JPH06348006A - Positive radiation sensitive resin composition - Google Patents

Abstract

PURPOSE:To enhance focal depth allowance, sensitivity, resolution, heat resistance, developability, and pattern form by incorporating an alkali-soluble novolak resin and a specified compound or its quinonediazido sulfonate. CONSTITUTION:This radiation sensitive resin composition contains the alkali- soluble novolak resin, and at least one of the compounds represented by formulae I and II in which Q is a univalent group represented by formula III; D is H or a quinonediazidosulfonyl group; R<1> is a 1-10C alkyl or the like; R<2> is a 1-6C alkyl or the like; each of R<3>-R<6> is H, halogen, or the like; each of R<7>-R<12> is H, 1-6C alkyl or the like: a is 1, 2, or 3; b is 0, 1, 2, or 3, a+b<=5; c is 1, 2, or 3; and d is 0, 1, or 2, and c+d<=3.

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, ultraviolet rays, far ultraviolet rays, X
The present invention relates to a positive-type radiation-sensitive resin composition suitable as a resist for producing a highly integrated circuit which is sensitive to radiation such as rays, electron rays, molecular rays, γ rays, synchrotron radiation, and proton beams.

[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 fine processing, a reduction projection exposure machine (stepper) is usually used to irradiate a positive resist with radiation through a predetermined mask pattern (hereinafter referred to as "exposure") and then develop it to form a resist pattern. One of the means for improving the resolution is to increase the numerical aperture (NA) of the stepper lens.

Generally, in the optical system in the fine processing as described above, the depth of focus (DOF) and the numerical aperture (NA) are set.
The relation with and is shown by the following Rayleigh equation. DOF = k × λ / (NA) ² (where, k: constant, λ: wavelength of radiation) The depth of focus (DOF) can form a dimension-controlled resist pattern even if the focus shifts in the optical axis direction. As is clear from the above formula, increasing the numerical aperture (NA) significantly reduces the depth of focus (DOF), that is, the focus allowance. Therefore, in order to cope with a stepper having a high numerical aperture, a positive resist having excellent focus tolerance is required.

However, the conventional positive resist is
Since it is practically used near the resolution limit, when using a high numerical aperture stepper for exposure, if the focus is misaligned, the pattern shape will be deformed, the difference between the design line width and the developability will decrease. Was remarkable, and it could not be said that it has sufficient focus tolerance.

[0006]

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 heat resistance, developability and pattern shape.

[0007]

According to the present invention, the above object is a positive-type radiation-sensitive resin composition containing a compound having a quinonediazidesulfonyl group, which comprises an alkali-soluble novolak resin (A) and the following formula: (1) and equation (2)

[0008]

[Chemical 3]

[Q in the equations (1) and (2) is the following equation (3)]

[0010]

[Chemical 4]

Is a monovalent group represented by the formula;
In the formulas (2) and (3), D represents a hydrogen atom or a quinonediazidesulfonyl group, and a plurality of Ds may be the same or different; R ¹ has 1 to ¹ carbon atoms.
10 alkyl group, C 3-10 cycloalkyl group, C 1-8 alkoxy group, C 7-15 aralkyloxy group, C 1-7 acyl group, C 6
To 14 aryl groups, C7 to C18 aralkyl groups,
Aryloxy group having 6 to 10 carbon atoms or 2 to 1 carbon atoms
0 represents an alkoxycarbonyl group, and when plural R ^{1 s} are present in the formula (1) or the formula (2), they may be the same or different from each other; R ² has 1 to 6 carbon atoms. An alkyl group, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms or an aralkyl group having 7 to 18 carbon atoms, and a plurality of R ^{2 s} are present in the formula (1) or the formula (2). R ^{3 to} R ⁶ may be the same or different from each other, and a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, Cycloalkyl group having 3 to 10 carbon atoms, 6 to carbon atoms
Represents an aryl group having 14 or an aralkyl group having ⁷ to 18 carbon atoms; R ^{7 to} R ⁹ may be the same or different from each other, and are a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a carbon number. 3-10 cycloalkyl group; R ¹⁰ and R ¹¹ may be the same or different from each other, and are a hydrogen atom, a C 1-6 alkyl group or a C 3-10.
Represents a cycloalkyl group of: R ¹² is a hydrogen atom and has 1 carbon atom.
~ 6 alkyl group, C3-10 cycloalkyl group, C6-14 aryl group or C7-18
Is an integer from 1 to 3 and b is 0 to 3
Is satisfied, a + b ≦ 5 is satisfied, c is an integer of 1 to 3, d is an integer of 0 to 2, and c + d ≦ 3 is satisfied. ] A positive type radiation sensitive resin composition comprising at least one compound (B) selected from the group of compounds represented by

The present invention will be specifically described below, but the purpose, constitution and effect of the present invention will be clarified by this.

First, the alkali-soluble novolak resin (A) used in the present invention (hereinafter referred to as "novolak resin (A)") is obtained by polycondensing phenols and aldehydes using an acidic catalyst. To be

Examples of phenols include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol and p.
-Ethylphenol, on-propylphenol, m
-N-propylphenol, pn-propylphenol, o-isopropylphenol, m-isopropylphenol, p-isopropylphenol, on-butylphenol, mn-butylphenol, pn-
Butylphenol, ot-butylphenol, mt
-Butylphenol, pt-butylphenol, p-
n-pentylphenol, pt-pentylphenol, pn-hexylphenol, pt-hexylphenol, pn-heptylphenol, pt-heptylphenol, pn-octylphenol, pt
-Octylphenol, pn-nonylphenol, p
-T-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,

O-n-propoxyphenol, m-n-
Propoxyphenol, pn-propoxyphenol, o-isopropoxyphenol, m-isopropoxyphenol, p-isopropoxyphenol, on
-Butoxyphenol, mn-butoxyphenol,
pn-butoxyphenol, ot-butoxyphenol, mt-butoxyphenol, pt-butoxyphenol, on-pentyloxyphenol, m-
n-pentyloxyphenol, pn-pentyloxyphenol, on-hexyloxyphenol, m
-N-hexyloxyphenol, pn-hexyloxyphenol, on-heptyloxyphenol,
m-n-heptyloxyphenol, pn-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-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, t-butylhydroquinone, 4-n-hexylresorcinol, 4-hexanoylresorcinol, 3 , 5-Dimethylcatechol, 2,5-dimethylresorcinol, 2,3-diethylhydroquinone, 2,5-dimethylhydroquinone, 3,
5-diethylcatechol,

2,5-diethylresorcinol, 2,5-
Diethylhydroquinone, 3,5-diisopropylcatechol, 2,5-diisopropylresorcinol, 2,3
-Diisopropylhydroquinone, 2,5-diisopropylhydroquinone, 3,5-di-t-butylcatechol, 2,5-di-t-butylresorcinol, 2,3-di-t-butylhydroquinone, 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 gallic acid
-Octyl, methyl salicylate, ethyl salicylate, n-propyl salicylate, methyl 2-hydroxybenzoate, ethyl 2-hydroxybenzoate, n-propyl 4-hydroxybenzoate, methyl 4-hydroxybenzoate, 4
-Ethyl hydroxybenzoate, propyl 4-hydroxybenzoate and the like can be mentioned.

Of these phenols, particularly 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 and pyrogallol are preferred.

These phenols may be used alone or in the form of 2
Combinations of more than one species can be used.

Examples of aldehydes to be polycondensed with 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, o-n-propylbenzaldehyde, m-n-propylbenzaldehyde, p-n-propylbenzaldehyde , O-n-butylbenzaldehyde, m-n-butylbenzaldehyde, pn-butylbenzaldehyde, furfural and the like. 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 generating source include hemiformals such as formalin, trioxane, paraformaldehyde, methyl hemiformal, ethyl hemiformal, propyl hemiformal, butyl hemiformal, and phenyl hemiformal. be able to. Of these, formalin and butyl hemiformal are particularly preferred. These aldehyde generating sources can also be used alone or in combination of two or more.

The amount of aldehyde used is 1 phenol.
It is preferably 0.7 to 3 mol per mol.

Examples of acidic catalysts usually used for polycondensation of phenols and aldehydes include hydrochloric acid, nitric acid,
Examples thereof include 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 mol of phenols.

In the polycondensation of phenols and aldehydes, water is usually used as a reaction medium, but when the phenols used are not dissolved in an aqueous solution of aldehydes and become heterogeneous from the initial reaction, A hydrophilic solvent can also be used as the reaction medium. Examples of the hydrophilic solvent include alcohols such as methanol, ethanol, propanol and butanol; diethylene glycol dimethyl ether, 1,2-dimethoxyethane,
Ethers such as 1,2-diethoxyethane; and cyclic ethers such as tetrahydrofuran and dioxane. The amount of these reaction media used is usually 20 to 1,000 parts by weight per 100 parts by weight of the reaction raw material.

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

The polycondensation method of phenols and aldehydes includes a method in which phenols, aldehydes, acidic catalysts, etc. are charged at the same time and reacted, or phenols, aldehydes, acidic catalysts, etc. in the presence of an acidic catalyst. It is possible to employ a method of reacting while gradually adding.

After completion of the polycondensation, the temperature of the reaction system is generally increased to 130 to 230 ° C. in order to remove the unreacted raw materials, the acid catalyst, the reaction medium and the like existing in the reaction system.
The volatile matter is distilled off under reduced pressure, for example, under a pressure of about 20 to 50 mmHg, and the produced novolac resin (A) is recovered.

The standard polystyrene-reduced weight average molecular weight (hereinafter referred to as "Mw") of the novolak resin (A) used in the present invention is the molecular weight of the novolak resin conventionally used in radiation-sensitive resin compositions. Although it can be appropriately selected from the range, it is usually 3,000 to 2
000, preferably 4,000 to 15,000
Is. When the Mw is in the above range, the developability, sensitivity and heat resistance of the composition of the present invention can be improved.

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

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

Next, in the compound (B) represented by the above formulas (1) and (2) (hereinafter referred to as “compound (B)”), examples of the alkyl group having 1 to 6 carbon atoms are: Examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group and a hexyl group. Of these, a methyl group and an ethyl group are preferable. Carbon number 1
Examples of the alkyl group of 10 include a heptyl group, an octyl group, a nonyl group, and the like in addition to the examples of the alkyl group having 1 to 6 carbon atoms. Among them,
Methyl and ethyl groups are preferred. Examples of the cycloalkyl group having 3 to 10 carbon atoms include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group,
Examples thereof include a cycloheptyl group and a cyclooctyl group. C1-C8 alkoxy group, C2-C1
In the alkoxycarbonyl group of 0, examples of the portion adjacent to these oxygen atoms include those shown in the examples of the alkyl group and cycloalkyl group described above.

Examples of the aryl group having 6 to 14 carbon atoms are phenyl group, 1-naphthyl group, 2-naphthyl group, tolyl group, xylyl group, cumyl group, mesityl group, hydroxyphenyl group, chlorophenyl group and methoxyphenyl group. A group etc. can be mentioned. Of these, a phenyl group is preferable. In the aryloxy group having 6 to 10 carbon atoms,
Examples of these aryl moieties include those shown in the examples of the aryl group above. Examples of the aralkyl group having 7 to 18 carbon atoms include benzyl group, phenethyl group,
Examples thereof include a phenylpropyl group. Of these, a benzyl group is preferable. In the aralkyloxy group having 7 to 15 carbon atoms, these aralkyl moieties include those shown in the above-mentioned examples of the aralkyl group. In the acyl group having 1 to 7 carbon atoms, examples of the portion adjacent to the carbonyl include those shown in the above examples of the alkyl group. Further, specific examples of the halogen atom include a chlorine atom, a bromine atom and an iodine atom. Among them, chlorine atom and bromine atom are preferable.

The compound (B) is represented by the following formula (4) and formula (5)

[0033]

[Chemical 5]

[Z in the formulas (4) and (5) is represented by the following formula (6).

[0035]

[Chemical 6]

A monovalent group represented by the following formulas, and in the formulas (4), (5) and (6), R ¹ to
R ¹¹ , a, b, c and d have the same meanings as in the case of formula (1), formula (2) and formula (3). ]

Examples thereof include compounds represented by (hereinafter referred to as "compound (B ')").

Further, the compound (B ') in which at least one hydrogen atom of the phenolic hydroxyl group is substituted with a quinonediazidesulfonyl group can also be mentioned as the compound (B). Examples of the substitution method here include a method of reacting compound (B ′) with a quinonediazidesulfonyl halide exemplified by quinonediazidesulfonyl chloride.

The reaction ratio between the compound (B ') and the quinonediazidesulfonyl halide is preferably 0.2 to 1 mol, more preferably 0.4 to 1 mol, of the quinonediazidesulfonyl halide per gram equivalent of the phenolic hydroxyl group of the compound (B'). 1
Molar is particularly preferred.

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. Of these, 1,2-naphthoquinonediazide-4-sulfonyl group and 1,2-
A naphthoquinonediazide-5-sulfonyl group is preferred.

The average condensation rate when introducing a quinonediazidesulfonyl group into the compound (B ′) [(the ratio of the phenolic hydroxyl group into which the quinonediazidesulfonyl group is introduced to the total phenolic hydroxyl groups in the compound (B ′)] is determined by the present invention. Considering the sensitivity of the composition, it is preferably 75% or less.

The compound (B ') represented by the above formulas (4) and (5) can be produced, for example, by the following method. That is, the following equations (7) and (8), respectively:

[0043]

[Chemical 7]

[In the formulas (7) and (8), R ²
To R ⁹ , R ¹² , c and d are represented by the above formulas (1) and (2).
And is synonymous with the case of formula (3). ]

A compound represented by the following formula (hereinafter referred to as "compound (C)") is reacted with, for example, an aldehyde or a ketone under a basic condition to give the following formula (9) and formula (10).

[0046]

[Chemical 8]

[In Expressions (9) and (10), Y
Is the following formula (11)

[0048]

[Chemical 9]

It is a monovalent group represented by: Then, R ^{2 to} R ¹² , c in the formulas (9), (10) and (11)
And d have the same meanings as in the above formulas (1), (2) and (3), and the two X's in the formula (11) may be the same or different from each other. , Carbon number 1-6
An alkoxy group, a C1-6 acyloxy group, a C2-6 alkoxyalkoxy group, a C2-6 dialkylamino group, a piperidino group or a morpholino group, preferably a hydroxyl group, a dimethylamino group, a diethylamino group, It is a piperidino group or a morpholino group, particularly preferably a hydroxyl group. ]

A compound represented by the following formula (hereinafter referred to as "compound (D)") was obtained, and thereafter, this compound (D) was obtained.
The following formula (12)

[0051]

[Chemical 10]

[In the formula (12), R ¹ , a and b
Is synonymous with the case of the above formula (3). ]

The compound (B ') can be produced by polycondensation with a phenol represented by (hereinafter referred to as "phenol (b)").

Examples of the aldehydes reacted with the compound (C) include the aldehydes exemplified in the production of the novolak resin (A). Of these, formaldehyde and acetaldehyde are 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 the aldehydes exemplified in the production of the novolak resin (A). Of these, formalin, trioxane and paraformaldehyde are particularly preferred. These aldehyde generating sources can be used alone or in combination of two or more kinds.

The ketones to be reacted with the compound (C) include acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, 3-hexanone, 2-heptanone, 3-heptanone, 4-heptanone and methyl. Examples thereof include isobutyl ketone, acetophenone and propiophenone. Of these,
Acetone and methyl ethyl ketone are especially preferred. These ketones can be used alone or in combination of two or more. The amount of the above-mentioned aldehydes or ketones used with respect to the compound (C) is usually 6 to 15 mol per 1 mol of the compound (C).

In the reaction of the compound (C) with aldehydes or ketones, a basic catalyst is usually used. For example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, aqueous ammonia, sodium hydride,
Inorganic bases such as lithium hydride, triethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, choline, pyridine, 1,8-diazabicyclo- (5.4.0) -7-undecene, 1,5-diazabicyclo -(4.3.0) -5-
Organic bases such as nonane, dimethylamine, diethylamine, piperidine and morpholine can be mentioned.
The amount of these basic catalysts used is usually 0.3 to 5 relative to 1 gram equivalent of the phenolic hydroxyl group in the compound (C).
It is a mole.

When the compound (C) is reacted with the aldehydes or ketones, the reaction may be carried out in the absence of a solvent, or by using an inert solvent such as water, toluene, xylene or dioxane. Good. The amount of these inert solvents used is usually 100 parts by weight of the reaction raw material,
It is 20 to 1,000 parts by weight.

The reaction temperature and reaction time of the compound (C) with aldehydes or ketones are appropriately adjusted depending on the reactivity of the reaction raw materials, but usually the reaction temperature is from -10 to -10.
The reaction time is 1 hour to 2 weeks at 150 ° C.

After completion of the reaction of the compound (C) with an aldehyde or a ketone, the reaction mixture is generally neutralized with an acid, and then the acid used for the neutralization in the reaction mixture is washed with a large amount of water. Then, unreacted aldehydes or ketones are washed with water, toluene / n-heptane, toluene / n-hexane, etc. and removed to recover the produced compound (D).

Further, specific examples of the phenols (b) used in the subsequent polycondensation with the compound (D) include the phenols (a) mentioned for the novolak resin (A) (however, o-allyl). (Excluding phenol, m-allylphenol, p-allylphenol, o-propenylphenol, m-propenylphenol and p-propenylphenol).

Of these phenols, particularly phenol, o-cresol, m-cresol, p-cresol, m-ethylphenol, p-ethylphenol,
2,3-xylenol, 2,5-xylenol, 2,6-
Xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, resorcinol, pyrogallol and the like are preferable.

The amount of the phenols (b) used is preferably 6 to 50 mol per mol of the compound (D).

In the polycondensation of the compound (D) and the phenols (b), an acidic catalyst is usually used. For example, hydrochloric acid, sulfuric acid, oxalic acid, p-toluenesulfonic acid, trifluoroacetic acid, methanesulfonic acid, Examples thereof include trifluoromethanesulfonic acid. The amount of these acidic catalysts used is 1 × 10 ^{−6 to} 5 per mol of the compound (D).
× 10 ^-1 mol is preferable.

The polycondensation of the compound (D) with the phenols (b) may be carried out without solvent, or may be carried out with toluene, xylene,
An inert solvent such as methyl isobutyl ketone may be used. The amount of these inert solvents used is usually 20 to 1,000 parts by weight per 100 parts by weight of the reaction raw material.

The polycondensation temperature and the polycondensation time of the compound (D) and the phenol (b) are appropriately adjusted depending on the reactivity of the reaction raw material, but the polycondensation temperature is usually 30 to 15
0 degreeC and polycondensation time are 10 minutes-24 hours.

After completion of the polycondensation of the compound (D) and the phenol (b), generally, the reaction mixture is put into water to elute the acidic catalyst into water, and then the unreacted raw materials and the reaction in the reaction mixture are carried out. In order to remove the solvent and the like, the reaction mixture is heated and the volatile matter is removed under reduced pressure to recover the produced compound (B ′).

Specific examples of the compound (D) include the following formulas (13) to (24).

[0069]

[Chemical 11]

[0070]

[Chemical 12]

[0071]

[Chemical 13]

[0072]

[Chemical 14]

[0073]

[Chemical 15]

[0074]

[Chemical 16]

In the composition of the present invention, the compound (B)
Can be used alone or in admixture of two or more.

In the composition of the present invention, the compound (B)
In addition to quinonediazide sulfonic acid ester of other phenolic compounds (hereinafter, referred to as “sulfonic acid ester (b)”)
Say. ), For example, a quinonediazide sulfonic acid ester of a phenol compound having about 2 to 5 benzene rings can be blended. In particular, when the compound (B) does not have a quinonediazidesulfonyl group [corresponding to the case where only the compound (B ′) is used as the compound (B)], the sulfonic acid ester (b) is blended.

Examples of such sulfonic acid ester (b) include 2,3,4-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,3, and
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', 4,4 1,2-naphthoquinonediazide-4-sulfonic acid esters or 1,2-naphthoquinonediazide-5-sulfonic acid esters of (poly) hydroxyphenyl aryl ketones such as ', 5', 6-hexahydroxybenzophenone;

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

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 1,2-naphtho of (poly) hydroxytriphenylalkane such as 1,1-bis (4-hydroxyphenyl) -4- [1- (4-hydroxyphenyl) -1-methylethyl] -1-phenylethane Quinonediazide-4-sulfonic acid ester or 1,2-naphthoquinonediazide-5-sulfonic acid ester;

2,4,4-Trimethyl-2 ', 4', 7-trihydroxy-2-phenylflavan, 2,4,4'-trimethyl-2 ', 4', 5 ', 6,7-penta Hydroxy-
1,2-naphthoquinonediazide-4-sulfonic acid ester or 1,2-naphthoquinonediazide-5 of polyhydroxyphenylflavan such as 2-phenylflavan
Sulfonic acid esters may be mentioned.

Further, quinonediazide sulfonic acid esters described in JP-A-1-144,463 and JP-A-1-156,738 can be used. These sulfonic acid esters (b) can be used alone or in admixture of two or more.

Among the sulfonic acid ester (b),
1,2-naphthoquinonediazide-5-sulfonic acid ester of 2,3,4-trihydroxybenzophenone, 2,3,
1,4-naphthoquinonediazide-5-sulfonic acid ester of 4,4'-tetrahydroxybenzophenone, 2,
1,2-naphthoquinonediazide-5-sulfonic acid ester of 2 ', 3,4,4'-pentahydroxybenzophenone, 2,2', 5,5'-tetramethyl-2 ", 4,4'-
1,2-naphthoquinonediazide-5-sulfonic acid ester of trihydroxytriphenylmethane, 1,2-naphthoquinonediazide-4-sulfonic acid ester of 1,1,1-tris (4-hydroxyphenyl) ethane or 1,
2-naphthoquinonediazide-5-sulfonic acid ester,
1,2-bis (4-hydroxyphenyl) -1-phenylethane 1,2-naphthoquinonediazide-4-sulfonic acid ester or 1,2-naphthoquinonediazide-5
-Sulfonic acid ester, 1,1-bis (4-hydroxyphenyl) -1- {4- [1- (4-hydroxyphenyl) -1-methylethyl]} phenylethane 1,2-
1,2-naphthoquinonediazide-4-sulfonic acid ester or 1,2-naphthoquinonediazide-5-sulfonic acid ester 2,2,4,4-trimethyl-2 ', 4', 7-trihydroxy-2-phenylflavane Naphthoquinonediazide-5-sulfonate, 1,2-naphthoquinonediazide-4-sulfonate or 1,2-naphthoquinonediazide of 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) butane 5-sulfonic acid ester, 1,1,3-tris (2,5-dimethyl-
1,2-naphthoquinonediazide-4-sulfonic acid ester of 4-hydroxyphenyl) propane or 1,2-
Naphthoquinonediazide-5-sulfonate, 1,
1, of 3,3-tris (4-hydroxyphenyl) butane
2-naphthoquinonediazide-4-sulfonic acid ester or 1,2-naphthoquinonediazide-5-sulfonic acid ester is preferred.

In the composition of the present invention, the compounding amount of the compound (B) is usually 3 to 75 parts by weight, preferably 5 to 50 parts by weight, per 100 parts by weight of the novolak resin (A). The compounding amount of the sulfonic acid ester (b) is usually 70 parts by weight or less per 100 parts by weight of the novolac resin (A),
It is preferably 5 to 40 parts by weight. In addition, the compound (B)
The total compounding amount of the sulfonic acid ester (b) and the sulfonic acid ester (b) is usually 3 to 10 relative to 100 parts by weight of the novolak resin (A).
It is 0 part by weight, preferably 5 to 50 parts by weight.

The composition of the present invention contains a quinonediazidesulfonyl group. This quinonediazidesulfonyl group is contained in the compound (B) and / or the sulfonic acid ester (b). The total amount of the quinonediazidesulfonyl group contained in the composition is usually 5 to 25 in terms of solid content.
% By weight, preferably 10 to 20% by weight.

The composition of the present invention may further contain various compounding agents such as a dissolution accelerator, a sensitizer and a surfactant, if necessary.

The dissolution accelerator is a novolac resin (A).
It is a compound used for the purpose of promoting the alkali solubility of As a preferable example, the number of benzene rings is 2
To about 6 phenol compounds, specifically, in addition to the compound (C) described above, the following formula (25)
A low molecular weight phenol compound represented by (35) can be mentioned.

[0087]

[Chemical 17]

[In the formula (25), R ¹³ has 1 carbon atom.
Indicates 6 alkyl group, if R ¹³ there are a plurality or different and be identical to one another, R ¹⁴ and R
^15's may be the same or different from each other and represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 14 carbon atoms or an aralkyl group having 7 to 18 carbon atoms,
e, f, x and y are each an integer of 0 to 3,
e and f are never 0 at the same time, and e + x ≦ 5
And f + y ≦ 5 are satisfied. ]

[0089]

[Chemical 18]

[In the formula (26), R ¹⁶ has 1 carbon atom.
When R ¹⁶ is present in plural numbers, they may be the same or different, and e, f, x and y are each an integer of 0 to 3, but e and f Never become 0 at the same time, and e + x ≦ 5 and f
+ Y ≦ 5 is satisfied. ]

[0091]

[Chemical 19]

[In the formula (27), R ¹⁷ has 1 carbon atom.
In the case where a plurality of R ^17's are present, they may be the same or different, and e, f, g,
x, y and z are each an integer of 0 to 3, but e,
f and g are never 0 at the same time, and e + x
≦ 5, f + y ≦ 5 and g + z ≦ 5 are satisfied. ]

[0093]

[Chemical 20]

[In the formula (28), R ¹⁸ has 1 carbon atom
And R ^{19 to} R 6 are the same as or different from each other when a plurality of R ^18's are present.
²² is the same or different from each other and is a hydrogen atom or a carbon number 1
~ 6 alkyl groups, C6-14 aryl groups or C7-18 aralkyl groups, e, f, g,
x, y and z are each an integer of 0 to 3, but e,
f and g are never 0 at the same time, and e + x
≦ 5, f + y ≦ 5 and g + z ≦ 5 are satisfied. ]

[0095]

[Chemical 21]

[In the formula (29), R ²³ has 1 carbon atom
Indicates 6 alkyl group, if R ²³ there are a plurality or different and be identical to one another, R ²⁴ to R
²⁸ are mutually the same or different and each is a hydrogen atom or a carbon number 1
~ 6 alkyl groups, C6-14 aryl groups or C7-18 aralkyl groups, e, f, g,
x, y and z are each an integer of 0 to 3, but e,
f and g are never 0 at the same time, and e + x
≦ 5, f + y ≦ 5 and g + z ≦ 5 are satisfied. ]

The dissolution accelerator may 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 novolak resin (A),
It is preferably 30 parts by weight or less.

The sensitizer has a function of improving the sensitivity of the resist to radiation. As an example thereof, 2H-pyrido- (3,2-b) -1,4-oxazine-3 (4H ) -Ones, 10H-pyrido- (3,2-
b)-(1,4) -benzothiazines, urazoles,
Hydantoins, barpituric acids, glycine anhydrides, 1-hydroxybenzotriazoles, alloxans, maleimides and the like can be mentioned. 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.

The above-mentioned surfactant has a function of improving the coatability and developability of the composition of the present invention, and examples thereof include polyoxyethylene lauryl ether,
Nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate; F-top EF122A, E
F122B, EF351, EF352, EF601, E
F801, EF802 (trade name, made by Mitsubishi Metals); Megafax F142D, F144D, F171, F17
2, F173, F177, F179A (trade name, manufactured by Dainippon Ink); Fluorard FC176, FC430, F
C431 (trade name, manufactured by Sumitomo 3M); Asahi Guard AG710, Surflon S-381, S-382,
SC-101, SC-102, SC-103, SC-1
04, SC-105, SC-106 (trade name, manufactured by Asahi Glass); KP341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.); acrylic acid-based or methacrylic acid-based (co) polymer Polyflow N
o.75, No.90, No.95, S, Floren A
C202, AC300, AC303, AC326F, A
C903, AC1190 (trade name, manufactured by Kyoeisha Oil & Fat Chemical Co., Ltd.); Hyonic PE40, PE90, PE10
0, PE120, Modicol L, X, Dapro S-6
5, Perenol F40, Color Sparse 188A
(Trade name, manufactured by San Nopco); Emazole O-15R,
O-30 (F), S-20 (trade name, made by Kao); ZON
YE FSN, FSN-100, FSO, FSO-10
0 (trade name, manufactured by DuPont); DS-401, DS-40
3, DS-406, DS-451 (trade name, manufactured by Daikin); Futgent 250, 251, PEF-20
3, PFE-800B, NBX-15 (trade name, manufactured by Neos) and the like.

These surfactants may 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.

Furthermore, 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 novolak resin (A) and the compound (B), and if necessary, the sulfonic acid ester (b) together with various additives, for example, It is prepared as a composition solution by dissolving in a solvent so that the solid content concentration becomes 20 to 40% by weight, and filtering through a filter having a pore size of about 0.2 μm.

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 monoethyl 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, ethyl 2-hydroxy-2-methylpropionate , 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 And so on. 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,
One high boiling 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.

Then, the composition of the present invention prepared as a composition solution is applied to 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 partially, and developed with a developing solution to form a resist pattern. As the radiation used at this time, ultraviolet rays such as i-rays are preferably used, but depending on the characteristics of the composition, ultraviolet rays, far ultraviolet rays, X-rays, electron beams, molecular beams, γ rays, synchrotron radiation, Various kinds of radiation such as a proton beam can be selected and used.

In the present invention, the composition is coated on a substrate, prebaked and exposed, and then heat-treated at 70 to 140 ° C. (hereinafter referred to as “post-exposure baking”), and thereafter. The effect of the present invention can be further improved by developing the film.

Examples of the developer for the composition of the present invention include sodium hydroxide, potassium hydroxide, sodium carbonate,
Sodium silicate, sodium metasilicate, aqueous ammonia,
Ethylamine, n-propylamine, diethylamine,
Di-n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide,
Tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5.4.
0] -7-undecene, 1,5-diazabicyclo- [4.
An alkaline aqueous solution in which an alkaline compound such as 3.0] -5-nonene is dissolved so that the concentration is usually 1 to 10% by weight, preferably 2 to 5% by weight is used.

The developing solution contains a water-soluble organic solvent,
For example, alcohols such as methanol and ethanol and a surfactant can be added in appropriate amounts. When a developer containing such an alkaline aqueous solution is used, it is generally washed with water after development.

[0109]

The present invention will be described in more detail with reference to the following examples and comparative examples, but the present invention is not limited to these examples as long as the gist thereof is not exceeded.
Here, measurement of Mw and evaluation of each resist were performed by the following methods.

Mw: GPC column (G2 manufactured by Tosoh Corporation)
000H _XL 2 Pieces, G3000H _XL 1 Piece, G4000H
_XL 1 piece), the flow rate was 1.0 ml / min, the elution solvent was tetrahydrofuran, and the column temperature was 40 ° C.

Sensitivity: NSR-2005 manufactured by Nikon Corporation
Using an i9C reduction projection exposure machine (numerical aperture of lens: 0.57), the exposure time was changed, and exposure was performed with i-line having a wavelength of 365 nm, and then 25 ° C. with a 2.4 wt% tetramethylammonium hydroxide aqueous solution. Developed for 60 seconds, washed with water, and dried to form a positive resist pattern on the wafer. At that time, a line with a line width of 0.35 μm
Exposure time for forming an and space pattern (1L1S) in a width of 1: 1 (hereinafter referred to as "optimum exposure time")
Was taken as the sensitivity.

Resolution: The dimension of the smallest 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 is observed with a scanning electron microscope, and the resolved pattern dimension is within ± 10% of the mask design dimension. If there is, and the ratio of the thickness of the film after development to the thickness of the film before development of the resist pattern (hereinafter referred to as "residual film ratio") is 90% or more, the focus swing range (focus range) The focus tolerance was evaluated by. The larger the focus range, the better the focus tolerance.

Production of Novolac Resin (A) Synthesis Example 1 m-cresol 60.6 g (0.56 mol) 2,3,5-trimethylphenol 19.1 g (0.14 mol) 37 wt% formaldehyde aqueous solution 51 in autoclave 0.1g (formaldehyde 0.63mol) Oxalic acid dihydrate 4.41g (0.035mol) Water 57.5g and dioxane 269g were charged, then the autoclave was immersed in an oil bath and the temperature of the reaction solution was 130 ° C. While maintaining the temperature at 60 ° C., polycondensation was performed for 6 hours while stirring. Then, after cooling the reaction solution 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 obtain the novolac resin (A).
Was recovered. This resin (Mw = 8,800) is referred to as novolac resin (A1).

Synthesis Example 2 m-Cresol 53.0 g (0.49 mol) 2,3-xylenol 17.1 g (0.14 mol) 2,3,5-trimethylphenol 9.53 g (0.07 mol) in an autoclave ) 37% by weight 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. Was treated in the same manner as in Synthesis Example 1 to recover the novolak resin (A). This resin (Mw = 8,400) is a novolac resin (A2)
And

Synthesis Example 3 m-cresol 53.0 g (0.56 mol) 2,3-xylenol 12.8 g (0.105 mol) 3,4-xylenol 4.28 g (0.035 mol) 37 wt% in autoclave % Aqueous formaldehyde solution 48.7 g (formaldehyde 0.60 mol) Oxalic acid dihydrate 4.41 g (0.035 mol) Water 48.0 g and dioxane 237 g were charged, and polycondensation was carried out for 8 hours. The novolak resin (A) was recovered in the same manner as in Example 1. This resin (Mw = 8,100) is a novolac resin (A3)
And

Synthesis Example 4 A flask equipped with a stirrer, a condenser and a thermometer was charged with m-cresol 103.8 g (0.96 mol) 2,3-xylenol 3.67 g (0.03 mol) 3,4-xylenol. 3.67 g (0.03 mol) Formaldehyde 40 wt% butanol solution (butyl hemiformal) 101.4 g (formaldehyde 1.35 mol) and oxalic acid dihydrate 945 mg (0.0075 mol) were charged, and then the flask was charged. Was immersed in an oil bath, the concentration of the reaction solution was maintained at 100 ° C., and polycondensation was performed for 30 minutes while 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 and the mixture was further added for 100 minutes. Condensation was performed. Next, 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 (A) was cooled to room temperature and recovered. This resin (Mw = 5,700) is referred to as novolac resin (A4).

Synthesis Example 5 The novolak resin (A4) was mixed with ethyl acetate to give a resin component of 30.
After the solution was dissolved to give a weight percentage of 0.
65 times the amount of methanol and 0.75 times the amount of water were added, and the mixture was left standing after stirring. Next, the lower layer separated into two layers was taken out, concentrated and dried to recover the novolac resin (A). This resin (Mw = 8,000) is referred to as a novolac resin (A5).

Synthesis of Compound (B) Synthesis Example 6 In a flask similar to that used in Synthesis Example 4, 1,1-bis (4-hydroxyphenyl) -1- {4- [1- (4-hydroxyphenyl) )-(1-Methyl) ethyl]} phenylethane (corresponding to formula (7) above) 42.5 g (0.1 mol) 10 wt% aqueous sodium hydroxide solution 132 g (sodium hydroxide 0.33 mol) were charged and stirred. Dissolved below. Then, the flask was immersed in an ice bath, and 53.6 g of a 37% by weight aqueous formaldehyde solution (0.66 mol of formaldehyde) was gradually added dropwise using a dropping funnel so that the temperature of the reaction solution did not exceed 5 ° C. After completion of the dropwise addition, the reaction was monitored by HPLC and stirred at room temperature until the reaction was completed. After completion of the reaction, the flask was immersed in an ice bath, and 42.0 g of a 50 wt% aqueous acetic acid solution (0.35 mol of acetic acid) was added to the reaction solution at a temperature of 5 ° C.
The mixture was gradually added dropwise using a dropping funnel so as not to exceed the range, to precipitate the product. Then, after returning to room temperature and adding the reaction solution to 2 liters of water with stirring, the precipitate was filtered off,
Further, this precipitate was washed out with a large amount of water until it became neutral, and was taken out and dried overnight in a vacuum dryer kept at 40 ° C. to obtain a compound. This is designated as compound (D1).

Synthesis Example 7 A flask similar to that used in Synthesis Example 4 was charged with 30.2 g (0.05 mol) of compound (D1), 47.1 g (0.5 mol) of phenol and 232 g of methyl isobutyl ketone. It was dissolved under stirring. Then, the flask was immersed in a water bath, and 0.143 g (7.5 × 10 ⁻⁴ mol) of p-toluenesulfonic acid and 1.29 g of methyl isobutyl ketone were gradually added thereto so that the temperature of the reaction solution did not exceed 50 ° C. Dropped. After the dropping, the reaction solution is heated to 50 ° C on a hot water bath,
Polycondensation was carried out for 3 hours with stirring. Then, the reaction solution was cooled to room temperature, 200 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 placed in a flask equipped with a stirrer and a cooling tube, the temperature was raised, and at the same time, volatile components were removed under reduced pressure to obtain a compound (B ′). This is designated as compound (B′1).

Synthesis Example 8 53.1 g (0.05 mol) of the compound (B'1), 48.4 g (0.18 mol) of 1,2-naphthoquinonediazide-5-sulfonic acid chloride and 330 g of dioxane were charged, and the mixture was stirred. Dissolved in. Then add 3 flasks
Immerse it in a water bath maintained at 0 ° C, and when the temperature of the reaction solution becomes constant at 30 ° C, add 19.2 g (0.19 mol) of triethylamine dropwise so that the temperature of the reaction solution does not exceed 35 ° C. It was gradually added dropwise using a funnel. Then, the produced 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 deposit, it was dried for one day in a vacuum dryer kept at 40 ° C. to obtain a compound (B) having a quinonediazidesulfonyl group. This is designated as compound (B1).

Synthetic Example 9 In a flask similar to that used in Synthetic Example 4, 19.2 g (0.1 mol) of 1,1,1-tris (4-hydroxyphenyl) methane (corresponding to formula (8)) was added. 132 g of 10% by weight sodium hydroxide aqueous solution (0.33 mol of sodium hydroxide) 53.6 g of 37% by weight aqueous formaldehyde solution (0.66 mol of formaldehyde) and 42.0 g of 50% by weight aqueous acetic acid solution (0.35 mol of acetic acid) were used. Compound (D) was obtained by the same procedure as in Synthesis Example 6 except for the above. This is designated as compound (D2).

Synthesis Example 10 A flask similar to that used in Synthesis Example 4 was charged with Compound (D2) 19.0 g (0.05 mol) 2,6-xylenol 61.1 g (0.5 mol) methyl isobutyl ketone 240 g. Synthesis Example 6 except that 0.143 g (7.5 × 10 ⁻⁴ mol) of p-toluenesulfonic acid and 1.29 g of methyl isobutyl ketone were charged and polycondensation was performed for 4.5 hours.
Compound (B ′) was obtained by the same treatment as described above. This is designated as compound (B′2).

Synthesis Example 11 Compound (B′2) 54.9 g (0.05 mol) 1,1,1-naphthoquinonediazide-4-sulfonic acid chloride 60.5 g (0.225 mol) dioxane 380 g and triethylamine 23. A compound (B) having a quinonediazidesulfonyl group was obtained by the same procedure as in Synthesis Example 6 except that 3 g (0.23 mol) was used. This is designated as compound (B2).

Synthesis Example 12 In a flask similar to that used in Synthesis Example 4, 10.6 g (0.1 mol) of 1,1,1-tris (4-hydroxyphenyl) ethane (corresponding to the above formula (8)) was added. ) 10 wt% aqueous sodium hydroxide solution 132 g (sodium hydroxide 0.33 mol) 37 wt% formaldehyde aqueous solution 53.6 g (formaldehyde 0.66 mol) and 50 wt% acetic acid aqueous solution 42.0 g (acetic acid 0.35 mol) were added. Compound (D) was obtained by the same treatment as in Synthesis Example 6 except that the compound (D) was used. This is designated as compound (D3).

Synthesis Example 13 In a flask similar to that used in Synthesis Example 4, compound (D3) 22.1 g (0.05 mol) o-cresol 54.1 g (0.5 mol) methyl isobutyl ketone 228 g p- Compound (B ′) was treated in the same manner as in Synthesis Example 6 except that 0.143 g (7.5 × 10 ⁻⁴ mol) of toluenesulfonic acid and 1.29 g of methyl isobutyl ketone were charged and polycondensation was performed for 4 hours. ) Got. This is designated as compound (B′3).

Synthesis Example 14 Compound (B'3) 51.4 g (0.05 mol) 1,2-naphthoquinonediazide-5-sulfonic acid chloride 60.5 g (0.225 mol) dioxane 369 g and triethylamine 23.3 g ( Compound (B) having a quinonediazidesulfonyl group was obtained by the same treatment as in Synthesis Example 6 except that 0.23 mol) was used. This is designated as compound (B3).

Examples 1 to 5, Comparative Examples 1 and 2 The novolak resin (A) synthesized in the above Synthesis Example and the compound (B), the sulfonic acid ester (b), the compound (B '), the dissolution accelerator and the solvent. Were mixed to form a uniform solution, which was then filtered through a membrane filter having a pore size of 0.2 μm to prepare a solution of the composition shown in Table 1. The numerical values in Table 1 are parts by weight.

The types of sulfonic acid ester (b), compound (B '), dissolution promoter and solvent used here are as follows.

Sulfonic acid ester (b) (b1); 1,1-bis (4-hydroxyphenyl)-
1- {4- [1- (4-hydroxyphenyl)-(1-
Condensation product of 1 mol of methyl) ethyl]} phenylethane and 2 mol of 1,2-naphthoquinonediazide-5-sulfonyl chloride (b2); 1 mol of 1,3,3-tris (4-hydroxyphenyl) butane and 1,2- Naphthoquinone diazide-5
-Sulfonyl chloride 2.5 mol condensate (b3); 1,1,3-tris (2,5-dimethyl-4-)
Condensation product of 1 mol of hydroxyphenyl) butane and 2.5 mol of 1,2-naphthoquinonediazide-4-sulfonyl chloride

Compound (B ′) (B′1); Compound represented by the above formula (13) (B′2); Compound represented by the above formula (19)

Dissolution accelerator (e1); 1,1-bis (4-hydroxyphenyl)-
1-phenylethane (corresponding to the above formula (25)) (e2); 1,1-bis (4-hydroxyphenyl)-
1- {4- [1- (4-hydroxyphenyl) -1-methylethyl]} phenylethane (corresponding to formula (7) above)

Solvent (α); Ethyl 2-hydroxypropionate (β); Ethyl 3-ethoxypropionate (γ); Methyl 3-methoxypropionate

A solution of each composition was applied onto a silicon wafer using a spinner, and then prebaked for 2 minutes on a hot plate kept at 100 ° C. to form a resist film having a thickness of 1.1 μm. Formed. As described above, a wavelength of 365n is applied to the resist film through a mask pattern.
After exposure by i-line of m, post-exposure baking was performed for 1 minute on a hot plate kept at 110 ° C. Then
Developing as described above, washing, and drying to form a resist pattern, based on the obtained resist pattern,
The performance of each resist was evaluated. Table 2 shows the evaluation results.

As shown in Table 2, in Examples 1 to 5, in particular, the focus tolerance was excellent, the sensitivity and the resolution were excellent, and the developability, the pattern shape and the heat resistance were good.

[0136]

[Table 1]

[0137]

[Table 2]

[0138]

The positive-working radiation-sensitive resin composition of the present invention is particularly excellent in focus tolerance as well as in sensitivity, resolution, heat resistance and pattern shape. Therefore, the positive-type radiation-sensitive resin composition of the present invention,
In particular, it is extremely useful as a positive resist for manufacturing integrated circuits, which is expected to have higher integration in the future.

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[Procedure amendment]

[Submission date] September 13, 1993

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Specific examples of the compound (B ') include the following formulas (13) to (24).

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

Claims (1)

[Claims] 1. A positive-type radiation-sensitive resin composition containing a compound having a quinonediazidesulfonyl group, which comprises an alkali-soluble novolak resin (A) and the following formula (1):
And the following formula (2) [Q in the formulas (1) and (2) is represented by the following formula (3): In formula (1), formula (2) and formula (3), D represents a hydrogen atom or a quinonediazidesulfonyl group, and a plurality of D may be the same or different. R ¹ is an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or 1 to 1 carbon atoms.
8 alkoxy group, aralkyloxy group having 7 to 15 carbon atoms, acyl group having 1 to 7 carbon atoms, aryl group having 6 to 14 carbon atoms, aralkyl group having 7 to 18 carbon atoms, and 6 to 10 carbon atoms
It indicates an aryl group or an alkoxycarbonyl group having 2 to 10 carbon atoms, if R ¹ there are a plurality Some of formula (1) or (2) may be different even mutually identical; R ² represents an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms;
^{When a} plurality of ² are present in the formula (1) or the formula (2), they may be the same or different from each other; R ^{3 to} R ⁶
May be the same or different from each other, and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, or a carbon number. ⁷ to 18 aralkyl groups are shown; R ⁷
To R ⁹ may be the same as or different from each other, and are a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or 3 to 3 carbon atoms.
10 represents a cycloalkyl group; R ¹⁰ and R ¹¹ may be the same or different from each other and represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms. R ¹² is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or 6 carbon atoms.
To an aryl group having 14 to 14 or an aralkyl group having 7 to 18 carbon atoms; a is an integer of 1 to 3, b is an integer of 0 to 3, and a + b ≦ 5 is satisfied, and c is an integer of 1 to 3. , D are integers of 0 to 2 and satisfy c + d ≦ 3. ] The positive type radiation sensitive resin composition containing at least 1 sort (s) of compound (B) selected from the compound group represented by these.