JP2000010269A - Radiation sensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin compsn. which can be applied in uniform thickness even onto a substrate made to have a large diameter by incorporating an alkali- soluble novolac resin and a specified compd. SOLUTION: This compsn. is made to contain an alkali-soluble novolac resin and a quinonediazide sulfonic acid ester of a polyphenol compd. expressed by formula I. In the formula I, R is hydrogen atom or an alkyl group, A is a bivalent group expressed by formula II, m is independently 1 to 3, n is independently an integer 0 to 3. The alkali-soluble novolac resin to be used is not specified as far as it is obtd. by polymn. condensation of phenols and aldehydes in the presence of an acidic catalyst, The phenols to be used in this case are phenol, o-cresol or the like. As for the aldehydes, formaldehyde, paraformaldehyde or the like can be used. As for the quinonediazide sulfonic acid ester, 1,2-benzoquinonediazide-4-sulfonic acid ester or the like can be used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a radiation-sensitive resin composition containing an alkali-soluble novolak resin. In particular, the present invention relates to a radiation-sensitive resin composition useful as a positive resist suitable for producing highly integrated circuits responsive to ultraviolet rays and far ultraviolet rays.

[0002]

2. Description of the Related Art Positive resists are widely used in the production of integrated circuits. However, with the recent increase in the degree of integration of integrated circuits, various factors such as resolution, depth of focus (focus tolerance), and cross-sectional shape of a pattern have been developed. A positive resist capable of forming a resist pattern having excellent characteristics is desired.
Further, with such high integration, it is important to apply a resist with a uniform film thickness in order to form a fine resist pattern with high dimensional accuracy. On the other hand, the area per substrate (for example, a silicon wafer) is increasing from 4 to 6 inches to 8 inches. Generally, the larger the area of the substrate, the more uniform the resist film is formed. It becomes difficult. Therefore, the radiation-sensitive resin composition used as a highly integrated circuit manufacturing resist,
It is important not only to have excellent characteristics such as the resolution, focus tolerance, and pattern cross-sectional shape described above, but also to be able to apply a uniform film thickness to a large-diameter substrate.

[0003]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a positive type, which has good resolution, pattern sectional shape, and exposure margin, and can be applied with a uniform film thickness even on a large-diameter substrate. It is to provide a radiation-sensitive resin composition suitable as a resist.

[0004]

According to the present invention, an object of the present invention is to provide (A) an alkali-soluble novolak resin, and (B) a quinonediazide sulfonic acid ester of a polyphenol compound represented by the following general formula (1). It can be achieved by a radiation-sensitive resin composition characterized by containing.

[0005]

Embedded image [In the formula (1), R is a hydrogen atom or an alkyl group,
A is the formula:

[0006]

Embedded image It is a divalent group represented by m is an integer of 1 to 3 independently, and n is an integer of 0 to 3 independently. ]

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. (A) Alkali-Soluble Novolak Resin The alkali-soluble novolak resin (hereinafter referred to as "novolak resin (A)") used in the present invention is obtained by polycondensing phenols and aldehydes in the presence of an acidic catalyst. If it is, there is no particular limitation. The phenols used at this time include, for example, phenol, o-
Cresol, m-cresol, p-cresol, 2,3
-Xylenol, 2,4-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, catechol,
Resorcinol, pyrogallol, phloroglucinol,
Examples thereof include 1-naphthol, 2-naphthol, and thymol, which can be used alone or in combination of two or more. Among the above examples, preferred phenols include phenol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 3,4-xylenol and 2,3,5 -Trimethylphenol.

Preferred combinations when two or more kinds are used in combination are, for example, m-cresol / 2,3-xylenol, m-cresol / 2,4-
Xylenol, m-cresol / 2,5-xylenol, m-cresol / 2,3-xylenol / 3,4-
Xylenol, m-cresol / 2,3,5-trimethylphenol and m-cresol / 2,3-xylenol / 2,3,5-trimethylphenol can be exemplified.

The aldehydes include, for example, formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, glyoxal, glutaraldehyde, terephthalaldehyde, isophthalaldehyde and the like. it can. Among these, formaldehyde and o-hydroxybenzaldehyde can be particularly preferably used. Aldehydes can be used alone or in combination of two or more. The amount of the aldehyde used is preferably from 0.4 to 2 mol, more preferably from 0.6 to 1.5 mol, per 1 mol of the phenol.

For the condensation reaction between phenols and aldehydes, an acidic catalyst is usually used. Examples of the acidic catalyst include hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, acetic acid, methanesulfonic acid, p-toluenesulfonic acid and the like. The amount of these acidic catalysts used is usually from 1 × 10 ^{−5 to} 5 × 10
^-1 mole.

The condensation reaction is carried out without a solvent or in a solvent. As the solvent, for example, methanol, ethanol,
Alcohols such as propanol, butanol and propylene glycol monomethyl ether, cyclic ethers such as tetrahydrofuran and dioxane, and ketones such as ethyl methyl ketone, methyl isobutyl ketone and 2-heptanone can be used. The amount of these reaction media used is usually from 20 to 1,000 per 100 parts by weight of the reaction raw materials.
0 parts by weight, preferably 50 to 800 parts by weight. Although the temperature of the condensation reaction can be appropriately adjusted according to the reactivity of the raw materials, it is usually 10 to 200 ° C. As a reaction method, a method in which phenols, aldehydes, acidic catalysts and the like are collectively charged into a reaction vessel, a method in which an acidic catalyst is charged in a reaction vessel in advance, and phenols, aldehydes, and the like are present in the presence thereof as the reaction proceeds. The addition method or the like can be appropriately adopted.

After the completion of the condensation reaction, the novolak resin is recovered by elevating the reaction temperature to 130 ° C. to 230 ° C. in order to remove unreacted raw materials, acidic catalyst, reaction medium and the like present in the system and volatilizing under reduced pressure. A method of removing the novolak resin, removing the generated novolak resin from ethylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, ethyl lactate, methyl isobutyl ketone,
After dissolving in a good solvent such as 2-heptanone, dioxane, methanol, and ethyl acetate, a poor solvent such as water, n-hexane, and n-heptane is mixed and precipitated. And the like. The polystyrene-equivalent weight average molecular weight (hereinafter referred to as “Mw”) of the novolak resin used in the present invention is defined as the workability when applying the composition of the present invention to a substrate and the developability when used as a resist. From the point of sensitivity and heat resistance, 2,000 to 20,
Preferably 3,000 to 15,000.
Is particularly preferred.

(B) Quinonediazidesulfonic acid ester
Compound The quinonediazidesulfonic acid ester compound (hereinafter referred to as "photosensitizer (B)") used as the component (B) in the present invention is a quinonediazidesulfonic acid ester of a polyphenol compound represented by the general formula (1). is there. Examples of the quinonediazidesulfonic acid ester include 1,2-benzoquinonediazide-4-sulfonic acid ester,
-Naphthoquinonediazide-5-sulfonic acid ester,
1,2-naphthoquinonediazide-6-sulfonic acid ester, 1,2-naphthoquinonediazide-4-sulfonic acid ester and the like, among which 1,2-naphthoquinonediazide-4-sulfonic acid ester and 1,2-naphthoquinonediazide -5-sulfonic acid esters are preferred.

The photosensitive agent (B) can be obtained by reacting the polyphenol compound of the general formula (1) with quinonediazide sulfonyl chloride in the presence of a basic catalyst.
As the basic catalyst, for example, triethylamine, tributylamine, pyridine, N, N-dimethylaminopyridine, sodium carbonate and the like are used. In the photosensitive agent (B), the average esterification ratio, that is, the ratio of all the hydroxyl groups in the polyhydroxy compound represented by the general formula (1) to quinonediazidesulfonic acid ester is usually 20 to 10.
It is in the range of 0%, preferably 40-90%. If the average esterification ratio is too low, the composition obtained will be difficult to form a pattern, and if it is too high, the sensitivity of the composition may decrease. The polyphenol compound represented by the general formula (1) is not particularly limited, but includes, for example, compounds represented by the following formulas (2-1) to (2-3).

[0015]

Embedded image

[0016]

Embedded image The compound represented by the general formula (1) is, for example, m =
When 1, n = 0 and R is a methyl group, it can be obtained by reacting 1 mol of a compound represented by the following formula (a) with 4 mol of isopropenylphenol under an acidic catalyst.

[0017]

Embedded image The amount of the photosensitive agent (B) is determined by the amount of the novolak resin (A).
5 to 50 parts by weight, preferably 1 to 100 parts by weight
0 to 40 parts by weight.

Other Components Other components can be added to the composition of the present invention, if necessary. ( A) Dissolution promoter For the purpose of promoting the alkali solubility of the novolak resin (A), a low molecular weight phenol compound (hereinafter, referred to as “dissolution promoter”) can be added. As the dissolution promoter, a phenol compound having 2 to 5 benzene rings is suitable, and for example, the following formulas (3-1) to (3-9)
Can be mentioned.

[0019]

Embedded image

[0020]

Embedded image

[0021]

Embedded image

[0022]

Embedded image [In the formulas (3-1) to (3-9), a, b, and c are each a number of 0 to 3 (however, except when all are 0), and x, y, and z are Each is a number from 0 to 3 and a + x ≦ 5, b + y ≦ 5 and c + z ≦ 5
(However, for (3-3) and (3-4), b + y
≦ 4. ). The amount of the dissolution accelerator is usually 50 parts by weight or less per 100 parts by weight of the novolak resin (A).

(B) Other quinonediazidesulfonic acids
A naphthoquinonediazidosulfonic acid ester compound (hereinafter, referred to as "photosensitizer (b)") other than the ester compound photosensitizer (B) can also be used. For example, 1,2-naphthoquinonediazidosulfonic acid ester of a polyphenol compound having the structure shown below can be mentioned.

[0024]

Embedded image [In the formula (4), Z _{1 to} Z ₁₅ are each independently a hydrogen atom, an alkyl group or a hydroxyl group. However, in each group of Z _{1 to} Z ₅ , Z _{6 to} Z ₁₀ and Z _{11 to} Z ₁₅ , at least one is a hydroxyl group. R _{1 to} R ₃ are each independently a hydrogen atom or an alkyl group. ]

[0025]

Embedded image [In the formula (5), Z _{16 to} Z ₂₉ are the same as Z _{1 to} Z _15, and at least one of each group of Z _{16 to} Z ₁₉ and Z _{20 to} Z ₂₄ is a hydroxyl group. R ₄ is a hydrogen atom or an alkyl group. ]

[0026]

Embedded image [In formula (6), Z _{30 to} Z ₄₂ are the same as Z _{1 to} Z _15, and at least one of each group of Z _{30 to} Z ₃₄ and Z _{35 to} Z ₃₇ is a hydroxyl group. R _{5 to} R ₈ are the same as defined above for R _{1 to} R ₃
Is the same as ]

[0027]

Embedded image [In formula (7), Z _{43 to} Z ₆₄ are the same as Z _{1 to} Z _15, and are Z _{43 to} Z ₄₇ , Z _{48 to} Z ₅₂ , Z _{53 to} Z ₅₇ and Z _58.
In each group of to Z _62, at least one is a hydroxyl group. ]

These photosensitive agents (b) may be used in combination of two or more kinds, and the compounding amount is 5 to 30 parts by weight based on 100 parts by weight of the resin. Further, the content of the quinonediazide group in the resist composition is adjusted so as to be preferably 5 to 50% by weight, more preferably 10 to 30% by weight, based on the solid content. Various additives can be further added to the composition of the present invention. For example, the following are mentioned.

Surfactant: Surfactants are added to improve the coating properties and developability of the composition, and the amount of the surfactant is 2 parts by weight or less per 100 parts by weight of the resin. Pigments and dyes: Dyes and pigments can be blended in order to visualize the latent image in the irradiated area when the composition is used as a resist and reduce the effects of halation during irradiation. Adhesion aid: An adhesion aid may be added to improve the adhesion of the composition to the substrate. Further, a storage stabilizer, an antifoaming agent and the like can be added as required.

Solvent: The composition of the present invention is used in the form of a solution from the viewpoint of coating workability. It is prepared by dissolving the solid content of the above-mentioned novolak resin (A) or the like in a solvent so that the solid content concentration becomes, for example, 20 to 40% by weight, and filtering the solution with a filter having a pore size of about 0.2 μm. As the solvent used, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether,
Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monopropyl ether acetate, toluene, xylene, methyl ethyl ketone, 2-heptanone, 3-heptanone,
4-heptanone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3
Examples thereof include methyl-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, butyl acetate, methyl pyruvate, and ethyl pyruvate. Further, N-methylformamide, N,
N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, benzylethylether, dihexylether, acetonylacetone, isophorone, caproic acid, caprylic acid, Add a high boiling point solvent such as 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, ethylene glycol monophenyl ether acetate. You can also. These solvents are used alone or in combination of two or more.

Use of the Composition In order to use the composition of the present invention as a resist, the composition prepared as a solution as described above is spin-coated, cast-coated, roll-coated, or the like, for example, a silicon wafer or aluminum. Is applied to the coated wafer. Next, a resist film is formed by pre-baking the coating film thus obtained, and after selectively irradiating the resist film with radiation so as to form a desired resist pattern, a pattern is formed by developing with a developer. I do. As the radiation used at this time, ultraviolet rays such as g-rays and i-rays are preferably used, but various radiations such as far-ultraviolet rays such as an excimer laser can also be used. At this time, after the irradiation, the film may be heated at 70 to 140 ° C. (hereinafter, referred to as “post-bake”), and then may be subjected to a development process. The effect of the present invention can be further improved by performing the post-baking.

Examples of the developer used for development include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, and di-
n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- (5,4,
0) -7-undecene, 1,5-diazabicyclo-
An alkaline compound such as (4,3,0) -5-nonane is
For example, an alkaline aqueous solution containing a concentration of 1 to 10% by weight is used. An appropriate amount of a water-soluble organic solvent, for example, an alcohol such as methanol or ethanol or a surfactant may be added to the developer. When a developer composed of such an alkaline aqueous solution is used, it is generally washed with water after development.

[0033]

EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited by these examples. The measurement of Mw and the evaluation of the resist in the examples were performed by the following methods. Mw: Tosoh GPC column (G2000HXL: 2
Gel permeation chromatograph using monodisperse polystyrene as a standard under the analysis conditions of flow rate: 1.0 ml / min, eluting solvent: tetrahydrofuran, column temperature: 40 ° C., using G3000HXL: 1, G4000HXL: 1). Resolution: 0.35 μm line and space (L /
S) The resist film is irradiated with an exposure amount (hereinafter, referred to as an appropriate exposure amount (Eop)) when the line width and the space width of the pattern are resolved one-to-one. The minimum dimension of the L / S pattern when lines and spaces are observed separately without film loss when observed with a scanning electron microscope. Exposure margin: Proper exposure (Eop) of 0.35 μm L
/ S Value obtained by dividing by the exposure amount (Ec) at which the pattern starts to be resolved. A large value means that a good exposure margin is provided. Film thickness uniformity: The film is coated on a 6-inch silicon wafer surface using an automatic coating phenomenon device (manufactured by Tokyo Electron Ltd .; trade name: Clean Track MARKII) so as to have a film thickness of 1.0 μm, and 90 ° C. To form a resist film. An optical film thickness meter (manufactured by Dainippon Screen Co., Ltd .; trade name: Lambda A VL) is used to measure the film thickness at 39 equally spaced points along the diameter direction of the resist film forming surface of the wafer.
-M6000-LS). The difference between the maximum value (maximum film thickness) and the minimum value (minimum film thickness) of the obtained measured values was determined and used as an index of film thickness uniformity. The smaller the difference in film thickness, the better the film thickness uniformity. Pattern cross-sectional shape: 0.3 obtained at appropriate exposure dose
The cross-sectional shape of the 5 μm L / S pattern in the depth direction is observed with a scanning electron microscope. The shape shown in FIG. 1 was identified as (A), and the shape shown in FIG. 2 was identified as (B).

<Synthesis of Novolak Resin (A)> Synthesis Example 1 In a 2 L separable flask equipped with a cooling tube and a stirrer, 129.6 g (1.2 mol) of m-cresol, 2,2
73.2 g (0.6 mol) of 3-xylenol, 3,4
Xylenol 24.4 g (0.2 mol), 37% by weight
150.0 g (formaldehyde: 1.85 mol) of an aqueous formaldehyde solution, 5.7 g (0.03 mol) of p-toluenesulfonic acid monohydrate and 568 g of methyl isobutyl ketone were charged, and the internal temperature was maintained at 90 to 100 ° C. The mixture was condensed for 8 hours while stirring. After the obtained resin solution was washed three times with 568 g of ion-exchanged water, 910 g of ethyl lactate was added to the washed solution, and methyl isobutyl ketone was distilled off under reduced pressure while heating. From the novolak resin solution thus obtained, methyl isobutyl ketone and water were completely distilled off under reduced pressure to obtain an ethyl lactate solution of the novolak resin having a solid content of 35%. Mw of the obtained novolak resin (referred to as (A-1)) was 7,300.

Synthesis Example 2 The raw materials charged in a separable flask were m-cresol (151.2 g, 1.4 mol) and 2,4-xylenol 7
3.2 g (0.6 mol), 37 wt% aqueous formaldehyde solution 120.0 g (formaldehyde 1.4 mol), oxalic acid dihydrate 12.6 g (0.1 mol) and methyl isobutyl ketone 561 g were changed. Except for the above, a novolak resin (referred to as novolak resin (A-2)) was obtained in the same manner as in Synthesis Example 1. Novolak resin (A-2)
Mw was 4,900.

Synthesis Example 3 600 g of n-hexane was added to 500 g of a solution of the novolak resin (A-2) obtained in Synthesis Example 2 in methyl isobutyl ketone.
Was added, and the mixture was stirred for 30 minutes and allowed to stand for 1 hour. The supernatant of the precipitated resin layer is removed by decantation,
After 896 g of ethyl lactate was added to the remaining resin layer, the remaining methyl isobutyl ketone and n-hexane were distilled off under reduced pressure under heating to obtain a resin solution containing ethyl lactate. Mw of the obtained novolak resin (referred to as (A-3)) is 6,
700.

Synthesis Example 4 151.2 g of m-cresol was placed in a 2 L autoclave.
(1.4 mol), 2,3,5-trimethylphenol 5
4.4 g (0.4 mol), 2,3-xylenol
4 g (0.2 mol), 142.7 g of a 37% by weight aqueous formaldehyde solution (1.76 mol of formaldehyde), 12.6 g (0.1 mol) of oxalic acid dihydrate and 575 g of propylene glycol monomethyl ether were charged.
While maintaining the internal temperature at 120 to 130 ° C., condensation was performed for 6 hours while stirring. 400 g of ethyl acetate and 695 g of ion-exchanged water were added to the obtained novolak resin solution, and the mixture was stirred for 30 minutes, and then allowed to stand for 1 hour. The upper layer thus separated was removed by decantation, and the remaining resin layer was washed twice with 695 g of ion-exchanged water. 920 g of ethyl lactate was added to the novolak resin solution obtained after washing with water, and concentrated under heating and reduced pressure to obtain a novolak resin solution containing ethyl lactate. Obtained novolak resin ((A-4)
) Was 6,900.

<Synthesis of Photosensitive Agent (B)> Synthesis Example 5 33.5 g of the compound represented by the formula (2-1) was placed in a flask equipped with a stirrer, a dropping funnel and a thermometer under shading.
(0.05 mol), 1,2-naphthoquinonediazide-5
-40.2 g (0.15 mol) of sulfonic acid chloride and 442 g of dioxane were charged and stirred to obtain a solution. Then, the flask was immersed in a water bath controlled at 30 ° C., and when the internal temperature became constant at 30 ° C., 17.2 g (0.17 mol) of triethylamine was added to the solution.
Was added using a dropping funnel so that the internal temperature did not exceed 35 ° C., and reacted at the same temperature for 2 hours. Thereafter, the precipitated triethylamine hydrochloride was removed by filtration, and the filtrate was poured into a large amount of a dilute hydrochloric acid aqueous solution to precipitate a reaction product. The precipitate is then filtered, collected and placed in a vacuum dryer.
After drying at 40 ° C. overnight, the compound of formula (2-1) 1,
As a result, 2-naphthoquinonediazide-5-sulfonic acid ester (photosensitive agent (B-1)) was obtained.

Synthesis Example 6 In place of the compound represented by the formula (2-1), 36.3 g (0.05 mol) of the compound represented by the formula (2-3) was charged.
Except that the amount of 1,2-naphthoquinonediazide-5-sulfonic acid chloride was changed to 40.2 g (0.15 mol),
By the same operation as in Synthesis Example 5, the compound (1-3)
2-Naphthoquinonediazide-5-sulfonic acid ester (photosensitizer (B-2) was obtained. <Synthesis of photosensitizer (b)> Synthesis Example 7 Instead of the compound represented by the formula (2-1), the following formula was used.

[0040]

Embedded image 21.2 g of polyphenol compound represented by the formula (0.05
Mol) using 1,2-naphthoquinonediazide-5
32.2 g (0.12 mol) of sulfonic acid chloride
, And the amount of dioxane was changed to 320 g, and the amount of triethylamine was changed to 13.1 g (0.13 mol) in the same manner as in Synthesis Example 5, except that 1,2-naphthoquinonediazide-5 of the above polyphenol compound was changed. -Sulfonate (photosensitive agent (b-1)) was obtained. Synthesis Example 8 Instead of the compound represented by the formula (2-1), the following formula:

[0041]

Embedded image 36.4 g (0.1) of the polyphenol compound represented by
Mol), and the amount of 1,2-naphthoquinonediazide-5-sulfonic acid chloride was adjusted to 53.7 g (0.2 mol).
Then, except that the amount of dioxane was changed to 540 g and the amount of triethylamine was further changed to 22.2 g (0.22 mol), 1,2-naphthoquinonediazide-5- of the above polyphenol compound was operated in the same manner as in Synthesis Example 5. As a result, a sulfonic acid ester (photosensitive agent (b-2)) was obtained. Synthesis Example 9 Instead of the compound represented by the formula (2-1), the following formula:

[0042]

Embedded image Using 39.2 g (0.1 mol) of the polyphenol compound represented by the formula, the amount of 1,2-naphthoquinonediazide-5-sulfonic acid chloride was 40.2 g (0.15 mol).
In the same manner as in Synthesis Example 5, except that the amount of dioxane was changed to 476 g and the amount of triethylamine was changed to 17.2 g (0.17 mol), 1,2-naphthoquinonediazide-5 of the polyphenol compound was changed. -Sulfonate (photosensitive agent (b-3)) was obtained. Synthesis Example 10 Instead of the compound represented by the formula (2-1), the following formula:

[0043]

Embedded image 28.0 g of polyphenol compound (0.05)
Mol) using 1,2-naphthoquinonediazide-5
40.2 g (0.15 mol) of sulfonic acid chloride
Except that the amount of dioxane was changed to 408 g
By the same operation as in Synthesis Example 5, 1,2-naphthoquinonediazide-5-sulfonic acid ester of the above-mentioned polyphenol compound (photosensitive agent (b-4)) was obtained.

Examples 1-5 In each of the examples, each component having the composition shown in Table 1 (parts are parts by weight) was dissolved in a solvent to form a uniform solution, and then a membrane filter having a pore size of 0.2 μm was obtained. , And
A composition was prepared. The composition solution was applied on a silicon wafer having a silicon oxide film on the surface using a spinner, and then prebaked on a hot plate at 90 ° C. for 2 minutes to form a resist film having a thickness of 1.07 μm. Then, the wafer surface on which the resist film was formed in this manner was exposed through a mask to a reduction projection exposure machine (lens numerical aperture = 0.57) (manufactured by Nikon Corporation, trade name: NSR-2).
205i12D) at a wavelength of 365 nm (i-line),
Next, post-baking was performed at 110 ° C. for 1 minute on a hot plate. Thereafter, the resist pattern was developed with a 2.38% by weight aqueous solution of tetramethylammonium hydroxide, rinsed with ultrapure water, and dried to resolve the resist pattern. The obtained pattern was examined, and the characteristics of the composition of each example were evaluated. Table 2 shows the results.

[0045]

[Table 1] (Note) In Table 1, the types of the dissolution promoter and the solvent are as follows.

Dissolution accelerator α: a phenol compound represented by the following formula:

[0047]

Embedded image β: a phenol compound represented by the following formula.

[0048]

Embedded image

Solvent S1: ethyl lactate S2: ethyl 3-ethoxypropionate S3: 2-heptanone

[0050]

[Table 2]

[0051]

The radiation-sensitive resin composition of the present invention has good resolution, pattern cross-sectional shape, and exposure margin, and also has excellent coatability on a large-diameter substrate. Therefore, this composition is excellent as a highly integrated resist for fabricating integrated circuits.

[Brief description of the drawings]

FIG. 1 is a cross-sectional shape of a preferable resist pattern (A type)
Is shown.

FIG. 2 shows a cross-sectional shape (B type) of a resist pattern that is more unfavorable than A type.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Shinichiro Iwanaga 2-11-24 Tsukiji, Chuo-ku, Tokyo JSR Co., Ltd. F-term (reference) 2H025 AA02 AA03 AB16 AC01 AC04 AD03 BE01 CB29 4J002 CC041 CC061 ED027 ED037 EE037 EH007 EH037 EH077 EH127 EH157 EL067 EP017 EU027 EV207 EV246 FD090 GP03

Claims (1)

[Claims] 1. A radiation-sensitive resin composition comprising (A) an alkali-soluble novolak resin, and (B) a quinonediazidesulfonic acid ester of a polyphenol compound represented by the following general formula (1). Embedded image [In the formula (1), R is a hydrogen atom or an alkyl group,
A is the formula: It is a divalent group represented by m is an integer of 1 to 3 independently, and n is an integer of 0 to 3 independently. ]