JPH03128959A - Radiation-sensitive resin composition - Google Patents

Abstract

PURPOSE:To obtain a radiation-sensitive resin composition having high sensitivity and excellent developability and being desirable as a positive resist having high resolution and excellent heat resistance by mixing a specified alkali-soluble novolac resin with a cyclic resorcinol/aldehyde condensate and a 1,2-quinone diazide compound. CONSTITUTION:A radiation-sensitive resin composition is prepared by mixing 100 pts.wt. alkali-soluble novolac resin [desirably a polysondensate of 1mol of a phenol of formula I (wherein (n) is 1-3) with desirably 0.8-1.5mol of an aldehyde, weight-average mol.wt. of 2000-15000)] with 1-50 pts.wt., desirably 3-30 pts. wt., cyclic oligomer of formula II (wherein R is an aldehyde residue, and (m) is desirably 4-7) (e.g. a condensate of 1mol of resorcinol with 0.8-1.2mol of aldehyde) and 3-100 pts.wt., desirably 5-50 pts.wt., 1,2-quinone diazide compound (e.g. 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester).

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a radiation-sensitive resin composition, and more specifically, it relates to a radiation-sensitive resin composition, and more specifically, it relates to a radiation-sensitive resin composition that is sensitive to radiation-sensitive resin compositions. The present invention relates to a radiation-sensitive resin composition suitable as a positive resist for producing highly integrated circuits that are sensitive to radiation such as beams.

[Conventional technology]

Positive resists are often used in the manufacture of integrated circuits because they provide high-resolution resist patterns.

However, in recent years, as integrated circuits have become more highly integrated, there has been a demand for positive resists that can form resist patterns with even higher resolution.

For example, when forming a fine resist pattern using a positive resist, when the latent image formed by exposure is developed with a developer consisting of an alkaline aqueous solution, the portion where the exposed area is in contact with the wafer (the bottom of the pattern) is quickly removed. It is necessary that the image be developed. In this regard, conventional positive resists have a problem in that when the interval between the resist patterns to be formed is 1 μm or less, the developability of the bottom portion of the resist pattern is poor and the resolution is reduced.

Furthermore, as the degree of integration of integrated circuits increases, the wafer etching method is shifting from the conventional wet etching, which causes large side etching, to anisotropic dry etching, which causes small side etching.

In this anisotropic dry etching, the shape of the resist pattern is directly reflected in the shape of the layer to be etched. Therefore, if the shape of the resist pattern is poor, parts that do not need to be etched will be etched, resulting in a defective integrated circuit or a decrease in yield.

Furthermore, in the dry etching process, it is necessary that the resist pattern does not change during etching, so the resist is required to have good heat resistance.

Under such circumstances, JP-A No. 62-89041 discloses that a cycloaddition condensate of P-alkylphenol, P-alkoxyphenol, or P-phenylphenol with formaldehyde and a condensate of 0-quinonediazide sulfonyl chloride are , 2-quinonediazide compound, a positive resist with improved heat resistance is disclosed. However, although this positive resist has improved heat resistance, there is a problem in that the sensitivity is insufficient.

[Problem to be solved by the invention]

An object of the present invention is to solve the problems of the prior art, and to provide a radiation-sensitive resist suitable for use as a positive resist, which has high sensitivity, excellent developability, good backbone shape after development, high resolution, and excellent heat resistance. An object of the present invention is to provide a resin composition.

[Means to solve the problem]

The present invention provides (a) an alkali-soluble novolac resin obtained by condensing at least one phenol represented by the structural formula (I) H (where n is an integer of 1 to 3) with an aldehyde; (b) Cyclic compounds obtained by condensing resorcinol and aldehydes and/or
or at least one hydrogen atom of the hydroxyl group of the cyclic compound
The present invention relates to a radiation-sensitive resin composition characterized by containing a cyclic compound substituted with one or more substituted cyclic compounds, and (C) a 1,2-quinonediazide compound.

The alkali-soluble novolak resin (a) used in the present invention (hereinafter simply referred to as "resin (A)") is a condensate of at least one phenol represented by the structural formula (1) above and an aldehyde. are synthesized.

Examples of the phenols represented by structural formula (1) include 0-cresol, m-cresol, p-cresol, and 2-cresol.
3-xylenol, 24-xylenol, 2,5-xylenol, 2,6-xylenol, 34-xylenol, 3.5-xylenol, 2,3,44-limethylphenol, 2.3.5-)limethylphenol, 3,4.5
Trimethylphenol is mentioned. Of these, 0-
Cresol, m-cresol, p-cresol, 2,5
-xylenol, 3,5-xylenol and 2,3.
5-) Limethylphenol is preferred. These may be used alone or in combination of two or more.

Examples of aldehydes include formaldehyde, paraformaldehyde, benzaldehyde, acetaldehyde, phenylacetaldehyde, α-phenylpropylaldehyde, β-phenylpropylaldehyde, 0-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, O-chlorobenzaldehyde, m -chlorobenzaldehyde, p-chlorobenzaldehyde, O-nitrobenzaldehyde, m
-nitrobenzaldehyde, p-nitrobenzaldehyde, 0-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, p-ethylbenzaldehyde, p-n-methylbenzaldehyde, furfural, and the like. Among these, formaldehyde is particularly preferred. These may be used alone or in combination of two or more.

The amount of aldehydes used is the total amount of the phenols 1
It is preferably 0.7 to 3 mol, more preferably 0.8 to 1.5 mol.

An acidic catalyst is usually used for the condensation.

Examples of the acidic catalyst include inorganic acids such as hydrochloric acid, nitric acid, and sulfuric acid, and organic acids such as formic acid, oxalic acid, and acetic acid, and the amount used is usually IX per mole of phenol.
10-5 to 5X10-' moles.

In condensation, water is generally used as a reaction medium, but if the phenol used is not dissolved in the aqueous solution of aldehydes and the reaction becomes a heterogeneous system from the early stage,
It is also possible to use hydrophilic solvents as reaction medium. Examples of the hydrophilic solvent include methanol, ethanol,
Examples include alcohols such as propatool and butanol, and cyclic ethers such as tetrahydrofuran and dioxane.

The amount of these reaction media used is usually 20 to 1000 parts by weight per 100 parts by weight of the reaction raw materials.

The reaction temperature for condensation can be adjusted as appropriate depending on the reactivity of the reaction raw materials, but is usually 10 to 20 O'C, preferably 70 to 130'C.

Examples of condensation methods include a method in which phenols, aldehydes, an acidic catalyst, etc. are charged all at once, and a method in which phenols, aldehydes, etc. are added as the reaction progresses in the presence of an acidic catalyst.

After the condensation reaction, the internal temperature is generally lowered to 1
30-230°C and under reduced pressure, e.g.
The resin (A) is recovered by distilling off volatile components at about 0 mmHg. Further, after the condensation reaction is completed, the resin (A) can be precipitated and recovered by dissolving the reaction mixture in the hydrophilic solvent and adding a precipitating agent such as water, n-hexane, or n-heptane.

The polystyrene equivalent weight average molecular weight (hereinafter referred to as "depression") of the resin (A) used in the present invention is 2°000 to 15,000 from the viewpoint of heat resistance and sensitivity of the composition of the present invention.
is preferred.

The cyclic compound (hereinafter simply referred to as "oligomer") obtained by condensing resorcinol and aldehydes used in the present invention has, for example, the structural formula () (wherein R is RCHO used in the condensation). m is 3 or more, preferably 3 to 9, particularly preferably 4 to 7).

Furthermore, in the present invention, an oligomer in which at least one hydrogen atom of the hydroxyl group of the oligomer is substituted can also be used.

A large number of papers have been published regarding the synthesis of oligomers, and one example is Hogberg.

A, G, S, J, 8m, Chem, Soc
, (1980), 102,6046, J.

5eph B, N1ederl, He1nz J,
Vogel J, Am, Chen+.

Soc, (1940), 62.2512, etc.

A specific example of the oligomer synthesis method is a method in which 1 mol of resorcinol and 0.8 to 1.2 mol of aldehydes are condensed in the presence of an acidic catalyst. As the acidic catalyst, the compounds exemplified in the synthesis of resin (A) can be used, preferably acidic or sulfuric acid, and the amount used is usually 5X10-2 to 5X10 mol per 1 mol of resorcinol. , preferably lXl0-'
~1×10 moles. If the amount of acidic catalyst used is too small, it may be difficult to obtain an oligomer, and if the amount used is too large, the oligomer may gel. In condensation, water is generally used as a reaction catalyst, as in the case of resin (A), but in order to increase the condensation efficiency, alcohols such as methanol, ethanol, propatool, butanol may be used alone or It can be used as a mixed solvent with water. The amount of these reaction media used is usually 100 to 5000 parts by weight per 100 parts by weight of the reaction raw materials. Further, the reaction temperature for condensation is preferably 70 to 1
00°C. Examples of the condensation method include a method of gradually adding an acidic catalyst to a mixed solution of resorcinol and an aldehyde, and a method of gradually adding an aldehyde to a mixed solution of resorcinol and an acidic catalyst.

After the condensation reaction is completed, the internal temperature is lowered to around room temperature, the precipitate is collected by filtration, washed with a large amount of water, and dried to recover the oligomer. At this time, methanol or
It can be purified by recrystallization using alcohols such as ethanol.

In addition, examples of the aldehydes used in the bottom of the oligomer include propionaldehyde, benzaldehyde, salicylaldehyde, isovaleraldehyde, and the like, in addition to those exemplified as the aldehydes used in the bottom of the resin (A). Among these, acetaldehyde is particularly preferred. These can be used alone or in combination of two or more.

Examples of oligomers in which at least one hydrogen atom of a hydroxyl group is substituted include an alkyl group such as a methyl group or an ethyl group, an alkoxyalkyl group such as a methoxymethyl group or an ethoxymethyl group, or an ether analog such as a benzyl group. ; The substituent is a sulfonic acid ester i [, tJ
-: Substituents include carboxylic acid ester analogs such as an acetyl group and a benzoyl group.

Here, the ether analog is an interphase between the oligomer and the alkyl halide compound, an alkyl halide compound, etc., and an inorganic base such as sodium carbonate, sulfur hydroxide, potassium hydroxide, and, if necessary, an ammonium salt. It can be obtained by reacting in the presence of a mobile catalyst. Further, the sulfonic acid ester analog can be obtained by reacting an oligomer and a sulfonyl halide compound in the presence of an organic base such as triethylamine. Further, carboxylic acid ester analogs can be obtained by reacting an oligomer and an acid anhydride compound in the presence of an organic base such as pyridine. In addition, when preparing the base of these analogs, an inert solvent such as acetone, dioxane, etc. can be used as a reaction raw material.

Among these oligomers, it is preferable to add 1,2-naphthoquinonediazide-4 to the oligomer obtained by polycondensation of acetonaldehyde and resorcinol.
-sulfonyl group, (1), 2-naphthoquinone diazide 5-sulfonyl group, or a carboxylic acid ester analog having an acetyl group or benzoyl group introduced.

The blend of oligomers used in the present invention is selected from the viewpoints of improving the heat resistance, phenomenon properties, and heat resistance of the composition of the present invention.
It is preferably 1 to 50 parts by weight, more preferably 3 to 30 parts by weight, based on 100 parts by weight of the total amount of A).

In the present invention, 1,2-quinonediazide compounds other than the oligomer into which the 1,2-quinonediazide sulfonyl group has been introduced can be used, such as 1°2-benzoquinonediazide-4-sulfonic acid ester, l2-naphthoquinonediazide- Examples include 4-sulfonic acid ester, 1,2-naphthoquinonediazide 35-sulfonic acid ester, and the like. Specifically, P
-1,2-benzoquinonediazide-4 sulfonic acid esters of (poly)hydroxybenzenes such as cresol, redulucin, pyrogallol, phloroglycitur, etc., 1,2-
Naphthoquinonediazide-4-sulfonic acid ester or 1,2-naphthoquinonediazide-5-sulfonic acid ester; 2,4-dihydroxyphenyl-propyl ketone,
2.4-dihydroxyphenyl-〇-hexylketone,
2.4-dihydroxybenzophenone, 2゜3.4-)
Dihydroxyphenyl-n-hexyl ketone, 2,3.
4-) Lihydroxyhenzophenone, 2,4.6-drihydroxyhenzophenone, 2 3 4 4'-tetrahydroxyhenzophenone, 2,3,4.3°-tetrahydroxybenzophenone, 2,3,4. 4″-tetrahydroxy-31-methoxybenzophenone, 22′
44'-tetrahydroxyhensiphenone, 2.2'3
, 4.6'-pentahydroxybenzophenone, 2,3
．． 3', 4.4', 5"-hexahydroxybenzophenone, 2.3', 4.4', 5
', 6-hexahydroxybenzophenone, etc. (poly)
1,2-benzoquinonediazide-4-sulfonic acid ester, 1,2-naphthoquinonediazide 4-sulfonic acid ester or 1,2-naphthoquinonediazide-5-sulfonic acid ester of hydroxyphenylalkyl ketone or (poly)hydroxyphenylaryl ketone ;Screw(
p-hydroxyphenyl)methane, bis(2゜4-dihydroxyphenyl)methane, bis(2゜3.4-)dihydroxyphenyl)methane, 2゜2-bis(p-hydroxyphenyl)propane, 2.2-bis (2,4-dihydroxyphenyl)propane, 2,2-bis(2,3,
1.2-benzoquinonediazide-4-sulfonic acid ester of bis[(poly)hydroxyphenyl coalkane such as 4-)dihydroxyphenyl)propane, 1. 2 naphthoquinone diazide-4-sulfonic acid ester or 1.
2-naphthoquinonediazide-5-sulfonic acid ester;
3,5-dihydroxybenzoic acid lauryl, 2,3.4-) phenyl dihydroxybenzoate, 3,4.5-) lauryl dihydroxybenzoate,
3,4.5-1 Propyl hydroxybenzoate, 3,4
．． (Poly) such as phenyl 5-1-lyhydroxybenzoate
1. of hydroxybenzoic acid alkyl esters or (poly)hydroxybenzoic acid aryl esters. 2-benzoquinonediazide-4-sulfonic acid ester, 1,2-naphthoquinonediazide-4-sulfonic acid ester or 1
゜2-naphthoquinonediazide-5-sulfonic acid ester; bis(2,5-dihydroxybenzoyl)methane, bis(2,3,4-)dihydroxybenzoyl)methane,
Bis(2,4,6-)dihydroxybenzoyl)methane, p-bis(2,5-dihydroxybenzoyl)benzene, p-bis(2゜3.4-trihydroxybenzoyl)benzene, p-bis(2,4 , 6-)dihydroxybenzoyl)benzene or other bis[(poly)hydroxybenzoyl]benzene, 1,2-benzoquinone 6-diazido-4-sulfonic acid ester, 1,2-naphthoquinonediazide- 4-sulfonic acid ester or 1,2-
Naphthoquinone diazide-5-sulfonic acid ester; ethylene glycol di(3,5 dihydroxybenzoate), polyethylene glycol di(3,5-dihydroxybenzoate), polyethylene glycol di(3,5 dihydroxybenzoate),
1,2-benzoquinonediazide-4-sulfonic acid ester of (poly)ethylene glycol di[(poly)hydroxybenzoate] such as (4,5-trihydroxybenzoate); 2 Naphthoquinone diazide-5-sulfonic acid ester; 1 of alkali-soluble phenolic resin
, 2-benzoquinonediazide-4-sulfonic acid ester,
(2) 2-naphthoquinonediazide 4-sulfonic acid ester or 1,2-naphthoquinonediazide 5-sulfonic acid ester.

In addition to these compounds, J. Kosar, “'Light
t-3ensitive Systems″339~3
52. ．． (1965), John 7 Wiley & 5ons (New York) and W.
"Photoresist" by S. DeFo, rest.
” 50. (1975), McGraw Hill + I
1 and 2 published in nc, (New York)
Quinonediazide compounds can also be used.

Among these 1,2-quinonediazide compounds, 2.3
．． 4-) Lyhydroxybenzophenone-1゜2-naphthoquinonediazide-4-sulfonic acid ester, 2,3.4
-) Lihydroxyhenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,3,4.
4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,
4.41-Tetrahydroxybenzophenone-1,2-
naphthoquinone diazide-5-sulfonic acid ester, 2.
3,4,4'-tetrahydroxy-3'-methoxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4°4''-tetrahydroxy-3'-methoxyhensiphenone-1 , 2-naphthoquinonediazide-5sulfonic acid ester, etc. polyhydroxybensif8 enone-1,2-quinonediazide sulfonic acid ester,
and alkali-soluble phenolic resin (hereinafter simply “
For example, 20 to 10
1,2-condensed 1,2-quinonediazide sulfonyl groups such as 1,2-naphthoquinonediazide-4-sulfonyl group and 1.2-naphthoquinonediazide-5-sulfonyl group at a ratio of 0%, preferably 40 to 100%. Quinonediazide sulfonic acid esters are preferred. Here, the resin (B) is obtained by condensation of phenols and aldehydes, and the phenols include phenol, 1-naphthol, 2-naphthol, in addition to the phenols used in the synthesis of the resin (A). etc. can be used. Moreover, as the aldehydes, those used in the synthesis of the resin (A) can be used. The amount of aldehydes used is preferably 0.1 to 3 moles, more preferably 0.2 to 1.5 moles, per mole of phenols. In this condensation, an alkaline catalyst can also be used in addition to the acidic catalyst used in the synthesis of the resin (A). Itsuki BF1 (B
) is usually 10,000 or less, preferably 20, from the viewpoint of ease of esterification reaction and solubility in solvents.
0~2000. Particularly preferably 300 to 1000. Examples of the 1°2-quinonediazide sulfonic acid ester of the resin (B) include phenol/formaldehyde condensed novolac resin-1,2-naphthoquinonediazide-4-sulfonic acid ester, phenol/formaldehyde condensed novolac resin-1,2- Naphthoquinonediazide-5-sulfonic acid ester, m-cresol/formaldehyde condensed novolac resin-1,2-naphthoquinonediazide-4-sulfonic acid ester, m-cresol/
Formaldehyde condensed novolak resin-1,2-naphthoquinonediazide-5-sulfonic acid ester, p-cresol/formaldehyde condensed novolak resin 12-naphthoquinonediazide-4-sulfonic acid ester, p-cresol/formaldehyde condensed novolak resin-1,2
-naphthoquinonediazide-5-sulfonic acid ester, 0
-Cresol/formaldehyde condensed novolac resin-
1,2-naphthoquinonediazide-4-sulfonic acid ester, 0-cresol/formaldehyde condensed novolak resin-1,2-naphthoquinonediazide-5-sulfonic acid ester, m-cresol/p-cresol/formaldehyde condensed novolak resin-1゜2 -Naphthoquinonediazide-4-sulfonic acid ester, m-cresol/p-
Cresol/formaldehyde condensation novolac resin-1
, 2-naphthoquinonediazide-5-sulfonic acid ester, and the like.

1. The blending amount of the 2-quinonediazide compound is as follows:
It is usually 3 to 100 parts by weight per 100 parts by weight, preferably 5 to 50 parts by weight, but 1.2- parts in 1 ull.
The total amount of quinonediazide sulfonyl groups is usually 5 to 25
The amount is adjusted to be 10 to 20% by weight, preferably 10 to 20% by weight.

The composition of the present invention may also contain a sensitizer in order to improve its sensitivity to radiation.

Examples of these sensitizers include 2H-pyrido [3゜1-
b) -L 4-oxazin-3(4H)ones, l0
H-pyrido(3,2-b)(14)benzothiazines,
Urazoles, hydantoins, barbylic acids, glycine anhydrides, 1-hydroxybenzotriazoles,
Examples include alloxanes and maleimides. The blending amount of these sensitizers is 1,2-quinonediazide compound 10
It is usually 100 parts by weight or less relative to 0 parts by weight.

Further, the composition of the present invention may contain a surfactant in order to improve the coating properties, for example, the striations and the developability of the radiation irradiated area after the dry coating film is formed. Examples of surfactants include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaureto, and polyethylene glycol distear. Nonionic surfactants such as Lato, Efthomp EF301, EF303, EF35
2 (manufactured by Shin-Akita Kaoru Co., Ltd.), Me2 Gakoac F171, F172, F173 (manufactured by Dainippon Ink Co., Ltd.), Florado FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard AG710, Surflon S-382, 5CIOI, 5C102, 5C103,
Fluorine surfactants such as 5C104, 5C105, 5C106 (manufactured by Asahi Glass Co., Ltd.), organosiloxane polymer K
P341 (manufactured by Shin-Etsu Chemical Co., Ltd.), acrylic acid-based or methacrylic acid-based (co)polymer Polyflow Nα75, Nα9
5 (manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.). The blending amount of these surfactants is usually 2% by weight or less based on the solid content of the composition of the present invention.

Furthermore, the composition of the present invention may contain dyes and pigments in order to visualize the latent image in the radiation-exposed area and reduce the effects of halation during radiation irradiation, as well as adhesion aids to improve adhesiveness. can. The composition of the present invention also includes:
Storage stabilizers, antifoaming agents, etc. can also be added as necessary.

As a method for applying the composition of the present invention to a substrate such as a silicon wafer, predetermined amounts of the resin (A), the oligomer 3,1,2-quinonediazide compound, and various compounding agents are applied, for example, to a solid content of 20 to 40%. % in a solvent, filtered through a filter with a pore size of about 0.2 μm, and then applied by spin coating, flow coating, roll coating, or the like. Examples of solvents used in this case include glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether, ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate, diethylene glycol monomethyl ether, and diethylene glycol monoethyl ether. Diethylene glycols such as propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol alkyl ether acetate such as propylene glycol probyl ether acetate, aromatic hydrocarbons such as toluene and xylene, ketones such as methyl ethyl ketone and cyclohexanone. , 2-human methyl 40oxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl oxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methyl -3
-Methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, 3-methyl-3-methoxybutylbutyrate, ethyl acetate, butyl acetate, and other esters can be used. These solvents can be used alone or in combination of two or more.

Furthermore, N-methylformado, N,N-dimethylformamide, N-methylformanilide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, benzylethyl ether, dihexyl ether, diethylene glycol Monomethyl ether, diethylene glycol monoethyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octatool, ■-nonanol, benzyl alcohol, benzyl acetate, di5thyl benzoate, diethyl oxalate, diethyl maleate, γ - It is also possible to add high-boiling solvents such as butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate.

Examples of the developer for the composition of the present invention include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, and tertiary amines such as ethylamine and n-propylamine. , tertiary amines such as diethylamine and di-n-propylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, tetramethyl Quaternary ammonium salts such as ammonium hydroxide, tetraethylammonium hydroxide, choline, or pyrrole, piperidine, 1°8-diazabicyclo(
The concentration of cyclic amines such as 5,4,0)-7-undecene and 1,5-diazabicyclo(4,3,0)5-nonane is usually 1 to 10% by weight, preferably 2 to 5% by weight. An alkaline aqueous solution prepared by melting 26' is used. Further, an appropriate amount of an aqueous organic solvent such as alcohols such as methanol and ethanol, or a surfactant may be added to the developer.

When using the composition of the present invention as a positive resist, the composition of the present invention is coated on a silicon wafer, prebaked and exposed, and then heated at 70 to 140''C. By performing development later, the effects of the present invention can be further improved.

〔Example〕

EXAMPLES Hereinafter, the present invention will be explained in detail with reference to Examples, but the present invention is not limited to these Examples.

In addition, in the examples, GPC columns manufactured by Toyo Soda Co., Ltd. (
C: 62 2000H, 61 G3000H, G400
0H, 1 tube), a flow rate of 1.5 m for 427 minutes, an elution solvent of tetrahydrofuran, and a column temperature of 40°C, using a Gelpar 5 needle chromatography method using monodisperse polystyrene as a standard. Further, various performances of the resist were evaluated by the following methods.

Sensitivity: Change the exposure time with a Nikon Corporation-NSR-150504D reduction projection exposure machine (lens numerical aperture: 0.45) and perform exposure using a g-line with a wavelength of 436 nm, or Nikon Corporation-NSR- 150546A reduction projection exposure a
Exposure was carried out using i-line with a wavelength of 365 nm by changing the exposure time at a numerical aperture of the lens (numerical aperture of the lens: 0°45), and then a 2.4% by weight aqueous solution of tetramethylammonium hydroxide was used as a developing solution at 25°C. A resist pattern is formed on the wafer by developing for 60 seconds at °C, rinsing with water, and drying. Exposure time (hereinafter referred to as , this is called the "optimal exposure time").

Resolution: The dimension of the smallest resist pattern that is resolved when exposed at the optimum exposure time was measured.

Remaining film rate: The thickness of the butter film after development at the optimum exposure time was divided by the thickness of the resist film before development, this value was multiplied by 100, and expressed in units of %.

The degree of developability varnish scum and development residue was examined.

Heat resistance: A wafer with a resist pattern formed thereon was placed in a clean oven, and the temperature at which the pattern began to collapse was measured.

Pattern shape: Using a scanning electron microscope, measure the lower side A and upper side B of the rectangular cross section after development of a 0.6 μm resist pattern, and if 0.85≦B/A≦1, the pattern shape is It was judged to be good.

<Synthesis of resin> ■) Synthesis of resin (A1) In a flask equipped with a stirrer, cooling tube and thermometer, m
-cresol 34.60 g (0,320 mol), 2.5
-xylenol 18.30 g (0,150 mol), 2,
3.5-)limethylphenol 8°17g (0,060
mol), 37% by weight formaldehyde aqueous solution 89.27
g (formaldehyde: 1° 10 mol) and oxalic acid dihydrate 0.605 g (4,8X 10-3 mol)
immerse the flask in an oil bath and raise the internal temperature to 100'C.
After linear combination was carried out for 2 hours with stirring, 8.65 g (0,080 mol) of m-cresol and 18.30 g (0,150 mol) of 2,5-xylenol were added.
32.68 g (0,240 mol) of 5-)limethylphenol was added, and linear combination was further carried out for 2 hours. After condensation, the temperature of the oil bath was raised to 180°C, and at the same time the pressure inside the flask was reduced to 30-50 mmH'g, and water, oxalic acid, unreacted formaldehyde, m-cresol, 25-xylenol, and 2,3 .5-trimethylphenol was removed.

The molten resin (A) was then returned to room temperature and recovered (hereinafter, this resin will be referred to as "resin (A1)").

2) Synthetic Resin (A2) Into the same flask as in the synthesis of resin (A1), 43.2 g (0.40 mol) of m-cresol and 172.2 g (0.40 mol) of m-cresol were added.
8 g (1,60 mol), 215.8 g (formaldehyde 0 12.66 mol) of 37% formaldehyde aqueous solution and 0.132 oxalic acid dihydrate
g (1,05xlO-3 mol) and the internal temperature was set to 10
The temperature was maintained at 0"C and condensation was carried out for 1 hour. After that, further m-
86.5 g (0.80 mol) of cresol was continuously charged into the flask as the condensation progressed, and condensation was carried out for 2 hours. Thereafter, resin (A) was synthesized in the same manner as in the synthesis of resin (A1).
was recovered (hereinafter, this resin will be referred to as "Resin (A2) J").

3) In a flask similar to the one used for synthesizing the synthetic resin (A I ) of resin (A3), 27.05 g (0.25 mol) of m-cresol and 2.3°5-
Trimethylphenol 4.0g (0.03 mol), p-
12.7 g (0.12 mol) of cresol, 42.85 g (formaldehyde: Q, 53 mol) of a 37% by weight formaldehyde aqueous solution, and 0.5 oxalic acid dihydrate.
33 g (4,2x 1 (1-'mol)) was charged,
The flask was immersed in an oil bath, the internal temperature was maintained at 100°C, and the condensation was carried out for 30 minutes with stirring.
．． 98 g (0.065 mol) and 16.0 g (0.12 mol) 1 of 2,3.5 trimethylphenol were added, and condensation was further carried out for 40 minutes. After that, the resin (
Resin (A) was recovered in the same manner as the synthesis of A1) (hereinafter, this resin will be referred to as "resin (A3) J").

4) Synthetic Resin (A4) Into the same flask as in the synthesis of resin (A1), add 10-8 g (0.1 mol) of m-cresol (32.4 g (0.1 mol) Lp-cresol).
0,3 mol L3,5-xylenol 19.5 g (0,1
6 mol), 37% by weight formaldehyde aqueous solution 43.8
g (0.54 mol of formaldehyde dihydrate) and 0.064 g (0,0656 mol) of oxalic acid dihydrate were charged, and the separable flask was immersed in an oil bath to bring the internal temperature to 100 mol.
43.2 g (0.4 mol) of m-cresol and 4.9 g (0.4 mol) of 3.5-dimethylphenol were continuously added as the reaction progressed. The mixture was charged into a flask and condensed for 0.5 hours. Thereafter, resin (A) was synthesized in the same manner as in the synthesis of resin (A1).
(hereinafter, this resin will be referred to as "Resin (A4) J").

2 5) Into a flask similar to that used in the synthesis of synthetic resin (A1) for novolak resin (5), 108 g (1 mol) of m-cresol, 24.3 g of a 37% by weight formaldehyde aqueous solution (formaldehyde: 0.3 mol), and oxalic acid. Dihydrate 0.302 g (2,4X 1
The flask was immersed in an oil bath, the internal temperature was kept at 1.00°C, and condensation was carried out for 40 minutes. after that,
Resin (A) was recovered in the same manner as in the synthesis of resin (AI) (hereinafter, this resin is referred to as "novolac resin (5)").
.

6) Into a flask similar to the one used for synthesizing the synthetic resin (AI) of novolak resin (6), m m cresol 64.9 g (0.6 mol Lp-cresol 43
．． 3 g (0.4 mol), 20.3 g (0.25 mol formaldehyde) of 37% by weight aqueous formaldehyde solution and 0.302 g (2.4 x 1
The flask was immersed in an oil bath, the internal temperature was kept at 100°C, and condensation was carried out for 0.5 hours.
Resin (A) was recovered in the same manner as the synthesis of resin (AI) (hereinafter, this resin will be referred to as ")3 Borac resin (6)".

<Synthesis of 1,2-quinonediazide compound> 1) Synthesis of quinonediazide (1) In a flask equipped with a stirrer, a dropping funnel, and a thermometer, 10.0 g of novolak resin (5) and 1.2
-naphthoquinone diazide-4-sulfonic acid chloride 4.
0g of dioxane was added, and 100g of dioxane was added and dissolved with stirring. Immerse the flask in a water bath controlled at 30°C, and when the internal temperature is constant at 30°C, add 1.65 g of triethylamine to this solution using a dropping funnel so that the internal temperature does not exceed 35°C. I dripped it slowly.

Thereafter, the precipitated triethylamine hydrochloride was removed by filtration, and the filtrate was poured into a large amount of diluted hydrochloric acid to precipitate quinonediazide (I). Then, the precipitate was collected by filtration and heated at 40°
It was dried all day and night in a heated vacuum dryer controlled at C.

2) Synthesis of quinonediazide (II) 10.0 g of novolac resin (6) and 3.45 g of quinonediazide-5-sulfonic acid chloride were prepared in the same manner as in the synthesis of quinonediazide (1).
After reacting 1.42 g of triethylamine, quinonediazide (U) was obtained by precipitating and drying.

<Synthesis of oligomers and oligomer analogs> l) Synthesis of oligomer (1) In a flask equipped with a stirrer, a cooling tube, and a thermometer, 110.1 g (1.0 mol) of resorcinol and 44.1 g (1.0 mol) acetaldehyde were added. ), 400 ml of water, and 100 mff1 of concentrated hydrochloric acid were charged, the flask was immersed in an oil bath, the internal temperature was maintained at 75°C, and the reaction was allowed to proceed for 1 hour. Thereafter, it was cooled and the precipitate was collected by filtration. The precipitate was then washed with a large amount of water and air-dried to obtain a pale yellow oligomer (1). Oligomer (1) has 'H-NMR, IR,, Mas
Analysis of s et al. revealed that it was a cyclic perikarya of resorcinol.

2) Bottom of oligomer (1a) [oligomer (1) and 12-naphthoquinonediazide-5
- Condensate with sulfonic acid chloride] 5 In a flask equipped with a stirrer, a dropping funnel and a thermometer under the shield from light, 100 g (0°178 mol L) of oligomer (1) was added.
1.2-Naphthoquinonediazide 148 g (0,551 mol) of 5-sulfonic acid chloride and 1000 g of ethyl 2-hydroxypropionate and 740 g of dioxane
A mixed solvent consisting of was prepared and dissolved with stirring.

The flask was immersed in a water bath controlled at 30°C, and when the internal temperature became constant at 30°C, 61.3 g of triethylamine was added to this solution from the dropping funnel until the internal temperature reached 35°C.
It was dripped slowly so as not to exceed C.

After that, the precipitated triethylaton hydrochloride was removed by filtration, and the filtrate was poured into a large amount of diluted hydrochloric acid, and the oligomer (l) was poured into a large amount of diluted hydrochloric acid.
a) was precipitated. Next, the precipitate was collected by filtration and dried in a heated vacuum dryer controlled at 40°C for one day and night.

3) Synthesis of oligomer (1b) [Oligomer (1) and 1. Condensate with 2-naphthoquinonediazide-5-sulfonic acid chloride] G In the synthesis of oligomer (Ia), oligomer (1)
90 g (0,160 mol), 177.6 g (
Oligomer (1b) was obtained in the same manner as in the synthesis of oligomer (1a), except that 900 g of ethyl 2-hydroxypropionate, 740 g of dioxane, and 73.6 g of triethylamine were used.

4) Synthesis of oligomer (lc) [condensate of oligomer (1) and para-toluenesulfonic acid chloride] In the synthesis of oligomer (1a), 27.23 g (0,0484 mol) of oligomer (1), para Toluenesulfonyl chloride 19.07g (0.1
0 mol) and acetone 250mf! Oligomer (1a) was prepared in the same manner as the base of oligomer (1a) except that 10.32 g of triethylamine was used.
c) was obtained.

5) Base of oligomer (1d) [condensate of oligomer (1) and l,2-naphthoquinone 7diazido-4-sulfonic acid chloride] In some cases, oligomer (1a) has 12naphthoquinonediazide-5-sulfonic acid. Oligomer (1a) was synthesized in the same manner as in the synthesis of oligomer (1a), except that 1,2-naphthoquinonediazide-4-sulfonic acid chloride was used instead of chloride.
1d) was obtained.

6) Synthesis of oligomer (le) [Condensation product of oligomer (1) and acetic anhydride] 5.62 g (0.01 mol) of oligomer (1) and 2.04 g (0.02 mol) of acetic anhydride in 100 mff of pyridine
The solution was refluxed for 3 hours under nitrogen atmosphere.

Next, the solvent was distilled off under reduced pressure, the residue was dissolved in a small amount of acetone, and separated into a 3% by weight aqueous hydrochloric acid solution to precipitate the product, which was filtered through a Nutsche filter, washed with water, and dried to obtain the oligomer (1e). I got it.

7) Synthesis of oligomer (2) In a flask equipped with a stirrer, a condenser, and a thermometer, add 55.1 g (0.5 mol) of resorcinol, 29.0 g (0.5 mol) propionaldehyde, and 400 mf of ethanol solution. Dissolve while stirring and add concentrated hydrochloric acid 100rr+j! added. The flask was immersed in an oil bath, the internal temperature was maintained at 75°C, and the reaction was allowed to proceed for 3 hours under a nitrogen stream.

After the reaction, the mixture was cooled to room temperature, and the precipitate was collected by filtration using a Nutsche filter, washed with a small amount of methanol, washed with a large amount of water, and then dried to obtain an oligomer (2). Analysis of 'H-NMR, IR, Mass, etc. revealed that the oligomer (2) was a pericyclic resorcinol.

8) Synthesis of oligomer (2a) [oligomer (2) and 1,2-naphthoquinonediazide-
Condensate of 5-sulfonic acid chloride] oligomer (la
) Oligomer (2a) was obtained in the same manner as in the synthesis of Oligomer (1a) except that 114 g of Oligomer (2) was used instead of 100 g of Oligomer (1).

9) Synthesis of oligomer (2b) [oligomer (2) and 1,2-naphthoquinonediazide-
Condensate of 4-sulfonic acid chloride] oligomer (1d
) Oligomer (2b) was obtained in the same manner as in the synthesis of oligomer (1d) except that 100 g of oligomer 9-(1) was replaced with 114 g of oligomer (2).

Examples 1-14 and Comparative Example 1 Resin A, oligomer and 23.4.
1 mole of 4'-tetrahydroxybenzophenone and 1,2
- A naphthoquinone diazide compound and a solvent were mixed to form a homogeneous solution, which was then filtered through a membrane filter with a pore size of 0.2 μm to prepare a solution of the compound of the present invention.

The obtained solution was applied onto a silicon wafer having a silicon oxide film using a spinner, and then prebaked on a hot plate at 90°C for 2 minutes to a thickness of 1.2 μm.
436 wavelength through the reticle.
After irradiating with nm (g-line) or 365 nm (i-line) radiation, developing, rinsing, and drying, the sensitivity, resolution, residual film rate, developability, heat resistance, and pattern shape of the resist film were evaluated. Ta. The results are shown in Table 1.

0 1) Examples 1 to 11 and Comparative Example 1
), and Examples 12 to 14 were irradiated with i-line (365 nm).

2) Part by weight 3) Condensate of 1 mol of 2,3,4,4'-tetrahydroxybenzophenone and 3 mol of 1,2-naphthoquinonediazide-5-sulfonic acid chloride 4) 2,3,4-)rihydroxy Condensate of 1 mol of benzophenone and 3.0 mol of 1,2-naphthoquinonediazide-5sulfonic acid chloride 5) 1 mol of 2,3,4,4'-tetrahydroxy-3'methoxybenzophenone and 1.2 -Condensation product of 3.5 mol of naphthoquinonediazide-5-sulfonic acid chloride 6) Condensation product of 1 mol of 2,3,4,4'-tetrahydroxybenzophenone and 4 mol of 1,2-naphthoquinonediazide-5-sulfonic acid chloride Condensate 7) 2,3,4.4'-
Condensation of 1 mol of tetrahydroxybenzophenone and 3.6 mol of 1,2-naphthoquinonediazide-5-sulfonic acid chloride 2 8) 1 mol of 2,3.4,5.4'-pentahydroxybenzophenone and 1,2-naphtho Condensate of quinonediazide with 4 moles of 5-sulfonic acid chloride 9) 1 mole of 2,3,4.3',4",5'-hexahydroxybenzophenone and 12-naphthoquinonediazide
Condensate with 3.8 mol of 5-sulfonic acid chloride [Effects of the invention] The radiation-sensitive resin composition of the present invention has high sensitivity and resolution, is excellent in developability and resist pattern shape, and is heat resistant. A positive resist with excellent properties can be obtained.

Claims (2)

[Claims] (1) (a) Structural formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (where n is an integer from 1 to 3) At least one type of phenol is condensed with an aldehyde. Alkali-soluble novolak resin obtained by (2) Contains a cyclic compound obtained by condensing resorcinol and aldehydes and/or a cyclic compound in which at least one hydrogen atom of the hydroxyl group of the cyclic compound is substituted, and (c) a 1,2-quinonediazide compound. A radiation-sensitive resin composition characterized by: