JPH06289607A - Positive radiation sensitive resin composition - Google Patents

Abstract

PURPOSE:To improve focus allowability, sensitivity, resolution, developing property, pattern shape and heat resistance by incorporating an alkali soluble novolak resin and a specific quinone diazide sulfonic acid ester. CONSTITUTION:The alkali soluble novolak resin and the quinone diazide sulfonic acid ester, which is a polymerization and condensation body having at least two of a repeating unit expressed by a formula 1 and/or a repeating unit expressed by a formula II, are incorporated. In the formulas 1 and II, each of R<1>-R<4> is hydrogen atom, 1-10C alkyl group or 6-15C alkyl group, each of R<5>-R<8> is hydrogen atom, halogen atom, 1-6C alkyl group or 6-15C allyl group, R<9> is 1-10 alkyl group, 1-8C alkoxyl group or the like. And each of (m) and (n) is an integer satisfying 1<=(m)<=3, 0<=(n)<=3, (m)+(n)<=4 in the formula 1 and an integer satisfying 1<=(m)<=6, 0<=(n)<=5, (m)+(n)<=6 in the formula II.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a positive type radiation sensitive resin composition. More specifically, it relates to a positive-type radiation-sensitive resin composition suitable as a resist for producing highly integrated circuits, which is sensitive to various radiations such as ultraviolet rays.

[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. In microfabrication, a reduction projection exposure machine (stepper) is usually used to irradiate the positive resist with radiation through a predetermined mask pattern (hereinafter referred to as “exposure”), and then develop to form a resist pattern. As one means for improving the resolution, there is a method of increasing the numerical aperture (NA) of the stepper lens. In general, in an optical system for fine processing as described above, the relationship between the depth of focus (DOF) and the numerical aperture (NA) is represented by the following Rayleigh equation. DOF = k × λ / (NA) ² (where, k: constant, λ: wavelength of radiation) The depth of focus (DOF) is to form a resist pattern whose dimension is controlled even if the focus shifts in the optical axis direction. As is clear from the above equation, the depth of focus (DOF), that is, the focus allowance becomes extremely small, as is clear from the above equation. 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 deformation of the pattern shape, the difference with the design line width, the deterioration of the developability, etc. become remarkable, It cannot be said that it has sufficient focus tolerance.

[0003]

DISCLOSURE OF THE INVENTION The present invention is particularly excellent in focus tolerance, and also has sensitivity, resolution, developability,
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 pattern shape, heat resistance and the like.

[0004]

According to the present invention, the above-mentioned problems are represented by (a) an alkali-soluble novolac resin, and (b) a repeating unit represented by the following formula (1) and / or a repeating unit represented by the formula (2). Positive radiation-sensitive resin composition containing a polycondensed quinonediazide sulfonic acid ester having at least two repeating units
Achieved by

[Chemical 1]

Embedded image [In the formulas (1) and (2), R ^{1 to} R ⁴ may be the same or different from each other, and a hydrogen atom and a carbon number of 1 to 1
10 represents an alkyl group or an aryl group having 6 to 15 carbon atoms, R ^{5 to} R ⁸ may be the same or different from each other,
A hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 15 carbon atoms, R ⁹ is 1 carbon atom
-10 alkyl group, C1-8 alkoxy group, C7-15 aralkyloxy group, C1-7 acyl group, C6-15 aryl group, C7-15
Represents an aralkyl group of, an aryloxy group having 6 to 10 carbon atoms or an alkoxycarbonyl group having 2 to 10 carbon atoms,
When a plurality of R ^9's are present, they may be the same as or different from each other, and m and n are 1 ≦ m ≦ 3 and 0 ≦ n in the formula (1).
An integer satisfying ≦ 3 and m + n ≦ 4, 1 ≦ in the formula (2)
It is an integer that satisfies m ≦ 6, 0 ≦ n ≦ 5, and m + n ≦ 6. ]

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 “novolak resin (A)”) is an acidic catalyst containing at least one phenol and an aldehyde selected from the following phenols (a). It is obtained by polycondensation using.

Examples of the phenols (a) 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-isobutylphenol, m-isobutylphenol, p-isobutylphenol, o-
sec-butylphenol, m-sec-butylphenol, p-sec-butylphenol, ot-butylphenol, mt-butylphenol, pt-butylphenol, pn-pentylphenol, pt-
Pentylphenol, pn-hexylphenol, p
-T-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-methoxy Phenol, o-ethoxyphenol, m-ethoxyphenol, p-ethoxyphenol, on-propoxyphenol, m-n-propoxyphenol, pn-propoxyphenol, o-isopropoxyphenol, m-isopropoxyphenol, p-isopropoxyphenol, on-butoxyphenol, mn-butoxyphenol, pn-butoxyphenol, ot-butoxyphenol, m-
t-butoxyphenol, pt-butoxyphenol, on-pentyloxyphenol, mn-pentyloxyphenol, pn-pentyloxyphenol, on-hexyloxyphenol, mn-hexyloxy Phenol, pn-hexyloxyphenol, on-heptyloxyphenol, mn-
Heptyloxyphenol, pn-heptyloxyphenol, o-phenoxyphenol, m-phenoxyphenol, p-phenoxyphenol, 2,3-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol , 5-n-propyl-3-methylphenol, 5-isopropyl-3-methylphenol, 2-n-butyl-5-methylphenol, 2-t
-Butyl-5-methylphenol, 2,5-di-n-butylphenol, 2,5-di-sec-butylphenol, 2,5-di-t-butylphenol, 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, n-
Butyl hydroquinone, t-butyl hydroquinone, 4
-N-hexyl resorcinol, 4-hexanoylresorcinol, 3,5-dimethylcatechol, 2,5-dimethylresorcinol, 2,3-dimethylhydroquinone, 2,5-dimethylhydroquinone, 3,5-diethylcatechol, 2,5 -Diethylresorcinol, 2,
3-diethylhydroquinone, 2,5-diethylhydroquinone, 3,5-di-n-propylcatechol, 2,
5-di-n-propylresorcinol, 2,3-di-n
-Propylhydroquinone, 2,5-di-n-propylhydroquinone, 3,5-diisopropylcatechol,
2,5-diisopropylresorcinol, 2,3-diisopropylhydroquinone, 2,5-diisopropylhydroquinone, 3,5-di-n-butylcatechol,
2,5-di-n-butylresorcinol, 2,3-di-
n-butylhydroquinone, 2,5-di-n-butylhydroquinone, 3,5-di-t-butylcatechol,
2,5-di-t-butylresorcinol, 2,3-di-
t-butyl hydroquinone, 2,5-di-t-butyl hydroquinone, 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-propyl salicylate, methyl 2-hydroxybenzoate, ethyl 2-hydroxybenzoate, n-hydroxybenzoate n- Examples thereof include propyl, methyl 4-hydroxybenzoate, ethyl 4-hydroxybenzoate, n-propyl 4-hydroxybenzoate and the like.

Among these phenols (a), especially 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. The phenols (a) can be used alone or in combination of two or more.

Examples of the aldehydes to be polycondensed with the phenols (a) 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, p-
n-propylbenzaldehyde, on-butylbenzaldehyde, mn-butylbenzaldehyde, pn
-Butylbenzaldehyde, furfural and the like can be mentioned. Of these, 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, paraformaldehyde and the like, as well as methyl hemiformal, ethyl hemiformal, propyl hemiformal, butyl hemiformal and phenyl hemiformal. And the like. Of these, formalin and butyl hemiformal are particularly preferable. These formaldehyde generating sources can be used alone or in admixture of two or more.

The amount of the aldehydes used is preferably 0.7 to 3 mol per 1 mol of the phenol (a).

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

In the polycondensation of the phenols (a) and the aldehydes, water is usually used as the reaction medium, but the phenols (a) used are not dissolved in the aqueous solution of the aldehydes and the In the case of non-uniformity, a hydrophilic solvent can be used as the reaction medium. Examples of the hydrophilic solvent include alcohols such as methanol, ethanol, propanol and butanol, acyclic ethers such as diethylene glycol dimethyl ether, 1,2-dimethoxyethane and 1,2-diethoxyethane, tetrahydrofuran, dioxane and the like. Cyclic ethers of The amount of these reaction media used is usually 20 to 1000 parts by weight per 100 parts by weight of the reaction raw material.

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

The polycondensation of the phenols (a) with the aldehydes may be carried out by charging the phenols (a), the aldehydes, the acidic catalyst, etc. all at once and reacting them in the presence of the acidic catalyst. It is possible to employ a method in which the reaction is carried out while gradually adding a), an aldehyde, an acidic catalyst and the like.

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 temperature of the reaction system is generally raised to 130 to 230 ° C., and the pressure is reduced, for example. The volatile matter is distilled off under a pressure of about 20 to 50 mmHg to recover the novolac resin (A) thus produced.

The standard polystyrene reduced weight average molecular weight (hereinafter referred to as "Mw") of the novolak resin (A) used in the present invention is within the range of the molecular weight of the novolak resin conventionally used in the radiation sensitive resin composition. It can be appropriately selected, but usually 3000 to 2000
It is 0, preferably 4000-15000. When the Mw of the novolac resin (A) exceeds 20,000, it may be difficult to uniformly apply the composition of the present invention onto a substrate, and the developability and sensitivity tend to be lowered, and the composition may be 3000. When it is less than 1, the heat resistance tends to decrease.

Particularly when a high molecular weight novolak resin (A) is desired, the novolak resin (A) obtained by the polycondensation is treated with ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, dioxane, methanol, acetic acid. After dissolving in a good solvent such as ethyl, a poor solvent such as water, n-hexane, n-heptane, toluene, xylene is added and mixed,
By separating the precipitated novolak resin (A) from the solution layer, a high molecular weight novolak resin (A) fractionated
Can be obtained.

In the present invention, novolac resin (A)
Can be used alone or in admixture of two or more.

Next, a polycondensate having at least two repeating units represented by the formula (1) and / or the repeating unit represented by the formula (2) (hereinafter referred to as "specific polycondensate") is obtained. For example, at least one of phenols represented by the following formula (3) or formula (4) (hereinafter referred to as “phenol (b)”) and a compound represented by the following formula (5) (hereinafter referred to as “2 It can be produced by polycondensing at least one of the functional compound (b) ”) in the presence of an acidic catalyst.

[0020]

[Chemical 3]

[Chemical 4] [In the formula (3), R ⁹ , m and n have the same meanings as in the formula (1), and in the formula (4), R ⁹ , m and n are the formula (2).
Is synonymous with. ]

[0021]

[Chemical 5] [In the formula (5), R ^{1 to} R ⁸ have the same meanings as in the formula (1),
X's may be the same or different from each other, and are a hydroxyl group, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, and 1 to 1 carbon atoms.
A C6 alkoxyalkoxy group, a C1-6 acyloxy group, a mercapto group or a C1-6 alkylthio group is shown. ]

Specific examples of the phenols (b) include the phenols (a) mentioned for the novolac resin (A).
(However, o-allylphenol, m-allylphenol, p-allylphenol, o-propenylphenol, m-propenylphenol and p-propenylphenol are excluded.), 1-naphthol, 2-naphthol, 1,2 -Dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene,
2,7-dihydroxynaphthalene, 2-methyl-1-naphthol, 4-methoxy-1-naphthol, 7-methoxy-2-naphthol and the like can be mentioned.

Examples of these phenols (b) include phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,5-xylenol and 3,4-xylenol. , 3,5-xylenol,
2,3,5-Trimethylphenol, 3,4,5-trimethylphenol, catechol, hydroquinone, resorcinol, pyrogallol, 1-naphthol, 2-naphthol and the like are preferable.

As the bifunctional compound (b), o
-Xylene-α, α'-diol, m-xylene-α,
α'-diol, p-xylene-α, α'-diol,
α, α, α ', α'-tetramethyl-1,3-benzenedimethanol, α, α, α', α'-tetramethyl-
1,4-benzenedimethanol, 2,3,5,6-tetramethyl-p-xylene-α, α'-diol, α,
α'-dibromo-o-xylene, α, α'-dibromo-
m-xylene, α, α′-dibromo-p-xylene,
α, α'-dichloro-o-xylene, α, α'-dichloro-m-xylene, α, α'-dichloro-p-xylene, α, α'-dimethoxy-o-xylene, α, α'-
Dimethoxy-m-xylene, α, α'-dimethoxy-p
-Xylene, α, α'-diethoxy-o-xylene,
α, α′-diethoxy-m-xylene, α, α′-diethoxy-p-xylene, α, α′-diisopropoxy-
o-xylene, α, α′-diisopropoxy-m-xylene, α, α′-diisopropoxy-p-xylene,
α, α′-di-t-butoxy-o-xylene, α, α ′
-Di-t-butoxy-m-xylene, α, α'-di-t
-Butoxy-p-xylene, α, α'-di (methoxymethoxy) -o-xylene, α, α'-di (methoxymethoxy) -m-xylene, α, α'-di (methoxymethoxy) -p- Xylene, α, α′-di (ethoxymethoxy) -o-xylene, α, α′-di (ethoxymethoxy) -m-xylene, α, α′-di (ethoxymethoxy) -p-xylene, α, α '-Diacetoxy-o-xylene, α, α'-diacetoxy-m-xylene, α,
α'-diacetoxy-p-xylene, o-xylene-
α, α′-dithiol, m-xylene-α, α′-dithiol, p-xylene-α, α′-dithiol, α,
α'-dimethylthio-o-xylene, α, α'-dimethylthio-m-xylene, α, α'-dimethylthio-p-
Xylene etc. can be mentioned.

As these bifunctional compounds (b),
m-xylene-α, α'-diol, p-xylene-
α, α'-diol, α, α, α ', α'-tetramethyl-1,3-benzenedimethanol, α, α, α',
α'-tetramethyl-1,4-benzenedimethanol,
2,3,5,6-tetramethyl-p-xylene-α,
α'-diol, α, α'-dibromo-m-xylene,
α, α'-dibromo-p-xylene, α, α'-dichloro-m-xylene, α, α'-dichloro-p-xylene, α, α'-dimethoxy-m-xylene, α, α'-
Dimethoxy-p-xylene, α, α′-diacetoxy-
Preferred are m-xylene, α, α′-diacetoxy-p-xylene and the like.

The amount of the phenols (b) used is usually 0.3 to 5 mol, preferably 1 to 1.5 mol, per mol of the bifunctional compound (b).

Examples of the acidic catalyst used in the production of the specific polycondensate include protic acids such as hydrochloric acid, sulfuric acid, oxalic acid, p-toluenesulfonic acid, trifluoroacetic acid, methanesulfonic acid and trifluoromethanesulfonic acid, trifluoride. Examples thereof include Lewis acids such as boron chloride, aluminum chloride, zinc chloride, and stannic chloride. The amount of these acidic catalysts used is 1 × 10 6 with respect to 1 mol of the bifunctional compound (b).
^{-6 to} 5 x 10 ^-1 mol is preferred.

When the specific polycondensate is produced, it may be polycondensed in the absence of a solvent, or may be polycondensed using an inert solvent such as toluene, xylene and methyl isobutyl ketone. The amount of these solvents used is usually 20 to 1000 parts by weight per mol of the reaction raw material.

The polycondensation temperature and the polycondensation time of the phenols (b) and the bifunctional compound (b) are appropriately adjusted depending on the reactivity of the reaction raw materials, but the polycondensation temperature is usually 0 to 180. C., polycondensation time is 0.5 to 48 hours.

As the polycondensation method of the phenols (b) and the bifunctional compound (b), phenols (b),
A method in which a bifunctional compound (b), an acidic catalyst and the like are collectively charged and reacted, a method in which phenols (b) and a bifunctional compound (b) and the like are gradually added and reacted in the presence of an acidic catalyst, Alternatively, a method of reacting in the presence of the phenol (b), the bifunctional compound (b) and the like while gradually adding an acidic catalyst or the like can be adopted.

After completion of the polycondensation of the phenol (b) and the bifunctional compound (b), generally, the reaction mixture is put into water to elute the acidic catalyst into water, and then the unreacted raw materials in the reaction mixture are mixed. In order to remove the reaction solvent and the like, the reaction mixture is heated to 130 to 230 ° C. and reduced pressure, for example, 20 to
The volatile matter is removed under a pressure of about 50 mmHg to recover the produced specific polycondensate.

The specific polycondensate obtained by such polycondensation is a polycondensate having at least two repeating units represented by the formula (1) and / or the repeating unit represented by the formula (2), or a polycondensate thereof. The main component is a mixture of polycondensates of, and its Mw is usually 500 to
It is 5000. When the Mw of the specific polycondensate is less than 500, the degree of improvement in focus tolerance tends to be slightly low, and when it exceeds 5,000, the developability tends to deteriorate.

In the present invention, as the specific polycondensate,
Mw is 600 to 4500, and a benzene ring and a naphthalene ring in the main chain (that is, R ^{1 to} R ^{9 in} formula (1) and formula (2)).
Those containing 50% by weight or more of a polycondensate having a total number of benzene rings and naphthalene rings other than those contained therein of 5 or more.

The number of moles of hydroxyl groups in 100 g of the specific polycondensate (hereinafter referred to as "hydroxyl value") is 0.2 to.
The amount is preferably 2.5 mol / 100 g, more preferably 0.3 to 2.0 mol / 100 g. The hydroxyl value is 0.
If it is less than 2 mol / 100 g, the sensitivity tends to decrease, and if it exceeds 2.5 mol / 100 g, the shape of the resist pattern tends to deteriorate.

In the present invention, the specific polycondensates may be used alone or in admixture of two or more.

The specific polycondensate quinonediazide sulfonic acid ester (hereinafter referred to as "sulfonic acid ester (B)")
Say. ) Can be produced, for example, by reacting the specific polycondensate with a quinonediazidesulfonyl halide such as quinonediazidesulfonyl chloride and substituting the hydrogen atom of the phenolic hydroxyl group in the specific polycondensate with a quinonediazidesulfonyl group.

Examples of the quinonediazidesulfonyl group include 1,2-naphthoquinonediazide-4-sulfonyl group, 1,2-naphthoquinonediazide-5-sulfonyl group, and 1,2-naphthoquinonediazide-6-sulfonyl group. You can

When producing the sulfonic acid ester (B), the average substitution rate of the specific polycondensate with the quinonediazidesulfonyl group (the ratio of the phenolic hydroxyl group substituted with the quinonediazidesulfonyl group to the total phenolic hydroxyl groups in the specific polycondensate) ) Is preferably 15 to 75%. When the average substitution rate is less than 15%, the degree of improvement in focus tolerance tends to be slightly low, although it depends on the blending amount of the sulfonate ester (B), and when it exceeds 75%, the sensitivity tends to decrease. is there.

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

Further, in the composition of the present invention, in addition to the sulfonic acid ester (B), a quinonediazide sulfonic acid ester of another phenol compound (hereinafter referred to as "sulfonic acid ester (b)"), 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 (b) include 2,3,4-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,
3,4,4'-tetrahydroxybenzophenone, 2,
2 ', 3,4'-tetrahydroxybenzophenone,
3'-methoxy-2,3,4,4'-tetrahydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,2'3,4,4'-pentahydroxybenzophenone, 2,2 '3,4,6'-pentahydroxybenzophenone, 2,3,3', 4,4 ',
5'-hexahydroxybenzophenone, 2,3'4
1,2-of (poly) hydroxyphenyl aryl ketones such as 4 ′, 5 ′, 6-hexahydroxybenzophenone
Naphthoquinone diazide-4-sulfonic acid ester or 1,2-naphthoquinone diazide-5-sulfonic acid ester;

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, 1,3
3-tris (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 of polyhydroxyphenyl flavans such as 4'-trimethyl-2 ', 4', 5 ', 6,7-pentahydroxy-2-phenyl flavan
-Sulfonic acid ester, 1,2-naphthoquinonediazide-5-sulfonic acid ester and the like can be mentioned.

Further, as the sulfonic acid ester (b), JP-A-1-144463 and JP-A-1-156 are available.
It is also possible to use the quinonediazide sulfonic acid esters described in Japanese Patent No. 738, etc.

Of these sulfonic acid esters (b), 1,3 of 2,3,4-trihydroxybenzophenone
2-naphthoquinonediazide-5-sulfonic acid ester,
1,2-naphthoquinonediazide-5-sulfonic acid ester of 2,3,4,4'-tetrahydroxybenzophenone, 1,2-naphthoquinonediazide-5-of 2,2'3,4,4'-pentahydroxybenzophenone Sulfonic acid ester, 2,2 ', 5,5'-tetramethyl-
1,2-naphthoquinonediazide-5-sulfonic acid ester of 2 ", 4,4'-trihydroxytriphenylmethane, 1,2-naphthoquinonediazide-4 of 1,1,1-tris (4-hydroxyphenyl) ethane -Sulfonic acid ester or 1,2-naphthoquinonediazide-5-sulfonic acid ester, 1,1-bis (4-hydroxyphenyl) -1-phenylethane 1,2-naphthoquinonediazide-4-sulfonic acid ester or 1, 2-naphthoquinonediazide-5-sulfonate, 1,1-bis (4-hydroxyphenyl) -4- [1- (4-hydroxyphenyl) -1-methylethyl] -1-phenylethane 1,2- Naphthoquinonediazide-4-sulfonic acid ester or 1,2-naphthoquinonediazide-5-
Sulfonic acid ester, 2,4,4-trimethyl-2 ',
1,2-naphthoquinonediazide-5-sulfonic acid ester of 4 ', 7-trihydroxy-2-phenylflavan, 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) butane 1,2 -Naphthoquinonediazide-4-sulfonic acid ester or 1,2-naphthoquinonediazide-5-sulfonic acid ester, 1,2-naphthoquinonediazide of 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) propane -4-sulfonic acid ester or 1,2-naphthoquinonediazide-5-
Sulfonic acid ester, 1,2-naphthoquinonediazide-4-sulfonic acid ester of 1,3,3-tris (4-hydroxyphenyl) butane, 1,2-naphthoquinonediazide-5-sulfonic acid ester and the like are preferable. The sulfonic acid ester (b) may be used alone or in combination of two or more.

In the present invention, the compounding amount of the sulfonic acid ester (B) is usually 3 to 75 parts by weight, preferably 5 to 50 parts by weight, per 100 parts by weight of the novolac resin (A). The compounding amount of the ester (b) is usually 100 parts by weight of the novolac resin (A),
It is 70 parts by weight or less, preferably 50 parts by weight or less, and the total amount of the sulfonic acid ester (B) and the sulfonic acid ester (b) is usually 3 to 100 parts by weight per 100 parts by weight of the novolac resin (A). Parts, preferably 5 to 50 parts by weight, but the total amount of quinonediazidesulfonyl groups in the composition is usually 5 to 25% by weight, preferably 10 to 20% by weight in terms of solid content.

If necessary, the composition of the present invention may further contain various additives such as a dissolution accelerator, a sensitizer and a surfactant. The dissolution accelerator is a compound having an action of promoting alkali solubility of the novolak resin (A). Examples of preferable dissolution accelerators include phenol compounds having a benzene ring number of about 2 to 6, and specifically, low molecular weight phenol compounds represented by the following formulas (6) to (16) are used. Can be mentioned.

[0049]

[Chemical 6]

[Chemical 7]

[Chemical 8] [In the formulas (6) to (8), a, b, x and y are each an integer of 0 to 3, but a and b are not 0 at the same time, and a + x ≦ 5 and b + y ≦ 5 are satisfied. Be satisfied. ]

[0050]

[Chemical 9]

[Chemical 10]

[Chemical 11] [In the formulas (9) to (11), a, b, c, x, y and z are each an integer of 0 to 3, but a, b and c do not become 0 at the same time, and a + x ≦ 5. , B + y ≦
4 and c + z ≦ 5 are satisfied. ]

[0051]

[Chemical 12]

[Chemical 13] [In Formulas (12) to (13), 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 a + x ≦ 5, b + y
≦ 5 and c + z ≦ 5 are satisfied. ]

[0052]

[Chemical 14] [In the formula (14), 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 a + x ≦ 5 and b + y ≦ 5. , C +
satisfies z ≦ 5, R ¹⁰ represents a hydrogen atom, an alkyl group or an aryl group having 6 to 10 carbon atoms having 1 to 4 carbon atoms. ]

[0053]

[Chemical 15] [In the formula (15), R ^{11 to} R ¹⁶ may be the same or different from each other, and are 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 ¹⁷ and R ¹⁸ may be the same or different from each other and represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms, and R ^{19 to} R ²¹ are the same as each other. May be different, and may be a hydrogen atom or a carbon number of 1
6 is an alkyl group, and a, b and c are each 0 to
It is an integer of 3, but a, b, and c are never 0 at the same time. ]

[0054]

[Chemical 16] [In the formula (16), 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 a + x ≦ 5 and b + y ≦ 5. , C +
satisfying z ≦ 5, R ²² represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms. ]

The dissolution accelerators 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, per 100 parts by weight of the novolac resin (A). Parts or less, particularly preferably 5 to 3
0 parts by weight.

The 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
Examples include -b)-(1,4) -benzothiazines, urazoles, hydantoins, parbituric acids, glycine anhydrides, 1-hydroxybenzotriazoles, alloxanes, maleimides and the like. These sensitizers can be used alone or in admixture of two or more, and the compounding amount thereof is novolac resin (A) 100.
It is usually 50 parts by weight or less per part by weight.

Further, the above-mentioned surfactant is used for coating the composition,
It has an effect of improving developability and the like, and examples thereof include polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol. Nonionic surfactants such as distearate: Ftop EF122A, EF12
2B, EF351, EF352, EF601, EF80
1, EF802 (trade name, made by Mitsubishi Metals): Megafax F142D, F144D, F171, F172, F
173, F177, F179A (trade name, manufactured by Dainippon Ink): Fluorard FC176, FC430, FC43
1 (trade name, made by Sumitomo 3M): Asahi Guard AG
710; Surflon S-381, S-382, SC-
101, SC-102, SC-103, SC-104,
SC-105, SC-106 (trade name, manufactured by Asahi Glass): K
P341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.): Polyflow N
o. 75, no. 90, No. 95-S; Floren A
C202, AC300, AC303, AC326F, A
C903, AC1190 (trade name, manufactured by Kyoeisha Oil and Fat Chemical Co., Ltd.): Hyonic PE40, PE90, PE10
0, PE120; Modicol L, N; Dapro S-
65; Perenol F40; Color Sparse 188A
(Product name, made by San Nopco): Emazole O-15R, O
-30 (F), S-20 (trade name, made by Kao): ZONY
E FSN, FSN-100, FSO, FSO-100
(Product name, made by DuPont): DS-401, DS-40
3, DS-406, DS-451 (trade name, manufactured by Daikin): Neosuftergent 250, 251; PEF
-203, 800B; NBX-15 (trade name, manufactured by Neos) and the like. These surfactants can be used alone or in admixture of two or more, and the compounding amount thereof is usually 2 parts by weight or less per 100 parts by weight of the solid content of the composition.

Further, the composition of the present invention can contain a dye or a pigment to visualize the latent image in the exposed area and reduce the effect of halation during exposure, and also contain an adhesion aid. 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, the novolac resin (A) and the sulfonic acid ester (B) are mixed as necessary with the sulfonic acid ester (b) or various kinds. A composition solution is prepared by dissolving it together with an additive in a solvent so that the solid content concentration becomes, for example, 20 to 40% by weight, and filtering through a filter having a pore size of about 0.2 μm.

Examples of the solvent used for preparing the composition solution include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether. Ethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monopropyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, 4-heptanone, ethyl 2-hydroxypropionate, 2-hydroxy-2-methyl Ethyl propionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2
-Methyl hydroxy-3-methylbutanoate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl acetate, butyl acetate Etc. can be mentioned.
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, benzylethyl are used. Ether, dihexyl ether, acetonylacetone, isophorone, caproic acid,
One high boiling point solvent such as caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate The above can be added.

Next, the composition of the present invention prepared as a composition solution is applied onto a substrate such as a silicon wafer or a wafer coated 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. The radiation used at this time is preferably ultraviolet rays such as i-rays, but various radiations can be selected and used according to the characteristics of the composition.

In the present invention, the composition is coated on a substrate, prebaked and exposed, and then, for example, 70 to 1
The effect of the present invention can be further improved by performing a heating treatment at 40 ° C. (hereinafter referred to as “post-exposure baking”) and then developing.

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, triethylamine. Ethanolamine, 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, an appropriate amount of a water-soluble organic solvent, for example, alcohols such as methanol and ethanol and a surfactant can be added to the developer. When a developer made of such an alkaline aqueous solution is used, it is generally washed with water after development.

[0065]

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 evaluation of each resist were performed as follows. Mw Tosoh Corp. GPC column (2 G2000H _XL ,
G3000H _{XL (} 1 bottle), 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 with monodisperse polystyrene as the standard. .

Hydroxyl Value of Specific Polycondensate Ind. Eng. Chem. , Anal Ed. , Vo
L17, p395 (1945), the acid anhydride method was used for the measurement, and it was shown by the number of moles of hydroxyl groups contained in 100 g of the specific polycondensate.

Sensitivity NSR-1755i7A reduction projection exposure machine manufactured by Nikon Corporation (numerical aperture = 0.50) was used to change the exposure time, and exposure was performed with i-line having a wavelength of 365 nm, and then 2.4.
A positive resist pattern was formed on the wafer by developing with a wt% tetramethylammonium hydroxide aqueous solution at 25 ° C. for 60 seconds, washing with water and drying. At that time, the exposure time for forming a line-and-space pattern (1L1S) having a line width of 0.35 μm in a width of 1: 1 (hereinafter referred to as “optimum exposure time”) was defined as the sensitivity.

Resolution The dimension of the smallest resist pattern resolved when exposed for the optimum exposure time was defined as the resolution.

Focus tolerance A line and space pattern (1L1S) having a line width of 0.35 μm is observed using a scanning electron microscope, and the resolved pattern dimension is within ± 10% of the mask design dimension. In addition, the focus allowance was evaluated by the range of focus deviation when the ratio of the thickness of the resist pattern after development to the thickness of the film before development (hereinafter referred to as "residual film rate") was 90% or more. . The larger the swing width, the better the focus tolerance.

[0070] The degree of development of scum and undeveloped were examined using a scanning electron microscope.

Pattern shape A line-and-space pattern (1L1S) having a line width of 0.35 μm was used to measure the lower side dimension L ₁ and the upper side dimension L _{2 of a} rectangular cross section using a scanning electron microscope. 85
When ≦ L ₂ / L ₁ ≦ 1, the pattern shape was considered good. However, even if 0.85 ≦ L ₂ / L ₁ ≦ 1, if the pattern shape has a skirt, it was not considered to be good.

A wafer on which a heat resistant 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, it was judged that the heat resistance was good.

[Production of Novolac Resin (A)] Synthesis Example 1 m-Cresol 53.0 g (0.49 mol) 2,3-xylenol 17.1 g (0.14 mol) 2,3 in an autoclave , 5-Trimethylphenol 9.54 g (0.07 mol) 37% by weight aqueous formaldehyde solution 51.1 g (formaldehyde 0.63 mol) oxalic acid dihydrate 4.41 g (0.035 mol) water 58.5 g After charging 272 g of dioxane and the autoclave, the autoclave was immersed in an oil bath, the temperature of the reaction solution was kept at 130 ° C., and polycondensation was carried out for 7.5 hours while stirring. Then, after cooling the reaction solution to room temperature,
The contents were transferred to a beaker and allowed to stand, the lower layer separated into two layers was taken out, concentrated, dehydrated and dried to obtain a novolak resin (A) (Mw = 8100). This resin is referred to as novolac resin (A1).

Synthesis Example 2 m-cresol 45.4 g (0.42 mol) 3,4-xylenol 25.7 g (0.21 mol) 2,3-xylenol 8.55 g (0 0.07 mol) 37 wt% aqueous formaldehyde solution 49.7 g (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 same treatment as in Synthesis Example 1 was carried out except that the novolak resin (A) (Mw = 890) was used.
0) was obtained. This resin is referred to as novolac resin (A2).

Synthesis Example 3 m-cresol 103.8 g (0.96 mol) 2,3-xylenol 3.67 g (0.03 mol) 3,4 was placed in a flask equipped with a stirrer, a condenser and a thermometer. -Xylenol 3.67 g (0.03 mol) 40 wt% butanol solution of formaldehyde (butyl hemiformal) 101.4 g (formaldehyde 1.35 mol) and oxalic acid dihydrate 0.945 g (0.0075 mol) ) Was charged, the flask was immersed in an oil bath, the temperature of the reaction solution was kept at 100 ° C., and polycondensation was carried out for 30 minutes under stirring. Then, 26.0 g (0.24 mol) of m-cresol, 14.7 g (0.12 mol) of 2,3-xylenol and 14.7 g (0.12 mol) of 3,4-xylenol were added. Then, polycondensation was performed for 100 minutes. Then
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 matter,
The molten resin was cooled to room temperature to obtain a novolak resin (A) (Mw = 5700). This resin is referred to as novolac resin (A3).

Synthesis Example 4 The novolak resin (A3) was mixed with ethyl acetate and the resin component was 30
After the solution was dissolved to have a weight percentage, 0.65 times the amount of methanol and 0.75 times the amount of water of this solution were added, and the mixture was stirred and allowed to stand. Then, the lower layer separated into two layers is taken out, concentrated and dried to obtain the novolak resin (A) (M
w = 8000) was obtained. This resin is referred to as novolac resin (A4).

[Synthesis of Sulfonic Acid Ester (B)] Synthesis Example 5 (Production of Specific Polycondensate) In a flask similar to that used in Synthesis Example 3, phenol 207.0 g (2.2 mol) p-xylene was added. -Α, α'-diol 138.2 g (1.0 mol) Toluene 220 g and p-toluenesulfonic acid (monohydrate) 3.80 g (0.02 mol) were charged, and then the flask was placed in an oil bath. Dip and under stirring,
The reaction solution was reacted under reflux for 7 hours. Then, the reaction solution was cooled to room temperature, 300 g of methyl isobutyl ketone was put into the flask under stirring, the reaction solution was transferred to a separating funnel, and washing with water was repeated until the aqueous layer became neutral. Then, the organic layer was put into a flask equipped with a stirrer and a cooling tube, the temperature of the oil bath was raised to 180 ° C., and at the same time, the pressure in the flask was reduced to 30 to 50 mmHg to remove volatile components and melt. The resin was cooled to room temperature to obtain a specific polycondensate. This specific polycondensate had Mw = 2100 and a hydroxyl value = 0.52 mol / 100 g. This is designated as a specific polycondensate (1).

Synthesis Example 6 In a flask similar to that used in Synthesis Example 3, 100 g of the specific polycondensate (1) 1,4,2-naphthoquinonediazide-5-sulfonic acid chloride 48.9 g (0.182 mol) and dioxane were added. 347 g was charged and dissolved under stirring. Then add 3 flasks
The reaction solution was immersed in a water bath maintained at 0 ° C., and when the temperature of the reaction solution became constant at 30 ° C., 19.7 g (0.195 mol) of triethylamine was added 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 (B) having an average substitution rate of 35%. This is designated as a sulfonic acid ester (B1).

Synthesis Example 7 Specific polycondensate (2) [Mirei XL-225-3L manufactured by Mitsui Toatsu Chemicals (in the above formula (1), R ^{1 to} R ⁹ are hydrogen atoms, m = 1 and n = 3) (Corresponding to compound), Mw = 1900, hydroxyl value = 0.56 mol / 100 g] 100 g 1,2-naphthoquinonediazide-5-sulfonic acid chloride 37.6 g (0.14 mol) dioxane 321 g and triethylamine 16.2 g ( 0.16 mol) was used and treated in the same manner as in Synthesis Example 6 to obtain a sulfonic acid ester (B) having an average substitution rate of 25%.
This is referred to as a sulfonic acid ester (B2).

Synthetic Example 8 Specific polycondensate (3) [Naphthol-Zyloc αNX-3.2 (manufactured by Mitsui Toatsu Chemicals, in the formula (2), R ^{1 to} R ⁹ are hydrogen atoms, m = 1, n = Mw = 800, hydroxyl value = 0.43 mol / 100 g] 100 g 1,2-naphthoquinonediazide-5-sulfonic acid chloride 34.7 g (0.129 mol) dioxane 314 g and triethylamine 13.7 g. The same treatment as in Synthesis Example 6 was carried out except that (0.135 mol) was used to obtain a sulfonic acid ester (B) having an average substitution rate of 30%.
This is designated as a sulfonic acid ester (B3).

Examples 1 to 4 and Comparative Example The novolak resin (A) and the sulfonic acid ester (B) obtained in each of the synthesis examples were mixed with a sulfonic acid ester (b), a dissolution accelerator and a solvent to prepare a uniform solution. After that, the mixture was filtered through a membrane filter having a pore diameter of 0.2 μm to prepare a solution of the composition shown in Table 1 (however, parts are based on weight).

The types of the sulfonic acid ester (b), the dissolution promoter and the solvent used here are as follows. Sulfonic acid ester (b) (b1): 1,1-bis (4-hydroxyphenyl)-
Condensate of 1 mol of 4- [1- (4-hydroxyphenyl) -1-methylethyl] -1-phenylethane and 2 mol of 1,2-naphthoquinonediazide-5-sulfonyl chloride (b2): 1,3 1-mol of 3-tris (4-hydroxyphenyl) butane and 1,2-naphthoquinonediazide-5
-Condensation product with 2.5 mol of sulfonyl chloride (b3): 1,1,3-tris (2,5-dimethyl-4)
-Hydroxyphenyl) butane 1 mol and 1,2-naphthoquinonediazide-4-sulfonyl chloride 2.5 mol condensate

Dissolution accelerator (c1): 1,1-bis (4-hydroxyphenyl)-
1-phenylethane (in the formula (13), a = b
= 1 and c = x = y = z = 0) (c2): 1,1-bis (4-hydroxyphenyl)-
1- [4- {1- (4-hydroxyphenyl) -1-methylethyl} phenyl] ethane (in the formula (15), R ^{11 to} R ¹⁸ are hydrogen atoms, R ^{19 to} R ²¹ are methyl groups, a
= Corresponding to b = c = 1)

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

Next, the solution of each composition was applied onto a silicon wafer by using a spinner, and then on a hot plate kept at 90 ° C. (other than Example 3) or 100 ° C. (Example 3). Pre-baked for 2 minutes, thickness 1.1
A μm resist film was formed. A wavelength of 365 nm was applied to this resist film through a mask pattern as described above.
After the exposure with the i-line, a post-exposure baking was performed for 1 minute on a hot plate kept at 110 ° C. Then, as described above, developed, washed, dried to form a resist pattern, based on the obtained resist pattern,
Each resist was evaluated. Table 2 shows the evaluation results.

As shown in Table 2, in Examples 1 to 4, the focus tolerance was particularly excellent, the sensitivity and the resolution were excellent, and the developability, the pattern shape, the heat resistance and the like were good.

[0087]

[Table 1]

[0088]

[Table 2]

[0089]

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

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] August 31, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0043

[Correction method] Change

[Correction content]

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, 1,3
3-tris (4-hydroxyphenyl) butane, 1,1
-Bis (4-hydroxyphenyl) -1-phenylethane, 1,1-bis (4-hydroxyphenyl) -1-
1,2-naphthoquinonediazide-4 of (poly) hydroxytriphenylalkane such as [4- {1- (4-hydroxyphenyl) -1-methylethyl} phenyl] ethane
-Sulfonates or 1,2-naphthoquinonediazide-5-sulfonates;

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0064

[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, triethylamine. Ethanolamine, 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, an appropriate amount of a water-soluble organic solvent, for example, alcohols such as methanol and ethanol and a surfactant can be added to the developer. When a developer made of such an alkaline aqueous solution is used, it is generally washed with water after development.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0074

[Correction method] Change

[Correction content]

Synthesis Example 2 m-cresol 45.4 g (0.42 mol) 2,3-xylenol 25.7 g (0.21 mol) 3,4-xylenol 8.55 g (0.07 mol) 37 wt% in an autoclave % Formaldehyde aqueous solution 49.7 g (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, except for the synthesis example. Novolak resin (A) (Mw = 890)
0) was obtained. This resin is referred to as novolac resin (A2).

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0082

[Correction method] Change

[Correction content]

The types of the sulfonic acid ester (b), the dissolution promoter and the solvent used here are as follows. Sulfonic acid ester (b) (b1): 1,1-bis (4-hydroxyphenyl)-
Condensate of 1- [4- {1- (4-hydroxyphenyl) -1-methylethyl} phenyl] ethane with 2 mol of 1,2-naphthoquinonediazide-5-sulfonyl chloride (b2): 1,3,3 1 mole of tris (4-hydroxyphenyl) butane and 1,2-naphthoquinonediazide-5
-Condensation product with 2.5 mol of sulfonyl chloride (b3): 1,1,3-tris (2,5-dimethyl-4)
-Hydroxyphenyl) butane 1 mol and 1,2-naphthoquinonediazide-4-sulfonyl chloride 2.5 mol condensate ──────────────────────── ──────────────────────────────

[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 (a) 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-isobutylphenol, m-isobutylphenol, p-isobutylphenol, o-
sec-butylphenol, m-sec-butylphenol, p-sec-butylphenol, ot-butylphenol, mt-butylphenol, pt-butylphenol, pn-pentylphenol, pt-
Pentylphenol, pn-hexylphenol, p
-T-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-methoxy Phenol, o-ethoxyphenol, m-ethoxyphenol, p-ethoxyphenol, on-propoxyphenol, m-n-propoxyphenol, pn-propoxyphenol, o-isopropoxyphenol, m-isopropoxyphenol, p-isopropoxyphenol, on-butoxyphenol, mn-butoxyphenol, pn-butoxyphenol, ot-butoxyphenol, m-
t-butoxyphenol, pt-butoxyphenol, on-pentyloxyphenol, mn-pentyloxyphenol, pn-pentyloxyphenol, on-hexyloxyphenol, mn-hexyloxy Phenol, pn-hexyloxyphenol, on-heptyloxyphenol, mn-
Heptyloxyphenol, pn-heptyloxyphenol, o-phenoxyphenol, m-phenoxyphenol, p-phenoxyphenol, 2,3-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol , 5-n-propyl-3-methylphenol, 5-isopropyl-3-methylphenol, 2-n-butyl-5-methylphenol, 2-t
-Butyl-5-methylphenol, 2,5-di-n-butylphenol, 2,5-di-sec-butylphenol, 2,5-di-t-butylphenol, 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, n-
Butyl hydroquinone, t-butyl hydroquinone, 4
-N-hexyl resorcinol, 4-hexanoylresorcinol, 3,5-dimethylcatechol, 2,5-dimethylresorcinol, 2,3-dimethylhydroquinone, 2,5-dimethylhydroquinone, 3,5-diethylcatechol, 2,5 -Diethylresorcinol, 2,
3-diethylhydroquinone, 2,5-diethylhydroquinone, 3,5-di-n-propylcatechol, 2,
5-di-n-propylresorcinol, 2,3-di-n
-Propylhydroquinone, 2,5-di-n-propylhydroquinone, 3,5-diisopropylcatechol,
2,5-diisopropylresorcinol, 2,3-diisopropylhydroquinone, 2,5-diisopropylhydroquinone, 3,5-di-n-butylcatechol,
2,5-di-n-butylresorcinol, 2,3-di-
n-butylhydroquinone, 2,5-di-n-butylhydroquinone, 3,5-di-t-butylcatechol,
2,5-di-t-butylresorcinol, 2,3-di-
t-butyl hydroquinone, 2,5-di-t-butyl hydroquinone, 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-propyl salicylate, methyl 3-hydroxybenzoate, ethyl 3-hydroxybenzoate, n-hydroxy-3-hydroxybenzoate. Examples thereof include propyl, methyl 4-hydroxybenzoate, ethyl 4-hydroxybenzoate, n-propyl 4-hydroxybenzoate and the like.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0050

[Correction method] Change

[Correction content]

[0050]

[Chemical 1] [In the formulas (9) to (11), a, b, c, x, y and z are each an integer of 0 to 3, but a, b and c do not become 0 at the same time, and a + x ≦ 5. , B + y ≦
4 and c + z ≦ 5 are satisfied. ]

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0081

[Correction method] Change

[Correction content]

Examples 1 to 4 The novolak resin (A) and the sulfonic acid ester (B) obtained in each of the synthesis examples were mixed with the sulfonic acid ester (b), the dissolution promoter and the solvent to prepare a uniform solution. Then, the solution was filtered through a membrane filter having a pore diameter of 0.2 μm to prepare a solution of the composition shown in Table 1 (however, parts are based on weight). Comparative Example A composition solution was prepared by using components having the composition shown in Table 1 (where parts are based on weight) and treating in the same manner as in the example.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0087

[Correction method] Change

[Correction content]

[0087]

Front Page Continuation (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 polycondensed quinonediazide sulfonic acid ester having at least two repeating units represented by the following formula (1) and / or formula (2). Radiation-sensitive resin composition. [Chemical 1] [Chemical 2] [In the formulas (1) and (2), R ^{1 to} R ⁴ may be the same or different from each other and represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms, R ⁵
To R ⁸ may be the same or different from each other and represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 15 carbon atoms, and R ⁹ is 1 to 10 carbon atoms.
Alkyl group, C1-8 alkoxy group, C7
~ 15 aralkyloxy group, C1-7 acyl group, C6-15 aryl group, C7-15 aralkyl group, C6-10 aryloxy group or C2-10 An alkoxycarbonyl group, and when there are plural R ^9's , they may be the same or different, m
And n are 1 ≦ m ≦ 3, 0 ≦ n ≦ 3 in the formula (1),
An integer satisfying m + n ≦ 4, in the formula (2), 1 ≦ m ≦
It is an integer that satisfies 6, 0 ≦ n ≦ 5, and m + n ≦ 6. ]