphenol, m-n-pentyloxyphenol,
p-n-pentyloxyphenol, o-n-hexyloxyphenol, m-n-hexyloxyphenol, p-n-hexyloxyphenol, o-n-hexyloxyphenol, m-n-hexyloxyphenol, p- n-heptyloxyphenol, o-phenoxyphenol, m-phenoxyphenol, p-phenoxyphenol, 2,3-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, 5-isopropyl-3 -Methylphenol, 2-
t-butyl-5-methylphenol, 2,5-di-se
c-Butyl-phenol, 2,5-di-t-butyl-phenol, 2,3,5-trimethylphenol, 3,
4,5-Trimethylphenol, 3-methoxy-4-methoxyphenol, 3-ethoxy-4-methoxyphenol, 3-methoxy-4-ethoxyphenol, 3-ethoxy-4-ethoxyphenol, catechol, resorcinol, hydroquinone, 3 -Methylcatechol, 4
-Methylcatechol, 2-methylresorcinol, 4-
Methylresorcinol, methylhydroquinone, 3-ethylcatechol, 4-ethylcatechol, 2-ethylresorcinol, 4-ethylresorcinol, ethylhydroquinone, n-propylhydroquinone, isopropylhydroquinone, t-butylhydroquinone, 4-n
-Hexyl resorcinol, 4-hexanoyl resorcinol, 3,5-dimethylcatechol, 2,5-dimethylresorcinol, 2,3-dimethylhydroquinone,
2,3-diethylhydroquinone, 2,5-dimethylhydroquinone, 3,5-diethylcatechol, 2,5-
Diethyl resorcinol, 2,5-diethylhydroquinone, 3,5-diisopropylcatechol, 2,5-diisopropylresorcinol, 2,3-diisopropylhydroquinone, 2,5-diisopropylhydroquinone, 3,5-di-t-butylcatechol, 2 , 5-di-
t-butyl resorcinol, 2,3-di-t-butylhydroquinone, 2,5-di-t-butylhydroquinone, pyrogallol, phloroglucinol, 1,2,4-
Benzenetriol, bisphenol A, methyl gallate, ethyl gallate, n-propyl gallate, n-butyl gallate, n-pentyl gallate, n-hexyl gallate, n-heptyl gallate, n-octyl gallate,
Methyl salicylate, ethyl salicylate, n-salicylic acid
Propyl, methyl 2-hydroxybenzoate, ethyl 2-hydroxybenzoate, n-propyl 2-hydroxybenzoate, methyl 4-hydroxybenzoate, ethyl 4-hydroxybenzoate, n-propyl 4-hydroxybenzoate and the like. be able to. These phenols may be used alone or in admixture of two or more.

Of the above-mentioned phenols, phenol, o-cresol, m-cresol, p-cresol, m-ethylphenol, p-ethylphenol,
2,3-xylenol, 2,5-xylenol, 3,4
-Xylenol, 3,5-xylenol, 2,3,5-
Trimethylphenol, 3,4,5-trimethylphenol, resorcinol, pyrogallol and the like are preferable.

Examples of the aldehydes to be polycondensed with the phenols include formaldehyde, benzaldehyde, acetaldehyde, propylaldehyde,
Phenylacetaldehyde, α-phenylpropylaldehyde, β-phenylpropylaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, o-nitrobenzaldehyde, m
-Nitrobenzaldehyde, p-nitrobenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, o-ethylbenzaldehyde, m-ethylbenzaldehyde, p-ethylbenzaldehyde, on-propylbenzaldehyde, m-n- Propylbenzaldehyde, pn-propylbutylbenzaldehyde, on-butylbenzaldehyde, mn-butylbenzaldehyde, pn
-Butylbenzaldehyde, furfural and the like can be mentioned. Of these aldehydes, formaldehyde is particularly preferable. These aldehydes can be used alone or in combination of two or more kinds.

When formaldehyde is used as the aldehyde, examples of the formaldehyde source include formalin, trioxane and paraformaldehyde, as well as hemiformals such as methyl hemiformal, ethyl hemiformal, propyl hemiformal, butyl hemiformal and phenyl hemiformal. Can be mentioned. Of these, formalin and butyl hemiformal are particularly preferred. These formaldehyde generating sources can be used alone or in admixture of two or more.

The amount of aldehyde used is 1 phenol.
0.7 to 3 mol is preferable with respect to mol.

Examples of the acidic catalyst used for polycondensation of phenols and aldehydes include hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid and acetic acid. The amount of these acidic catalysts used is usually 1 × 10 ^{−5 to} 5 × 10 ⁻¹ mol per 1 mol of phenols.

In the polycondensation of phenols and aldehydes, water is usually used as the reaction medium, but when the phenols used do not dissolve in the aqueous solution of aldehydes and become a heterogeneous system from the beginning of the reaction. It is also possible to use hydrophilic solvents as reaction medium. Examples of the hydrophilic solvent include alcohols such as methanol, ethanol, propanol, butanol, diethylene glycol dimethyl ether, 1,2-dimethoxyethane, 1,
Examples thereof include ethers such as 2-diethoxyethane, and cyclic ethers such as tetrahydrofuran and dioxane. The amount of these hydrophilic solvents used is usually the reaction raw material 1
20 to 1,000 parts by weight per 00 parts by weight.

The polycondensation temperature of phenols and aldehydes is appropriately adjusted depending on the reactivity of the reaction raw materials, but is usually 10 to 200 ° C.

As the polycondensation method of phenols and aldehydes, phenols, aldehydes, acidic catalysts and the like are charged all at once and reacted, or phenols, aldehydes and the like are gradually added in the presence of an acidic catalyst. While reacting, a method or the like can be adopted.

After completion of the polycondensation, in order to remove unreacted raw materials, acidic catalyst, reaction medium and the like existing in the reaction system, the reaction system is generally heated to 130 to 230 ° C. under reduced pressure. ,
For example, the volatile matter is removed under a pressure of about 20 to 50 mmHg, and the produced novolac resin is recovered.

The polystyrene-equivalent weight average molecular weight (hereinafter referred to as "Mw") of the novolac resin used in the present invention is appropriately selected from the range of the molecular weight of the novolac resin conventionally used in radiation-sensitive resin compositions. However, it is usually 3,000 to 20,000, preferably 4,000 to 15,000. Mw
When it exceeds 20,000, it may be difficult to uniformly apply the composition of the present invention onto the substrate, and the developability and sensitivity tend to be lowered. On the other hand, when Mw is less than 3,000, heat resistance tends to decrease.

Particularly when a high molecular weight novolac resin is desired, the novolac resin obtained by the polycondensation is used as a good solvent such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, dioxane, methanol or ethyl acetate. After dissolution, a poor solvent such as water, n-hexane, n-heptane, toluene or xylene is added and mixed to separate the precipitated novolak resin from the solution layer, thereby fractionating the high molecular weight novolak resin. Should be collected.

In the composition of the present invention, the novolac resin may be used alone or in combination of two or more kinds.

Next, in the quinonediazide sulfonic acid ester (hereinafter referred to as "sulfonic acid ester (A)") of a copolymer of phenols and dicyclopentadiene, the precursors thereof are phenols and dicyclopentadiene. As the phenols constituting the copolymer (hereinafter, referred to as "precursor copolymer"), the same phenols as those mentioned for the novolac resin are used alone or in combination of two or more. be able to.

Phenols in the precursor copolymer include phenol, o-cresol, m-cresol and p.
-Cresol, 2,3-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3,4,5-
Trimethylphenol, catechol, hydroquinone,
Resorcinol and pyrogallol are preferred.

The amount of dicyclopentadiene used in the precursor copolymer is preferably 0.05 to 1 mol, more preferably 0.1 to 1 mol, per mol of the phenol.
It is 0.75 mol.

A method for copolymerizing phenols and dicyclopentadiene is, for example, 200 ° C. in the absence of a catalyst.
Examples include a method of reacting at the above temperature, a method of reacting at a temperature of 0 to 200 ° C. using an acidic catalyst composed of a Lewis acid (Friedel-Crafts catalyst) or a protonic acid, and the like. Is preferred. Examples of the Lewis acid include aluminum chloride,
Examples thereof include boron trifluoride, titanium tetrachloride, tin tetrachloride, aluminum aluminum dichloride, diethyl aluminum chloride, trimethyl aluminum, triethyl aluminum, and the like. Examples of the protic acid include hydrochloric acid, nitric acid,
Sulfuric acid, trifluoroacetic acid, trichloroacetic acid, p-toluenesulfonic acid and the like can be mentioned. The amount of these acidic catalysts used is preferably 1 × 10 ⁻⁶ to 1 mol per mol of phenols. In addition to the acidic catalysts, perfluoroalkanesulfonic acid type ion exchange resins such as Nafion (trade name, manufactured by EI DuPont), Amberlyst (trade name, manufactured by Organo), Dowex (trade name,
A strongly acidic ion exchange resin such as a sulfonic acid type ion exchange resin having a huge network structure (such as Dow Chemical Co.) can also be used. The amount of these strongly acidic ion exchange resins used is 10 to 200 per 100 parts by weight of phenols.
Parts by weight are preferred.

In the above-mentioned method, a method of heating and polymerizing in the absence of a solvent is generally used, but a solvent inert to the reaction such as dioxane, cyclohexane or heptane may be used. Further, as the above-mentioned method, phenols, dicyclopentadiene, an acidic catalyst and the like may be charged all at once and reacted, but a preferable method is to dilute phenols containing an acidic catalyst and the like at a predetermined temperature. In this method, cyclopentadiene is gradually added to react.

After completion of the copolymerization of phenols and dicyclopentadiene, the reaction system (a) is generally set to 130-
A method of raising the temperature to 230 ° C. and removing the acidic catalyst together with volatile components under reduced pressure, for example, under a pressure of about 20 to 50 mmHg,
(B) The acidic catalyst existing in the reaction system is removed by a method of separating the acidic catalyst by filtration, (c) a method of introducing the reaction mixture into water and eluting the acidic catalyst into water, and the like.

After removing the acidic catalyst as described above, in order to remove unreacted raw materials, reaction solvent and the like in the reaction mixture, the reaction mixture is generally heated to 130 to 200 ° C. and depressurized. Under a pressure of, for example, about 20 to 50 mmHg, the volatile matter is removed, and the produced precursor copolymer is recovered.

M of the copolymer used in the present invention
w is preferably 300 to 1500, and more preferably 300 to 800.

The number of moles of hydroxyl groups in 100 g of the precursor copolymer (hereinafter referred to as "hydroxyl value") is 0.15.
˜1.5 mol / 100 g is preferable, and more preferably 0.20 to 1.5 mol / 100 g. When the hydroxyl value is less than 0.15 mol / 100 g, the solubility of the sulfonic acid ester (A) obtained from the precursor copolymer in the composition of the present invention tends to decrease, and also 1.5 mol / 100 If it exceeds 100 g, the residual film rate tends to decrease and the shape of the resist pattern tends to deteriorate.

In the present invention, the precursor copolymer may be used alone or in combination of two or more kinds.

The sulfonic acid ester (A) can be produced by condensing the precursor copolymer with a quinonediazidesulfonyl halide such as quinonediazidesulfonyl chloride to introduce a quinonediazidesulfonyl group.

Examples of the quinonediazidesulfonyl group include 1,2-naphthoquinonediazide-4-sulfonyl group, 1,2-naphthoquinonediazide-5-sulfonyl group, 1,2-naphthoquinonediazide-6-sulfonyl group, and 2,1. -Naphthoquinonediazide-4-sulfonyl group, 2,1-naphthoquinonediazide-5-sulfonyl group, 2,1-naphthoquinonediazide-6-sulfonyl group, 1,2-benzoquinonediazide-4-sulfonyl group, 1,2-benzo Examples thereof include a quinonediazide-5-sulfonyl group.

A preferred quinonediazidesulfonyl group is
1,2-naphthoquinonediazide-4-sulfonyl group,
1,2-naphthoquinonediazide-5-sulfonyl group,
1,2-naphthoquinonediazide-6-sulfonyl group and the like.

Average condensation rate when introducing a quinonediazidesulfonyl group into a precursor copolymer for producing a sulfonic acid ester (A) (phenol having a quinonediazidesulfonyl group introduced to all phenolic hydroxyl groups in the precursor copolymer) Ratio of the functional hydroxyl group) is preferably 15 to 75%
Is. If the average condensation rate is lower than 15%, the degree of improvement in focus acceptance tends to be slightly low, depending on the amount of the sulfonic acid ester (A) compounded.
If it exceeds%, the sensitivity of the composition tends to decrease.

In the composition of the present invention, the sulfonic acid ester (A) can be used alone or in admixture of two or more.

In the composition of the present invention, in addition to the sulfonic acid ester (A), a quinonediazide sulfonic acid ester of another phenol compound (hereinafter referred to as "sulfonic acid ester (a)"), for example, a benzene ring. It is also possible to add a quinonediazide sulfonic acid ester of a phenol compound having a number of about 2 to 5.

Examples of such sulfonic acid ester (a) include 2,3,4-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,
3,4,4'-tetrahydroxybenzophenone, 2,
2 ', 3,4'-tetrahydroxybenzophenone,
2,2 ', 4,4'-tetrahydroxybenzophenone, 3'-methoxy-2,3,4,4'-tetrahydroxybenzophenone, 2,2', 3,4,4'-pentahydroxybenzophenone, 2, 2 ', 3,4,6'-
Pentahydroxybenzophenone, 2,3,3 ', 4
4 ', 5'-hexahydroxybenzophenone, 2,
1,2-naphthoquinonediazide-4-sulfonic acid ester or 1,2-naphthoquinonediazide-5-sulfonic acid ester of (poly) hydroxyphenyl aryl ketone such as 3 ', 4,4', 5 ', 6-hexahydroxybenzophenone Esters;

Bis (4-hydroxyphenyl) methane,
Bis (2,4-dihydroxyphenyl) methane, bis (2,3,4-trihydroxyphenyl) methane, 2,
2-bis (4-hydroxyphenyl) propane, 2,2
-Bis (2,4-dihydroxyphenyl) propane,
2,2-bis (2,3,4-trihydroxyphenyl)
1,2-naphthoquinonediazide-4-sulfonic acid ester or 1,2-naphthoquinonediazide-5-sulfonic acid ester of bis [(poly) hydroxyphenyl] alkane such as propane;

4,4'-dihydroxytriphenylmethane, 4,4 ', 4 "-trihydroxytriphenylmethane, 2,2', 5,5'-tetramethyl-2", 4
4'-trihydroxytriphenylmethane, 3,3 ',
5,5'-tetramethyl-2 ", 4,4'-trihydroxytriphenylmethane, 4,4 ', 5,5'-tetramethyl-2,2', 2" -trihydroxytriphenylmethane, 2 , 2 ', 5,5'-tetramethyl-4,
4 ', 4 "-trihydroxytriphenylmethane, 1,
1,1-tris (4-hydroxyphenyl) ethane,
1,1,3-Tris (2,5-dimethyl-4-hydroxyphenyl) propane, 1,1,3-Tris (2,5-
Dimethyl-4-hydroxyphenyl) butane, 1,1-
Bis (4-hydroxyphenyl) -1-phenylethane, 1,1-bis (4-hydroxyphenyl) -4′-
1,2-naphthoquinonediazide-4 of (poly) hydroxytriphenylalkane such as [1- (4-hydroxyphenyl) -1-methylethyl] -1-phenylethane
-Sulfonates or 1,2-naphthoquinonediazide-5-sulfonates;

2,4,4-trimethyl-2 ', 4', 7
-Trihydroxy-2-phenylflavan, 2,4
1,2-naphthoquinonediazide-4-sulfonic acid ester of (poly) hydroxyphenyl flavan such as 4'-trimethyl-2 ', 4', 5 ', 6,7-pentahydroxy-2-phenyl flavan or 1,2 -Naphthoquinonediazide-5-sulfonic acid esters and the like can be mentioned,

JP-A-1-14463 and JP-A-1-1443
The quinonediazide sulfonic acid esters described in JP-A-156738 and the like can also be used. These sulfonic acid esters (a) can be used alone or in admixture of two or more.

Of the sulfonic acid ester (a),
1,2- of 2,3,4-trihydroxybenzophenone
Naphthoquinonediazide-5-sulfonate, 2,
1,4,3,4,4'-tetrahydroxybenzophenone
2-naphthoquinonediazide-5-sulfonic acid ester,
1,2-naphthoquinonediazide-5-sulfonic acid ester of 2,2 ′, 3,4,4′-pentahydroxybenzophenone, 2,2 ′, 5,5′-tetramethyl-2 ″,
1,4 of 4,4'-trihydroxytriphenylmethane
-Naphthoquinonediazide-5-sulfonic acid ester,
1,2-naphthoquinonediazide-5-sulfonic acid ester of 1,1,1-tris (4-hydroxyphenyl) ethane, 1 of 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) propane , 2-naphthoquinonediazide-5-sulfonate, 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) butane 1,2-naphthoquinonediazide-5-sulfonate, 1,1- Bis (4-hydroxyphenyl) -1-
Phenylethane 1,2-naphthoquinonediazide-5-
Sulfonate, 1,1-bis (4-hydroxyphenyl) -4 '-[1- (4-hydroxyphenyl)-
1,2-naphthoquinonediazide-5-sulfonic acid ester of 1-methylethyl] -1-phenylethane, 2,
Preferred is 1,2-naphthoquinonediazide-5-sulfonic acid ester of 4,4-trimethyl-2 ', 4', 7-trihydroxy-2-phenylflavan.

In the composition of the present invention, the compounding amount of the sulfonic acid ester (A) is usually 3 to 75 parts by weight, preferably 5 to 50 parts by weight, per 100 parts by weight of the novolak resin. The total amount of the sulfonic acid ester (A) and the sulfonic acid ester (a) is 1
It is usually 3 to 100 parts by weight, preferably 5 to 50 parts by weight, per 100 parts by weight, but the total amount of the quinonediazidesulfonyl group in the composition is usually 5 to 25 in terms of solid content.
% By weight, preferably 10 to 20% by weight.

Further, various additives such as a dissolution accelerator, a sensitizer, and a surfactant can be added to the composition of the present invention, if necessary. The dissolution promoter has a function of promoting the alkali solubility of the novolak resin. As a preferable example thereof, the number of benzene rings is 2 to 6
A phenol compound of a certain degree can be mentioned, and specifically, a low molecular weight phenol compound represented by the following formulas (1) to (10) (hereinafter referred to as “low molecular weight phenol compound”) can be mentioned. .

[Chemical 1]

[Chemical 2]

[Chemical 3] [In the formulas (1) to (3), a, b, x and y are each an integer of 0 to 3, but a and b are not 0 at the same time. ]

[0043]

[Chemical 4]

[Chemical 5]

[Chemical 6]

[Chemical 7]

[Chemical 8] [In the formulas (4) to (8), a, b, c, x, y and z are integers of 0 to 3, respectively, but a, b and c
Cannot be 0 at the same time. ]

[0044]

[Chemical 9] [In the formula (9), a, b, c, x, y and z are each an integer of 0 to 3, but a, b and c are not 0 at the same time, and R ¹ is a hydrogen atom or a carbon atom. An alkyl group having 1 to 4 or an aryl group having 6 to 10 carbon atoms is shown. ]

[0045]

[Chemical 10] [In the formula (10), R ^{2 to} R ⁷ may be the same or different from each other and represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, or a hydroxyl group, R ⁸ and R ⁹ may be the same or different from each other, represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms, and R ^{10 to} R ¹² may be the same or different from each other,
A hydrogen atom or an alkyl group having 1 to 6 carbon atoms is shown. ]

The low molecular weight phenol compounds may be used alone or in admixture of two or more, and the compounding amount thereof is usually 50 parts by weight or less, preferably 30 parts by weight or less per 100 parts by weight of the novolac resin. Is.

The above-mentioned sensitizer has a function of improving the sensitivity of the resist to radiation, and its example is 2H-pyrido- (3,2-b) -1,4-oxazine-3 (4H. ) -Ones, 10H-pyrido- (3,2
-B) -1,4-benzothiazines, urazoles, hydantoins, parbituric acids, glycine anhydrides,
1-hydroxybenzotriazoles, alloxans,
Maleimides etc. can be mentioned. These sensitizers can be used alone or in admixture of two or more, and the compounding amount thereof is usually 50 parts by weight or less per 100 parts by weight of the novolac resin.

The above-mentioned surfactant has a function of improving the coatability, developability and the like of the composition of the present invention.
Examples thereof include polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, and nonionic surfactants such as polyethylene glycol distearate. KP341 (trade name,
Shin-Etsu Chemical Co., Ltd.), Polyflow No. 75, no. 95
(Trade name, manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.), and F-top EF301, EF303, EF352 (trade name, manufactured by Shin-Akita Kasei), Megafax F171, F172, F17.
3 (trade name, made by Dainippon Ink), Florard FC43
0, FC431 (trade name, manufactured by Sumitomo 3M), Asahi Guard AG710, Surflon S-382, SC-10
1, SC-102, SC-103, SC-104, SC
Fluorine-based surfactants such as -105 and SC-106 (trade name, manufactured by Asahi Glass) can be mentioned. These surfactants are
Can be used alone or in combination of two or more,
The compounding amount is usually 2 parts by weight or less per 100 parts by weight of the novolak resin of the composition.

Further, in the composition of the present invention, by blending a dye or a pigment, the latent image in the exposed area can be visualized and the effect of halation during exposure can be reduced, and an adhesion aid is blended. Thereby, the adhesiveness of the composition to the substrate can be improved. Further, other additives such as a storage stabilizer and an antifoaming agent can be added.

When a resist pattern is formed using the composition of the present invention, a novolac resin and a sulfonic acid ester (A) are added as necessary, a sulfonic acid ester (a), a low molecular weight phenol compound. Or, together with various additives, for example, the solid content concentration is 20 to 40% by weight.
It is dissolved in a solvent so that it becomes, and filtered through a filter having a pore size of about 0.2 μm to prepare a composition solution.

As the solvent used for preparing the composition solution, 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 acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, toluene, xylene, methyl ethyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone, ethyl 2-hydroxypropionate, 2-hydroxy Ethyl-2-methylpropionate, ethoxyacetic acid Chill, hydroxyethyl acetate, 2
-Methyl hydroxy-3-methylbutyrate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate,
Examples thereof include methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate and the like. These solvents may be used alone or in admixture of two or more.

Further, as the solvent, N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide and benzylethyl are used. Ether, dihexyl ether, acetonylacetone, isophorone, caproic acid,
High boiling solvents such as caprylic acid, 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 1
It is also possible to add one or more species.

Then, the composition of the present invention prepared as a composition solution is applied onto a substrate such as a silicon wafer or a wafer covered with aluminum by a coating method such as spin coating, cast coating, or roll coating. Then, a radiation sensitive resin layer is formed, exposed through a predetermined mask pattern, and developed with a developing solution to form a resist pattern. Examples of the radiation used at this time include ultraviolet rays such as i-rays of a mercury lamp, far ultraviolet rays such as excimer lasers, X-rays such as synchrotron radiation, and charged particle beams such as electron beams.

The composition of the present invention is applied on a substrate, pre-baked and exposed, and then heat-treated at 70 to 140 ° C. (hereinafter referred to as "post-exposure baking"), and thereafter. By developing, the effects of the present invention can be further improved.

The developer for the composition of the present invention is:
For example, 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, 1,8-diazabicyclo-
The concentration of the alkaline compound such as [5,4,0] -7-undecene and 1,5-diazabicyclo- [4,3,0] -5-nonane is usually 1 to 10% by weight, preferably 2 to
An alkaline aqueous solution which is dissolved so as to be 5% by weight is used. Further, a proper amount of a water-soluble organic solvent, for example, alcohol such as methanol or ethanol, or a surfactant can be added to the developer. In addition, when a developer including such an alkaline aqueous solution is used, in general,
After development, wash with water.

[0056]

EXAMPLES The present invention will be described in more detail below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples as long as the gist thereof is not exceeded.
Here, the measurement of Mw and the performance evaluation of each resist were performed by the following methods. Mw: Toso Corp. GPC column (G2000H _XL :
2, G3000H _XL : 1, G4000H _XL L: 1
Liquid), a liquid volume of 1.0 ml / min, an elution solvent of tetrahydrofuran, and a column temperature of 40 ° C.
It was measured by gel permeation chromatography using monodisperse polystyrene as a standard.

Hydroxyl Value of Precursor Copolymer: Ind. En
g. Chem. , Anal. Ed. , Vol. 17,
p. It was measured by the acid anhydride method described in 395 (1945).

Sensitivity: NSR-1755i manufactured by Nikon Corporation
A 7A reduction projection exposure machine (numerical aperture of lens: 0.50) was used, the exposure time was changed, and exposure was performed with i-line having a wavelength of 365 nm, and then 25 ° by a 2.4 wt% tetramethylammonium hydroxide aqueous solution. It was developed at C for 60 seconds, washed with water, and dried to form a positive resist pattern on the wafer. At that time, the exposure time for forming the line-and-space pattern (1L1S) with a line width of 1: 1 (hereinafter referred to as “optimum exposure time”) was defined as the sensitivity.

Resolution: The minimum dimension of the resist pattern resolved when exposed for the optimum exposure time was taken as the resolution.

Focus tolerance: A line and space pattern (1L1S) having a line width of 0.35 μm was observed using a scanning electron microscope, and the resolved pattern dimension was within ± 10% of the mask design dimension. In this case, the focus allowance was evaluated by the focus swing range (focus range). The larger the focus range, the better the focus tolerance.

Residual film ratio: When exposed for an optimum exposure time,
The ratio (%) of the thickness after development to the thickness before development of the resist pattern was defined as the residual film rate.

Developability: The extent of scum and residual development was examined using a scanning electron microscope.

Pattern shape: The length L _a of the lower side and the length L _{b of the} upper side of _a rectangular cross section of a line-and-space pattern (1L1S) having a line width of 0.35 μm were measured using a scanning electron microscope. , 0.85 ≦ L _b / L _a ≦ 1 the pattern shape was considered good. However, 0.8
Even if 5 ≦ L _b / L _a ≦ 1, the pattern was not considered to be good when the pattern had a skirt or an inverse taper shape.

Heat resistance: A wafer on which a resist pattern was formed was placed in a clean oven and heated at 130 ° C. for 2 minutes, and when the pattern shape did not collapse, heat resistance was considered good.

Production of Novolac Resin Synthesis Example 1 53.0 g (0.4%) of m-cresol was placed in an autoclave.
9 mol), and 2,3-xylenol (17.1 g, 0.14).
Mol), and 2,3,5-trimethylphenol (9.54 g)
(0.07 mol), 37 wt% aqueous formaldehyde solution 51.1 g (formaldehyde 0.63 mol) oxalic acid dihydrate 4.41 g (0.035 mol) water 58.5 g and dioxane 272 g were charged, and then the autoclave. Was immersed in an oil bath, the temperature of the reaction solution was maintained at 130 ° C, and polycondensation was carried out for 7.5 hours while stirring. Then, the reaction solution was cooled to room temperature, the contents were transferred to a beaker and left to stand, the lower layer separated into two layers was taken out, concentrated, dehydrated and dried to recover the novolak resin. This resin (Mw = 8100)
The novolak resin (1) is used.

Synthesis Example 2 45.4 g (0.4%) of m-cresol was placed in an autoclave.
2 mol), 2,3-xylenol 25.7 g (0.21)
Mol), 3,4-xylenol 8.55 g (0.07 mol), 37 wt% aqueous formaldehyde solution 49.7 g
Synthesis Example 1 except that (formaldehyde 0.61 mol), oxalic acid dihydrate 4.41 g (0.035 mol), water 58.3 g and dioxane 369 g were charged and polycondensation was carried out for 8 hours.
The novolak resin was recovered in the same manner as in 1. This resin (Mw = 8900) is referred to as novolac resin (2).

Synthesis Example 3 60.6 g (0.5%) of m-cresol was placed in an autoclave.
6 mol), 8.53 g of 2,3-xylenol (0.07)
Mol), 3,4-xylenol 8.55 g (0.07 mol), 37 wt% formaldehyde aqueous solution 51.1 g
Synthesis Example 1 except that (formaldehyde 0.63 mol), oxalic acid dihydrate 4.41 g (0.035 mol), water 26.1 g and dioxane 175 g were charged and polycondensation was carried out for 8 hours.
The novolak resin was recovered in the same manner as in 1. This resin (Mw = 8800) is referred to as novolac resin (3).

Synthesis Example 4 A flask equipped with a stirrer, a condenser and a thermometer was charged with m-
Cresol 69.2 g (0.64 mol), 2,3-xylenol 9.77 g (0.08 mol), 3,4-xylenol 9.77 g (0.08 mol), 40 wt% butanol solution of formaldehyde (butyl) Hemiformal) 36.0 g (formaldehyde 0.48 mol) and oxalic acid dihydrate 0.189 g (0.0015 mol) were charged, and then the flask was immersed in an oil bath and the temperature of the reaction solution was 100 ° C. The temperature was maintained at 60 ° C., and polycondensation was performed for 60 minutes under stirring. Then, 17.3 g of m-cresol (0.1
6 mol), 9.77 g (0.08) of 2,3-xylenol
Mol), 3,4-xylenol 9.77 g (0.08 mol), 40% by weight formaldehyde butanol solution (butyl hemiformal) 36.0 g (formaldehyde 0.48 mol) and oxalic acid dihydrate 1.70 g. (0.0135 mol) was added, and polycondensation was further performed for 150 minutes. afterwards,
The temperature of the oil bath was raised to 180 ° C., and at the same time, the pressure inside the flask was reduced to 30 to 50 mmHg to remove volatile components, and the molten novolac resin was cooled to room temperature and recovered. This resin (Mw = 6100) is referred to as novolac resin (4).

Synthesis Example 5 The novolak resin (4) was dissolved in methyl 3-methoxypropionate so that the resin component would be 30% by weight, and 0.5 times the weight of this solution was added to n-heptane. , And left to stand after stirring. Then, the lower layer separated into two layers was taken out, concentrated and dried to recover the novolak resin.
This resin (Mw = 8500) is the novolac resin (5)
And

Synthesis of Sulfonic Acid Ester (A) Synthesis Example 6 (Production of Precursor Copolymer) In a flask similar to that used in Synthesis Example 4, 64.9 g (0.60 mol) of p-cresol and sulfonic acid were added. Type ion exchange resin [trade name Dowex (H
CR-S type)] 45.5 g, the flask was immersed in an oil bath, the temperature of the reaction solution was kept at 100 ° C., and 26.4 g (0.20 mol) of dicyclopentadiene was added under stirring. Was added dropwise over 40 minutes, and the temperature of the reaction solution was changed to 135 ° C.
And allowed to react for another 9 hours. Then, the reaction liquid was cooled to room temperature, dioxane 70 cc was added under stirring, and then the sulfonic acid type ion exchange resin was filtered off. Then, the filtrate was placed in a flask equipped with a stirrer and a condenser, and the temperature of the oil bath in which the flask was immersed was raised to 180 ° C.,
After removing the dioxane, the pressure in the flask was adjusted to 30-
The pressure was reduced to 50 mmHg to remove volatile matter. Then, the melted copolymer was cooled to room temperature and recovered. This copolymer has Mw = 630, hydroxyl value = 0.35 mol / 100
It was g. This is referred to as a precursor copolymer (1).

Synthesis Example 7 100 g of the precursor copolymer (1) and 1,2-naphthoquinonediazide-5 were placed in a flask similar to that used in Synthesis Example 4.
-Sulfonyl chloride 24.2 g (0.09 mol) and dioxane 290 g were charged and dissolved under stirring. Then add 3 flasks
Immerse it in a water bath kept at 0 ° C., and when the temperature of the reaction solution became constant at 30 ° C., add 10.1 g (0.10 mol) of triethylamine so that the temperature of the reaction solution did not exceed 35 ° C. Gradually dropwise was added using a dropping funnel. 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. After filtering this precipitate,
It was dried overnight in a vacuum dryer kept at 40 ° C. to obtain a sulfonic acid ester (A) having an average condensation rate of 25%. This is referred to as a sulfonic acid ester (A1).

Synthesis Example 8 (Production of Precursor Copolymer) In a flask similar to that used in Synthesis Example 4, 94.1 g (1.0 mol) of phenol and 1.44 g of boron trifluoride / diethyl ether complex were added.
After charging (boron trifluoride 0.01 mol), the flask was immersed in an oil bath, the temperature of the reaction solution was kept at 80 ° C, and 52.9 g (0.40 mol) of dicyclopentadiene was stirred under stirring. ) Was added dropwise over 60 minutes, the temperature of the reaction solution was raised to 120 ° C., and the reaction was further performed for 180 minutes. Then, the temperature of the oil bath was raised to 170 ° C., and at the same time, the pressure in the flask was raised to 30 to 5
The pressure was reduced to 0 mmHg to remove volatile matter. Then, the melted copolymer was cooled to room temperature and recovered. This copolymer has an Mw of 590 and a hydroxyl value of 0.33 mol / 100.
It was g. This is referred to as a precursor copolymer (2).

Synthesis Example 9 100 g of the precursor copolymer (2), 35.5 g (0.13) of 1,2-naphthoquinonediazide-5-sulfonyl chloride
2 mol), dioxane 316 g and triethylamine 15.2 g (0.15 mol) were used and treated in the same manner as in Synthesis Example 7 to obtain a sulfonic acid ester (A) having an average condensation rate of 40%. .
This is designated as a sulfonic acid ester (A2).

Synthesis Example 10 (Preparation of Precursor Copolymer) In a flask similar to that used in Synthesis Example 4, 66.1 g (0.60 mol) of resorcinol and 8.0 g (0.06 mol) of aluminum chloride were added. After charging, the flask was immersed in an oil bath, the temperature of the reaction solution was kept at 40 ° C, and 27.8 g (0.20 mol) of dicyclopentadiene was added dropwise over 45 minutes with stirring. Liquid temperature 100 ℃
And allowed to react for another 5 hours. Then, the reaction solution was allowed to cool to room temperature, and the contents were stirred with water 540
It poured into cc and separated the organic layer. Next, this organic layer was placed in a flask equipped with a stirrer and a cooling tube, and treated in the same manner as in Synthesis Example 6 to recover a copolymer. This copolymer has an Mw of 680 and a hydroxyl value of 0.65 mol / 1.
It was 00 g. This is referred to as a precursor copolymer (3).

Synthesis Example 11 100 g of the precursor copolymer (3) and 52.4 g (0.19) of 1,2-naphthoquinonediazide-5-sulfonyl chloride.
5 mol), dioxane 356 g and triethylamine 20.2 g (0.20 mol) were used and treated in the same manner as in Synthesis Example 7 to obtain a sulfonic acid ester (A) having an average condensation rate of 30%. .
This is designated as a sulfonic acid ester (A3).

Examples 1 to 5 and Comparative Examples 1 to 2 The novolak resin and sulfonic acid ester (A) obtained in each of the above synthesis examples, and if necessary, the sulfonic acid ester (a), a low molecular weight phenol compound and a solvent were added. After mixing to form a uniform solution, the solution was filtered using a membrane filter having a pore size of 0.2 μm to prepare a solution of the composition shown in Table 1. Here, parts are based on weight.

The types of sulfonic acid ester (a), low molecular weight phenolic compound and solvent used here are as follows:
It is as follows. Sulfonic acid ester (a) a1: 1,1-bis (4-hydroxyphenyl) -4-
[1- (4-Hydroxyphenyl) -1-methylethyl] -1-phenylethane 1 mol and 1,2-naphthoquinonediazide-5-sulfonyl chloride 2 mol condensate, a2: 1,1-bis (4 -Hydroxyphenyl) -4-
[1- (4-Hydroxyphenyl) -1-methylethyl] -1-phenylethane 1 mol and 1,2-naphthoquinonediazide-5-sulfonyl chloride 2.5 mol condensate, a3: 1,1,3 A condensate of 1 mol of tris (2,5-dimethyl-4-hydroxyphenyl) butane and 2.5 mol of 1,2-naphthoquinonediazide-5-sulfonyl chloride.

Low molecular weight phenol compound b1: 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) butane (corresponding to the above formula (9)), b2: 1,1-bis (4-hydroxy) Phenyl) -1-
Phenylethane (corresponding to the above formula (8)), b3: 1,1-bis (4-hydroxyphenyl) -4-
[1- (4-hydroxyphenyl) -1-methylethyl] -1-phenylethane (corresponding to the above formula (10)).

Solvents α: Ethyl 2-hydroxypropionate, β: Methyl 3-methoxypropionate, γ: Ethylene glycol monoethyl ether acetate.

A solution of each composition was applied onto a silicon wafer using a spinner, and then hot held at 90 ° C. (other than Example 4 and Comparative Example 2) or 100 ° C. (Example 4 and Comparative Example 2). Pre-baking was performed for 2 minutes on the plate to form a resist film having a film thickness of 1.1 μm. This resist film is exposed to i-line having a wavelength of 365 nm as described above through a mask pattern, and then 110
After the exposure, baking was performed for 1 minute on a hot plate kept at ℃. Then develop and wash as described above,
After drying, a resist pattern was formed, and the performance of each resist was evaluated based on the obtained resist pattern. Table 2 shows the evaluation results.

[0081]

[Table 1]

[0082]

[Table 2]

[0083]

The positive radiation-sensitive resin composition of the present invention is particularly excellent in focus acceptability, and also excellent in sensitivity, resolution, residual film rate, developability, pattern shape and heat resistance. Therefore, the positive-type radiation-sensitive resin composition of the present invention is extremely useful especially as a positive-type resist for manufacturing integrated circuits, which is expected to have higher integration in the future.

[Procedure amendment]

[Submission date] September 10, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0006

[Correction method] Change

[Correction content]

Examples of the phenols include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p.
-Ethylphenol, on-propylphenol, m
-N-propylphenol, p-n-propylphenol, o-isopropylphenol, m-isopropylphenol, p-isopropylphenol, o-n-butylphenol, m-n-butylphenol, p-n-butylphenol, o-t- Butylphenol, mt-
Butylphenol, pt-butylphenol, pn
-Pentylphenol, pt-pentylphenol,
pn-hexylphenol, pt-hexylphenol, pn-heptylphenol, pt-heptylphenol, pn-octylphenol, pt-octylphenol, pn-nonylphenol, pt
-Nonylphenol, o-allylphenol, m-allylphenol, p-allylphenol, o-propenylphenol, m-propenylphenol, p-propenylphenol, o-cyclopentylphenol, m-cyclopentylphenol, p-cyclopentylphenol, o- Cyclohexylphenol, m-cyclohexylphenol, p-cyclohexylphenol, o-phenylphenol, m-phenylphenol, p-phenylphenol, p-cumylphenol, o-methoxyphenol, m-methoxyphenol, p-methoxyphenol, o -Ethoxyphenol, m-ethoxyphenol, p-ethoxyphenol, on-propoxyphenol, mn-propoxyphenol, pn-
Propoxyphenol, o-isopropoxyphenol, m-isopropoxyphenol, p-isopropoxyphenol, on-butoxyphenol, mn-
Butoxyphenol, pn-butoxyphenol, o
-T-butoxyphenol, m-t-butoxyphenol, pt-butoxyphenol, on-pentyloxyphenol, m-n-pentyloxyphenol,
p-n-pentyloxyphenol, o-n-hexyloxyphenol, m-n-hexyloxyphenol, p-n-hexyloxyphenol, o-n-hexyloxyphenol, m-n-hexyloxyphenol, p- n-heptyloxyphenol, o-phenoxyphenol, m-phenoxyphenol, p-phenoxyphenol, 2,3-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, 5-isopropyl-3 -Methylphenol, 2-
t-butyl-5-methylphenol, 2,5-di-se
c-Butyl-phenol, 2,5-di-t-butyl-phenol, 2,3,5-trimethylphenol, 3,
4,5-Trimethylphenol, 3-methoxy-4-methoxyphenol, 3-ethoxy-4-methoxyphenol, 3-methoxy-4-ethoxyphenol, 3-ethoxy-4-ethoxyphenol, catechol, resorcinol, hydroquinone, 3 -Methylcatechol, 4
-Methylcatechol, 2-methylresorcinol, 4-
Methylresorcinol, methylhydroquinone, 3-ethylcatechol, 4-ethylcatechol, 2-ethylresorcinol, 4-ethylresorcinol, ethylhydroquinone, n-propylhydroquinone, isopropylhydroquinone, t-butylhydroquinone, 4-n
-Hexyl resorcinol, 4-hexanoyl resorcinol, 3,5-dimethylcatechol, 2,5-dimethylresorcinol, 2,3-dimethylhydroquinone,
2,3-diethylhydroquinone, 2,5-dimethylhydroquinone, 3,5-diethylcatechol, 2,5-
Diethyl resorcinol, 2,5-diethylhydroquinone, 3,5-diisopropylcatechol, 2,5-diisopropylresorcinol, 2,3-diisopropylhydroquinone, 2,5-diisopropylhydroquinone, 3,5-di-t-butylcatechol, 2 , 5-di-
t-butyl resorcinol, 2,3-di-t-butylhydroquinone, 2,5-di-t-butylhydroquinone, pyrogallol, phloroglucinol, 1,2,4-
Benzenetriol, bisphenol A, methyl gallate, ethyl gallate, n-propyl gallate, n-butyl gallate, n-pentyl gallate, n-hexyl gallate, n-heptyl gallate, n-octyl gallate,
Methyl salicylate, ethyl salicylate, n-salicylic acid
Propyl, methyl 3-hydroxybenzoate, ethyl 3-hydroxybenzoate, n-propyl 3-hydroxybenzoate, methyl 4-hydroxybenzoate, ethyl 4-hydroxybenzoate, n-propyl 4-hydroxybenzoate and the like. be able to. These phenols may be used alone or in admixture of two or more.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] 0027

[Correction method] Change

[Correction content]

The number of moles of hydroxyl groups in 100 g of the precursor copolymer (hereinafter referred to as "hydroxyl value") is 0.15.
˜1.5 mol / 100 g is preferable, and more preferably 0.20 to 1.5 mol / 100 g. If the hydroxyl value is less than 0.15 mol / 100 g, the sensitivity and heat resistance tend to decrease, and if it exceeds 1.5 mol / 100 g, the residual film rate decreases and the shape of the resist pattern deteriorates. Tend to do.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0043

[Correction method] Change

[Correction content]

[0043] [In the formulas (4) to (8), a, b, c, x, y and z are integers of 0 to 3, respectively, but a, b and c
Cannot be 0 at the same time. ]

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0044

[Correction method] Change

[Correction content]

[0044] [In the formula (9), a, b, c, x, y and z are each an integer of 0 to 3, but a, b and c are not 0 at the same time, and R ¹ is a hydrogen atom or a carbon atom. An alkyl group having 1 to 4 or an aryl group having 6 to 10 carbon atoms is shown. ]

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0055

[Correction method] Change

[Correction content]

The developer for the composition of the present invention is:
For example, 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, 1,8-diazabicyclo-
The concentration of the alkaline compound such as [5,4,0] -7-undecene and 1,5-diazabicyclo- [4,3,0] -5-nonene is usually 1 to 10% by weight, preferably 2 to
An alkaline aqueous solution which is dissolved so as to be 5% by weight is used. Further, a proper amount of a water-soluble organic solvent, for example, alcohol such as methanol or ethanol, or a surfactant can be added to the developer. In addition, when a developer including such an alkaline aqueous solution is used, in general,
After development, wash with water.

[Procedure correction 6]

[Document name to be amended] Statement

[Correction target item name] 0056

[Correction method] Change

[Correction content]

[0056]

EXAMPLES The present invention will be described in more detail below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples as long as the gist thereof is not exceeded.
Here, the measurement of Mw and the performance evaluation of each resist were performed by the following methods. Mw: Tosoh Corp. GPC column (G2000
H _XL : 2, G3000H _XL : 1, G4000H
_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 conditions were gel permeation chromatography using monodisperse polystyrene as a standard.

[Procedure Amendment 7]

[Document name to be amended] Statement

[Name of item to be corrected] 0070

[Correction method] Change

[Correction content]

Synthesis of Sulfonic Acid Ester (A) Synthesis Example 6 (Production of Precursor Copolymer) In a flask similar to that used in Synthesis Example 4, 64.9 g (0.60 mol) of p-cresol and sulfonic acid were added. Type ion exchange resin [trade name Dowex (H
CR-W2 type)] 45.5 g, and then the flask was immersed in an oil bath, the temperature of the reaction solution was maintained at 100 ° C, and 26.4 g (0.20 mol) of dicyclopentadiene was added under stirring. Was added dropwise over 40 minutes, and the temperature of the reaction solution was changed to 135 ° C.
And allowed to react for another 9 hours. Then, the reaction liquid was cooled to room temperature, dioxane 70 cc was added under stirring, and then the sulfonic acid type ion exchange resin was filtered off. Then, the filtrate was placed in a flask equipped with a stirrer and a condenser, and the temperature of the oil bath in which the flask was immersed was raised to 180 ° C.,
After removing the dioxane, the pressure in the flask was adjusted to 30-
The pressure was reduced to 50 mmHg to remove volatile matter. Then
The melted copolymer was cooled to room temperature and recovered. This copolymer has an Mw-630 and a hydroxyl value of 0.35 mol / 1.
It was 00 g. This is referred to as a precursor copolymer (1).

[Procedure Amendment 8]

[Document name to be amended] Statement

[Correction target item name] 0076

[Correction method] Change

[Correction content]

Examples 1 to 5 The novolac resin and the sulfonic acid ester (A) obtained in each of the above-mentioned synthesis examples were mixed with the sulfonic acid ester (a) depending on the case.
And a low molecular weight phenolic compound together with a solvent to form a uniform solution, which was then filtered using a membrane filter having a pore size of 0.2 μm to give the composition shown in Table 1 (however,
Parts are by weight. ) Solution was prepared. Comparative Examples 1-2 A composition solution was prepared by using components having the compositions shown in Table 1 (however, parts are based on weight) in the same manner as in the examples.

 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Akira Tsuji 2-11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd.

Claims (1)

[Claims] 1. (a) Alkali-soluble novolac resin,
And (b) a positive-type radiation-sensitive resin composition containing a quinonediazide sulfonic acid ester of a copolymer of phenols and dicyclopentadiene.