JPS60154248A - Positive type photosenstive resin composition - Google Patents

Abstract

PURPOSE:To obtain a positive type photosensitive resin compsn. superior in heat resistance and dry etching resistance by mixing an alkali-soluble novolak resin and/or polyhydroxystyrene or its deriv. with 1,2-quinonediazide and a cross-linking agent. CONSTITUTION:An intended photosensitive resin compsn. suitable as a resist for use in fabrication of semiconductor integrated circuits is obtained by dissolving in an org. solvent, such as cellosolve acetate, (A) 100pts.wt. of alkali-soluble novolak resin obtained by additionally condensing phenols with aldehydes in the presence of an acid catalyst, and/or polyhydroxystyrene or its deriv., (B) 5- 100pts.wt. of 1,2-quinonediazide, such as 1,2-benzoquinonediazide sulfonic ester, and (C) 0.5-50pts.wt. of a cross-linking agent, such as ditertiarybutyl peroxide.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a positive photosensitive resin composition, and more particularly to a positive photosensitive resin composition having excellent heat resistance, dry etching resistance, and film retention rate.

In recent years, advances in semiconductor integrated circuit manufacturing technology have been remarkable, and the resists used for manufacturing highly integrated semiconductor integrated circuits are
A shift is being made from cyclized isoprene rubber-based negative photoresists, which have a large reduction in resolution due to swelling, to positive (1) photoresists, which are made by combining an alkali-soluble resin and a 1,2-naphthoquinone diazide compound, which have little swelling. However, even if a positive type photoresist is used, side etching development occurs when wet etching is performed, making it difficult to increase the degree of integration of semiconductor integrated circuits. This side etching phenomenon is an unavoidable phenomenon as long as wet etching is used, since wet etching progresses to uniform etching. Therefore, in recent years,
Reactive ion etching, which performs anisotropic etching by sputtering charged ions perpendicular to the surface to be etched, and dry etching, also known as ion milling, are attracting attention and are already at the stage of practical application. However, this method generates a large amount of heat because charged particles are sputtered onto the resist surface. Therefore, a resist to which this dry etching can be applied is required to have excellent dry etching resistance and good heat resistance.

An object of the present invention is to improve the above-mentioned drawbacks of the prior art and to provide a positive photosensitive resin composition having excellent heat resistance, dry etching resistance, and film retention rate.

(2) In order to achieve the above object, the present inventors, as a result of intensive research, found that an alkali-soluble novolac resin and/or polyhydroxystyrene or a derivative thereof and 1,2
- The present invention was achieved by discovering that by adding a crosslinking agent to a positive photosensitive resin composition comprising a quinone diazide compound, dry etching resistance and heat resistance are improved, and the residual film rate is also improved.

The positive photosensitive resin composition of the present invention is characterized by comprising an alkali-soluble novolac resin and/or bolyhyloxystyrene or a derivative thereof, a 1,2-quinonediazide compound, and a crosslinking agent.

Examples of the crosslinking agent used in the present invention include organic peroxides, organic azo compounds, N-methylol compounds, aldehyde polymers, hexamethylenetetramine, and the like.

Examples of the organic peroxides include isobutyryl peroxide, diisopropyl peroxy dicarbonate, di-n-propyl peroxy dicarbonate, di(2-ethoxyethyl) peroxy dicarbonate, di(methoxyethyl) isopropyl) peroxydicarbonate, di(2-ethylhexyl)peroxydicarbonate, t-butylperoxyneodecanoate,
2,4-dichlorobenzoyl peroxide, t-butylperoxypivalate, 3.5.5-)limethylhexanoyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, stearoyl peroxide, propionyl peroxide, succinic peroxide, acetyl Peroxide, t-butylperoxy(2-ethylhexanoate), benzoylperoxide, t-butylberoxyisobutyrate,
1.1-bis(butylperoxy)-3,3,5-
) Limethylcyclohexane, 1,1-bis(t-7'' tylheloxy)cyclohexane, t-butylperoxymaleic acid, t-butylperoxylaurate, t-butylduroxy-3.5.57 trimethyl 1-hexanoate, cyclohexanone peroxide, (4) t-butylperoxyisopropyl carbonate, 2,
5-dimethyl-2,5-di(benzoylperoxy)
Hexane, t-phdelperoxyacetane, t-
Butyl peroxybenzoate, n-butylperoxybenzoate, 4.4-bis(t-butylperoxy)valerate, methyl ethyl ketone peroxide, dicumyl peroxide, 2.5
-dimethyl-2.

5-di(t-butylperoxy)hexane, 1-butylcumyl peroxide, t-butyl hydroperoxide,
Dilisopropylbenzene hydroperoxide, dibutyl peroxide, rhomenthane hydroperoxide, 2,5-dimethyl-2.5-di(t-butylperoxy)hexyne-3,1,1,3.3-tetramethylbutyl Hydroperoxide, 2,5-dimethylhexane-
2.

Examples include 5-dihydroperoxide and cumene hydroperoxide.

Examples of organic azo compounds include 2,2'-azobis-(2-amidinopropane)dihydroc(5), α. α1-azobis-l-butyronitrile, 4,4'-azobis(4-cyanovaleric acid), 1,1'
-Azobis(cyclohexane-1-carbonitrile),
Examples include 2.2'-azobis(2.4-dimethylvaleronitrile), 2.2'-azobis(4-methoxy, 2.4'' dimethylvaleronitrile), and dimethyl 2.2'-azobisisobutyrate. - Examples of N-methylol compounds include N-methylol acrylamide, trimethylol melamine, hexamethylol melamine, and the like.

Examples of aldehyde polymers include paraformaldehyde and trioxane.

The amount of the crosslinking agent added is 0.5 to 50 parts by weight, preferably 1 to 30 parts by weight, particularly preferably 1 to 20 parts by weight, based on 100 parts by weight of the alkali-soluble novolac resin and/or polyhydroxystyrene or its derivative. Department.

The amount of crosslinking agent added is O. If the amount is less than 5 parts by weight, the effect of improving heat resistance will be low, and if it exceeds 50 parts by weight (6), the stability of the resist coating will be poor.

In the present invention, when N-methylol compounds, aldehyde polymers, or hexamethylenethiolamines are used as crosslinking agents, organic acids such as formic acid, oxalic acid, and acetic acid, or para-toluenesulfonic acid are used as auxiliary agents to enhance the effect. Can be added.

In this case, the amount of the auxiliary agent added is 0.01-10 parts by weight per 100 parts by weight of the alkali-soluble novolak resin and/or polyhydroxystyrene or its derivative.
Preferably 0.01 to 5 parts by weight, particularly preferably 0.0
It is 1 to 2 parts by weight.

The alkali-soluble novolac resin used in the present invention is
It is obtained by addition condensation of phenols and aldehydes under an acid catalyst, preferably at a ratio of 0.7 to 1 mole of aldehyde per mole of phenol. The phenols used in this case include, for example, phenol, 0-cresol, m-cresol, p-cresol, 0-ethylphenol, m-ethylphenol, p-ethylphenol, 0-butylphenol, m-butylphenol (7
)-ru, p-butylphenol, 2,3-xylenol,
2.4-xylenol, 2.5-xylenol, 2,6
-xylenol, 3,4-xylenol, 3,6-xylenol, p-phenylphenol, resorcinol,
Examples include hydroquinone, pyrogallol, phloroglucinol, and the like. These phenols are used singly or in combination of two or more, taking into account their alkali solubility.

Examples of aldehydes include formaldehyde,
Examples include paraformaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, acetaldehyde and the like. As the acid catalyst, for example, inorganic acids such as hydrochloric acid, nitric acid, and sulfuric acid, and organic acids such as formic acid, oxalic acid, and acetic acid are used.

Examples of the polyhydroxystyrene or its derivatives used in the present invention include poly-low hydroxystyrene, poly-m-hydroxystyrene, poly-p-hydroxystyrene, poly-α-methyl-0-hydroxystyrene, poly-α -methyl (-m-hydroxystyrene,
Examples include poly-α-methyl-(8) p-hydroxystyrene, partially acetylated products, and silylated products thereof. The number average molecular weight of these polyhydroxystyrenes or derivatives thereof is preferably 3,000 to 200,000, particularly preferably 5.
000-10'0.00 The 1,2-quinonediazide compound used in the present invention is, for example, 1,2-benzoquinonediazide sulfonic acid ester, 1,2-naphthoquinonediazide sulfonic acid ester, 1,2-benzoquinonediazide sulfonic acid amide, 1,2-naphthoquinonediazide sulfonic acid amide, etc., and known 1°2-quinonediazide compounds can be used as they are. More specifically, J, 1 (“Light-3ensi
tive 5yst'ems"339~3352. (
1965), John'Wiie & 5ons (
Ne*'Y.

rk) and “photo” by W. S. De F'orest.
oresIst”50. (1975), McGraw
Hill, Inc. (New Y.

(9) 1,2-quinonediazide compounds described in rk) can be mentioned. That is, 1,2-benzoquinonediazide-4-sulfonic acid phenyl ester, di(1'', 2
"-benzoquinonediazide-4"-sulfonyl)-4,
4'-dihydroxybiphenyl, 1,2-benzoquinonediazide-4-(N-ethyl-N-β-naphthyl)-sulfonamide, 1,2-naphthoquinonediazide-5-sulfonic acid cyclohexyl ester, 1-(1', 2'-
naphthoquinonediazide-51-sulfonyl)-3,5-
Dimethylpyrazole, 1,2-naphthoquinonediazide-
5" sulfonic acid-4'-hydroxydiphenyl-4"-
Azo-β-naphthol ester, N,N-di(1,2
-naphthoquinonediazide-5-sulfonyl)-aniline, 2- (1'.

21-naphthoquinonediazide-5@-sulfonyloxy)-1-hydroxy-anthraquinone, 2 moles of 112-naphthoquinonediazide-5-sulfonic acid chloride and 4.
Condensate with 1 mol of 41-diaminobenzopheno y, 1,
2-naphthoquinone diazide (10) Condensate of 2 moles of do-5-sulfonic acid chloride and 1 mole of 4,4'-dihydroxy-1,11-diphenylsulfone, 1,2-naphthoquinone diazide-5-sulfonic acid chloride 1 Condensate of mol and Purpro 5921 mol, 1.
Examples include 2-naphthoquinonediazide-5-(N-dihydroabiethyl)-sulfonamino.

Also, Special Publications No. 37-1953, No. 37-3627, No. 37-13109, No. 40-26126, No. 40-
No. 3801, No. 45-5604, No. 45-27345
1,2-quinonediazide compounds described in JP-A No. 51-13013, JP-A-48-96575, JP-A-4B-63802, JP-A-4B-63803, JP-A-58-75149, etc. are also used. be able to.

Furthermore, the following general formula (1), the following general formula (II), (wherein a and b are the same or different and an integer of 3 or 4, ! and m are the same or different and 0 or 1 to 3
C is an integer of 1 to 4, n is an integer of 0 or 1 to 3, and (a-0, (b-m) and (c-n)
are all integers of 1 or more, R1, R, and R7 are the same or different, 1,2-naphthoquinonediazide-4-sulfonyl group, 1,2-naphthoquinonediazide-5-sulfonyl group, or 1,2-benzoquinonediazide- 4-sulfonyl group, R2, R4SRB and R1i are the same or different, hydrogen atom, halogen atom, alkyl group, aryl group, aralkyl group, alkoxy group, cyano group or nitro group, R3, R4, R.

and Rlo are the same or different and mean a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group, and R3 and R4 and R9 and R (□ can form a ring with a carbon-carbon bond or an ether bond). Formula (1), (where n is an integer of 2 to 4, E is 0 or an integer of 1 to 3, m is an integer of 1 to 4, k is an integer of 1 to 4, and +J+
m-5, and R1 is 1,2-naphthoquinonediazide-
4-sulfonyl group, 1,2-naphthoquinonediazide-5
-sulfonyl group or 1,2-benzoquinonediazide-4-sulfonyl group, R2 is a hydrogen atom, a halogen atom,
Alkyl group, aryl group, aralkyl group, alkoxy group, cyano group or nitro group, Z means methane or a residue of an aromatic compound) The following general formula (IV), (13) or general formula (V), ( In the formula, a, , b and C are the same or different, and 1 to 4
, 11m and n are the same or different, 0 or an integer of 1 to 3, (a - 6), (b - m) and (c
-n) is an integer of 1 or more, R1, R2 and R are the same or different, 1,2-naphthoquinonediazide-5-sulfonyl group or 1,2-benzoquinonediazide-4-sulfonyl group, R3, R4 and R6 are Same or different, hydrogen atom, halogen atom, alkyl group, aryl group,
aralkyl group, alkoxy group, cyano group or nitro group, R7 is an alkyl group, aryl group or aralkyl group (1
4) 1,2-quinonediazide compounds represented by the group Z means an alkylene group or an oxaalkylene group with or without substituents can also be used.

The 1,2-quinonediazide compound represented by the above general formula (I) is, for example, di(2,3,4-)dihydroxyphenyl)methane, 1,1-di(2,3°4-trihydroxyphenyl)propane. , 2,2-di(2,3,4-)dihydroxyphenyl)propane, 1,1-di(2,3,4
-)dihydroxyphenyl)butane, 1,1-di(2,
3,4-trihydroxycyclohexane, 1. l-di(
2゜3.4-1-dihydroxy)-4-oxacyclohexadi, di(2,4,6-trihydroxyphenyl)methane, 1. 1-di(2,4,6-)dihydroxyphenyl)propane, 2.2-di(2,4°6-trihydroxyphenyl)propane, 1. l-di(2,4,6-trihydroxyphenyl)butane, 1,1-di(2,4,
6-1 hydroxyphenyl) cyclohexane, 1.1
-di(2,4°6-trihydroxyphenyl)-4-oxacyclohexane, di(2,3,4-)dihydroxy-5-bromophenyl)methane, 2,2-di(2°4.
6-)dihydroxy-3-chlorophenyl)propane,
Di(2,3,4-1-dihydroxy-5-methylphenyl)methane, 2,2-(2,4゜6-dolihydroxy-3-methyl)propane, di(2,3,4-)dihydroxy- 5-cyanophenyl>methane, 2,2-di(2,
4,6-)lihydroxy3-nitrophenyl)propane, di(1,2,3,4-tetrahydroxyphenyl)
polyhydroxy compounds such as methane, 2,2-di(1,2,3,5-tetrahydroxyphenyl)propane) and 1
, 2-naphthoquinonediazide-5-sulfonyl chloride, 1,2-naphthoquinonediazide-4-sulfonyl chloride or 1,2-benzoquinonediazide-4-sulfonyl chloride at an equivalent ratio of 0.125 to 1. Ka, 7o. 1 The 1,2=quinonediazide compound represented by the above general formula (II) is, for example, 2. 3',4-)dihydroxydiphenylmethane, 2,4□,'6-2-)dihydroxydiphenylmethane, 2,3.4-trihydroxyme 5-chlorodiphenylmethane, 2. 4. 6=trihydroxy-3-pyromodiphenylmethane, 2.3.4-1-
Dihydroxy-5-methylsilaenylmethane, 2,4.
6-1-dihydroxy-3-cyanodiphenylmethane, 2,3.4-1-sodroxy-5-nitrodiphenylmethane, 2,3゜4-trihydroxy-4'-methyldiphenylmethane, 2.4.6-)dihydroxy -4'
-Methyldiphenylmethane, 2,3.4-)dihydroxy=4'-t-butyldiphenylmethane, 2,3°4.5-tetrahydroxy-phenylmethane, 2°3.
4.6-tetrahydroxydiphenylmethane, 2.5-
Dihydroxydiphenylmethane, 2.4-dihydroxydiphenylmethane, 2.4-dihydroxy-4'-methyldiphenylmethane, 2゜5-dihydroxy-4'-t
-butyldiphenylmethane, 1-(2,3,4-)dihydroxy)-(17) 1-phenylpropane, 1-(2,4,6-)dihydroxyphenyl)-1-phenylpropane, 1-(2
, 3,4-trihydroxy-5-chloro)-1-phenyltylopane, 1-(2,3,4-trihydroxy-5
-methyl)-1-phenyltylopane, 1-(2,4,6
-Dolihydroxy-3-cyanophenyl)-1-phenyltylopane, 1-(2,3,4-)dihydroxy-5-nitrophenyl)-1-phenylpropane, 1-
(2,3゜4-trihydroxyphenyl)-1-(p
-Tolyl)propane, 1-(2,4,6-)dihydroxyphenyl> -1-(4-t-butylphenyl)propane, 1-(2,3,4,5-tetrahydroxyphenyl) '-1-phenylbrapan, 1-(2,3
,4,6-tetrahydroxy)-1-phenylpropane, 1-(2,5-dihydroxy)-1-phenylpropane, 1-(2,4-dihydroxy)-1-phenylpropane, 1-(2,4-dihydroxy)-1-phenylpropane, -Dihydroxyphenyl)-1-(p-)lyl)propane and other polybitroxy compounds and 1,2-naph(18)toquinonediazido-5-sulfonyl chloride, 1゜2-
It can be obtained by condensing naphthoquinonediazide-4-sulfonyl chloride or 1,2-benzoquinonediazide-4-sulfonyl chloride at an equivalent ratio of 0.25 to 1.

Details of the 1゜2-quinonediazide compound represented by the above general formula (1) or (II) can be found in the applicant's Japanese Patent Application No.
No. 230328 (filed on December 6, 1982).

The 1,2-quinonediazide compound represented by the above general formula (1) is, for example, p-bis(4-hydroxybenzoyl)
Benzene, p-bis(2,5-dihydroxybenzoyl)benzene, p-bis(2゜3.4-)I7hydroxybenzoyl)benzene, m-bis(2,4,6-1-dihydroxybenzoyl)benzene, p -bis(4-hydroxy-3-chlorobenzoyl)benzene, p-bis(
2,3゜4-trihydroxy-5-methylbenzoyl)
Benzene, p-bis(2,4,6-dryhydroxy-3
-nitrobenzoyl)benzene, p-bis(2,3,4
-) dihydroxy-5-cyanobenzoyl)benzene,
1,3,5-)tris(2,5-dihydroxybenzoyl)benzene, 1,2,3-tris(2,3,4-trihydroxybenzoyl)benzene, 1,2,4-tris(
2,4,6-trihydroxybenzoyl)benzene, 1
,2゜4.5-tetrakis(2,3,4-)dihydroxybenzoyl)benzene, α,α'-bis(2゜3.4
-trihydroxybenzoyl)-p-xylene, α, α
', α'-tris(2,3,4-trihydroxybenzoyl)mesitylene, 1,2-bis(2,3,4-trihydroxybenzoyl)naphthalene, and other polyhydroxy compounds and 1,2-nafdoquinonediazide. 5-sulfonyl chloride, 1,2-naphthoquinonediazide-4-sulfonyl chloride or 1,2-benzoquinonediazide-4
-sulfonyl chloride at an equivalent ratio of 0.083 to 1, and the details are described in the application filed by the present applicant on December 23, 1983.

The 1,2-quinonediazide compound represented by the above general formula (IV) is, for example, ethylene glycol di(2-hydroxybenzoate), diethylene glycol di(2,
3-dihydroxybenzoate), triethylene glycol di(2,6-dihydroxybenzoate), ethylene glycol di(3,4,5-trihydroxybenzoate), diethylene glycol di(2,4,s-
i Dihydroxybenzoate, triethylene glycol rouge (2-hydroxy-3-methylbenzoate), ethylene glycol rouge (4-chloro-2-hydroxybenzoate), polyethylene glycol rouge (5-bromo-2-hydroxybenzoate), propylene glycol rouge (3-chloro-4-hydroxybenzoate)
, styrene glycoluge (2-hydroxy-3-methoxybenzoate), polypropylene glycoluge (
2-Hydroxy-5-methoxybenzoate, poly-3
, 3-bischloromethyloxetane glycoluge (3
-Hydroxy-4-methoxyben (21) shade), 1,3-propanedioluge (3°4.
5-)dihydroxybenzoate), 1,4-butanedioludi(3-hydroxybenzoate), polytetrahydrofuran glycoludi(3,4,5-1-dihydroxybenzoate), etc. and 1
．． It can be obtained by condensing 2-naphthoquinonediazide-5-sulfonyl chloride, 1,2-naphthoquinonediazide-4-sulfonyl chloride, or 1,2-benzoquinonediazide-4-sulfonyl chloride at an equivalent ratio of 0.17 to 1. can.

The 1,2-quinonediazide compound represented by the above general formula (V) is, for example, ethylene glycol-monomethyl-mono(3,4,5-trihydroxybenzoate), ethylene glycol-monoethyl-mono(2,4,6- ) dihydroxybenzoate), diethylene glycol-monoethyl-mono(2,3-dihydroxybenzoate)
, triethylene glycol-monoethyl-mono(3,5
-dihydroxybenzoate), ethylene glycol (
22) Polyhydroxy compounds such as -monophenyl-mono(3,4,5-)lihydroxybenzoate), 1,2-benzenedimethanol-monoethyl-mono(3,4,5-)lihydroxybenzoate) and 1 .2-naphthoquinonediazido-1'-5-sulfonyl chloride, 1.2-naphthoquinonediazido-4-sulfonyl chloride or l,2
-benzoquinonediazide-4-sulfonyl chloride at an equivalent ratio of 0.3 to 1.

The details of the 1゜2-quinonediazide compound represented by the above general formula (IV) or (V) were published in 1982 by the present applicant.
It is stated in the application dated May 10th.

1. The amount of the 2-quinonediazide compound added is 5 to 10 parts by weight per 100 parts by weight of the alkali-soluble novolak resin and/or polyhydroxystyrene or its derivative.
0 parts by weight, preferably 10 to 50 parts by weight.

When the amount of the 1,2-quinonediazide compound added is less than 5 parts by weight, the amount of carboxylic acid produced by the 1,2-quinonediazide compound absorbing light is small, so the photosensitive resin composition film can be used before and after irradiation. It is not possible to differentiate the dissolved carbon from the developing solution consisting of an alkaline aqueous solution, making patterning difficult. On the other hand, when this amount exceeds 100 parts by weight, most of the added 1,2-quinonediazide compound still remains in the same form after short-time light irradiation, so that it becomes insolubilized in the developing solution consisting of an alkaline aqueous solution. If the effect is too high, it becomes difficult to develop the photosensitive resin composition film, and the film-forming ability and mechanical properties of the film deteriorate.

The photosensitive resin composition of the present invention can be obtained by dissolving the alkali-soluble novolac resin and/or polyhydroxystyrene or its derivative, a 1,2-quinonediazide compound, and a crosslinking agent in an organic solvent.

Examples of organic solvents used in this case include ethyl glycol monomethyl ether, diethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, glycol ethers such as diethylene glycol dibutyl ether, methyl cellosolve acetate, ethyl hexyl acetate, and butyl cellosolve acetate. cellosolve esters such as toluene, aromatic hydrocarbons such as xylene, ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetonylacetone, acetophenone, isophorone, benzyl ethyl ether,
1.2-Ethers such as dibutoxyethane and dihexyl ether, fatty acids such as caproic acid and caprylic acid, 1-
Alcohols such as octatool, 1-nonanol, l-decanol, benzyl alcohol, ethyl acetate, butyl acetate, 2-ethylhexyl acetate, benzyl acetate,
Examples include esters such as benzyl benzoate, diethyl oxalate, dibutyl oxalate, diethyl malonate, dimethyl maleate, diethyl maleate, dibutyl maleate, dimethyl phthalate, ethylene carbonate, and propylene carbonate. These organic solvents may be used alone or in combination of two or more.

The amount of this organic solvent used varies depending on the required film thickness when applying the photosensitive resin composition film (25), but generally it is 100 parts by weight of the alkali-soluble novolak resin and/or polyhydroxystyrene or its derivative. 100 to 2,000 parts by weight, preferably 30'0 to
It is 1.500 parts by weight.

A surfactant can be added to the photosensitive resin composition of the present invention in order to improve the developability of the light-irradiated area after dry coating film formation. Examples of the surfactant include polyoxyethylene lauryl Ether, polyoxyethylene alkyl ethers such as polyoxyethylene stearyl ether and polyoxyethylene oleyl ether, polyoxyethylene alkyl phenol ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether, polyethylene glycol dilaurate, polyethylene glycol distear Polyethylene glycol dialkyl esters such as esters and the like can be mentioned.

Furthermore, storage stabilizers, dyes, pigments, etc. may be added to the photosensitive resin composition of the present invention (26), if necessary.

Since the photosensitive resin composition of the present invention has excellent heat resistance, dry etching resistance, and film retention rate, it is not only particularly useful as a positive photoresist for manufacturing integrated circuits, but also as a positive photoresist for manufacturing masks. It is also useful in other applications where these properties are required, such as mold photoresists.

EXAMPLES Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited in any way by these Examples.

Examples 1 to 5 and Comparative Example 1 After charging 75 g of m-cresol and 25 g of p-cresol into a 500 ml Mitsuro separable flask,
66 ml of 37% by weight formalin aqueous solution and 0.0 oxalic acid
4g was added. While stirring, the separable flask was immersed in an oil bath, the reaction temperature was adjusted to 100° C., and the reaction was carried out for 10 hours. After the reaction was completed, water was distilled off under reduced pressure to 30 as Hg, and the internal temperature was roughly raised to -130°C to remove unreacted substances. Next, the molten alkali-soluble novolac resin, which was a reaction product, was returned to room temperature and collected.

To 4.3 g of this alkali-soluble novolac resin, 2.3.4-trihydroxybenzophenone-1 was added as a photosensitizer.
, 067 g of 2-naphthoquinonediazide-5-sulfonic acid triester was added, and each compound shown in Table 1 was added as a crosslinking agent in the amount shown in Table 1. This was dissolved in cellosolve acetate, and the pore size was 0.2 μm. A solution of the photosensitive resin composition was prepared by filtration through a membrane filter.

The obtained solution was applied onto a silicon wafer having a silicon oxide film using a spinner so that the coating thickness was 1.2 μm, and then brebaked for 25 minutes in an air circulating oven kept at 90°C. A photosensitive resin composition film was obtained. This photosensitive resin composition film was exposed to light using a PLA501F mask aligner manufactured by Canon Co., Ltd. using a test pattern mask with equal line width and space width (IL/lS pattern), and then tetramethylammonium hydroxide 2. It was developed with a 4% by weight aqueous solution for 1 minute, and then rinsed with running water. After determining the sensitivity and resolution of this resist pattern using a droplet microscope, it was post-baked for 9.0 minutes in an open air circulation system maintained at 100 to 200°C. After post-baking, the cross section of the bread was observed with a scanning electron microscope at a magnification of 10,000 times, and the temperature at which the pattern became semicircular was observed. ,did. These results are shown in Table 1.
Education. As Comparative Example 1, the same sandwiching was carried out without adding a crosslinking agent, and the results are also shown in Table 1.

(Left below) (29) Table 1 (30) *1) IL/Is 2. Sensitivity for resolving um-wide patterns.

*2) Minimum IL/Is pattern size to be resolved.

*3) The temperature at which a 2 μm wide pattern of II7/IS becomes semicircular as observed with a scanning electron microscope.

*4) Film thickness tO1 of photosensitive resin composition film after pre-beta
Calculated by the following formula based on the film thickness t of a 5 μm wide photosensitive resin composition film of IL/Is obtained by exposing and developing the amount shown in the sensitivity section of the table above.

Remaining film rate (%) = t/1oX100 Test Example 1 The dry etching resistance of the resist patterns obtained in Examples 1 to 6 and Comparative Example 1 was evaluated using a parallel plate dry etching device (electrode spacing 40 mm) as an etching gas. The test was conducted using carbon tetrachloride under conditions of an output of 1 OOW and a gas pressure of 15 Pa. PMMA (polymethyl methacrylate)
Table 2 shows the relative speed when the etching speed of is set to 1. From this, it was found that the dry etching resistance was good. Table 2 Examples 6 to 8, Comparative Example 2 4.3 g of polyhydroxystyrene (number average molecular weight 8000) manufactured by Maruzen Petrochemical Co., Ltd. was added with a photosensitive agent. As 2.3.4-
1.1 g of trihydroxybenzophenone-1゜2-naphthoquinonediazide-5-sulfonic acid triester was added, and each compound shown in Table 3 was added as a crosslinking agent in the amount shown in Table 3. A solution of the photosensitive resin composition was prepared by dissolving it in acetate and filtering it through a membrane filter with a pore size of 0.2 μm.

The obtained solution was applied onto a silicon wafer having a silicon oxide film using a spinner so that the coating thickness was 1.2 μm, and then prebaked for 25 minutes in an air circulation oven kept at 90°C. A photosensitive resin composition film was obtained. Using a test pattern with equal line width and space width (IL/13 pattern) on this photosensitive resin composition film,
After exposure using a PLA501F mask aligner manufactured by Canon Inc., development was performed with a 2.4% by weight aqueous solution of tetramethylammonium hydroxide for 1 minute, followed by rinsing with running water. After determining the sensitivity and resolution of this resist pattern using an optical microscope, it was post-baked for 30 minutes in an air circulating oven maintained at 100 to 200°C. The cross section of the pattern after the post-baking was observed with a scanning electron microscope at a magnification of 10,000 times, and the temperature at which the pattern became semicircular was observed. These results are shown in Table 3. Similar studies were conducted for Comparative Example 2, in which no crosslinking agent was added, and the results are also shown in Table 3.

(33) Table 3 (34) *1) IL/Is 2. Sensitivity for resolving um-wide patterns.

*2) Minimum IL/Is pattern size to be resolved.

*3) The temperature at which a 2 μm wide pattern of 1/IS becomes semicircular as observed with a scanning electron microscope.

*4) Film thickness tO1 of photosensitive resin composition film after pre-beta
Calculated by the following formula based on the film thickness t of a 5 μm wide photosensitive resin composition film of IL/Is obtained by exposing and developing the amount shown in the sensitivity section of the table above.

Remaining film rate (%) = t/1oX100 Test Example 2 The dry etching resistance of the resist patterns obtained in Examples 1 to 6 and Comparative Example 1 was evaluated using a parallel plate dry etching device (electrode spacing: 40 mm) using etching gas. The test was conducted using carbon tetrachloride as a gas under conditions of an output of 100 W and a gas pressure of 15 Pa. PMM'A (polymethyl methacrylate)
Table 4 shows the relative speed when the etching speed of is set to 1. It was found that this had good dry etching resistance.・352

Claims (1)

[Claims] (1) 100 parts by weight of an alkali-soluble novolak resin and/or polyhydroxystyrene or its derivative, 5 to 100 parts by weight of a 1,2-quinonediazide compound, and 0.5 to 50 parts by weight of a crosslinking agent are dissolved in an organic solvent. A positive photosensitive resin composition characterized by: