JPH04274242A - Radiation sensitive resin composition - Google Patents

Abstract

PURPOSE:To prevent any scrum from occurring at the time of development by mixing a specified compound in a resign composition in addition to alkaline soluble resin and 1,2 quinonediazide compounds as a sensitive ingredient. CONSTITUTION:Compounds being expressed in a formula I and 1,2 quinonediazide compounds as sensitive radioactive ingredients are mixed in a resin composition containing alkaline soluble resin. Q in the formula I shows a group (a shows integers of 0-4) being expressed in a formula II or a phenylene group, and X<1>-X<15> show-either of a hydrogen atom, an alkyl group, an alkoxyl group and a hydroxyl group, and in each combination of X<1>-X<5>, X<6>-X<10>, X<11>-X<15>, at least one piece should be set to the hydroxyl group. R<1>-R<4> show the hydrogen atom or the alkyl group, and Y shows the hydrogen atom, the alkyl group or a nonsubstitute or substitute phenyl group.

Description

[Detailed description of the invention]

0001

[Industrial Field of Application] The present invention relates to a radiation-sensitive resin composition containing an alkali-soluble resin, and more specifically to radiation-sensitive resin compositions containing an alkali-soluble resin, and more particularly to radiation-sensitive resin compositions containing an alkali-soluble resin. The present invention relates to a radiation-sensitive resin composition suitable as a resist for producing highly integrated circuits sensitive to radiation such as beams.

0002

[Prior Art] Positive resists are often used in the manufacture of integrated circuits because they can provide resist patterns with high resolution. A positive resist that can form patterns is desired. In other words, when forming 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 (the bottom of the pattern) is ).

0003

[Problems to be Solved by the Invention] However, in the case of conventional positive resists, when the interval between resist patterns to be formed is less than 0.8 μm, development residue called scum tends to occur, causing problems in developability. Ta. Furthermore, as the degree of integration of integrated circuits increases, the wafer etching method is shifting from the conventional wet etching with large side etching to dry etching with small side etching. In this dry etching, it is necessary that the resist pattern does not change during etching, so it is necessary to have good heat resistance. Therefore, an object of the present invention is to provide a radiation-sensitive resist suitable for use as a positive type resist, which effectively suppresses the generation of scum, has excellent developability, has high sensitivity, high resolution, and has excellent heat resistance, residual film rate, etc. An object of the present invention is to provide a synthetic resin composition.

0004

[Means for Solving the Problems] According to the present invention, there is provided a radiation-sensitive resin composition containing an alkali-soluble resin (hereinafter referred to as "resin (A)"), which has the following general formula (
1),

[Formula 1] In the formula, Q is the following formula (2),

Formula 2 represents a group represented by (a represents an integer of 0 to 4) or a phenylene group, and X1 to X15 are hydrogen atoms,
Indicates either an alkyl group, an alkoxy group or a hydroxyl group (X1 to X5, X6 to X10 and X11 to X1
5), R1 to R4 represent a hydrogen atom or an alkyl group, and Y represents a hydrogen atom, an alkyl group, or an unsubstituted or substituted phenyl group. At least one of the compounds (hereinafter abbreviated as "compound (A)")
A radiation-sensitive resin composition is provided, which contains a 1,2-quinonediazide compound as a seed and a radiation-sensitive component. The radiation-sensitive resin composition of the present invention effectively suppresses the generation of scum, has excellent developability, and is suitable as a positive resist with high sensitivity, high resolution, and excellent heat resistance, residual film rate, etc. Can be used for

Alkali-soluble resin The resin (A) used in the present invention includes, for example, novolac resin, resol resin, polyvinylphenol or its derivatives, styrene-maleic anhydride copolymer, polyvinyl hydroxybenzoate, carboxyl group-containing (meth) Examples include acrylic acid resins, and novolak resins are particularly preferred. Also, among novolac resins, the following general formula (3),

embedded image In the formula, n represents an integer of 1 to 3, and those obtained by polycondensing phenols and aldehydes are preferred.

Examples of the above phenols include o-cresol, m-cresol, p-cresol, 2,3
-xylenol, 2,4-xylenol, 2,5-
Xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,4-
Examples include trimethylphenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, among others 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), m-cresol/
2,3,5-trimethylphenol/p-cresol=
It is a combination system of 95/5/0 to 30/70/65 (molar ratio).

Examples of aldehydes to be polycondensed with the above phenols include formaldehyde, trioxane, paraformaldehyde, benzaldehyde, acetaldehyde, propylaldehyde, phenylacetaldehyde, α-phenylpropylaldehyde, β-phenylpropylaldehyde, and o-hydroxybenzaldehyde. , m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-chlorobenzaldehyde, m
-chlorobenzaldehyde, p-chlorobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, p-nitrobenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, p-ethylbenzaldehyde,
Examples include p-n-butylbenzaldehyde and furfural, with formaldehyde being particularly preferred. These aldehydes can also be used singly or in combination.
More than one species can be used in combination.

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. An acidic catalyst is usually used for polycondensation of phenols and aldehydes. Examples of the acidic catalyst include hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, and acetic acid. The amount of these acidic catalysts used is usually 1 mole of phenol.
The amount is 1×10 −5 to 5×10 −1 mol.

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, water may be used as the reaction medium. Hydrophilic solvents can also be used. 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 100 parts by weight of the reaction raw material.
It is 1000 parts by weight.

[0010] 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 130℃. As a method for polycondensation, it is possible to adopt a method in which phenols, aldehydes, acidic catalysts, 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. can. After the completion of polycondensation, the temperature of the reaction system is generally kept at 130-23°C in order to remove unreacted raw materials, acidic catalyst, reaction medium, etc. present in the system.
0 °C and under reduced pressure, e.g. 20-50 mmHg.
The volatile components are distilled off at a moderate temperature, and the resulting resin (A) is recovered.

The polystyrene equivalent weight average molecular weight (hereinafter referred to as "Mw") of the resin (A) used in the present invention is preferably from 2,000 to 20,000, preferably from 3,000 to 15,000. It is even more preferable that there be. When Mw exceeds 20,000, it may be difficult to uniformly apply the composition of the present invention to a wafer, and furthermore, developability and sensitivity tend to decrease; When present, heat resistance tends to decrease. Note that in order to obtain resin (A) with a high Mw, the resin obtained above is dissolved in a good solvent such as ethyl cellosolve acetate, dioxane, methanol, or ethyl acetate, and then dissolved in water, n-hexane, or n- The resin (A) may be recovered by mixing a poor solvent such as heptane, then separating the precipitated resin solution layer.

Further, in the present invention, the above resin (A)
A low molecular weight phenol compound can also be used as a solubility promoter for the purpose of promoting the alkali solubility of. 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, a compound represented by the following formula (4) can be exemplified. .

[Image Omitted] In the above formula, a, b and c are each a number from 0 to 3 (excluding the case where each is 0), and x, y and z
is a number from 0 to 3. The amount of such a low molecular weight phenol compound to be blended is usually 50 parts by weight or less, particularly preferably 32 parts by weight or less, per 100 parts by weight of the resin (A).

For the same purpose as above, a low molecular weight alkali-soluble novolac resin or an alkali-soluble resol resin (hereinafter simply referred to as "resin (B)") is used as a solubility promoter.
) can also be used. Here, resin (B
) is obtained by polycondensation of phenols and aldehydes, but as phenols, the resin (A)
In addition to those exemplified as phenols used in the synthesis, phenol, 1-naphthol, 2-naphthol, etc. can be used. Also, as aldehydes,
Those used in the synthesis of the resin (A) can be used. The amount of aldehydes used is phenols 1
It is preferably 0.1 to 3 mol, more preferably 0.2 to 1.5 mol. In this polycondensation, an alkaline catalyst can also be used in addition to the acidic catalyst used in the polycondensation of the resin (A). Resin (B)
The Mw of is usually preferably 10,000 or less, more preferably 200 to 2,000, particularly preferably 300 to 1,000. Such resins (B) include phenol/formaldehyde condensed novolak resin, m-cresol/formaldehyde condensed novolak resin, p-cresol/formaldehyde condensed novolak resin,
Formaldehyde condensed novolak resins, o-cresol/formaldehyde condensed novolak resins, m-cresol/p-cresol/formaldehyde condensed novolak resins, and the like can be mentioned. The blending amount of such resin (B) is usually 60 parts by weight per 100 parts by weight of resin (A).
It is preferably at most 40 parts by weight, particularly at most 40 parts by weight.

Compound (A) In the composition of the present invention, the compound (A) has the above-mentioned general formula (1), that is,

At least one compound (A) represented by Formula 1 is blended.

In this general formula (1), Q is represented by the following formula (
2),

It is a group represented by Formula 2 or a phenylene group. Here, R3 and R4 are a group selected from a hydrogen atom or an alkyl group, and the alkyl group is preferably a lower alkyl group, such as a methyl group, ethyl group, n-propyl group, isopropyl group, or n-butyl group. and t-butyl groups having 1 to 4 carbon atoms. In this formula (2), when a is 0, it represents a single bond, and a
When is an integer of 1 to 4, examples include methylene group, ethylene group, ethylidene group, trimethylene group, isopropylidene group, and tetramethylene group. Further, as the phenylene group, various O-, m- and p-phenylene groups can be exemplified, but preferred ones are p-
It is a phenylene group.

Further, X1 to X15 are groups selected from a hydrogen atom, an alkyl group, an alkoxy group, or a hydroxyl group, and X1 to X5, X6 to X10 and X11 to X
In each of the 15 combinations, at least one is a hydroxyl group. That is, each benzene ring is substituted with at least one hydroxyl group. Here, examples of the alkyl group include the groups exemplified for R3 and R4 above, and examples of the alkoxy group include the groups having 1 carbon number.
-4 are preferable, and include, for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and the like. Further, R1 and R2 are hydrogen atoms or alkyl groups, and the alkyl groups include the above R3 and R4.
The groups exemplified above can be mentioned.

Y represents a hydrogen atom, an alkyl group, or an unsubstituted or substituted phenyl group. Here, examples of the substituent in the substituted phenyl group include an alkyl group, an alkoxy group, and a hydroxyl group, and preferred examples of the alkyl group and alkoxy group include X1 to X1
The alkyl groups and alkoxy groups having 1 to 4 carbon atoms exemplified with respect to 5 can be mentioned. These substituents may be bonded to the benzene ring singly or in combination of two or more.

Specific examples of such compound (A) include:
Compounds represented by the following formulas (5) to (11) can be exemplified.

[C5]

[C6]

[C7]

[Chemical formula 8]

[Chemical formula 9]

[Chemical formula 10]

[Chemical Formula 11] These compounds (A) are synthesized, for example, by an acid-catalyzed condensation reaction between a dicarbonyl compound and a phenol, or an acid-catalyzed condensation addition reaction between an α,β-unsaturated carbonyl compound and a phenol. be able to.

In the present invention, the above-mentioned compound (A)
is 0.5 to 90 per 100 parts by weight of resin (A)
It is preferred to use it in a proportion of 2 to 50 parts by weight, particularly 2 to 50 parts by weight.

1,2-quinonediazide compound In the present invention, in addition to the resin (A) and the compound (A), 1
, 2-quinonediazide compound are blended. This 1, 2
- The quinonediazide compound is a radiation-sensitive component and is used to impart radiation sensitivity to the composition of the present invention. Such 1,2-quinonediazide compounds include:
For example, 1,2-quinonediazide sulfonic acid ester such as 1,2-benzoquinonediazide-4-sulfonic acid ester, 1,2-naphthoquinonediazide-4-sulfonic acid ester, 1,2-naphthoquinonediazide-5-sulfonic acid ester, etc. Examples include the following:

2,3,4-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 3'-methoxy-2,3,4,4'-tetrahydroxybenzophenone, 2,2',5 , 5'-tetramethyl-2", 4,4'-trihydroxytriphenylmethane, 1,1,1-tris(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-4-
[1-(4-hydroxyphenyl)-1-methylethyl]-1-phenylethane, 2,4,4-trimethyl-2
',4',7-trihydroxy-2-phenylflavan, 1,1,3-tris(4-hydroxyphenyl)butane, 1,1,3-tris(2,5-dimethyl-4-
1,2-benzoquinonediazide-4-sulfonic acid ester, 1,2-naphthoquinonediazide-4-sulfonic acid ester, 1,2-naphthoquinonediazide-5-sulfonic acid ester such as hydroxyphenyl)propane. Then, the hydrogen atoms of the hydroxyl groups of the resin (B) explained as a solubility promoter in the section of the alkali-soluble resin are added at a ratio of, for example, 0.2 to 1 mol %, preferably 0.4 to 1 mol % per hydrogen atom. , 1,2-quinonediazide sulfonic acid ester substituted with a 1,2-quinonediazide sulfonyl group such as 2-naphthoquinonediazide-5-sulfonyl group.

In the composition of the present invention, the amount of the 1,2-quinonediazide compound is usually 3 to 100 parts by weight, preferably 5 to 100 parts by weight, based on 100 parts by weight of the resin (A).
It is 50 parts by weight.

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 composition, and examples of such a sensitizer include 2H-pyrido-(3,2
-b) -1,4-oxazin-3(4H)-ones, 10H-pyrido-(3,2-b)-(1,4)-benzothiazines, urazoles, hydantoins, parbituric acids, glycine anhydride 1-hydroxybenzotriazoles, alloxanes, maleimides, and the like. 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.

[0024] Furthermore, surfactants are added to improve the coating properties and developability of the composition, and examples of such surfactants include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, etc. ,
Polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, FTOP 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-106 (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) heavy body Polyflow No. 75, No. 95 (trade name, manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.). The blending amount of these surfactants is based on the solid content of the composition 100
It is usually 2 parts by weight or less per part by weight.

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 to 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 contains the resin (A), the compound (A), the 1,2-quinonediazide compound, and the various compounding agents described above at a solid content of, for example, 20%. It is prepared by dissolving it in a solvent to a concentration of ~40% by weight and filtering it through a filter with a pore size of about 0.2 μm.

Examples of the solvent used in this case include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol methyl ether acetate, propylene glycol propyl Ether acetate, toluene, xylene, methyl ethyl ketone, 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. Furthermore, N-methylformamide, N,N-dimethylformamide, N-methylformanilide, N-methylacetamide, N,N-dimethylacetamide, N-
Methylpyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate , γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, and other high-boiling point solvents 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 radiation-sensitive layer, and then applied to a predetermined mask. The pattern is formed by irradiating the radiation-sensitive layer with radiation through the pattern and developing it with a developer. Furthermore, when using the composition of the present invention as a positive resist, the composition is applied onto a wafer, etc., prebaked and irradiated with radiation, and then heated at 70 to 140°C. The effects of the present invention can also be further improved by developing the image.

Developer Solution Examples of the developer solution for the composition of the present invention include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, and diethylamine. -n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine,
Tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo-(5,4,0)-7
-undecene, 1,5-diazabicyclo-(4,3,
An alkaline aqueous solution prepared by dissolving an alkaline compound such as 0)-5-nonane to a concentration of, for example, 1 to 10% by weight is used. Further, a suitable amount of a water-soluble organic solvent such as alcohols such as methanol and ethanol, or a surfactant may be added to the developer. In addition, when development is performed using a developer made of such an alkaline aqueous solution, rinsing with water is generally performed subsequently.

[0030]

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 performed by the following method.

Mw: GPC column manufactured by Toyo Soda Co., Ltd. (G2
000H6 2 pieces, G3000H6 1 piece, G4000
H6 (1 bottle) under the analysis conditions of a flow rate of 1.5 ml/min, elution solvent tetrahydrofuran, and column temperature of 40 °C.
It was measured by gel permeation chromatography using monodisperse polystyrene as a standard.

Sensitivity: Nikon Corporation-NSR-1505G4
D Change the exposure time with a reduction projection exposure machine (numerical aperture of the lens: 0.45) and perform exposure using a g-line with a wavelength of 436 nm, or use a Nikon-NSR-1505i
6A Reduction projection exposure machine (numerical aperture of lens: 0.45)
The exposure time was changed at
Developed at ℃ for 60 seconds, rinsed with water, and dried to form a resist pattern on the wafer. Hereinafter, this will be referred to as the "optimal exposure time").

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, and 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.

<Synthesis of Resin A> Synthesis Example 1 In a flask equipped with a stirrer, a cooling tube and a thermometer, m
-Cresol 67.6g (0.63mol)
2,3,5-trimethylphenol 10.0g (0
．． 073 mol) p-cresol 31.8g
(0.29 mol) 37% by weight formaldehyde aqueous solution
107.1g (formaldehyde: 1.32 mol) and oxalic acid dihydrate 1.33g (1.06×1
After immersing the flask in an oil bath and carrying out polycondensation for 30 minutes with stirring while maintaining the internal temperature at 100°C, m-cresol 17.5g (
0.16 mol) and 2,3,5-trimethylphenol 40.0 g (
0.29 mol) was added thereto, and polycondensation was further carried out for 40 minutes. Next, the oil bath temperature was raised to 180°C, and at the same time the pressure inside the flask was reduced to 30 to 50 mmHg, and water,
Oxalic acid, unreacted raw materials, etc. were removed. 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 there. After being separated into two layers by standing, the resin solution layer (lower layer) was taken out, concentrated, dehydrated, and dried to recover the resin. This resin was mixed with resin (A2
).

Synthesis Example 3 In an autoclave, m-cresol 69.2g (0.64 mol) and 2,3,5-trimethylphenol 21.8g (
0.16 mol) 37% by weight formaldehyde aqueous solution
61.0g (formaldehyde: 0.75 mol) Oxalic acid dihydrate 6.3g (0.05 mol)
Charge 52.6g of water and 182g of dioxane, immerse the autoclave in an oil bath, and bring the internal temperature to 130g.
Condensation was carried out for 6 hours while maintaining the temperature at °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, take out the lower layer,
The resin was recovered by concentration, dehydration, and drying. This resin is called resin (A3).

Synthesis Example 4 In a flask similar to that used in Synthesis Example 1, 13.0 g (0.12 mol) of m-cresol and 32.4 g (0.3 mol) of p-cresol were added.
Xylenol 39.0g (0.32mol)37
Weight% formaldehyde aqueous solution 56.9 g (formaldehyde: 0.70 mol) and oxalic acid dihydrate 0.083 g (6.59 x 1
After immersing the flask in an oil bath and stirring while maintaining the internal temperature at 100°C to carry out polycondensation for 30 minutes, m-cresol (51.9 mol) was added.
(0.48 mol) and 9.77 g (0.08 mol) of 3,5-dimethylphenol were continuously charged into the flask as the reaction progressed, and polycondensation was performed for 45 minutes. Thereafter, the resin was collected in the same manner as in Synthesis Example 1. This resin is called resin (A4).

Synthesis Example 5 In a flask similar to that used in Synthesis Example 1, 95.2 g (0.88 mol) of m-cresol was added.
-Trimethylphenol 24.4g (0.18 mol) 37% by weight formaldehyde aqueous solution 154g (
Formaldehyde: 1.90 mol) and oxalic acid dihydrate 1.82 g (0.014 mol) were charged, the flask was immersed in an oil bath, and the internal temperature was adjusted to 100 mol.
After polycondensation was carried out for 90 minutes by stirring while maintaining the temperature at °C, 23.8 g (0.
22 mol) and 2,3,5-trimethylphenol 97.6 g (0
．． 72 mol) was added thereto, and polycondensation was further carried out for 60 minutes. Then, the resin was collected in the same manner as in Synthesis Example 1. This resin was dissolved in ethyl cellosolve acetate so that the solid content was 20% by weight, and then 1.8 times the weight of methanol and the same amount of water were added to the resin solution, stirred, and allowed to stand. After being separated into two layers by standing, the resin solution layer (lower layer) was taken out, concentrated, dehydrated, and dried to recover the resin. This resin is called resin (A5).
That's what it means.

<Synthesis of Resin B> Synthesis Example 6 Into a flask similar to that used in Synthesis Example 1, 108.0 g (1.00 mol) of 37% by weight m-cresol was added.
Formaldehyde aqueous solution 24.3g (formaldehyde: 0.30 mol) and oxalic acid dihydrate 0.30g (2.40 x 1
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 Example 7 In a flask similar to that used in Synthesis Example 1, 64.9 g (0.60 mol) of m-cresol, 43.3 g (0.40 mol) of p-cresol, and a 37% by weight formaldehyde aqueous solution were added. 3g (formaldehyde: 0.25 mol) and oxalic acid dihydrate 0.30g (2.40×1
The flask was immersed in an oil bath, and polycondensation was carried out for 30 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 (B2).

<Abbreviation of compound (A)> The following is an abbreviation of compound (A) used in the examples. The following formula (12),

1,1,3-tris (2,5-dimethyl-
4-Hydroxyphenyl)-3-phenylpropane is abbreviated as compound (A1). The following formula (13),

1,1,3-tris (2,5-dimethyl-
4-Hydroxyphenyl)-3-phenylbutane is abbreviated as compound (A2). The following formula (14),

1,1,3-tris (3,5-dimethyl-
4-Hydroxyphenyl)-3-phenylbutane is abbreviated as compound (A3). The following formula (15),

1,1,3-tris (4,5-dimethyl-
4-Hydroxyphenyl)-3-phenylbutane is abbreviated as compound (A4). The following formula (16),

[Chemical formula 16] 1,1,2,2-tetrakis(2,5-dimethyl-4-hydroxyphenyl)ethane represented by the compound (
It is abbreviated as A5). The following formula (17),

[Chemical formula 17] 1,1,2,2-tetrakis(3,5-dimethyl-4-hydroxyphenyl)ethane represented by the compound (
It is abbreviated as A6). The following formula (18),

[Chemical 18] α, α, α', α'-Tetrakis (3,
5-dimethyl-4-hydroxyphenyl)-p-xylene is abbreviated as compound (A7).

<Synthesis of 1,2-quinonediazide compound>
Synthesis Example 8 In a flask equipped with a stirrer, a dropping funnel, and a thermometer, 10.0 g of resin (B1), 13.9 g of 1,2-naphthoquinonediazide-5-sulfonic acid chloride, and 100 g of dioxane were charged and stirred in the dark. It was dissolved while The flask was then immersed in a water bath controlled at 30°C until the internal temperature reached 30°C.
When the temperature became constant, 5.75 g of triethylamine was slowly added dropwise to this solution 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 vacuum dryer controlled at 40°C. −
A quinonediazide compound (C1) was obtained.

Synthesis Example 9 Resin (B2) 10.0g1,2-
Naphthoquinonediazide-5-sulfonic acid chloride
1,2-quinonediazide compound (
C2) was obtained.

Synthesis Example 10 2,3,4-trihydroxybenzophenone 2
3.0 g (0.10 mol) 1,2-naphthoquinonediazide-5-sulfonic acid chloride 69.9 g (0.26 mol) and triethylamine 28.9 g (0.286
1,2-
A quinonediazide compound (C3) was obtained.

Synthesis Example 11 2,3,4,4'-tetrahydroxybenzophenone 24.6 g (0.10 mol) 1,2-naphthoquinonediazide-5-sulfonic acid chloride 107.5 g (0.40 mol) and triethylamine A 1,2-quinonediazide compound (C4) was obtained in the same manner as in Synthesis Example 8 except that 44.5 g (0.44 mol) was used.

Synthesis Example 12 1,1-bis(4-hydroxyphenyl)-4-[1
-(4-hydroxyphenyl)-1-methylethyl]-1-phenylethane 42.4g (0
．． 10 mol) 1,2-naphthoquinonediazide-5-sulfonic acid chloride 67.2 g (0.25 mol) and triethylamine 27.8 g (0.275 mol)
1,2-
A quinonediazide compound (C5) was obtained.

Examples 1 to 9, Comparative Examples 1 to 3 Resin A, 1,
A 2-quinonediazide compound, compound (A) 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 composition 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 form a resist film with a thickness of 1.2 μm. via wavelength 436nm (g-line) or 36nm as above
Expose using 5 nm (i-line), develop, rinse,
After drying, the sensitivity, resolution, residual film rate,
The developability and heat resistance were evaluated. The results,
Table 1 shows the resins used. In addition, Example 1~
4 and Comparative Examples 1 to 2 were irradiated with g-rays, and Examples 5 to 9
And Comparative Example 3 was irradiated with i-line.

[0051]

[Table 1]

Note: The solubility promoters α and β are as follows. α; 1,1,1-tris(4-hydroxyphenyl)
Ethane B1; Resin (B1) B2 obtained in Synthesis Example 6;
Resin (B2) obtained in Synthesis Example 6 Note: The types of solvents are as follows. S1; Ethyl cellosolve acetate S2; Ethyl 2-hydroxypropionate S3; Methyl 3-methoxypropionate

[0053]

Effects of the Invention The radiation-sensitive resin composition of the present invention effectively suppresses the generation of scum and has excellent developability, as well as high sensitivity, high resolution, and excellent heat resistance and residual film rate. It can be suitably used as a positive resist.

Claims (1)

[Claims] [Claim 1] A radiation-sensitive resin composition containing an alkali-soluble resin, which has the following general formula (1), [Chemical formula 1] where Q is the following formula (2), [Chemical formula 2] (a represents an integer of 0 to 4) or a phenylene group, and X1 to X15 represent a hydrogen atom, an alkyl group, an alkoxy group, or a hydroxyl group (X1
- In each combination of ~X5, 1. A radiation-sensitive resin composition comprising at least one compound represented by the following formula representing a substituted phenyl group and a 1,2-quinonediazide compound as a radiation-sensitive component.