JPS59165053A - Positive type photosensitive resin composition - Google Patents

Abstract

PURPOSE:To enhance sensitivity and insolubilization yield by mixing a specified 1,2-quinonediazide compd. with an alkali-soluble novolak resin. CONSTITUTION:Hundred pts.wt. alkali-soluble novolak resin contains 5- 100pts.wt. mixture of a compd. of general formula I and a compd. of general formula II in (60-90):(40-10) molar ratio. In formulae I , II, R1, R5 are each alkyl, aryl, or aralkyl; R2, R3, R4, R6, R7 are each 1,2-naphthoquinonediazide-4- sulfonyl group or 1,2-naphthoquinonediazide-5-sulfonyl group, or 1,2-benzoquinonediazide-4-sulfonyl group.

Description

[Detailed description of the invention] The present invention relates to a positive photosensitive resin composition.

More specifically, the present invention relates to a positive photosensitive resin composition made of an alkali-soluble novolac resin, which has high sensitivity and a high residual film rate, has excellent developability, and is suitable as a photoresist for producing integrated circuits.

The mainstream resist used to fabricate integrated circuits is negative photoresist, which is made by adding a bisazide compound to cyclized isoprene rubber. However, this negative type photoresist is not suitable for the production of integrated circuits in the future. On the other hand, a positive photoresist with excellent resolution is a resist that can sufficiently cope with the miniaturization of integrated circuits.

Most of the positive photoresists currently used for producing integrated circuits are made by adding a 1,2-quinonediazide compound to an alkali-soluble novolac resin, which makes it difficult to dissolve in an alkaline aqueous solution as a developer. be. This novolac resin-based positive photoresist has a lower sensitivity than cyclized rubber-based negative photoresists because it has to contain a large amount of 1,2-quinonediazide compound.Despite these drawbacks, it can be used for integrated circuits. The reason why it is used in the manufacturing process is that it has extremely high resolution.

The substance that characterizes novolak resin-based positive photoresists is a 1,2-quinonediazide compound. The 1,2-quinonediazide compound dissolves only in organic solvents and does not dissolve in alkaline aqueous solutions, but when irradiated with ultraviolet light, it converts into ketene and becomes indenecarboxylic acid, making it extremely easy to dissolve in alkaline aqueous solutions. That is, a pattern with excellent resolution can be formed by exposing a coating film of a novolac resin-based positive photoresist to ultraviolet light through a photomask and using an alkaline aqueous solution as a developer.

Furthermore, the exposure method for increasing the degree of integration of integrated circuits will be changed from the current mainstream contact exposure method to a reduction projection exposure method5. The reduced projection exposure method is a method in which the mask pattern is exposed stepwise rather than all at once, and is excellent as a means of increasing resolution, but has the drawback of decreasing productivity.

In order to restore this productivity, it is necessary to improve the reduction projection exposure apparatus itself, but it is also important to increase the sensitivity of the positive photoresist used. The novolak resin-based positive photoresists currently on the market have the drawback of low sensitivity as described above.

Further, conventional novolak resin-based positive photoresists have a drawback of having a low residual film rate. That is, a coating film of a novolac resin-based positive photoresist before exposure is dissolved in a developer consisting of a liquid as described above, so that K<<, but it does not mean that it does not dissolve at all. If the solubility of the novolac resin itself in an alkaline aqueous solution is increased or the amount of the 1,2-quinonediazide compound added is lowered, the solubility of the resist coating film in an alkaline aqueous solution before exposure will be somewhat high, and the development after exposure through a photomask will be improved. It appears that the sensitivity has improved and the sensitivity has increased. However, the unexposed portions that should remain as a pattern, but not the exposed portions, dissolve to some extent, resulting in a reduction in the height of the pattern. The ratio of the height of the unexposed portion that should remain as a pattern before exposure and after development is called the residual film ratio5, and commercially available novolak resin-based positive photoresists have a low film residual ratio. If a pattern is formed by coating a substrate with a step structure with a positive photoresist with a low residual film rate, exposing it to light, and developing it, the pattern cannot sufficiently cover the step portions, so it is difficult to fabricate a normal integrated circuit. This becomes difficult.

The inventors of the present invention have conducted intensive research to improve the above drawbacks, and have found that when a specific 1,2-quinonediazide compound is added to an alkali-soluble novolac resin, the above drawbacks can be improved, and the present invention has been achieved. did.

That is, the gist of the present invention is to add 5 parts by weight of a compound represented by the following general formula (I) and a compound represented by the following general formula (II) to 100 parts by weight of an alkali-soluble novolac resin.
~100 parts by weight, and the ratio of the compound represented by general formula (I) to the compound represented by general formula (II) is 6.
0 to 90:40 to 10 (molar ratio).

[In the formula, R1 and R5 are the same or different, and are an alkyl group, an ar group (Ra and Rb are the same or different, and represent a hydrogen atom or a carbon 1-carbon group (R. is a hydrogen atom or
is an alkyl group having 177 to 4 carbon atoms, n is 1 or 2), R2, R3, R4, R6 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. ] The 1,2-quinonediazide compounds used in the present invention, that is, the compounds represented by the general formula (I) and the general formula (II)
) is disclosed in US Pat. No. 3,046,118, for example.
2,3,4-trihydroxyphenylmethylketone, 2,3,4-)rihydroxyphenylethylketone, 2,3,4-trihydroxy phenyl butyl ketone,
2,3.4-) Lihydroxyphenyl-n-hexyl ketone 13.4.5-) Lihydroxyphenylmethylketone, 3.4.5-) 'J Hydroxyphenyl ethyl ketone, 31415-1J Hydroxyphenyl butyl ketone , 3.4.5-) trihydroxyphenyl-n-hexyl ketone, 2,4.6-trihydroxyphenylethyl ketone, 2+4+6-)! J Hydroxyphenyl ethyl ketone, 2,4.6-1-lyhydroxyphenylbutyl ketone, 2,4.6-trihydroxyphenyl-n-hexyl ketone, 2,314-) IJ Hydroxyphenyldecyl ketone, 2,3. 4-trihydroxyphenyldodecylketone, 2,3.4-) IJ Hydroxybenzophenone, 3,4.5-trihydroxybenzophenone, 2,4.6-)lyhydroxybenzophenone, 2,3.4-)ly Trihydroxy compounds represented by the following general formula (m) such as hydroxyphenylbenzyl ketone, 3.4', 5-)lihydroxyphenylbenzyl ketone, 214.6-) IJ hydroxyphenylbenzyl ketone (wherein R8 is alkyl 1,2-naphthoquinonediazide-4-sulfonyl chloride, 1,2-naphthoquinonediazide-5-sulfonyl chloride, l, 2
-benzoquinonediazide-4-sulfonyl chloride etc., preferably 1. , 2- f7 toquinone diazido 5
- It can be obtained by condensing and purifying sulfonyl chloride in the presence of an alkali catalyst. As the alkali catalyst, inorganic alkalis such as sodium hydroxide and sodium carbonate, and amines such as diethylamine and triethylamine are mainly used.

Specifically, the compound represented by the general formula (I) obtained in this way is 2+3,4-trihydroxyphenylmethylketone-1,2-naphthoquinonediazide-5
-sulfonic acid triester, 2.3.4-trihydroxyphenylethylketone-1,2-su7toquinonediazide 5-sulfonic acid triester, 2,3.4-)trihydroxyphenylbutylketone-1,2 -Naphthoquinonediazide-5-sulfonic acid triester, 2,3.4-
) lyhydroxyphenyl n-hexyl ketone-1,
2-naphthoquinonediazide-5-sulfonic acid triester, 3,4.5-tribitroxyphenylmethylketone-1,2-naphthoquinonediazide-5-sulfonic acid triester, 3+4+5-)') Hydroxyphenylethylketone-1 , 2-naphthoquinonediazide-5-sulfonic acid triester, 2,3.4-trihydroxyphenyldodecylketone-1,2-naphdoquinonediazide-5-sulfonic acid triester, 2,3.4-)rihydroxypene Zophenone-1,2-naphthoquinonediazide-5-sulfonic acid triester, 3,4.5-)lyhydroxypenzophenone-1,2-naphthoquinone cyasito-5-sulfonic acid triester, 2,3.4 −)! J
Hydroxyphenylbenzylketone-1,2-1 phthoquinonediazide-5-sulfonic acid triester, 2°3.
4-) Lihydroxyphenylmethylketone-1,2-naphthoquinonediazide-4-sulfonic acid triester, 2
,3.4-)lyhydroxyphenylethylketone-1,
2-naphthoquinonediazide-4-sulfonic acid triester, 2,3.4-)lyhydroxybenzophenone-1,
2-naphthoquinonediazide-4-sulfonic acid triester, 3,4゜5-) IJ Hydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid triester, 2t314-trihydroxyphenylbenzylketone-1,2-naphtho Quinonediazide-4-sulfonic acid triester, 3,4.5-trihydroxyphenylbenzylketone-1,2-naphthoquinonediazide-4
-sulfonic acid triester, 2,3゜4-trihydroxyphenylmethylketone-1゜2-benzoquinonediazide-4-sulfonic acid triester, 2,3.4-)lyhydroxyphenylethylketone-1,2-benzo Quinonediazide-4-sulfonic acid triester% 213
14-)! J Hydroxyphenyl-n-hexylketone-1,2-benzoquinonediazide-4-sulfonic acid triester, 2.3.4-)dihydroxybenzophenone-1,2-penzoquinonediazide-4-sulfonic acid triester, 3, 4.5-) Lihydroxybenzophenone-1,2-benzoquinonediazide-4-sulfonic acid triester, 2,3.4-) Lihydroxyphenylpenzyl ketone-1,2-benzoquinonediazide-4-sulfonic acid triester , 3,4.5-) lyhydroxyphenylbenzylketone-1,2-benzoquinonediazide-4-sulfonic acid triester, 2,4.6-) IJ hydroxyphenylbenzylketone-1,2-benzoquinonediazide-4- Examples include sulfonic acid triesters and the like.

Further, as the compound represented by the general formula (II), specifically, 2,3.4-trihydroxyphenylmethylketone-1,2-naphthoquinonediazide-5-sulfonic acid diester, L3+4-t')hydroxyphenyl Ethyl ketone-1,2-naphthoquinonediazide-5-sulfonic acid diester, 2,3.4-trihydroxyphenyl-n-hexylketone-1,2-naphthoquinonediazide-5-sulfonic acid diester, 3,4.5- Trihydroxyphenylmethylketone-1,2-naphthoquinonediazide-5-sulfonic acid diester, 3+4+5-)!
j hydroxyphenylethyl ketone-1,2-naphthoquinonediazide-5-sulfonic acid diester, 2,3.
4-″trihydroxyphenyldodecylketone-1,2
-naphthoquinonediazide-5-sulfonic acid dieth 7/
l/, 2.3 + 4-) lyhydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid diester, 3,4.5-)lyhydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfone Acid diester, 2.3.4-) Lihydroxyphenylpenzyl ketone-1,2-1-7toquinone diazido 5-sulfonic acid diester, 2,3.4-) Lihydroxyphenylpenzyl ketone-1,2- 1-phthoquinonediazide-4-sulfonic acid diester, 2.3.4-)lyhydroxyphenylethyl-1,2-naphthoquinonediazide-4-sulfonic acid diester, Hydroxyphenylbutylketone-1,2-naphthoquinonediazide-4-sulfonic acid diester, 2,3.4-
Trihydroxyphenyl-n-hexylketone-1,2
-su7toquinone diazido 4-sulfonic acid diester,
2.3.4-) Lyhydroxybenzophenone-1,2-
naphthoquinonediazide-4-sulfonic acid diester, 3
, 4.5-) lyhydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid diester,
2,3.4-)lyhydroxyphenylbenzylketone-
1,2-naphthoquinonediazide-4-sulfonic acid diester, 3,4.5-)lyhydroxyphenylbenzylketone-1,2-naphthoquinonediazide-4-sulfonic acid diester, 2゜3.4-trihydroxyphenylmethylketone -1,2-benzoquinonediazide-4-sulfonic acid diester, 2+3 #4-trihydroxyphenylethylketone-1,2-benzoquinonediazide-4-sulfonic acid diester, 2,3.4-)rihydroxyphenyl- n-hexylketone-1,2-benzoquinonediazide-4-sulfonic acid diester, 2°3.
4-trihydroxybenzophenone-1,2-benzoquinonediazide-4-sulfogudiester, 314+5
-) ') Hydroxybenzophenone-1,2-benzoquinonediazide-4-sulfogudiester, 2,3,
4-trihydroxyphenylbenzylketone-1,2-
Examples include benzoquinonediazide-4-sulfonic acid diester.

The ratio of the compound represented by general formula (I) and the compound represented by general formula (II) in the present invention is 60 to 90:4O.
-10 (molar ratio), preferably 65-85:35-
15 (molar ratio). If the proportion of the compound represented by the general formula (I) exceeds 90, it will not be possible to obtain the highly sensitive photosensitive resin composition aimed at by the present invention, and the developability will not only deteriorate, but also the edges of the pattern and the substrate A development residue may be left on the interface with the photosensitive resin composition, and the photosensitive resin composition may become brittle.
There is a drawback that the pattern may be chipped due to

If the proportion of the compound represented by the general formula (I) is less than 60, the residual film rate of the pattern after development will decrease, coverage in the step structure will deteriorate, and the heat resistance of the photosensitive resin composition will decrease. . Furthermore, if the proportion of the compound represented by general formula (II) exceeds 40, not only the residual film rate will decrease, but also the heat resistance of the photosensitive resin composition will deteriorate, and if it is less than 10, the sensitivity and developability will decrease. Not only that, but it also leads to defects such as undeveloped parts and pattern chipping.

The total amount of the compound represented by the general formula (I) and the compound represented by the general formula (II) in the present invention is 5 to 100 parts by weight per 100 parts by weight of the alkali-soluble novolak resin.
Parts by weight, preferably 10 to 50 parts by weight. General formula (
If the total amount of the compound represented by I) and the compound represented by general formula (II) is less than 5 parts by weight, the residual film rate after development will be insufficient and the pattern obtained will be deformed. . Moreover, if the total amount of the compound exceeds 100 parts by weight, a highly sensitive photosensitive resin composition cannot be obtained.

The photosensitive resin composition of the present invention comprises a compound represented by the general formula (I) and a compound other than the compound represented by the general formula (II).
, 2-quinonediazide compound can be blended, for example, in an amount of about 20 parts by weight or less, preferably 1° part by weight or less, per 100 parts by weight of the alkali-soluble novolak resin.

Examples of these 1°2-quinonediazide compounds include compounds represented by the following general formula (IV), and compounds represented by the following general formula (IV).
Examples include compounds represented by V) and compounds represented by the following general formula (Vl).

H [wherein, Rg, R1□, and R□4 are the same or different, an alkyl aryl group (Re and Rd are the same -
or different, an aralkyl group represented by a hydrogen atom (Re
is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, m is 1 or 2), and R□. , R12, R□3 and R□5 are the same or different, and are a 1,2-naphthoquinonediazide-4-sulfonyl group, a 1,2-naphthoquinonediazide-5-sulfonyl group, or a 1,2-benzoquinonediazide-4-sulfonyl group It is. ] Specific examples of these 1,2-quinonediazide compounds include 2,4-dihydroxyphenylmethylketone-1,
2-naphthoquinonediazide-5-sulfonic acid monoester, 2,4-dihydroxyphenylethyl ketone-1,
2-naphthoquinone diazido)”-5-sulfonic acid monoester, 3,4-dihydroxyphenyl-n-hexylketone-1,2-su7toquinone diazido 5-sulfonic acid monoester, 2,4-dihydroxyphenyldodecyl Ketone-1,2-naphthoquinonediazide-5-sulfonic acid monoester, 2,4-dihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid monoester, 3,4-dihydroxyphenylbenzyl ketone-1,2- Naphthoquinone di'razido-5-sulfonic acid monoester, 2,4-dihydro-roxyphenylmethylketone-1,r2-naphthoquinonediazide-4-sulfonic acid monoester, 2,4-dihydroxyphenylethyl ketone-1゜2 -naphthoquinonediazide-4-sulfonic acid monoester, 3,4-dihydroxyphenyl-n-hexylketone-1,2-naphthoquinonediazide-4-sulfonic acid monoester, 2
, 4-dihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid monoester, 3,4-
Dihydroxyphenylbenzylketone-1,2-+7 toquinone diazido 4-sulfonic acid monoester, 2.4
-dihydroxyphenylmethylketone-1゜2-benzoquinonediazide-4-sulfonic acid monoester, 2.4
-dihydroxyphenylethylketone-1,2-benzoquinonediazide-4-sulfonic acid monoester, 3,4
-dihydroxyphenyl-n-hexylketone-1,2
-Benzoquinonediazide-4-sulfonic acid monoester, 2,4-dihydroxybenzophenone-1,2-penzquinonediazide-4-sulfonic acid monoester, 3゜4-dihydroxyphenylbenzyl ketone-1゜2-benzoquinonediazide-4- Sulfonic acid monoester, 2
, 4-dihydroxyphenylmethylketone-1,2-naphthoquinonediazide-5-sulfonic acid diester, 2,
4-dihydroxyphenylethylketone-1,2-naphthoquinonediazide-5-sulfonic acid diester, 3r4
-dihydroxyphenyl-n-hexylketone-1,2
-1-Atoquinonediazide-5-sulfonic acid diester, 2゜4-dihydroxyphenyldodecylketone-1゜2-naphthoquinonediazide-5-sulfonic acid diester, 2,4-dihydroxybenzophenone-1,2-naphthoquinonediazide-5- Sulfonic acid diester, 3,4
-dihydroxyphenylbenzylketone-1,2-naphthoquinonediazide-5-sulfonic acid diester, 2,4
-dihydroxyphenylmethylketone-1,2-naphthoquinonediazide-4-sulfonic acid diester, 3,4-
Dihydroxyphenyl-n-hexylketone-1,2-
naphthoquinonediazide-4-sulfonic acid diester, 2
．． 4-dihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid diester, 3,4-dihydroxyphenylbenzylketone-1,2-7toquinonediazide 4-sulfonic acid diester, 2,4-dihydroxyphenylmethyl ketone -1,2-benzoquinonediazide-4-sulfonic acid diester, 3,4-dihydroxyphenyl-n-hexylketone-1,2-benzoquinonediazide-4-sulfonic acid diester, 2.4
-dihydroxybenzophenone-1,2-benzoquinonediazide-4-sulfonic acid diester, 3,4-dihydroxyphenylbenzylketone-1,2-benzoquinonediazide-4-sulfonic acid diester, 2゜3,4-
) dihydroxyphenylmethylketone-1,2-naphthoquinonediazide-5-sulfonic acid mo) x f /l/
, 2,3.4- ) dihydroxyphenylethyl ketone-1,2-naphthoquinonediazide-5-sulfonic acid monoester, 2.3.4- )! J Hydroxyphenyl-n-hexylketone-1,2-naphthoquinonediazide-5-sulfonic acid monoester, 3,4,5-
) Dihydroxyphenylmethylketone-1,2-naphthoquinonediazide-5-sulfonic acid monoester, 3,
4.5-) Lihydroxyphenylethyl ketone-1,
2-Naftuki 2, 3, 4-)! J Hydroxyphenyldodecylketone-1,2-naphthoquinonediazide-5
-sulfonic acid monoester, 2,3.4-)lyhydroxypenzophenone-1,2-naphthoquinonediazide-5
-sulfonic acid monoester, 3 r 4 r s-)
! J Hydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid monoester, 2I3.4-
h) Hydroxyphenylbenzylketone-1,2-naphthoquinonediazide-5-sulfonic acid monoester, 2
,3.4-)lyhydroxyphenylmethylketone-1,
2-naphthoquinonediazide-4-sulfonic acid monoester, 2,3.4-)beryhydroxyphenylethylketone-1,21-naphthoquinonediazide-4-sulfonic acid monoester/', 2
#3z 4-) Lihydroxyphenyl-n-hexylketone-1,2-naphthoquinonediazide-4-sulfonic acid monoester, 2,3.4-) Lihydroxyphenyl-n-hexylketone-1,2-naphthoquinonediazide- 4-sulfonic acid monoester, 2.3.4-trihydroxybenzophenone-1゜2-naphthoquinonediazide-4-sulfonic acid monoester, 3,4.5-)lyhydroxybenzophenone-1,2-naphthoquinonediazide -4-sulfonic acid monoester, 2,3.4-)rihydroxyphenylbenzyl ketone-1,2-1-7toquinonediazide 4-sulfonic acid monoester, 3,4゜5-trihydroxyphenylbenzyl ketone- 1゜2-
naphthoquinonediazide-4-sulfonic acid monoester,
2,3,4-)lyhydroxyphenylmethylketone-
1,2-benzoquinonediazide-4-sulfonic acid monoester, 2,3,4-trihydroxyphenylethylketone-1,2-benzoquinonediazide-4-sulfonic acid monoester, 2゜3.4-)rihydroxyphenylene Ru n-hexylketone-1,2-benzoquinonediazide-
4-sulfonic acid monoester, 2,3.4-)lyhydroxybenzophenone-1,2-benzoquinonediazide-
4-sulfonic acid monoester, 3,4,5. -) Lihydroxypenzophenone-1,2-benzoquinonediazide-4-sulfonic acid monoester, 2゜3.4-trihydroxyphenylbenzyl ketone-1,2-benzoquinonediazide-4-sulfonic acid monoester, etc. be able to.

Other than the compound represented by the above general formula (IV), the compound represented by the general formula (V), and the compound represented by the general formula (Vl), Ω1,2-naphthoquinonediazide compounds include:
Alkali-soluble novolak resins, such as phenol novolak resins, 0-cresol novolak resins, m-cresol novolak resins, p-cresol novolak resins, phenol/p-cresol novolak resins, 0-cresol/p-cresol novolak resins, rn- Cresol/p-cresol novolac resin etc. and 1,2-
Examples include compounds obtained by condensing nutoquinone diazide-5-sulfonyl chloride.

The alkali-soluble novolac resin used in the present invention preferably contains phenols and aldehydes.
It is produced by addition condensation of aldehydes at a ratio of 0.7 to 1 mole per mole under an acid catalyst. Phenols include phenol, o-cresol, m-cresol, p-cresol, 0-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol,
m-butylphenol, p-butylphenol, 2,3
-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,6-xylenol, p-phenylphenol and the like. These phenols can be used singly or in combination of two or more, taking into consideration the alkali solubility. Examples of aldehydes include formaldehyde, paraformaldehyde, and furfural. Inorganic acids such as hydrochloric acid, nitric acid, and sulfuric acid, and organic acids such as formic acid, oxalic acid, and acetic acid sulfur are used as the acid catalyst.

The photosensitive resin composition of the present invention is prepared by dissolving the alkali-soluble novolac resin and the 1,2-quinonediazide compound in a solvent that dissolves them.
For example, glycol ethers such as ethylene glycol = + -/l/monomethyl ether and ethylene glycol monoethyl ether, cellosolve esters such as methyl cellosolve acetate and ethyl cellosolve acetate, aromatic hydrocarbons such as toluene and xylene, and methyl ethyl ketone. , ketones such as cyclohexanone, and esters such as ethyl acetate and butyl acetate. Several types of these solvents should be used in combination, taking into consideration the solubility of the photosensitive resin composition, the solvent evaporation rate after coating the photosensitive resin composition on the substrate, and the influence on the surface shape of the coated film. You can also do it.

Furthermore, if necessary, it is also possible to add storage stabilizers, dyes, pigments, etc. to the photosensitive resin composition of the present invention.

In addition, in order to improve the adhesion between the coating film of the photosensitive resin composition of the present invention and a substrate such as a silicon oxide film, hexamethyldisilazane, chloromethylsilane, etc. may be applied to the substrate in advance. can.

The developing solution for the photosensitive resin composition of the present invention includes inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia, and inorganic alkalis such as ethylamine and n-propylamine. monoamines, secondary amines such as diethylamine and di-n-propylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethyl Aqueous solutions of alkalis such as quaternary ammonium salts such as ammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo(5,4,0) near-wendecene, 1,5-
Aqueous solutions of cyclic amines such as diazabicyclo(4,3,0)-5-nonane are used, and aqueous solutions of quaternary ammonium salts and cyclic amines are used when manufacturing integrated circuits, where the use of metal-containing developers is a problem. It is preferable to use Further, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as an alcohol such as methanol or ethanol or a surfactant to the aqueous solution of the alkali mentioned above can also be used as the developer.

The photosensitive resin composition of the present invention is not only particularly useful as a positive photoresist for producing integrated circuits, but also useful as a positive photoresist for producing masks.

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.

Example 1 After phenol 309 and p-cresol 709 were charged into a flask having an internal volume of 500 d, 66 samples of a 37% by weight formalin aqueous solution and 0.049 grams of oxalic acid were added. Next, while stirring, the flask was immersed in an oil bath and the reaction temperature was adjusted to 100C.
A novolak resin was synthesized by keeping the temperature at After the reaction, the pressure inside the system was reduced to 30 rrm Hq to remove water, and the internal temperature was further raised to 130C to distill off unreacted substances. Then, the molten alkali-soluble novolac resin was returned to room temperature and recovered. Alkali-soluble novolak resin obtained above 49,2,3.4-)lyhydroxybenzophenone-1,2-naphthoquinonediazide-5
-Sulfonic acid triester [hereinafter referred to as compound (a)]
800 m9.2.3.4-trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid diester [hereinafter referred to as compound (b)] 180 m9 and 2,3.4-trihydroxybenzophenone-1,2
-Naphthoquinonediazide-5-sulfonic acid heptanoester [hereinafter referred to as compound (C)] 20m9 [compound (a)/
Compound (b) = 77/23 (molar ratio)] was dissolved in ethyl cellosolve acetate 159 and filtered through a membrane filter with a pore size of 0.2 μm to prepare a photosensitive resin composition solution.

After applying the above photosensitive resin composition solution onto a silicon oxide film wafer using a spinner, the solution was heated at 90C.

It was prebaked in an oven for 25 minutes to form a 1 μm thick photosensitive resin composition coating. Exposure to ultraviolet light with an intensity of 9 mJArn20 through a photomask manufactured by Toppan Printing Co., Ltd.
j) When developed with a 2.4% by weight aqueous solution of lame glutammonium hydroxide at 20C for 60 seconds, the line width was 1.0μ.
The pattern of m could be resolved. Further, the remaining film rate was 92 inches. Therefore, it was found that this photosensitive resin composition had high sensitivity and high film residual rate.

Comparative Example 1 Compound (a) used in Example 1 19. The alkali-soluble novolak resin synthesized in Example 1 was dissolved in 15 ml of ethylceronlube acetate, and filtered through a glass filter with a pore size of 0.2 μm. A photosensitive resin composition solution was prepared. Next, the photosensitive resin composition was evaluated in the same manner as in Example 1, and the line width was 1.0.
In order to resolve a μm pattern, the ultraviolet exposure energy must be 25 mJ/cm 2 , and it was found that the sensitivity was low. In addition, development residue was observed at the interface between the pattern and the substrate, and chipping was observed in a part of the pattern.

Examples 2 and 3, Comparative Example 2.3 The same procedure as in Example 1 was carried out except that the amounts of compound (a), compound (b) and compound (c) used in Example 1 were changed to the amounts shown in Table-1. A photosensitive resin composition solution was prepared.

Next, the above photosensitive resin composition was evaluated in the same manner as in Example 1. The results are shown in Table-1. From Table 1, it can be seen that the lower the proportion of compound (a) used, the lower the residual film rate.

Example 4 In place of compound (a), compound (b) and compound (C) in Example 1, 2.3.4-)rihydroxyphenyl-n-hexylketone-1,2-su7toquinone diazido -Sulfonic acid triester [hereinafter compound (d)
] 770m9.2,3.4-trihydroxyphenyl-n-hexylketone-1,2-naphthoquinonediazide-5-sulfonic acid diester [hereinafter referred to as compound (e)] 200η and 2. s, 4-) lyhydroxyphenyl-n-hexylketone-1,2-naphthoquinonediazide-5-sulfonic acid monoester [hereinafter compound (f
)) aom9 (compound (d)/compound (e) = 7
A photosensitive resin composition solution was prepared in the same manner as in Example 1 except that 4/26 (molar ratio)] was used. Next, Example 1
When the above photosensitive resin composition was evaluated in the same manner as above, the ultraviolet exposure energy for resolving a pattern with a line width of 1.0 μm was 10.5 rnJ/cm2, and the residual film rate was 9.
It was 0chi. Therefore, this photosensitive resin composition
It was found that both sensitivity and residual film rate were high.

Claims (1)

[Claims] Based on 100 parts by weight of alkali-soluble novolac resin,
Compounds represented by the following general formula (I) and the following general formula (
5 to 100 parts by weight of the compound represented by It), the compound represented by the general formula (I) and the general formula (II)
The ratio with the compound shown is 60-90: 40-1
A positive photosensitive resin composition characterized in that the molar ratio is 0 (molar ratio). R4 (wherein R□ and R″5 are the same or different and are an alkyl group, an aryl group, or an aralkyl group, and R2, R
3, R4, R6 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. )