JPH03236053A - Radiation sensitive resin composition - Google Patents

Abstract

PURPOSE:To make improvement in the resolution, pattern shape and developability of a resist by using a cocondensed alkaline-soluble novolak resin which is of a specific value or below in the standard deviation of the compsn. CONSTITUTION:This compsn. is compounded with the cocondensed alkaline- soluble novolak resin which has <=5 standard deviation of the compsn. of the respective compsns. varying in mol. wt. The degradation in the resolution and pattern shape is resulted if the standard deviation exceeds 5 and, therefore, such standard deviation is undesirable. This resin is formed by supplying a part of, for example, phenols and aldehydes used for a condensation reaction to a reaction system, condensing the same in the presence of a basic catalyst, adding an inorg. acid to the condensate to neutralize the same, supplying the remaining phenols and aldehydes to the reaction system after washing and condensing the same again in the presence of an acidic catalyst.

Description

Detailed Description of the Invention a. Industrial Field of Application The present invention relates to a radiation-sensitive resin composition, and more specifically, it relates to a radiation-sensitive resin composition that can be used for radiation-sensitive resin compositions that are sensitive to ultraviolet rays, deep ultraviolet rays, X-rays, electron beams, molecular beams, T-rays, synchrotron radiation, and proton radiation. 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.

b. Prior Art Resists containing alkali-soluble novolac resins are widely used in the manufacture of integrated circuits because they provide resist patterns with high resolution. By the way, with the progress of semiconductor technology, higher integration, that is, miniaturization has progressed, and submicron resolution from 1 μ- to less than that is now required. In this situation, -a
Specifically, if the resist is made highly sensitive, developability, resolution,
The pattern shape, etc. is poor, and improving developability, resolution, pattern shape, etc. results in low sensitivity. Therefore, there has been a strong demand for a resist that has high sensitivity, good developability, high resolution, and excellent pattern shape.

Problems to be Solved by the C0 Invention The purpose of the present invention is to achieve high resolution and excellent pattern shape by using a specific alkali-soluble novolak resin.
It is an object of the present invention to provide a radiation-sensitive resin composition from which a resist with good developability and high sensitivity can be obtained.

60 Means for Solving the Problems The radiation-sensitive resin composition of the present invention is a radiation-sensitive resin composition containing a co-condensed alkali-soluble novolak resin. It is characterized in that the standard deviation of the composition is 5 or less.

The radiation-sensitive resin composition of the present invention (hereinafter referred to as composition J) includes, for example, a composition mainly containing a cocondensed alkali-soluble novolak resin, a 1,2-quinonediazide compound, and a solvent.

Next, each of these components will be explained.

Purchased alkali-compatible novolak The co-condensed alkali-soluble novolak resin (hereinafter referred to as "resin J") used in the present invention is obtained by condensing phenols and aldehydes in the presence of a catalyst.

The phenols include phenol, 0-cresol, m-cresol, P-cresol, 2,5 xylenol, 3.5-xylenol, 2.3.5 trimethylphenol, resorcinol, 2-methylresorcinol,
Examples include bisphenol A, among which m-cresol, p-cresol, 25-xylenol, 3,5
-xylenol and 2,3.5-)limethylphenol are preferred.

Two or more of these phenols are used in combination.

Here, when m-cresol and p-cresol are used as phenols, the usage ratio of m-cresol and p-cresol is m-cresol/p-cresol=7
It is preferably 0/95 to 5/30 (mol%), more preferably 75 to 90/10 to 25 (mol%).

When the proportion of m-cresol used is less than 70%, the sensitivity of the composition tends to decrease and the developability tends to be poor. Furthermore, if the proportion of m-cresol used exceeds 95%, pattern shape, resolution, and developability tend to be poor. As the phenol, at least one selected from m-cresol, P-cresol, 2.5-xylenol, 3.5-xylenol, and 2゜3.5-trimethylphenol (hereinafter referred to as "xylenol") is used. In this case, the usage ratio of these is m-cresol/p-cresol/xylenol =
50-94/3-47/3-47 (mol%), preferably 60-9015-3515-35 (mol%).

When the proportion of m-cresol used is less than 50%, the sensitivity of the composition tends to decrease and the developability tends to be poor, and when it exceeds 94%, the pattern shape, resolution and developability tend to be poor. Furthermore, if the proportion of P-cresol used is less than 3%, the pattern shape tends to be poor, and if it exceeds 47%, the sensitivity tends to be poor. Furthermore, if the proportion of xylenol used is less than 3%, the pattern shape tends to be poor, and if it exceeds 47%, the sensitivity tends to be poor. Further, the polystyrene equivalent weight average molecular weight (hereinafter referred to as rMwJ) of the resin is preferably 3.500 to 15,000. Mw is 3,
When Mw is less than 500, pattern shape, resolution and developability tend to be poor, and when Mw exceeds 15,000, pattern shape, developability and sensitivity may be poor.

Examples of the aldehydes include formaldehyde,
Examples include benzaldehyde, furfural, acetaldebide, etc. Among these, formaldehyde is particularly preferred. These aldehydes can be used alone or in combination of two or more. The ratio of aldehydes used is 0.7 to 1 mole of phenols.
The amount is preferably 3 mol, more preferably 0.75 to 1.3 mol.

In the composition of the present invention, a resin is used in which the standard deviation of the composition of each condensate having different molecular weights (hereinafter simply referred to as "standard deviation of resin composition") is 5 or less.

If the standard deviation of the resin composition exceeds 5, the resolution and pattern shape will deteriorate. The standard deviation of the resin composition is preferably 3 or less.

As a method for producing the resin used in the present invention, for example, some of the phenols and aldehydes used in the condensation reaction are supplied to the reaction system and condensed in the presence of a basic catalyst. A method may be mentioned in which, after neutralizing by adding an acid and washing with water, the remaining phenols and aldehydes are supplied to the reaction system and condensed again in the presence of an acidic catalyst.

The ratio of the phenols and aldehydes condensed under a basic catalyst to the phenols and aldehydes used in the entire condensation reaction can be determined by the reactivity of the phenols and aldehydes used, reaction conditions, etc.

Specifically, when condensing at 10 to 200°C using m-cresol and p-cresol as phenols and formaldehyde as aldehydes, 0 to 30% of m-cresol used in the condensation reaction, p-cresol 70-100% of and 1-50% of formaldehyde
is supplied to the reaction system and condensed in the presence of a basic catalyst, and a 1 to 10% by weight aqueous solution of hydrochloric acid, nitric acid, sulfuric acid, etc. is added to neutralize it to precipitate the resin. After washing with water, the remaining m -Cresol (70-100%), p-cresol (0-30%)
, a method of adding formaldehyde (50 to 99%) and an acidic catalyst and condensing again can be exemplified.

Furthermore, when condensing at 10 to 200'C using m-cresol, p-cresol, and xylenols as phenols and formaldehyde as aldehyde, 0 to 30% of each of m-cresol and xylenol used in the condensation reaction is used. %, 70- of P-cresol
100% and 1-50% of formaldehyde are supplied to the reaction system and condensed in the presence of a basic catalyst, and hydrochloric acid, nitric acid,
After adding a 1-10% by weight aqueous solution of sulfuric acid etc. to neutralize and precipitate the resin, washing with water, remaining m-cresol, xylenols (70-100% each), p-cresol (0-100%)
30%), formaldehyde (50 to 99%) and an acidic catalyst to perform condensation again.

Examples of the basic catalyst include alkali metal or alkaline earth metal hydroxides such as sodium hydroxide, calcium hydroxide, and lithium hydroxide. The amount of these basic catalysts used is 1X per 1 mole of the total amount of phenols.
10-' to 5X10-' moles.

Examples of the acidic catalyst include inorganic acids such as hydrochloric acid, nitric acid, and sulfuric acid; organic acids such as formic acid, oxalic acid, and acetic acid. The amount of these acidic catalysts used is usually 1X10-S to 5X10-' moles per 1 mole of phenol.

In the condensation reaction, water is usually used as the reaction medium, but a hydrophilic solvent can also be used as the reaction medium. Examples of these hydrophilic solvents include alcohols such as methanol, ethanol, propatool, and butanol; and cyclic ethers such as tetrahydrofuran and dioxane. The amount of these reaction media used is usually 20 to too many parts by weight per 100 parts by weight of the reaction raw materials.

The reaction temperature of the condensation reaction can be adjusted as appropriate depending on the reactivity of the reaction raw materials, but is usually 10 to 200°C.
Preferably it is 70-130°C.

After the completion of the condensation reaction again, in order to remove the unreacted raw materials, acidic catalyst, and reaction medium present in the system, the temperature in the system is raised to 130 to 230°C, and the temperature is increased under reduced pressure, e.g. Volatile components are distilled off using approximately 20 to 50 wf 1 g, and the resin is recovered. After the condensation reaction is completed again, the reaction mixture is dissolved in the hydrophilic solvent, and a precipitant such as water, n-hexane, or n-hebutane is added to precipitate the resin, and the precipitate is separated. It can also be collected.

12-quinonediazide A Examples of the 1,2-quinonediazide compound used in the composition of the present invention include the following compounds. For example, 2,3.4-)lyhydroxybenzophenone-1,
2-naphthoquinonediazide-4-sulfonic acid ester,
2.3.4-1-lyhydroxybenzophenone-1,2-
Naphthoquinonediazide-5-sulfonic acid ester 7L/,
2. 4. 6-) Lyhydroxybenzophenone-1
, 2-naphthoquinonediazide 4-sulfonic acid ester,
2.4.6-trihydroxybenzophenone-1.2-
1,2-naphthoquinonediazide sulfonic acid ester of trihydroxybenzophenone such as naphthoquinonediazide-5-sulfonic ester, 2.2', 4.4'
-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2.2',
4.4'-tetrahydroxybenzophenone-1,2
-naphthoquinonediazide-5-sulfonic acid ester, 2
,3゜3',4-tetrahydroxybenzophenone-1
, 2-naphthoquinonediazide-4-sulfonic acid ester,
2.3.3',4-tetrahydroxybenzophenone-
1,2-naphthoquinonediazide-5-sulfonic acid: L ster, 2,3.4.4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4=sulfonic acid ester, 2,3.4.4'- Tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,2',3,4-tetrahydroxy-
4'-Methylbenzophenone-112-naphthoquinonediazide-4-sulfonic acid ester, 2.2', 3.4-
Tetrahydroxy-4'-methylhensiphenone-1,
2-naphthoquinonediazide 5-sulfonic acid ester, 2
．． 3,4.4'-tetrahydroxy-3'-methoxybenzophenone-1゜2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4.4'-tetrahydroxy-3'-methoxybenzophenone-1,2 -Naphthoquinonediazide-5-sulfonic acid esters of tetrahydroxybenzophenone can be mentioned.

Of these 1,2-quinonediazide compounds, 2.3
, 4.4'-tetrahydroxyhensiphenone 1.2-
naphthoquinonediazide-4-sulfonic acid ester, 2,
3,4.4'-tetrahydroxybenzphenone-1,
Preference is given to 2-naphthoquinonediazide-5-su/L, honic acid ester and 2,3.4-)lyhydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester.

These 1,2-quinonediazide compounds may be used alone or in combination of two or more.

In addition, in the 1.2-naphthoquinonediazide sulfonic acid ester of trihydroxybenzophenone or the 1.2-naphthoquinonediazide sulfonic acid ester of tetrahydroxybenzophenone, 1,2-naphthoquinonediazide bonded to trihydroxybenzophenone or tetrahydroxybenzophenone The number of sulfonic acid groups (condensation ratio) is preferably 1.5 to 3 on average in the case of trihydroxybenzophenone, and 2 to 4 on average in the case of tetrahydroxybenzophenone.

The amount of the 1.2-quinonediazide compound is usually 5 to 100 parts by weight, preferably 10 to 50 parts by weight, based on 100 parts by weight of the resin. If the amount of the l,2-quinonediazide compound is too small, it will be difficult to differentiate between the solubility of the irradiated area and the non-irradiated area in a developer consisting of an alkaline aqueous solution, making it difficult to carry out patterning. If the amount is too large, it may not be possible to completely decompose the added 1,2-quinonediazide compound by short-time radiation irradiation, and development with a developer consisting of an alkaline aqueous solution may be difficult.

Examples of the solvent used in the composition of the present invention include glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; diethylene glycol monomethyl ether; Diethylene glycols such as diethylene glycol monoethyl ether; propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol probyl ether acetate; aromatic hydrocarbons such as toluene and xylene; methyl ethyl ketone, cyclohexanone Ketones of the following types: methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl oxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3- Esters such as methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, 3-methyl-3-methoxybutylbutyrate, ethyl acetate, and butyl acetate can be used. These solvents can be used alone or in combination of two or more. Furthermore, benzyl ethyl ether, dihexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether,
Acetonylacetone, isophorone, caproic acid, caprylic acid, 1-octatool, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, T-butyrolactone, ethylene carbonate, propylene carbonate, phenyl High-boiling solvents such as cellosolve acetate can also be added.

Such a solvent is preferably used in an amount such that the solid content concentration is in the range of 5 to 50% by weight.

ffl planning■ The composition of the present invention may contain various additives such as aggravating agents and surfactants.

The aggravating agent is added to improve the sensitivity to radiation, and for example, 2H-pyrido-(3゜2-b
)-1,4-oxazin-3(4)1)-ones, 10
Examples include 14-pyrido-(3,2-b)-(1,4)-benzothiazines, urazoles, hydantoins, barbylic acids, glycine anhydrides, 1-hydroxybenzotriazoles, alloxanes, maleimides, etc. It will be done. The amount of these sensitizers added is usually 100 parts by weight or less per 100 parts by weight of the 1°2-quinonediazide compound.

The surfactant is blended to improve coating properties, such as striae and developability of the radiation irradiated area after dry coating film formation, and includes, for example, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether,
Nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate; trade name: Efthomp EF301
, EF303, EF352 (manufactured by Shin-Akita Kasei), Megafac F171, F172, F173, (manufactured by Dainippon Ink), Florado FC430, FC431 (manufactured by Sumitomo 3M), Asahi Guard AG710, Surflon S-382, 5C- 101,5C-102,5C-10
Fluorosurfactants such as 3,5C-104, 5C-105, and 5C-106 (manufactured by Asahi Glass Co., Ltd.); trade name KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), which is an organosiloxane polymer; acrylic acid-based or methacrylic acid-based ( Co)polymer product name Polyflow Na75, Na90. Na95
(manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.). The blending amount of these surfactants is usually 2% by weight or less based on the solid content of the composition.

Furthermore, the composition of the present invention may contain a dye, for example, 1,7-bis(3-methoxy-4-hydroxyphenyl)-1,6, to visualize the radiation irradiated area and reduce the effect of halation during radiation irradiation. -Dye having β-diketone structure such as heptadiene-3,5-dione; 5-hydroxy-4-(4methoxyphenylazo)-3-methyl-1
- A dye or pigment having a pyrazole or imidazole structure such as phenylpyrazole, and an adhesion aid for improving adhesion can also be blended. The compositions of the present invention may also contain storage stabilizers such as alkylamines such as diethylamine, triethylamine, butylamine, tributylamine, and the like. Furthermore, an antifoaming agent and the like may be added to the composition of the present invention, if necessary.

Distance m The composition of the present invention comprises the resin, 1. It is prepared by dissolving predetermined amounts of the 2-quinonediazide compound and various compounding agents in the above-mentioned solvent, and filtering the solution through a filter with a pore size of about 0.2 μm, for example.

The composition of the present invention can be applied to a substrate such as a silicon wafer, a silicon wafer coated with aluminum or an aluminum alloy by spin coating, flow coating, roll coating, etc. to form a radiation-sensitive layer. Pattern formation is carried out by irradiating the radiation-sensitive layer with radiation through, for example, a predetermined mask pattern and developing it with a developer.

In addition, in order to further enhance the effect of the present invention when using the composition of the present invention as a positive resist, the composition of the present invention was coated on a silicon wafer, and after brebake and exposure, 70 to 140 It is also possible to develop the film after heating it at C.

Examples of the developer for the composition of the present invention include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di-n- Propylaminomi triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, virol, piperidine, 1,8-diazabicyclo-(5,4,0)-7
-undecene, 1,5-diazabicyclo-(4,3,0
)-5-nonane or the like is used.

Further, an appropriate amount of a water-soluble organic solvent such as alcohols such as methanol and ethanol, or a surfactant may be added to the developer.

e. Examples Hereinafter, the present invention will be explained in detail by examples, but the present invention is not limited to these examples.

In addition, Mw in the examples is GPC columns manufactured by Toyo Soda Co., Ltd. (G2000H6, G3000H61, G4000H
Measured using gel verminion chromatography (hereinafter referred to as rGPC method) using monodisperse polystyrene as the standard, using a flow rate of 1.5 d/min, elution solvent tetrahydrofuran, and column temperature of 40°C. death,
The composition of the resin was determined using the pyrolysis gas chromatography method (hereinafter referred to as rPG).
It is called "C method". Equipment: Hitachi Model GC-6^, thermal decomposition temperature: 800°C, column temperature = 160°C, column length: 2m, carrier gas: helium, combustion gas: hydrogen, air, packing material: Chromosorb KGO2U
niport HP 80/100),
Further, the performance of the resist was evaluated by the following method.

Sensitivity: Using a Nikon-made NSR1505G4D reduction projection exposure machine, the exposure time was varied, and then development was performed at 25°C for 60 seconds using a tetramethylammonium hydroxide aqueous solution (2.4% by weight), and rinsed with water. Dry to form a resist pattern on the wafer, with a resist pattern of 0.6 μ-
1 line and space pattern (ILIS)
:1 exposure time (hereinafter referred to as "optimal exposure time (Hop
) was calculated.

The dimensions of the minimum resist pattern that was resolved when exposed at resolution 2 and the optimum exposure time were measured using a scanning electron microscope.

Remaining film rate (2) The thickness of the remaining pattern at the optimum exposure time was divided by the thickness of the applied resist film, this value was multiplied by 100, and the unit of % was given.

The presence or absence of developable varnish scum and development residue was examined.

Pattern shape: Measure the dimensions of the cross-sectional shape of the 0.6 μI residual pattern (dimensions a and b shown in Figure 1) with a scanning electron microscope at the optimum exposure time, and calculate a / b.
=0.85 to 1 was considered to be a good pattern shape.

Example 1 27.0 g of P-cresol (0,2
The separable flask was immersed in an oil bath, and the system was reacted for 40 minutes while maintaining the temperature at 100°C. After cooling to room temperature, the resin was neutralized with a 5% by weight aqueous HCffi solution. was precipitated and washed with water. Next, water was removed by decantation, and 108.1 g (1,
00 mole) and oxalic acid 0.83 g (0,00 mole)
66 mol) was continuously charged into a separable flask as the reaction progressed, and the reaction was allowed to proceed for 1 hour.

Next, the oil bath temperature was raised to 180° C., and at the same time the pressure inside the separable flask was reduced to remove water, unreacted formaldehyde, m-cresol, p-cresol, and oxalic acid. The melted novolac resin (hereinafter referred to as "resin A") was then returned to room temperature and recovered.

This resin A was dissolved in tetrahydrofuran, and the Mw was measured by GPC method and found to be 8,900.

Furthermore, add 2 resin A long and 300 g of methanol.
1. Mix in a flask and stir for 24 hours to dissolve.
Next, 40g of water was added to precipitate the resin (hereinafter referred to as “Resin A-
1) were separated. Next, 20 g of water was further added and the precipitated resin (hereinafter referred to as "resin A-2") was separated. After repeating this process to separate the resin and adding a total of 220g of water, the solution is as follows:
After heating and concentrating, the final component C (hereinafter referred to as "resin ALJ") was obtained.After that, the Mw and resin composition (m-cresol/p-cresol) of each component were investigated by GPC method and PGC method, and the results are as shown in the table below. It became so.

Resin composition [-cresol/p-cresol (mole%)
)] [where n is the number of samples, ma is the average composition (arithmetic mean) of all samples, and xl is the composition of the i-th sample. ] As a result, the resin composition of Resin A was m-cresol/p-cresol=80.2/19.8 (mol %), and the standard deviation of the resin composition was 1.40.

Note that the standard deviation of the resin composition was calculated using the following formula.

100 g of the resin A thus obtained and 2.3.
4. 1 mole of 4'-tetrahydroxybenzophenone and 1
, 2-naphthoquinonediazide-5-sulfonic acid chloride condensate (hereinafter referred to as "1,2-quinonediazide (1
), 30 g of ethyl cellosolve acetate 3
After dissolving for 1 hour, the mixture was filtered through a membrane filter with a pore size of 0.2 μm to prepare a composition.

This composition was then applied to a silicon wafer and breaked on a hot plate at 90°C for 2 minutes, 1.2
After forming a resist film with a thickness of μm, it was exposed using a Nikon reduction projection exposure machine (NSR-1505G4D) with varying exposure times, and developed with a tetramethylammonium hydroxide aqueous solution (2.4% by weight). , rinsed with water.

The obtained resist pattern was measured using a scanning electron microscope to determine the optimum exposure time (Eop). The performance of the composition at the optimum exposure time was evaluated, and the results are shown in Table 1 together with the resin used.

Example 2 100 g of resin A obtained in Example 1, and 1 mol of 2,3,4°4'-tetrahydroxybenzophenone and 1,2
-naphthoquinone diazide-5-sulfonic acid chloride 3.
Condensate with 5 mol (hereinafter referred to as 1,2-quinonediazide (2)
In the same manner as in Example 1 except that 30 g of
Compositions were prepared, performance was evaluated, and the results are shown in Table 1 together with the resins used.

Example 3 (1) A co-condensate of m-cresol and p-cresol with formaldehyde. Resin PS- manufactured by Gunei Chemical Co., Ltd.
100 g of 6822M and 300 g of methanol were mixed in a 22 flask and stirred for 24 hours to dissolve.

Next, 40g of water was added to precipitate the resin (hereinafter referred to as “Resin P-
1) were separated. Next, 20 g of water was further added and the precipitated resin (hereinafter referred to as "resin P-2") was separated. After repeating this process to separate the resin and adding a total of 220g of water, the solution is as follows:
The final component (hereinafter referred to as "resin PL") was obtained by heating and concentrating.The Mw and composition of each component (m-cresol/P-
Cresol) was investigated using the GPC method and PGC method, and found that
It became as shown in the table below.

As a result, the resin composition of the resin PS-6822M was m-talesol/P-cresol=80.0/20.0 (mol %), and the standard deviation of the resin composition was 1.35.

In addition, Mw of resin PS-6822 was 9200 when measured by GPC method.

(2) A composition was prepared in the same manner as in Example 1, except that 100 g of resin PS-6822M manufactured by Gunei Kagaku Co., Ltd. and 30 g of 1゜2-quinonediazide (1) were used, and the performance was evaluated. The results are shown in Table 1 together with the resins used.

Example 4 Resin ps6828B manufactured by Gunei Kagaku Co., Ltd., which is a co-condensate of m-cresol and p-cresol with formaldehyde
[Resin composition acid dim-cresol/p-cresol-90
, 0/10.0 (mol%), standard deviation of the resin composition determined in the same manner as in Example 3: 1,40) A composition was prepared in the same manner as in Example 1, except that 100 g was used, and the performance was evaluated. were evaluated, and the results are shown in Table 1 together with the resins used.

In addition, Mw of resin PS-68288 was 10.100 when measured by GPC method.

Example 5 100 g of resin PS-6822M manufactured by Gunei Chemical Co., Ltd. and 2.3°4.4'-tetrahydroxybenzophenone 1
Except that 25 g of a condensate of 1,2-naphthoquinonediazide-5-sulfonic acid chloride (hereinafter referred to as [1,2-quinonediazide (3))] and 310 g of ethyl 2-hydroxypropionate were used. A composition was prepared in the same manner as in Example 1, and its performance was evaluated. The results are shown in Table 1 together with the resin used.

Example 6 Resin PS-68288100g manufactured by Gunei Chemical Co., Ltd., and 1
．． A composition was prepared in the same manner as in Example 1 except that 30 g of 2-quinonediazide (2) was used, and the performance was evaluated. The results are shown in Table 1 together with the resin used.

Example 7 100 g of resin PS-6828B manufactured by Gunei Chemical Co., Ltd., and a condensate of 1 mol of 2.34.4'-tetrahydroxybenzophenone and 2.5 mol of 1.2-naphthoquinonediazide-5-sulfonic acid chloride (hereinafter Example 1 except that 35 g of "l,2-quinonediazide (4)" was used.
A composition was prepared in the same manner as above, and its performance was evaluated, and the results are shown in Table 1 together with the resin used.

Example 8 100 g of resin PS-6828B manufactured by Gunei Chemical Co., Ltd. and 1 of 2,3°4.4'-tetrahydroxybenzophenone
In the same manner as in Example 1, except that 30 g of a condensate of 2.5 moles of 1.2-naphthoquinonediazide-4-sulfonic acid chloride (hereinafter referred to as "1.2-quinonediazide (5)") was used. Compositions were prepared, performance was evaluated, and the results are shown in Table 1 together with the resins used.

Comparative Example 1 86.5 g of m-cresol (0,8
0 mol) P-cresol 21.6 g
(0.20 mol) from which water, unreacted formaldehyde, etc. were removed in the same manner as in Example 1 (hereinafter referred to as "Resin X").
) was obtained. Next, by GPC method, Mw of resin
When measured, it was 8500. In addition, by the PGC method, the composition of resin 79.9/20.1 (mol%)
, standard deviation of resin composition: 7.33). The results are shown in the table below.

and oxalic acid 0.83 g (0,
0066 mol), immersed the separable flask in an oil bath, and reacted for 2 hours while maintaining the internal temperature at 100°C. [-Cresol/p Cresol (mol%)] Resin X 100g , and 1,2-quinonediazide (3
) A composition was prepared in the same manner as in Example 1 except that 30 g was used, and the performance was evaluated. The results are shown in Table 1 together with the resin used.

10 Effects of the Invention According to the present invention, it is possible to provide a radiation-sensitive resin composition suitable for a positive resist having high resolution, excellent pattern shape, good developability, and high sensitivity.

[Brief explanation of drawings]

FIG. 1 shows a cross section of the resist pattern.

Claims (1)

[Claims] A radiation-sensitive resin composition containing a co-condensed alkali-soluble novolak resin, characterized in that the standard deviation of the composition of each condensate having a different molecular weight of the co-condensed alkali-soluble novolak resin is 5 or less. thing.