JPH04343359A - Radiation-sensitive resin composition - Google Patents

Abstract

PURPOSE:To improve developing property, sensitivity, heat resistance and resolution and to obtain a high residual film rate by incorporating an alkali-soluble resin and a specified ester of quinone diazidesulfon acid. CONSTITUTION:This resin compsn. contains an alkali-soluble resin and at least one kind of quinone diazidesulfon acid ester of phenol compd. expressed by formula I. In formula I, Q is a bivalent group expressed by formula II, bivalent alicyclic hydrocarbon group or bivalent aromatic hydrocarbon group, X<1>-X<20> are same of different hydrogen atom, hydroxyl groups, alkyl groups of 1-4 carbon number, alkoxy groups of 1-4 carbon number (however, at least one of X<1>-X<5>, at least one of X<6>-X<10>, at least one of X<11>-X<15>, at least one of X<16>-X<20> are hydroxyl groups). R<1> and R<2> hydrogen atom, or alkyl groups of 1-4 carbon number. In formula II, R<3> and R<4> are hydrogen atom, hydroxyl groups or alkyl groups of 1-4 carbon number or alkoxy groups of 1-4 carbon number, and n is an integer from 1 to 10.

Description

[Detailed description of the invention]

0001

FIELD OF THE INVENTION The present invention relates to a radiation-sensitive resin composition. More specifically, it is a radiation-sensitive resin composition that is sensitive to radiation such as ultraviolet rays, deep ultraviolet rays, X-rays, electron beams, molecular beams, γ-rays, synchrotron radiation, and proton beams, and is suitable as a resist for producing highly integrated circuits. Regarding.

0002

[Prior Art] Positive resists are often used in the manufacture of integrated circuits because they provide resist patterns with high resolution.However, as integrated circuits have become more highly integrated in recent years, resist patterns with higher resolution have been used. There is a need for a positive resist that can form .

In order to form a fine resist pattern using a positive resist, when developing a latent image formed by radiation irradiation with a developer consisting of an alkaline aqueous solution, the portion where the radiation irradiation area is in contact with the wafer ( It is necessary that the pattern be developed quickly up to the hem of the pattern. However, in the case of conventional positive resists, when the interval between the resist patterns to be formed was less than 0.8 μm, the developability and pattern shape were insufficient in areas with low exposure such as fine patterns and holes. .

Furthermore, as integrated circuits become more highly integrated, the wafer etching method is shifting from a wet etching method that causes large side etching to a dry etching method that causes less side etching. In this dry etching method, the resist pattern must not be changed by heat during etching, so the positive resist is required to have heat resistance. however,
Conventional positive resists cannot be said to have sufficient heat resistance.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a radiation-sensitive resin composition. Another object of the invention is to
The object of the present invention is to provide a radiation-sensitive resin composition that provides a positive resist that has excellent developability, high sensitivity, excellent heat resistance, resolution, and pattern shape, and has a high residual film rate. Further objects and advantages of the present invention will become apparent from the description below.

[0006]

[Means for Solving the Problems] According to the present invention, the above objects and advantages of the present invention are achieved by: (A) an alkali-soluble resin; and (B) the following general formula (1):

[0007]

[Case 2]

This is achieved by a radiation-sensitive resin composition containing at least one quinonediazide sulfonic acid ester of a phenol compound represented by the following formula. Components (A) and (B) of the present invention will be described below first.

Alkali-soluble resin (A): Alkali-soluble resin used in the present invention (hereinafter referred to as "resin (A)")
Examples of the novolak resin, resol resin, polyvinylphenol or its derivatives, styrene-maleic anhydride copolymer, polyvinyl hydroxybenzoate, carboxyl group-containing methacrylic acid resin, etc. Resins are preferably used. Also, among novolac resins, the following general formula (3),

0010

[Chemical formula 3]

Those obtained by polycondensation of phenols represented by the following formula and aldehydes are preferred.

[0012] Examples of the suitable phenols include o-cresol, m-cresol, p-cresol, 2
, 3-xylenol, 2,5-xylenol, 3,4-
Xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol and the like can be mentioned. Among these, o-cresol, m-cresol, p-cresol, 2,5-xylenol, 3,5-xylenol and 2,3,5-trimethylphenol are preferred. More preferably, m
-Cresol/3,5-xylenol/p-cresol = 95/5/0 to 20/80/25 (mole ratio) mixture and m-cresol/2,3,5-trimethylphenol/p-cresol = 95/ 5/0~30/70/
65 (molar ratio). These phenols may be used alone or in combination of two or more as described above.

Examples of aldehydes to be polycondensed with the above phenols include formaldehyde, trioxane, paraformaldehyde, benzaldehyde, acetaldehyde, propylaldehyde, phenylacetaldehyde, α-phenylpropylaldehyde, β-phenylpropylaldehyde, o-hydroxy Benzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-chlorobenzaldehyde,
m-chlorobenzaldehyde, p-chlorobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, p-nitrobenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-
Examples include methylbenzaldehyde, p-ethylbenzaldehyde, p-n-butylbenzaldehyde, pt-butylbenzaldehyde, and furfural. In particular, formaldehyde can be suitably used. These aldehydes can also be used alone or in combination of two or more.

The amount of the aldehyde used is preferably 0.7 to 3 mol, more preferably 0.8 to 1.5 mol, per 1 mol of the phenol.

[0015] An acidic catalyst is usually used for polycondensation of phenols and aldehydes. As the acid catalyst,
Examples include hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, and acetic acid. The amount of these acidic catalysts used is usually 1 x 10-5 to 5 x 10 per mole of phenols.
-1 mole.

In polycondensation, water is usually used as a reaction medium, but if the phenols used in polycondensation do not dissolve in the aqueous solution of aldehydes and the reaction becomes a heterogeneous system from the initial stage, the reaction Hydrophilic solvents can also be used as media. Examples of these hydrophilic solvents include alcohols such as methanol, ethanol, propanol and butanol; and cyclic ethers such as tetrahydrofuran and dioxane. The amount of these reaction media used is usually 20 to 1 per 100 parts by weight of reaction materials.
,000 parts by weight.

The temperature of polycondensation can be adjusted as appropriate depending on the reactivity of the reaction raw materials, but is usually 10 to 200°C.
, preferably 70 to 150°C.

Examples of the polycondensation method include, for example, a method in which phenols, aldehydes, acidic catalysts, etc. are charged all at once;
Alternatively, a method can be adopted in which phenols, aldehydes, etc. are added as the reaction progresses in the presence of an acidic catalyst.

After the polycondensation reaction is completed, the temperature of the reaction system is generally raised to 130°C to 230°C in order to remove unreacted raw materials, acidic catalysts, reaction medium, etc. present in the system.
Volatile components are distilled off under reduced pressure, for example, about 20 to 50 mmHg. Thereafter, the resin (A) is recovered.

[0020] The resin (A) used in the present invention is
The polystyrene equivalent weight average molecular weight (hereinafter referred to as "Mw") is preferably 2,000 to 20,000, more preferably 3,000 to 15,000. When the Mw exceeds 20,000, it may be difficult to uniformly apply the composition of the present invention to a wafer, etc., and the developability and sensitivity tend to decrease. If so, heat resistance tends to decrease.

Note that in order to obtain resin (A) with a high Mw, resin (A) is dissolved in a good solvent such as ethyl cellosolve acetate, dioxane, methanol, or ethyl acetate, and then water, n-hexane, n-hexane, or - A poor solvent such as heptane may be mixed, and then the high molecular weight resin (A) may be recovered from the precipitated resin solution layer.

[0022] In the composition of the present invention, the resin (A) may be blended singly or in combination of two or more. Moreover, a low molecular weight phenol compound can also be used as a solubility promoter for the purpose of promoting the alkali solubility of the resin (A). As this low molecular weight phenol compound, a phenol compound having about 2 to 6 benzene rings is suitable, and although it is not particularly limited, compounds represented by the following formula can be exemplified.

[0023]

[C4]

As the solubility promoter, a low molecular weight alkali-soluble novolak resin or a low molecular weight alkali-soluble resol resin (hereinafter simply referred to as "resin (B)") can also be used.

Here, the resin (B) is obtained by polycondensation of phenols and aldehydes, and the phenols include those exemplified as the phenols used in the synthesis of the novolac resin, as well as phenols. , 1-naphthol, 2-naphthol, etc. can be used. Furthermore, as the aldehydes, those used in the synthesis of the novolak resin can be used. The amount of aldehydes used is 0.1 to 3 per mole of phenols.
The amount is preferably mol, more preferably 0.2 to 1.5 mol. In this polycondensation, an alkaline catalyst can also be used in addition to an acidic catalyst.

The Mw of the resin (B) is generally preferably less than 2,000, particularly preferably from 200 to 1,000. Such resins (B) include phenol/formaldehyde condensation novolac resins, m-
Cresol/formaldehyde condensed novolac resin, p
- cresol/formaldehyde condensed novolak resin,
Examples include o-cresol/formaldehyde condensed novolak resin, m-cresol/p-cresol/formaldehyde condensed novolak resin, and the like. The amount of the solubility promoter to be blended is usually 50 parts by weight or less, particularly preferably 35 parts by weight or less, per 100 parts by weight of the resin (A).

Quinonediazide sulfonic acid ester (B)
: In the composition of the present invention, at least one quinonediazide sulfonic acid ester of the phenol compound represented by the above-mentioned general formula (1) (hereinafter referred to as "compound (B)") is blended.

In this general formula (1), R1 and R
2 is the same or different, and has a hydrogen atom or a carbon number of 1 to
It is a group selected from No. 4 alkyl groups. Here, examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, and t-butyl group.

Furthermore, in the general formula (1), Q is a divalent group represented by the general formula (2), a divalent alicyclic hydrocarbon group, or a divalent aromatic hydrocarbon group. General formula (2)
R3 and R4 are the same or different and are a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, or a C1 to C4 alkyl group.
-4 alkoxy groups. This carbon number is 1~
Examples of the alkyl group of 4 include the groups exemplified above for R1 and R2. Examples of the alkoxy group having 1 to 4 carbon atoms include methoxy group, ethoxy group, n-propoxy group, and t-butoxy group. Moreover, n in General formula (2) shows an integer of 1-10, Preferably it is an integer of 1-5.

Examples of the divalent alicyclic hydrocarbon group represented by Q include 1,3-cyclopentamethylene group, 1,3-cyclohexamethylene group, 1,4-cyclohexamethylene group, and 2,3-cyclohexamethylene group. Examples include norbornylene group, 2,5-norbornylene group, and 2,6-norbornylene group.

The divalent aromatic hydrocarbon group represented by Q includes o-phenylene group, m-phenylene group, p-phenylene group, 1,5-naphthylene group, 2,6-naphthylene group,
Examples include 2,7-naphthylene group, and p-phenylene group is particularly preferred.

Furthermore, in the general formula (1), X1 to X2
0 is the same or different, hydrogen atom, hydroxyl group, carbon number 1
-4 alkyl group or an alkoxy group having 1 to 4 carbon atoms. However, at least one of X1 to X5,
At least one of X6 to X10, at least one of X11 to X15, and at least one of X16 to X20 are hydroxyl groups. Here, examples of the alkyl group having 1 to 4 carbon atoms include the groups exemplified for R1 and R2, and examples of the alkoxy group having 1 to 4 carbon atoms include the groups exemplified for R3 and R4. .

Specific examples of such compound (B) include compounds represented by the following formula.

[0034]

[C5]

[0035]

[C6]

[0036]

[C7]

[0037]

[Chemical formula 8]

These compounds (B) can be synthesized, for example, by a polycondensation reaction between a dicarbonyl compound and a phenol using an acidic catalyst.

As the quinonediazide sulfonic acid ester of compound (B) in the present invention, for example, compound (B)
1,2-benzoquinonediazide-4-sulfonic acid ester, 1,2-naphthoquinonediazide-4-sulfonic acid ester, 1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,1-naphthoquinonediazide-4-sulfone Acid ester, 2,1-naphthoquinonediazide-5
-sulfonic acid esters and the like. Among them, preferred is 1,2-naphthoquinonediazide-4-
These are sulfonic acid ester and 1,2-naphthoquinonediazide-5-sulfonic acid ester.

Quinonediazide sulfonic acid ester (B)
can be obtained, for example, by an esterification reaction between compound (B) and 1,2-naphthoquinonediazide-4-sulfonyl chloride, 1,2-naphthoquinonediazide-5-sulfonyl chloride, or the like. The average condensation rate of this esterification reaction [(number of esterified phenolic hydroxyl groups/number of phenolic hydroxyl groups before reaction) x 100] is usually
It is 20-100%, preferably 40-100%.

These quinonediazide sulfonic acid esters (B) can be used alone or in combination of two or more. In addition, other quinonediazide sulfonic acid esters, such as 2,3,4-trihydroxybenzophenone, 2,
3,4,4'-tetrahydroxybenzophenone, 3'
-methoxy-2,3,4,4'-tetrahydroxybenzophenone, 2,2',5,5'-tetramethyl-2"
,4,4'-trihydroxybenzophenylmethane, 1
,1,1-tris(4-hydroxyphenyl)ethane, 1
, 1-bis(4-hydroxyphenyl)-1-phenylethane, 1,1-bis(4-hydroxyphenyl)-4-[
1-(4-hydroxyphenyl)-1-methylethyl]-
1-phenylethane, 2,4,4-trimethyl-2',
1,2-benzoquinonediazide-4-sulfonic acid ester, 1,2-naphthoquinonediazide-4-sulfonic acid ester, or 1,2-naphthoquinonediazide-5-sulfone such as 4',7-trihydroxy-2-phenylflavan Acid esters and the like can be used in combination.

The content of the quinonediazide sulfonic acid ester in the composition of the present invention is preferably 0.5 to 90 parts by weight, more preferably 2 to 50 parts by weight, per 100 parts by weight of the resin (A).

Various compounding agents: Various compounding agents such as sensitizers and surfactants can be added to the composition of the present invention. A sensitizer is added to improve the sensitivity of the resist. Examples of such sensitizers include 2H-pyrido-
(3,2-b)-1,4-oxazin-3(4H)-ones, 10H-pyrido-(3,2-b)-(1,4)-
Examples include benzithiazines, urazoles, hydantoins, parbituric acids, glycine anhydrides, 1-hydroxybenzotriazoles, alloxanes, and maleimides. The blending amount of these sensitizers is as follows: resin (A) 1
00 parts by weight, it is usually 50 parts by weight or less.

[0044] A surfactant is also added to improve the coating properties and developability of the composition. Examples of such surfactants include polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, EFTOP EF301, EF303, EF352 (product name, manufactured by Shin-Akita Kasei Co., Ltd.), Megafax F171
, F172, F173 (product name, manufactured by Dainippon Ink Co., Ltd.),
Florado FC430, FC431 (product name, manufactured by Sumitomo 3M), Asahi Guard AG710, Surflon S-382, SC-101, SC-102,
SC-103, SC-104, SC-105, SC-1
06 (trade name, manufactured by Asahi Glass Co., Ltd.), organosiloxane polymer KP341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), acrylic acid-based or methacrylic acid-based (co)polymer Polyflow N
o. 75, No. 95 (trade name, manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.) and the like. The blending amount of these surfactants is
It is usually 2 parts by weight or less per 100 parts by weight of solid content of the composition.

Furthermore, dyes and pigments can be added to the composition of the present invention in order to visualize the latent image in the radiation irradiated area and reduce the effect of halation during radiation irradiation, and also to improve adhesion. In order to do this, an adhesion aid may be added. Furthermore, storage stabilizers, antifoaming agents, etc. can be added as necessary.

Preparation of composition and pattern formation: The composition of the present invention comprises the above-mentioned resin (A) and quinonediazide sulfonic acid ester (B) of compound (A) as a photosensitive component.
) and the various compounding agents mentioned above are dissolved in a solvent such that the solid content concentration is 20 to 40% by weight, and the pore size is 0.
．． It is advantageously prepared by filtration through a filter of about 2 μm.

Examples of the solvent used in this case include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and methyl cellosolve acetate.
ethyl cellosolve acetate, diethylene glycol
diethylene glycol monoethyl ether, propylene glycol methyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclohexanone, ethyl 2-hydroxypropionate, 2
-Ethyl hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, 3 -Methyl ethoxypropionate, ethyl acetate, butyl acetate, etc. can be used. These organic solvents may be used alone or in combination of two or more.

Furthermore, N-methylformamide, N,N
-dimethylformamide, N-methylformanilide,
N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, benzylethyl ether, dihexyl ether, acetonylacetone, isophorone, caproic acid, caprylic acid, 1
-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate,
High boiling point solvents such as diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, and phenyl cellosolve acetate can also be added.

The composition of the present invention is applied to a silicon wafer or a wafer coated with aluminum or the like by spin coating, flow coating, roll coating, etc. to form a resist layer, and a resist layer is formed by applying the composition using a predetermined mask. A pattern is formed by irradiating the resist layer with radiation through the pattern and developing it with a developer.

Further, the composition of the present invention can be applied by applying the composition onto a wafer etc., pre-baking and exposing it to light.
The effect of the present invention can be further improved by heating at 70 to 140° C. and then developing.

[0051] As the developer for the composition of the present invention,
For example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine. amine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo(5
, 4,0)-7-undecene, 1,5-diazabicyclo-(4,3,0)-5-nonane, etc., dissolved at a concentration of, for example, 1 to 10% by weight. An alkaline aqueous solution is used.

[0052] The developing solution may also be used by adding an appropriate amount of a water-soluble organic solvent, such as alcohols such as methanol and ethanol, or a surfactant.

[0053] When development is performed using a developer made of such an alkaline aqueous solution, rinsing with water is generally performed subsequently.

[0054]

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

In addition, the measurement of Mw and the evaluation of the resist in the examples were carried out by the following method.

[0056] Mw: Tosoh GPC column (G200
0H6 2 pieces, G3000H6 1 piece, G40
00H6 (1 bottle) under the analysis conditions of a flow rate of 1.5 ml/min, an elution solvent of tetrahydrofuran, and a column temperature of 40° C., the measurement was carried out by gel permeation chromatography using monodisperse polystyrene as a standard.

Sensitivity: Nikon Corporation-NSR-1505G4
You can change the exposure time using a D-reducing projection exposure machine (lens numerical aperture: 0.45) and perform exposure using the G-line with a wavelength of 436 nm, or use a Nikon NSR-1505i6A reduction projection exposure machine (lens aperture: 0.45). The exposure time was changed by 0.45), and exposure was performed using i-line with a wavelength of 365 nm.
Next, using a 2.4% by weight aqueous solution of tetramethylammonium hydroxide as a developer, development was carried out at 25°C for 60 seconds, rinsed with water, and dried to form a resist pattern on the wafer. - An exposure time (hereinafter referred to as "optimal exposure time") for forming a space pattern (1L1S) with a width of 1:1 was determined.

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

Remaining film rate: The thickness of the pattern 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 %.

Developability: The degree of 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,
The lower side A and upper side B of the rectangular cross section of the 0.6 μm resist pattern after development were measured, and the pattern shape was determined to be good if 0.85≦B/A≦1. however,
If the pattern shape is tapered or reversely tapered, it is not judged to be good even if B/A is within the above range.

<Synthesis of Resin (A)> Synthesis Example 1 m-cresol was placed in a flask equipped with a stirrer, a cooling tube, and a thermometer.
67.6g (0.63mol) p-cresol
31
．． 8g (0.29 mol) 37% by weight formaldehyde aqueous solution 107.1g (formaldehyde: 1.3
2 moles)

and oxalic acid dihydrate
After charging 1.33 g (1.06 x 10-2 mol) of m-cresol and immersing it in a flask oil bath, polycondensation was carried out for 30 minutes while keeping the internal temperature at 100°C and stirring.
17.5g (0.16 mol) p-cresol
8.0
g (0.073 mol) and 2,3,5-trimethylphenol 4
0.0 g (0.29 mol) was added and polycondensation was further carried out for 40 minutes.

[0065] Next, the oil bath temperature was raised to 180°C,
At the same time, the pressure inside the flask was reduced to 30 to 50 mmHg to remove water, oxalic acid, unreacted raw materials, and the like. The molten resin was then returned to room temperature and collected. This resin is called resin (A1).

Synthesis Example 2 Resin (A1) was dissolved in ethyl cellosolve acetate so that the solid content was 20% by weight, and then twice the weight of methanol and the same amount of water were added to the weight of this resin solution and stirred. I left it alone. After being separated into two layers by standing, the resin solution layer (lower layer) is taken out, concentrated, dehydrated,
The resin was recovered by drying. This resin is called resin (A2).

Synthesis Example 3 m-cresol in autoclave
69.2g (0.64mol) 3,
5-xylenol
19.5g (0.16 mol) 37% by weight formaldehyde aqueous solution 58.4g
(Formaldehyde: 0.72 mol) Oxalic acid dihydrate
0.90g (7.14 x 10-3 mol) water

54.4g and dioxane
After charging 228 g, the autoclave was immersed in an oil bath, and polycondensation was carried out for 10 hours while maintaining the internal temperature at 130° C. and stirring. After the reaction, the temperature was returned to room temperature, and the contents were taken out into a beaker. After separating into two layers in this beaker, the lower layer was taken out, concentrated, dehydrated, and dried to recover the resin. This resin is called resin (A3).

Synthesis Example 4 m-cresol in autoclave
69.2g (0.64mol)
2,3,5-trimethylphenol 2
1.8g (0.16 mol) 37% by weight formaldehyde aqueous solution 61.0g (
Formaldehyde: 0.75 mol) Oxalic acid dihydrate 6.
30g (0.05mol) water

52.6g and dioxane
182 g was charged, polycondensation was carried out for 6 hours, and the resin was recovered in the same manner as in Synthesis Example 3. This resin is called resin (A4).

<Synthesis of Resin (B)> Synthesis Example 5 In a flask similar to that used in Synthesis Example 1, m-cresol was added.
108.0
g (1.00 mol) 37% by weight formaldehyde aqueous solution 24.3 g (formaldehyde: 0.75 mol) and oxalic acid dihydrate
0.30g (2.40 x 10-3 mol)
The flask was immersed in an oil bath, and polycondensation was carried out for 40 minutes while maintaining the internal temperature at 100°C. Then, the resin was collected in the same manner as in Synthesis Example 1. This resin is called resin (B1).

<Synthesis of Compound (B)> Synthesis Example 6 94 g (1.0 mol) of phenol and 6 terephthaldehyde
．． 7g (0.05 mol) in acetic acid/hydrochloric acid = 50ml/50
ml, added 2 ml of mercaptoacetic acid, and reacted at 50° C. for 13 hours. After the reaction, the reaction solution was poured into about 2 liters of water to solidify the product, and then the product was separated by filtration. The separated product was then washed with water, further washed with hot toluene, and dried to give 18.5 g (67% yield).
α,α,α',α'-tetra(4-hydroxyphenyl)-p-xylene (structural formula 5-16 in the example of the compound (B)) was obtained. This compound is designated as compound (B1).

Synthesis Example 7 36.7 g (0.3 mol) of 2,5-xylenol and 13.4 g (0.1 mol) of terephthalaldehyde were dissolved in toluene, and 1.0 g of p-toluenesulfonic acid monohydrate was dissolved.
After heating and refluxing for 5 hours, the mixture was cooled to room temperature and the precipitate was collected by filtration. The precipitate was washed with hot toluene, dried, and α,α,α',α'-tetra(2
, 5-dimethyl-4-hydroxyphenyl)-p-xylene (Structural Formula 5-18 in the example of the compound (B)) was obtained. This compound is designated as compound (B2).

Synthesis Example 8 2.5-xylenol (30.5 g) and 20 g (0.05 mol) of glutaraldehyde (25% aqueous solution) were dissolved in acetic acid/hydrochloric acid = 70 ml/80 ml and reacted at room temperature for 5 hours. . After the reaction, the reaction solution was poured into about 2 liters of water to solidify the product, and then the product was separated by filtration. The separated product was washed with water, further washed with hot toluene, and dried to give 24.0 g (87% yield) of 1,1,5,
5-tetra(2,5-dimethyl-4-hydroxyphenyl)-pentane (structural formula 5 in the example of compound (B))
-6) was obtained. This compound is designated as compound (B3).

Synthesis Example 9 94 g (1.0 mol) of phenol and 6.3 g (0.05 mol) of 1,3-diformylcyclopentane were dissolved in acetic acid/hydrochloric acid = 50 ml/50 ml, and 2 ml of mercaptoacetic acid was dissolved.
was added and reacted at 50°C for 8 hours. After the reaction, the solution was poured into about 2 liters of water to solidify the product, and then the product was separated by filtration. The separated product was washed with water, further washed with hot toluene, and dried to give 14.6 g (yield 63%) of 1,3
-Bis(di-4-hydroxyphenylmethyl)cyclopentane (structural formula 5-10 in the example of compound (B))
I got it. This compound is designated as compound (B4).

<Quinonediazide sulfonic acid ester (B
) > Synthesis Example 10 In a flask equipped with a stirrer, a dropping funnel, and a thermometer, in the dark, compound (B1) was added.
47.5g (0.1 mol) 1,2-naphthoquinonediazide-5-sulfonic acid chloride
80.6g (0
．． 3 mol) and dioxane 300g
was added and dissolved while stirring. Next, the flask was immersed in a water bath maintained at 30°C, and when the internal temperature became constant at 30°C, 33.6 g (0.3 g) of triethylamine was added to this solution.
3 mol) was slowly added dropwise using a dropping funnel so that the internal temperature did not exceed 35°C.

Thereafter, the precipitated triethylamine hydrochloride was removed by filtration, and the filtrate was poured into a large amount of diluted hydrochloric acid to precipitate it.Then, the precipitate was collected by filtration and dried overnight in a heated vacuum dryer kept at 40°C. A reaction product was obtained. This reaction product is called NQD1.

Synthesis Example 11 Compound (B1) 47.5g (
0.1 mol) 1,2-naphthoquinonediazide-4-
Sulfonic acid chloride
67.2g (0.25mol)
Dioxane 300g and triethylamine 28.0g (0
．． A reaction product was obtained in the same manner as in Synthesis Example 10, except that 275 mol) was used. This reaction product is called NQD2.

Synthesis Example 12 Compound (B2) 58.7g (
0.1 mol) 1,2-naphthoquinonediazide-5-
Sulfonic acid chloride
73.9g (0.275mol)
Dioxane 300g and triethylamine 30.9g (0
．． A reaction product was obtained in the same manner as in Synthesis Example 10, except that 303 mol) was used. This reaction product is called NQD3.

Synthesis Example 13 Compound (B3) 55.3g (
0.1 mol) 1,2-naphthoquinonediazide-5-
Sulfonic acid chloride
80.6 g (0.3 mol) dioxane 300 g and triethylamine 33.6 g (0
．． A reaction product was obtained in the same manner as in Synthesis Example 10, except that 33 mol) was used. This compound is called NQD4.

Synthesis Example 14 Compound (B4) 46.7g (
0.1 mol) 1,2-naphthoquinonediazide-5-
Sulfonic acid chloride
80.6 g (0.3 mol) dioxane 300 g and triethylamine 33.6 g (0
．． A reaction product was obtained in the same manner as in Synthesis Example 10, except that 33 mol) was used. This compound is called NQD5.

<Examples 1 to 8, Comparative Examples 1 to 3> Resin A,
The quinonediazide sulfonic acid ester (B), a solvent, and other ingredients as necessary 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 composition. 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 form a resist film with a thickness of 1.2 μm. As mentioned above, the wavelength is 436 μm (g-line).
Or expose and develop using wavelength 365μm (i-line),
After rinsing and drying, the resist was evaluated. The results are shown in Table 1. In addition, Examples 1 to 4 and Comparative Example 1 are as follows:
In Examples 5 to 8 and Comparative Examples 2 to 3, i-line was irradiated.

[0081]

[Table 1]

Notes to Table 1: (Note 1) The amount added is shown in parts by weight. (Note 2) α and β of the solubility promoters are as follows. α: 1,1,1-tris(4-hydroxyphenyl)ethane β: 1,1-bis(4-hydroxyphenyl)-1-phenylethane

(Note 3) I and II of the quinonediazide sulfonic acid ester (B) are as follows. I: 2,3,4-trihydroxybenzophenone 1
．． A condensate of 0 mol and 2.6 mol of 1,2-naphthoquinonediazide-5-sulfonic acid chloride. II: 1 mol of 2,3,4,4'-tetrahydroxybenzophenone and 5 1,2-naphthoquinone diazide
- Condensate with 4.0 mol of sulfonic acid chloride.

(Note 5) The types of solvents are as follows. S1: Ethyl cellosolve acetate S2: Ethyl 2-hydroxypropionate S3: Methyl 3-methoxypropionate

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Effects of the Invention The radiation-sensitive composition of the present invention has excellent developability, high sensitivity, heat resistance, resolution, and pattern shape, and is a positive type with a high residual film rate. It can be suitably used as a resist.

Claims (1)

[Claims] Claim 1: (A) an alkali-soluble resin, and (
B) A radiation-sensitive resin composition comprising at least one quinonediazide sulfonic acid ester of a phenol compound represented by the following general formula (1).