JPH09304924A - Positive type photosensitive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a positive type photosensitive composition for hyperfine working, which has high sensitivity and high resolution and further is improved in exposure margin by containing alkali soluble resin and a specified photosensitive compound. SOLUTION: A positive type photosensitive composition contains alkali soluble resin and a photosensitive compound expressed by the formula. In the formula, R1 -R10 may be the same or different, and represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group and so on. At least one of R1 -R10 is -NR25 D or -N(D)2 (D is 1, 2-naphthoquinone diazide- 5 -or -4sulfonyl group). R11 -R18 may be the same or different and represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group and so on. At least one of R11 -R18 is a hydroxyl group or -OD. R19 -R25 may be the same or different and represent a hydrogen atom, an alkyl group and so on.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention contains an alkali-soluble resin and a specific 1,2-quinonediazide compound, and emits radiation such as ultraviolet rays, far ultraviolet rays, X-rays, electron beams, molecular beams, γ-rays and synchrotron radiation. The present invention relates to a positive photoresist composition which is sensitive to, and more specifically, to a positive photosensitive composition for microfabrication which is capable of obtaining high resolution and high sensitivity.

[0002]

2. Description of the Related Art A positive photoresist is applied on a substrate such as a semiconductor wafer, glass, ceramics or metal to a thickness of 0.5 to 2 .mu.m by a spin coating method or a roller coating method. Thereafter, the film is heated and dried, and a circuit pattern or the like is baked by ultraviolet irradiation or the like through an exposure mask. If necessary, the film is baked after exposure and then developed to form a positive image. As a positive photoresist composition, a composition containing an alkali-soluble resin binder such as novolak and a naphthoquinonediazide compound as a photosensitive material is generally used.

The degree of integration of integrated circuits is increasing, and 0.5 is used in the manufacture of semiconductor substrates such as VLSI.
It is becoming necessary to process an ultrafine pattern composed of a line radiation of μm or less. In such applications, there is a demand for a photoresist that can obtain a particularly high resolution and that has a wide development latitude in order to always maintain a constant processing radiation. In addition, in order to prevent processing defects of the circuit, the resist pattern after development,
It is required that no resist residue is generated.

Further, Japanese Examined Patent Publication No. 8-7436 is -NH-
The present invention relates to a positive photosensitive composition containing a photosensitive diazoquinone compound having a structure of 1,2-naphthoquinonediazide-5- or -4-sulfonyl group, but the obtained resolving power was not sufficient.

[0005]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a positive type photosensitive composition for ultrafine processing which has high sensitivity and high resolution and has an improved exposure margin.

[0006]

DISCLOSURE OF THE INVENTION The inventors of the present invention have found that the above problems can be solved by using a quinonediazide sulfonic acid ester having a specific structure as a photosensitive material, as a result of diligent study in consideration of the above characteristics. The present invention has been completed based on this finding. That is, the object of the present invention was achieved by a positive photosensitive composition containing an alkali-soluble resin and a photosensitive compound represented by the following general formula [I].

[0007]

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(R _{1 to} R ₁₀ : which may be the same or different, hydrogen atom, halogen atom, alkyl group, alkenyl group, cycloalkyl group, aryl group, aralkyl group, acyl group, hydroxyl group, -OD, -NR ₂₅ D, -N (D)
₂ (D is 1,2-naphthoquinonediazide-5- or-
4-sulfonyl group). However, at least one of R _{1 to} R ₁₀ is —NR ₂₅ D or —N (D) ₂ . R _{11 to} R ₁₈ : may be the same or different, and are a hydrogen atom,
Halogen atom, alkyl group, alkenyl group, cycloalkyl group, aryl group, aralkyl group, acyl group, hydroxyl group, -OD (D is 1,2-naphthoquinonediazide-5-
Or -4-sulfonyl group). However, R ₁₁ ~
At least one of R ₁₈ is a hydroxyl group or -OD. R _{19 to} R ₂₅ : the same or different, a hydrogen atom,
Represents an alkyl group. )

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
In the above general formula (I), R₁~ R₁₈With halogen atom
Is preferably a chlorine atom, a bromine atom or an iodine atom, and a salt
Elementary atoms are particularly preferred. R₁~ R_{twenty four}As an alkyl group
Is methyl, ethyl, propyl, isopropyl
Group, n-butyl group, isobutyl group, sec-butyl group,
an alkyl group having 1 to 4 carbon atoms such as a tert-butyl group
is there. More preferably methyl group, ethyl group, propyl
Group, an isopropyl group. R₁~ R₁₈Alkenyl group of
As a vinyl group, a propenyl group, an allyl group is preferable.
In particular, an allyl group is particularly preferable. R₁~ R₁₈The cycloal
As the kill group, a cyclopentyl group, a cyclohexyl group
Is preferred. R₁~ R₁₈Phenyl as the aryl group of
Group, toluyl group, xylyl group, cumenyl group, mesityl group
And an aryl group having 6 to 10 carbon atoms such as
Preferred is a phenyl group. R₁~ R₁₈Aral
As the kill group, benzyl group, phenethyl group and the like are preferable.
Yes. R₁~ R₁₈Examples of the acyl group include formyl group and aceton group.
A tyl group, a propionyl group, a benzoyl group and the like are preferable.
In the general formula (I), R₁~ R_TenAs a hydrogen source
Child, chlorine atom, bromine atom, methyl group, ethyl group, propiyl group
Group, isopropyl group, allyl group, cyclohexyl group,
Phenyl group, benzyl group, -NR_{twenty five}D, -N (D)_TwoBut
Preferably, more preferably, a hydrogen atom, a chlorine atom and a methyl group.
Group, allyl group, benzyl group, -NR_{twenty five}It is D. R₁₁
~ R₁₈As, hydrogen atom, chlorine atom, methyl group, ethyl
Group, allyl group, cyclohexyl group, phenyl group, benzene
A zyl group is preferable, and a hydrogen atom or methyl is more preferable.
A group, an allyl group, a cyclohexyl group, and a phenyl group.
R ₁₉~ R_{twenty five}As, a hydrogen atom and a methyl group are preferable,
Hydrogen atoms are particularly preferred.

The photosensitive compound [I] of the present invention has the formula [I]
Was obtained by carrying out esterification and amidation reaction of 1,2-naphthoquinonediazide-5- or -4-sulfonyl chloride with a polyamino compound in which D was H (hydrogen) in is there. That is, a predetermined amount of polyamino compound and 1,2-naphthoquinonediazide-5- or -4-sulfonyl chloride and acetone, methyl ethyl ketone, dioxane, dimethoxyethane, tetrahydrofuran, diglyme, ethyl acetate, dichloromethane, chloroform, γ-butyrolactone, N. A solvent such as -methylpyrrolidone is charged into a flask, and a base catalyst such as sodium hydroxide, sodium carbonate, triethylamine, 4-dimethylaminopyridine, N-methylmorpholine, N-methylpiperazine, N is added.
-Methylpyrrolidine, etc., preferably triethylamine,
N-methylpyrrolidine is added dropwise and condensed. The obtained product is crystallized in water, washed with water, and further purified and dried.

In the above reaction, a mixture having different esterification or amidation numbers and esterification or amidation positions is obtained. However, only certain specific isomers can be selectively synthesized by selecting the synthesis conditions or the structure of the polyamino compound. Specific examples of the compound represented by formula (I) in the present invention are shown below.
However, the content of the present invention is not limited to these. These may be used alone or in combination of two or more.

[0012]

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[0013]

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When the photosensitive compound of the present invention synthesized by the above-mentioned method is used as a resin composition, it may be used alone or as a mixture of two or more kinds thereof in an alkali-soluble resin. The compounding amount is 1
It is 5 to 100 parts by weight, preferably 20 to 60 parts by weight, relative to 00 parts by weight. When the use ratio is less than 5 parts by weight, the residual film rate is remarkably lowered, and when it exceeds 100 parts by weight, the sensitivity and the solubility in a solvent are lowered.

In the present invention, the above-mentioned photosensitive material should be used, but if necessary, 1,2-naphthoquinonediazide-5- (and / or-) of the polyhydroxy compound shown below is used.
4-) An esterified product with sulfonyl chloride can be used in combination. At this time, the ratio of the naphthoquinone diazide ester photosensitive material of these polyhydroxy compounds to the photosensitive material in the present invention is 20/80 to 80/20 (weight ratio).
Is preferable. That is, if the photosensitive material of the present invention is less than 20% by weight of the total photosensitive material, the effect of the present invention cannot be sufficiently exhibited.

As the polyhydroxy aromatic compound,
For example, 2,3,4-trihydroxybenzophenone,
2,4,4'-trihydroxybenzophenone, 2,
4,6-trihydroxybenzophenone, 2,3,4
4'-tetrahydroxybenzophenone, 2,2 ',
4,4'-tetrahydroxybenzophenone, 2,4
Polyhydroxybenzophenones such as 6,3 ′, 4 ′, 5′-hexahydroxybenzophenone and 2,3,4,3 ′, 4 ′, 5′-hexahydroxybenzophenone
2,3,4-trihydroxyacetophenone, 2,3
Polyhydroxyphenyl alkyl ketones such as 4-trihydroxyphenylhexyl ketone, bis (2,4-dihydroxyphenyl) methane, bis (2,3,4-trihydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) Bis ((poly) hydroxyphenyl) alkanes such as propane-1, polyhydroxybenzoic acid esters such as propyl 3,4,5-trihydroxybenzoate and phenyl 3,4,5-trihydroxybenzoate
Bis (polyhydroxybenzoyl) alkanes such as bis (2,3,4-trihydroxybenzoyl) methane, bis (2,3,4-trihydroxybenzoyl) benzene or bis (polyhydroxybenzoyl) aryls, ethylene glycol-di Alkylene-di (polyhydroxybenzoates) such as (3,5-dihydroxybenzoate), 3,5,3 ′, 5′-biphenyl tetrol,
2,4,2 ', 4'-biphenyl tetrol, 2,4
6,3 ', 5'-biphenylbentol, 2,4,6
Polyhydroxybiphenyls such as 2 ′, 4 ′, 6′-biphenylhexol,

4,4 ', 4 "-trihydroxy-3,
5,3 ', 5'-tetramethyltriphenylmethane,
4,4 ', 4 "-trihydroxy-3" -methoxy-
3,5,3 ', 5'-tetramethyltriphenylmethane, 4,4', 2 "-trihydroxy-3,5,3 ',
5'-tetramethyltriphenylmethane, 4,4 ',
2 "-trihydroxy-2,2'-dimethyl-5,5 '
-Dicyclohexyltriphenylmethane, 4,4 ',
2 "-trihydroxy-2,5,2 ', 5'-tetramethyltriphenylmethane, 4,4', 3", 4 "-tetrahydroxy-3,5,3 ', 5'-tetramethyltriphenyl Methane, 4,4 ', 2 ", 3", 4 "-pentahydroxy-3,5,3', 5'-tetramethyltriphenylmethane, 2,3,4,2 ', 3', 4 ', 3 ″,
Polyhydroxytriphenylmethanes such as 4 ″ -octahydroxy-5,5′-diacetyltriphenylmethane, 3,3,3 ′, 3′-tetramethyl-1,1′-spirobi-indane-5,6,6. 5 ', 6'-tetrol,
3,3,3 ', 3'-Tetramethyl-1,1'-spirobi-indan-5,6,7,5', 6 ', 7'-hexool, 3,3,3', 3'-tetra Methyl-1,1 '
-Spirobiindane-4,5,6,4 ', 5', 6'-
Hexool, 3,3,3 ', 3'-tetramethyl-
1,1'-spirobi-indane-4,5,6,5 ',
Polyhydroxyspirobi-indanes such as 6 ', 7'-hexool,

3,3-bis (3,4-dihydroxyphenyl) phthalide, 3,3-bis (2,3,4-trihydroxyphenyl) phthalide, 3 ', 4', 5 ', 6'-
Polyhydroxyphthalides such as tetrahydroxyspiro [phthalide-3,9'-xanthene], 2- (3,4-
Dihydroxyphenyl) -3,5,7-trihydroxybenzopyran, 2- (3,4,5-trihydroxyphenyl) -3,5,7-trihydroxybenzopyran, 2
-(3,4-dihydroxyphenyl) -3- (3,4,
5-trihydroxybenzoyloxy) -5,7-dihydroxybenzopyran, 2- (3,4,5-trihydroxyphenyl) -3- (3,4,5-trihydroxybenzoyloxy) -5,7-dihydroxy Polyhydroxybenzopyrans such as benzopyran, 2,4,4-trimethyl-2- (2 ', 4'-dihydroxyphenyl)
-7-hydroxychroman, 2,4,4-trimethyl-
2- (2 ', 3', 4'-trihydroxyphenyl)-
Polyhydroxyphenyl chromanes such as 7,8-dihydroxychroman, 2,4,4-trimethyl-2- (2 ', 4', 6'-trihydroxyphenyl) -5,7-dihydroxychroman, 2,6- Screw (2,3,4-
Trihydroxybenzyl) -4-methylphenol,
2,6-bis (2,4-dihydroxybenzyl) -4-
Methylphenol, 2,6-bis (5-chloro-2,4
-Dihydroxybenzyl) -4-methylphenol,
2,6-bis (2,4,6-trihydroxybenzyl)
-4-Methylphenol, 2,6-bis (2-acetyl-3,4,5-trihydroxybenzyl) -4-methylphenol, 2,4,6-tris (2,3,4-trihydroxybenzyl) Phenol, 2,6-bis (3,5
-Dimethyl-4-hydroxybenzyl) -4-methylphenol, 2,6-bis (2,5-dimethyl-4-hydroxybenzyl) -4-methylphenol, 2,6-bis (2,5-dimethyl-4) -Hydroxybenzyl) -4
-Phenylphenol, 2,6-bis (2,5-dimethyl-4-hydroxybenzyl) -4-cyclohexylphenol, 2,6-bis (4-hydroxybenzyl)-
4-cyclohexylphenol, 2,6-bis {3'-
(4 "-hydroxybenzyl) -4'-hydroxy-
5'-methylbenzyl} -4-cyclohexylphenol, 2,6-bis {3 '-(3 "-methyl-4" -hydroxybenzyl) -4'-hydroxy-5'-methylbenzyl} -4-cyclohexylphenol , 2, 4, 6
-Tris (3,5-dimethyl-4-hydroxybenzyl) -phenol, 4,6-bis (3,5-dimethyl-
4-hydroxybenzyl) pyrogallol, 2,6-bis (3-methyl-4-hydroxybenzyl) -4-methylphenol, 2,6-bis (3,5-dimethyl-4-hydroxybenzyl) phloroglucinol, etc. Hydroxybenzylphenols,

2,2'-dihydroxy-5,5'-bis (4 "-hydroxybenzyl) biphenol, 2,2 '
-Dihydroxy-3,3'-dimethoxy-5,5'-bis (4 "-hydroxybenzyl) biphenol, 2,
2'-dihydroxy-3,3'-dimethoxy-5,5 '
-Bis (3 ", 5" -dimethyl-4 "-hydroxybenzyl) biphenol, 2,2'-dihydroxy-3,
3'-dimethoxy-5,5'-bis (3 "-methyl-
4 "-hydroxybenzyl) biphenol, 4,4'-
Dihydroxy-3,3'-dimethyl-5,5'-bis (3 ", 5" -dimethyl-4 "-hydroxybenzyl)
Biphenols such as biphenols, 1,3,3,5-
Tetrakis (4-hydroxyphenyl) pentane, 1,
1-bis {3 '-(4 "-hydroxybenzyl) -4'
-Hydroxy-5'-methylphenyl} cyclohexane, 1,1-bis {3 '-(3 "-methyl-4" -hydroxybenzyl) -4'-hydroxy-5'-methylphenyl} cyclohexane, 1, 1-bis {3'-
(3 ", 6" -dimethyl-4 "-hydroxybenzyl)
-4'-hydroxy-5'-methylphenyl} cyclohexane, 4,4'-methylenebis {2- (4 "-hydroxybenzyl) -3,6-dimethylphenol}, 4,
4'-methylenebis {2- (3 "-methyl-4" -hydroxybenzyl) -3,6-dimethylphenol},
4,4'-methylenebis {2- (3 "-methyl-4"-
(Hydroxybenzyl) -3-cyclohexyl-6-methylphenol}, 4,4'-methylenebis {2-
(2 ", 4" -dihydroxybenzyl) -6-methylphenol}, 1,8-bis {3 '-(4 "-hydroxybenzyl) -4'-hydroxy-5'-methylphenyl} menthane, 1,8 -Bis {3 '-(3 "-methyl-
4 "-hydroxybenzyl) -4'-hydroxy-5 '
Hydroxyphenylalkanes such as -methylphenyl} menthane,

3,3'-bis (4 "-hydroxybenzyl) -4,4'-dihydroxy-5,5" -diallyldiphenyl ether, 3,3'-bis (4 "-hydroxybenzyl) -4 , 4'-dihydroxy-5,5 "-dimethyldiphenyl thioether, 3,3'-bis (3"-
Methyl-4 ″ -hydroxybenzyl) -4,4′-dihydroxy-5,5 ″ -dimethyldiphenylthioether, 3,3′-bis (3 ″, 6 ″ -dimethyl-4 ″ -hydroxybenzyl) -4,4 ′ -Dihydroxy-5,
5 "-dimethyldiphenyl thioether, 3,3'-bis (3" -methyl-4 "-hydroxybenzyl) -4,
Diphenyl ethers such as 4'-dihydroxy-5,5 "-diallyl diphenyl ether, 2,6-bis (4 '
-Hydroxybenzyl) -4-benzenesulfonamide-phenol, 2,6-bis (3 ', 6'-dimethyl-4'-hydroxybenzyl) -4-benzenesulfonamide-phenol and other sulfonamide phenols or quercetin, Flavono pigments such as rutin,
Furthermore, a low nucleolar form of novolac, or an analogue thereof can be used.

Further, a polymer containing an aromatic hydroxyl group such as acetone pyrogallol condensation resin or polyvinyl phenol can be used instead of these low molecular weight compounds. Further, it is possible to substitute the hydroxyl group of novolac itself with quinonediazide in an appropriate amount so that it also functions as a photosensitive material or as a binder.

Among these, in particular, a portion having one or more aromatic hydroxyl groups on the same aromatic ring is included, and a total of 3
Those having a structure having one or more hydroxyl groups are preferable.
In addition, 1,2-naphthoquinonediaside-5- (and / or-, which is a known aromatic or aliphatic polyhydroxy compound,
4-) Sulfonic acid ester compounds include, for example, JP-B-56-2333, JP-B-62-3411, JP-B-3-2293, JP-B-3-42656, JP-A-58-150948, and JP-A-58-150948. 60-154249
No. 60-134235, JP-A 62-10646, JP-A 62-
153950, JP60-146234A, JP62-178562A, JP63-113451A, JP64-76047A, JP1-147538A.
No. 1, JP-A 1-189644, JP-A 1-309052, JP-A 2-19
846, JP2-84650, JP2-72363, JP2-1
03543, JP-A-2-285351, JP-A-2-296248, JP-A-2-296249, JP-A-3-48251, JP-A-3-48249, JP-A-3-119358, JP-A-3-144454 No. 3-185447
No. 4-1652, No. 4-60548, No. 5-15823
No. 4, JP-A-5-224410, JP-A No. 5-303198, JP-A No. 5-2
97580, Japanese Unexamined Patent Publication No. 5-323597, Japanese Patent Application No. 5-251781, Japanese Patent Application No. 5-251780, Japanese Patent Application No. 5-233537, U.S. Pat.No. 4,797,34
No. 5, No. 4,957,846, No. 4,992,356, No. 5,151,340,
Examples thereof include compounds described in JP-A-5,178,986, European Patent Nos. 530,148 and 573,056.

Examples of the alkali-soluble resin used in the present invention include novolac resin, acetone-pyrogallol resin, polyhydroxystyrene and derivatives thereof. Of these, novolak resins are particularly preferred,
It is obtained by subjecting a given monomer as a main component to addition condensation with an aldehyde in the presence of an acidic catalyst. As the predetermined monomer, phenol, m-cresol, p
Cresols such as -cresol, o-cresol, 2,
Xylenols such as 5-xylenol, 3,5-xylenol, 3,4-xylenol, 2,3-xylenol, m-ethylphenol, p-ethylphenol, o
Alkylphenols such as -ethylphenol and pt-butylphenol, trialkylphenols such as 2,3,5-trimethylphenol and 2,3,4-trimethylphenol, p-methoxyphenol, m-methoxyphenol and 3,5 Alkoxyphenols such as -dimethoxyphenol, 2-methoxy-4-methylphenol, m-ethoxyphenol, p-ethoxyphenol, m-propoxyphenol, p-propoxyphenol, m-butoxyphenol and p-butoxyphenol; Bisalkylphenols such as methyl-4-isopropylphenol, m-chlorophenol, p-chlorophenol, o-chlorophenol, dihydroxybiphenyl, bisphenol A, phenylphenol,
Hydroxy aromatic compounds such as resorcinol and naphthol can be used alone or in combination of two or more, but are not limited thereto.

Examples of aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, propylaldehyde, benzaldehyde, 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, p-ethylbenzaldehyde, pn-butylbenzaldehyde, furfural,
Chloroacetaldehyde and its acetal form, such as chloroacetaldehyde diethyl acetal, can be used, and among these, formaldehyde is preferably used. These aldehydes are
They are used alone or in combination of two or more. As the acidic catalyst, hydrochloric acid, sulfuric acid, formic acid, acetic acid, oxalic acid and the like can be used.

Further, JP-A-60-45238 and 60-
97347, 60-14235, 60-1897
39, 64-14229, JP-A-1-276131,
2-60915, 2-275555, 2-282
745, 4-101147, 4-122938, etc., that is, it is preferable to use a technique in which low-molecular components of novolac resin are removed or reduced.

The novolak resin thus obtained preferably has a weight average molecular weight in the range of 1,500 to 25,000. If it is less than 1500, the film loss of the unexposed portion after development is large, and if it exceeds 25,000, the developing speed is reduced. Here, the weight average molecular weight is defined as a value in terms of polystyrene by gel permeation chromatography. Also, the degree of dispersion of the novolak resin (ratio of weight average molecular weight Mw to number average molecular weight Mn, ie, Mw / Mn)
Is preferably 1.5 to 7.0, and more preferably 1.5 to 5.0. When the dispersity exceeds 7, the effect of the present invention is difficult to obtain. If the dispersity is less than 1.5,
Since a high-level purification step is required for synthesizing the novolac resin, it is not suitable for practical use and is inappropriate. The weight average molecular weight and dispersity of the novolak resin can be appropriately set depending on the type of the novolac resin.

The alkali-soluble resin is a novolak resin synthesized by a condensation reaction between a mixture containing two or more kinds of phenol, cresol, xylenol and trimethylphenol (however, m-cresol is essential) and an aldehyde compound. In this case, the weight average molecular weight is 5500.
~ 25,000, more preferably 6
2,000 to 25,000. Further, the novolak resin has a ratio of the weight average molecular weight to the number average molecular weight of 1.5 to 5.0.
It is preferably 0. The alkali-soluble resin is p
It was synthesized by a condensation reaction of a mixture containing at least four of o-cresol, o-cresol, 2,3-xylenol, 2,6-xylenol and trimethylphenol (o-cresol is essential) with an aldehyde compound. If at least one novolak resin,
The ratio between the weight average molecular weight and the number average molecular weight is 1.5 to 5.0, and the weight average molecular weight is preferably 1500 to 6000. As described above, the effect of the present invention becomes more remarkable by setting the weight average molecular weight and the polydispersity within predetermined ranges depending on the type of novolac resin used.

The low molecular compound having a phenolic hydroxyl group (water-insoluble alkali-soluble low molecule) that can be used in the present invention will be described.

The composition of the present invention preferably further contains a water-insoluble alkali-soluble low molecule in order to accelerate the dissolution in the developing solution. Thereby, the development latitude can be improved. Specific examples of the water-insoluble alkali-soluble low molecular weight include polyhydroxy compounds. Preferred polyhydroxy compounds include:
Phenols, resorcin, phloroglucin, 2,3
4-trihydroxybenzophenone, 2,3,4,4 '
-Tetrahydroxybenzophenone, 2,3,4
3 ', 4', 5'-hexahydroxybenzophenone,
Acetone-pyrogallol condensation resin, phloroglucide,
2,4,2 ', 4'-biphenyl tetrol, 4,4'
-Thiobis (1,3-dihydroxy) benzene, 2,
2 ', 4,4'-tetrahydroxydiphenyl ether, 2,2', 4,4'-tetrahydroxydiphenyl sulfoxide, 2,2 ', 4,4'-tetrahydroxydiphenyl sulfone, tris (4-hydroxyphenyl) ) Methane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4 '-(α-methylbenzylidene) bisphenol, α, α', α "-tris (4-
Hydroxyphenyl) -1,3,5-triisopropylbenzene, α, α ′, α ″ -tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene,
1,2,2-tris (hydroxyphenyl) propane,
1,1,2-Tris (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2,5,5-tetrakis (4-hydroxyphenyl) hexane, 1,2-tetrakis (4-hydroxyphenyl) ethane , 1,1,3-
Tris (hydroxyphenyl) butane, para [α, α,
α ', α'-tetrakis (4-hydroxyphenyl)]
-Xylene and the like.

Among these, as the water-insoluble alkali-soluble low-molecular compound, the total number of carbon atoms in one molecule is 60 or less, and the water-insoluble alkali-soluble low-molecular compound having 2 to 8 phenolic hydroxyl groups in one molecule is used. Compounds are preferred. Further, the water-insoluble alkali-soluble low molecular weight compound has a ratio of phenolic hydroxyl group to aromatic ring of 0.5 to 1.
4, and preferably at least one water-insoluble alkali-soluble low-molecular compound having 12 to 60 phenolic hydroxyl groups in one molecule, having a total carbon number of 12 to 60 in one molecule. . Among these compounds, compounds that increase the alkali dissolution rate of the alkali-soluble resin when added to the water-insoluble alkali-soluble resin are particularly preferable. As a result, the development latitude is further improved. If the compound has more than 60 carbon atoms, the above effect is reduced. If the number is smaller than 12, new drawbacks such as a decrease in heat resistance occur. In order to exert the above effects, it is necessary to have at least two hydroxyl groups in the molecule, but if it exceeds 10, the effect of improving the development latitude is lost. Further, the ratio of the phenolic hydroxyl group to the aromatic ring is 0.
If it is less than 5, the film thickness dependency is large and the development latitude tends to be narrow. If this ratio exceeds 1.4, the stability of the composition deteriorates, and it becomes difficult to obtain high resolution and good film thickness dependence, which is not preferable.

The low molecular weight compound is preferably added in an amount of 1 to 100% by weight, more preferably 2 to 80% by weight, based on the alkali-soluble resin. An addition amount exceeding 100% by weight is not preferable because the development residue deteriorates and a new defect that a pattern is deformed during development occurs. The water-insoluble alkali-soluble low molecular weight compound having an aromatic hydroxyl group used in the present invention is described in, for example,
22938, 2-28531, 2-242973,
2-275959, 4-251849, 5-30
3199, 5-22440, 6-301204, U.S. Pat. Nos. 4,916,210 and 5,210,657,
It can be easily synthesized by those skilled in the art with reference to the methods described in US Pat. No. 5,318,875 and European Patent No. 219294.

Solvents for dissolving the photosensitive material and the alkali-soluble novolac resin used in the present invention include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Propylene glycol methyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, 4-methoxy-4-methyl-2-pentanone, ethyl 2-hydroxypropionate, 2-hydroxy-2-methyl Ethyl propionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-
Methyl hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, etc. Can be used.
These organic solvents are used alone or in combination of two or more.

Further, N-methylformamide, N, N-
Dimethylformamide, N-methylacetamide, N,
High-boiling solvents such as N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, and benzylethyl ether can be mixed and used.

The positive photoresist composition of the present invention may contain a surfactant in order to further improve the coating properties such as striation. Examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, and other polyoxyethylene alkyl ethers, polyoxyethylene octylphenol ether, polyoxyethylene nonylphenol ether. Polyoxyethylene alkyl allyl ethers, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate, etc. Sorbitan fatty acid esters, polyoxyethylene sorbitan monolaurate, polyoxyethylene sol Monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, nonionic surfactants of polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan tristearate, Eftop EF
301, EF303, EF352 (Shin-Akita Kasei Co., Ltd.)
, MegaFac F171, F173 (Dainippon Ink Co., Ltd.), Florado FC430,431 (Sumitomo 3M Ltd.), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103,
SC104, SC105, SC106 (Asahi Glass Co., Ltd.)
Manufactured by Shin-Etsu Chemical Co., Ltd., an acrylic acid-based or methacrylic acid-based (co) polymerized polyflow No.
75, no. 95 (manufactured by Kyoeisha Yushi Kagaku Kogyo KK) and the like. The content of these surfactants is usually 2 parts by weight or less, preferably 1 part by weight or less, per 100 parts by weight of the alkali-soluble resin and the quinonediazide compound in the composition.

These surfactants may be added alone or in some combinations.

The developer for the positive photoresist composition of the present invention includes sodium hydroxide, potassium hydroxide,
Inorganic alkalis such as sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia; primary amines such as ethylamine and n-propylamine; secondary amines such as diethylamine and di-n-butylamine; triethylamine and methyldiethylamine Tertiary amines such as
Use aqueous solutions of alkali amines such as alcoholamines such as dimethylethanolamine and triethanolamine, quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline, and cyclic amines such as pyrrole and piperidine. can do. Furthermore, alcohols such as isopropyl alcohol and surfactants such as nonionic surfactants may be added to the aqueous solution of the above alkalis in appropriate amounts.

A light absorber, a cross-linking agent, and an adhesion aid may be added to the positive photoresist composition of the present invention, if necessary. The light absorbing agent is added as needed for the purpose of preventing halation from the substrate or for enhancing the visibility when applied to a transparent substrate. For example, commercially available light-absorbing agents described in “Technologies and Markets of Industrial Dyes” (CMC Publishing) and Dye Handbook (edited by the Society of Synthetic Organic Chemistry), for example, CI Di
sperse Yellow 1, 3,4, 5, 7, 8, 13, 23, 31, 49, 50,
51, 54, 56, 60, 64, 66, 68, 79, 82, 88, 90, 93, 10
2, 114 and 124, CI Disperse Orange 1, 5, 13, 25,
29, 30, 31, 44, 57, 72 and 73, CI Disperse Red
1, 5, 7, 13, 17, 19, 43, 50, 54, 58, 65, 72, 73, 8
8, 117, 137, 143, 199 and 210, CI Disperse Viole
t 43, CI Disperse Blue 96, CI Fluorescent Br
ightening Agent 112, 135 and 163, CI Solvent Yel
low 14, 16, 33 and 56, CI Solvent Orange 2 and 4
5, CI Solvent Red 1, 3, 8, 23, 24, 25, 27 and 4
9, CI Pigment Green 10, CI Pigment Brown 2, and the like can be suitably used. The light absorbing agent is usually added in an amount of 100 parts by weight or less, preferably 50 parts by weight or less, and more preferably 30 parts by weight or less with respect to 100 parts by weight of the alkali-soluble resin.

The cross-linking agent is added within a range that does not affect the formation of a positive image. The purpose of adding the crosslinking agent is mainly
These include sensitivity adjustment, improvement of heat resistance, improvement of dry etching resistance, and the like. Examples of the cross-linking agent include melamine, benzoguanamine, glycoluryl, etc., which are reacted with formaldehyde, or alkyl modified products thereof, epoxy compounds, aldehydes, azide compounds, organic peroxides, hexamethylenetetramine, etc. You can These crosslinking agents can be blended in a proportion of less than 10 parts by weight, preferably less than 5 parts by weight, based on 100 parts by weight of the photosensitive agent. If the amount of the crosslinking agent exceeds 10 parts by weight, the sensitivity is lowered, and scum (resist residue) is undesirably generated.

The adhesion aid is mainly added for the purpose of improving the adhesion between the substrate and the resist and preventing the resist from being peeled off especially in the etching step. Specific examples include trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, chlorosilanes such as chloromethyldimethylchlorosilane, trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, dimethylvinylethoxysilane,
Alkoxysilanes such as diphenyldimethoxysilane and phenyltriethoxysilane, hexamethyldisilazane, N, N′-bis (trimethylsilyl) urea, dimethyltrimethylsilylamine, silazanes such as trimethylsilylimidazole, vinyltrichlorosilane, γ-
Silanes such as chloropropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, benzotriazole, benzimidazole, indazole, imidazole, 2-
Heterocyclic compounds such as mercaptobenzimidazole, 2-mercaptobenzthiazole, 2-mercaptobenzoxazole, urazole, thiouracil, mercaptoimidazole, mercaptopyrimidine, and urea such as 1,1-dimethylurea and 1,3-dimethylurea, or Thiourea compounds may be mentioned.

These adhesion aids are usually mixed in an amount of less than 10 parts by weight, preferably less than 5 parts by weight, based on 100 parts by weight of the alkali-soluble resin.

The positive photoresist composition is spin-coated on a substrate (eg, a silicon / silicon dioxide coating, a glass substrate, a transparent substrate such as an ITO substrate, etc.) which is used for the production of precision integrated circuit devices. , Roll coating method,
After applying by a suitable coating method such as a flow coating method, a dip coating method, a spray coating method, and a doctor coating method, pre-baking is performed, exposure is performed through a predetermined mask, and post-heating (PEB: Post Exposure Bake) is performed as necessary. ,
By developing, rinsing and drying, a good resist can be obtained.

[0042]

【Example】

Synthesis Example (1) Synthesis of Compound [I-2] 102 g of bis (2,5-dimethyl-4-hydroxyphenyl) methane and 700 mL of ethanol were placed in a four-necked flask equipped with a stirrer, a reflux condenser, a dropper, and a thermometer. Was added and dissolved uniformly, then 50% aqueous solution of dimethylamine 3
60 g was added. Further, 322 g of a 37.3% formalin aqueous solution was added dropwise over 1 hour, and the mixture was heated with stirring at 50 ° C. for 20 minutes. Since white powdery Intermediate 1 was deposited, it was collected by filtration. 296 g of Intermediate 1 obtained by the above operation and 820 g of acetic anhydride were added to a similar reaction apparatus, and the mixture was stirred at 120 ° C. for 5 minutes.
The mixture was heated and stirred for hours. The obtained reaction mixture was concentrated under reduced pressure to obtain Intermediate 2 as a white powder. In a similar reactor, add 100 g of the intermediate 2 obtained above and 20 g of dichloromethane.
After adding 0 mL to homogenize, 30% HBr acetic acid solution 10
0 mL was added, and the mixture was stirred at room temperature for 1 hour. Again, white powder was deposited and filtered to obtain Intermediate 3.

Further, acetanilide 6 was added to the same reactor.
8 g and 500 mL of chlorobenzene were added and stirred, and 7 g of aluminum chloride was added. 25 g of the intermediate 3 obtained above
It was added in portions over 1 hour, and this was heated and stirred at 80 ° C. for 3 hours. The obtained reaction mixture is subjected to steam distillation to remove the solvent chlorobenzene, followed by alkali hydrolysis, neutralization,
Further purification by silica gel column chromatography,
A precursor [I] of the target substance was obtained. Finally, to the same apparatus, 4.7 g of the target precursor [I], 1,2-naphthoquinonediazide-5-sulfonyl chloride 8.06 g, and 200 mL of acetone were added, and the mixture was stirred and dissolved, and triethylamine 3.
2 g was added dropwise over 30 minutes, and the mixture was stirred for 2.5 hours. The obtained reaction mixture was crystallized in 600 mL of a 1% hydrochloric acid aqueous solution and filtered,
10.7 g of the target compound [I-2] was obtained. As a result of the analysis, the obtained compound is a mixture of the following compound groups (1) to (9), which are substantially compounds (1), (2), (3),
(4), (5), (8), among which compound (4), (5),
It contained a large amount of (8), and particularly contained a large amount of compound (8). The amounts of the compounds (6) and (7) were so small that they were hardly contained.

[0044]

Embedded image

Synthesis Example (2) Synthesis of Compound [I-4] Diphenolmethane, allyl bromide and dimethylacetamide were added to a four-necked flask equipped with a stirrer, a reflux condenser, a dropper and a thermometer, and the mixture was heated to 120 ° C. After heating to obtain an allylated product of diphenolmethane, compound [I-4] was obtained according to the above method. The molar ratio of 1,2-naphthoquinonediazide-5-sulfonyl chloride / precursor of the target substance when the photosensitive material was charged was set to 3. As a result of analysis, the obtained compound [I-4] is a mixture of the following compound groups (1) to (9), and is substantially the compounds (1), (2), (3), (4) , (5), (7)
Consisting of a large amount of compounds (4), (5), and (7),
In particular, it contained a large amount of compound (4).

[0046]

[Chemical 6]

Synthesis Example (3) Synthesis of Comparative Photosensitive Material [II] A comparative photosensitive material [II] having the following structure was synthesized according to Example 1 of JP-B-8-7436.

[0048]

[Chemical 7]

Synthesis Example (4) Synthesis of Novolac Resin 30 g of p-cresol, 14 g of o-cresol, 50 g of 2,3-dimethylphenol, 20 g of 2,3,5-trimethylphenol and 4.9 g of 2,6-dimethylphenol. It was mixed with 50 g of diethylene glycol monomethyl ether and charged into a three-necked flask equipped with a stirrer, a reflux condenser and a thermometer. Next, 85 g of a 37% formalin aqueous solution was added, and the mixture was stirred while heating in an oil bath at 110 ° C. When the internal temperature reached 90 ° C, 6.3 g of oxalic acid dihydrate was added. Then, set the oil bath temperature to 1 for 18 hours.
The reaction was continued while maintaining the temperature at 30 ° C., the reflux condenser was removed, and the unreacted monomer was removed by distillation under reduced pressure at 200 ° C. The obtained novolak resin has a weight average molecular weight of 328.
It was 0 (polystyrene conversion) and the dispersity was 2.75.

Preparation and Evaluation of Positive Photoresist Compositions Examples 1 and 2 and Comparative Example Photosensitive material species [I-
2], [I-4], [II], the novolak resin obtained in the above Synthesis Example (4), a solvent, a polyhydroxy compound: α, α, α′-tris (4-hydroxyphenyl) -1-ethyl- 4-Isopropylbenzene was mixed at a ratio shown in Table 1 to form a uniform solution, which was then filtered using a Teflon microfilter having a pore size of 0.10 μm to prepare a photoresist composition. This photoresist composition was applied onto a silicon wafer by using a spinner while changing the rotation speed, and then a vacuum contact type hot plate was used to coat the composition.
After drying at 0 ° C. for 60 seconds, a resist film having a film thickness of 1.02 μm was obtained. This film was exposed using a reduction projection exposure apparatus (reduction projection exposure apparatus NSR-2005i9c manufactured by Nikon Corporation), PEB was performed at 110 ° C. for 60 seconds, and developed with a 2.38% tetramethylammonium hydroxide aqueous solution for 1 minute. It was washed with water for 30 seconds and dried. The resist pattern of the silicon wafer thus obtained was observed with a scanning electron microscope to evaluate the resist. Table 2 shows the results. The amount added in the table is in grams.

The relative sensitivity is defined by the reciprocal of the exposure amount for reproducing a mask pattern of 0.50 μm, and shown as a relative value with respect to the sensitivity of the comparative example. The resolving power represents a limiting resolving power at an exposure amount for reproducing a mask pattern of 0.50 μm.

[0052]

[Table 1]

The results show that the resist composition of the present invention has high sensitivity and excellent resolution.

[0054]

INDUSTRIAL APPLICABILITY The present invention can provide a positive type photosensitive composition for ultrafine processing, which has high sensitivity and high resolution.

Claims (1)

[Claims] 1. A positive type photosensitive composition comprising an alkali-soluble resin and a photosensitive compound represented by the following general formula [I]. Embedded image (R _{1 to} R ₁₀ : may be the same or different, and are a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an aralkyl group, an acyl group, a hydroxyl group, -OD, -NR ₂₅ D, -N (D) ₂ (D is 1, 2
-Naphthoquinonediazide-5- or -4-sulfonyl group). However, at least one of R _{1 to} R ₁₀ is —NR ₂₅ D or —N (D) ₂ . R _{11 to} R ₁₈ : may be the same or different, and are a hydrogen atom,
Halogen atom, alkyl group, alkenyl group, cycloalkyl group, aryl group, aralkyl group, acyl group, hydroxyl group, -OD (D is 1,2-naphthoquinonediazide-5-
Or -4-sulfonyl group). However, R ₁₁ ~
At least one of R ₁₈ is a hydroxyl group or -OD. R _{19 to} R ₂₅ : the same or different, a hydrogen atom,
Represents an alkyl group. )