JP2000066406A - Coating fluid for forming positive type resist film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a high resolution and high sensitivity resist compsn. which eliminates a harmful effect due to an amine, is faithful to a mask pattern and does not sustain the damage of pattern shape during, the time from image formation to post exposure baking, that is, has excellent aging stability. SOLUTION: (A) A component which generates an acid when irradiated, (B) a resin component whose solubility to an aq. alkali soln. is increased by the action of the acid and (C) an amine component are dissolved as basic components in an org. solvent and (D) an org. carboxylic acid is added to the resultant soln. to obtain the objective coating fluid for forming a positive type resist film. The contents of the components C and D are 0.01-1 wt.% and 0.01-5 wt.%, respectively, based on the weight of the component B. The coating fluid is a chemical amplification type resist compsn., forms a resist pattern having good aging stability and is suitable for fine working in the production of super- LSI because it has high resolution and high sensitivity.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a mask pattern which is faithful to an image forming exposure and is used for PEB (POSTE E).
The present invention relates to a coating solution for forming a chemically amplified positive resist film with high resolution and high sensitivity, which can provide a resist pattern having good stability up to XPOSURE BAKE, that is, stable stability with time of the deposition.

[0002]

2. Description of the Related Art Conventionally, in the process of manufacturing semiconductor devices such as ICs and LSIs, fine processing by lithography using a photoresist composition has been performed. This is a resist pattern obtained by forming a thin film of a photoresist composition on a silicon wafer, irradiating it with actinic rays such as ultraviolet rays through a mask pattern on which a semiconductor device pattern is drawn, and developing it. Is a method of etching the silicon wafer using as a protective film. As a suitable photoresist composition used in this method, a positive photoresist composition in which a photosensitive component comprising a quinonediazide group-containing compound is combined with an alkali-soluble novolak resin for forming a coating film is known.

However, in recent years, the degree of integration of semiconductor devices has been rapidly increased, and in the manufacture of VLSI and the like, the processing accuracy of an ultra-fine pattern in a sub-micron region or a quarter-micron region has been required. The exposure wavelength is accordingly changed from g-line to i-line or deep-UV.
In addition, there is a tendency for the wavelength to be shorter, such as in excimer laser light such as KrF laser light.
Lithography using eep-UV or excimer laser light has become an important processing technique in this field.

The novolak-quinonediazide resist for g-line and i-line is a chemically amplified resist using polyhydroxystyrene as a base resin, which has a low absorption for deep-UV and excimer laser light because of its large absorption. Is getting attention.

This chemically amplified resist is a resist utilizing the catalytic action of an acid generated by irradiation, and has a high sensitivity and resolution, and is a compound capable of generating an acid upon irradiation with a small amount of radiation (hereinafter referred to as a resist). Acid generator). Incidentally, there are two types of chemically amplified resists, a positive type and a negative type. Positive resists are generally a resin component (hereinafter referred to as a resin component) whose solubility in an alkaline aqueous solution is increased by the action of an acid generator and this acid. ). On the other hand, a negative resist is composed of an acid generator, a crosslinking agent, and an alkali-soluble resin component.

With respect to such a chemically amplified positive resist, recently, due to a reaction mechanism between an acid generator and a dissolution inhibiting group peculiar to the chemically amplified resist, an acid scavenger is added as a third component. Attempts have been made to improve the resist properties by preventing diffusion of the generated acid.
As an example, those to which an amine is added have been proposed (JP-A-5-127369, JP-A-5-232706, JP-A-5-249662, JP-A-5-28).
9322, JP-A-6-317902, JP-A-7-92678, JP-A-7-120929).

However, the addition of an amine as described above improves the resolution to some extent, but is still insufficient for manufacturing a semiconductor device having a super-integration of 64 megabits and 1 gigabit class, and also has a high sensitivity. I cannot help but drop.

On the other hand, it has been attempted to add a carboxylic acid alone to a chemically amplified resist composition for the purpose of improving sensitivity and improving the shape of a resist pattern (see JP-A-5-181279 and JP-A-5-181279). This is not practical because the shape of the resist pattern is not sufficiently improved and the resolution is low.

In addition, a substrate provided with a thin film of silicon nitride, titanium nitride, aluminum / silicon / copper alloy, tungsten, or the like is used in the manufacture of a semiconductor device. There is a demand for a resist composition that may be pulled and is not affected by the presence of such a thin film.

[0010]

SUMMARY OF THE INVENTION The present invention is particularly directed to a chemically amplified resist composition containing an amine, which eliminates the above-mentioned adverse effects based on the amine, is faithful to a mask pattern, and is capable of removing PEB ( POST E
The purpose of the present invention is to obtain a resist composition which does not lose its pattern shape during XPOSURE BAKE, that is, has excellent stability over time, and has high resolution and high sensitivity.

[0011]

The present inventors have conducted various studies on a chemically amplified resist composition containing an amine as a component, and as a result, selected the amine content within a specific range, By adding a specific proportion of organic carboxylic acid, it is possible to provide a resist pattern having a rectangular cross section that is faithful and accurate to the mask pattern, and that a coating solution exhibiting high sensitivity and high resolution can be obtained. The present invention has been made based on this finding.

That is, the present invention comprises, as basic components, (A) a component that generates an acid upon irradiation with radiation, (B) a resin component whose solubility in an alkaline aqueous solution is increased by the action of an acid, and (C) an amine component. Organic solvent solution
(D) An organic carboxylic acid is added, and the content of the component (C) is 0.01 to 1% by weight based on the weight of the component (B), and the content of the component (D) is 0.01 to 5%. It is intended to provide a coating solution for forming a positive resist film, which is characterized in that the amount is% by weight.

The coating solution for forming a positive resist film of the present invention comprises: (A) a component which generates an acid upon irradiation with radiation;
The basic components are a resin component and an amine component (C) whose solubility in an aqueous alkaline solution is increased by the action of an acid, and such basic components are already known.

The component (A) and the component (B) in the coating liquid of the present invention are arbitrarily selected from the component (A) and the component (B) used in the conventionally known basic composition. Can be.

Examples of such component (A) include (a) bis (p-toluenesulfonyl) diazomethane, methylsulfonyl-p-toluenesulfonyldiazomethane, 1-cyclohexylsulfonyl-1- (1,1
-Dimethylethylsulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane,
Bis (1-methylethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (2,4-dimethylphenylsulfonyl) diazomethane, bis (4-ethylphenylsulfonyl) diazomethane, bis (3-methylphenylsulfonyl) diazomethane, bis Bis-sulfonyldiazomethanes such as (4-methoxyphenylsulfonyl) diazomethane, bis (4-fluorophenylsulfonyl) diazomethane, bis (4-chlorophenylsulfonyl) diazomethane, bis (4-tert-butylphenylsulfonyl) diazomethane, (b) 2 -Methyl-2- (p-toluenesulfonyl) propiophenone, 2- (cyclohexylcarbonyl) -2- (p-toluenesulfonyl) propane, 2-
Sulfonylcarbonylalkanes such as methanesulfonyl-2-methyl- (p-methylthio) propiophenone and 2,4-dimethyl-2- (p-toluenesulfonyl) pentan-3-one; (c) 1-p-toluene Sulfonyl-1-cyclohexylcarbonyldiazomethane, 1-
Diazo-1-methylsulfonyl-4-phenyl-2-butanone, 1-cyclohexylsulfonyl-1-cyclohexylcarbonyldiazomethane, 1-diazo-1-cyclohexylsulfonyl-3,3-dimethyl-2-butanone, 1-diazo-1 -(1,1-dimethylethylsulfonyl) -3,3-dimethyl-2-butanone, 1-acetyl-1- (1-methylethylsulfonyl) diazomethane, 1-diazo-1- (p-toluenesulfonyl)-
3,3-dimethyl-2-butanone, 1-diazo-1-benzenesulfonyl-3,3-dimethyl-2-butanone,
1-diazo-1- (p-toluenesulfonyl) -3-methyl-2-butanone, cyclohexyl 2-diazo-2- (p-toluenesulfonyl) acetate, tert-butyl 2-diazo-2-benzenesulfonylacetate, 2 -Diazo-
2-isopropyl 2-methanesulfonyl acetate, 2-diazo-
Sulfonylcarbonyldiazomethanes such as cyclohexyl 2-benzenesulfonylacetate and tert-butyl 2-diazo-2- (p-toluenesulfonyl) acetate;
(D) 2-nitrobenzyl p-toluenesulfonate, p
-Toluenesulfonic acid 2,6-dinitrobenzyl, p-
Nitrobenzyl derivatives such as 2,4-dinitrobenzyl trifluoromethylbenzenesulfonate, (e) methanesulfonic acid ester of pyrogallol, benzenesulfonic acid ester of pyrogallol, p-toluenesulfonic acid ester of pyrogallol, p-methoxybenzene of pyrogallol Sulfonates, mesitylenesulfonate of pyrogallol, benzylsulfonate of pyrogallol, methanesulfonate of alkyl gallate, benzenesulfonate of alkyl gallate, p-toluenesulfonate of alkyl gallate, alkyl gallate Such as p-methoxybenzenesulfonate, mesitylenesulfonate of alkyl gallate and benzylsulfonate of alkyl gallate Carboxymethyl compound with an aliphatic or esters of aromatic sulfonic acids and the like. The alkyl group in the alkyl gallate has 1 to 1 carbon atoms.
Preferred are 15 alkyl groups, especially octyl and lauryl groups. In addition, (f) onium salts such as bis (p-tert-butylphenyl) iodonium trifluoromethanesulfonate and triphenylsulfonium trifluoromethanesulfonate can also be used.
Among these compounds, bissulfonyldiazomethanes are particularly preferred, and bis (cyclohexylsulfonyl) diazomethane and bis (2,4-dimethylphenylsulfonyl) diazomethane are particularly preferred. These compounds may be used alone or in combination of two or more.

On the other hand, in the basic composition of the coating solution of the present invention,
There is no particular limitation on the resin component whose solubility in an aqueous alkali solution is increased by the action of an acid used as the component (B). Among the known synthetic resins conventionally used as a resin component in a chemically amplified positive resist, there is no particular limitation. Can be arbitrarily selected and used. Examples of such a material include polyhydroxystyrene in which a hydrogen atom of a hydroxyl group is substituted with a protecting group. Examples of this protective group include a tert-butoxycarbonyl group,
t-butyl group, tert-amyloxycarbonyl group,
And alkoxyalkyl group, tetrahydropyranyl group,
Acetal groups such as a tetrahydrofuranyl group are exemplified. Polyhydroxystyrene in which a hydrogen atom of a hydroxyl group is substituted by the above-mentioned protecting group may be obtained by copolymerizing a hydroxystyrene monomer and a styrene monomer having a protecting group according to a conventional method, or by chemically forming a protecting group on polyhydroxystyrene. May be introduced. Specifically, tert-
Copolymer of butoxycarbonyloxystyrene and p-hydroxystyrene (JP-A-2-209977), p-tetrahydropyranyloxystyrene and p-hydroxystyrene
Copolymer with hydroxystyrene (JP-A-2-1984)
No. 7), a copolymer of tert-butoxystyrene and p-hydroxystyrene (JP-A-2-62544), a polyhydroxystyrene in which a hydroxyl group is protected by an acetal group (JP-A-3-282550). Polyhydroxystyrene in which a hydroxyl group is protected by an alkoxyalkyl group (JP-A-5-24968)
No. 2), and these polyhydroxystyrenes can be used alone or in combination of two or more. Preferred resin components are (a) 10 to 10 hydroxyl groups.
Polyhydroxystyrene in which 60 mol% of hydrogen atoms are protected by a tert-butoxycarbonyl group and (ii) 10 to 60 mol% of hydrogen atoms in hydroxyl group are, for example, 1-methoxyethyl group, 1-ethoxyethyl group, -N-propoxyethyl group, 1-isopropoxyethyl group, 1-n-butoxyethyl group, 1-isobutoxyethyl group, 1-
(1,1-dimethylethoxy) -1-methylethyl group,
1-methoxy-1-methylethyl group, 1-ethoxy-1
-Methylethyl group, 1-n-propoxy-1-methylethyl group, 1-isobutoxy-1-methylethyl group, 1-
It is a mixture with a polyhydroxystyrene protected with an alkoxyalkyl group such as a methoxy-n-propyl group and a 1-ethoxy-n-propyl group. (B) Among the alkoxyalkyl groups of the component, 1-ethoxyethyl group and 1-ethoxyethyl group
A methoxy-n-propyl group is preferred because sensitivity and resolution are improved in a well-balanced manner. The mixing ratio is 10 to 70% by weight of the component (A) and 30 to 90% by weight of the component (B), preferably 20 to 50% by weight of the component (A) and 50% by weight of the component (B).
８０80% by weight is desirable. In such a resin component, the acid generated from the component (A) removes the tert-butoxycarbonyl group and the above-mentioned alkoxyalkyl group as protecting groups, and these dissolve the resin component and the tert-butoxycarbonyl group. Inhibition ability is moderately balanced, and high sensitivity, high resolution and high heat resistance can be achieved. When the resin component composed of the mixture is used, if the mixing ratio of the component (a) and the component (b) is out of the above range, these characteristics are undesirably deteriorated.

The component (A) is obtained by converting a hydrogen atom of a hydroxyl group of polyhydroxystyrene with, for example, di-tert-butyl-dicarbonate according to a known reaction.
substituted and protected with a t-butoxycarbonyl group,
Its protection rate is 10 to 60 mol%, preferably 20 to 50 mol%.
A mole percent range is desirable. If the protection ratio is less than 10 mol%, a resist pattern excellent in profile shape cannot be obtained, and if it exceeds 60 mol%, sensitivity is undesirably reduced.

On the other hand, the component (b) converts the hydrogen atom of the hydroxyl group of the polyhydroxystyrene into, for example, 1-chloro-1-ethoxyethane or 1-chloro-1-methoxypropane, etc., according to a known reaction. , And the degree of protection is desirably 10 to 60 mol%, preferably 20 to 50 mol%. If the protection ratio is less than 10 mol%, a pattern having an excellent profile cannot be obtained, and if it exceeds 60 mol%, the sensitivity of the resist is undesirably reduced.

Further, the weight average molecular weight of the component (B) is determined by gel permeation chromatography (GP
C), usually 3,000-
It is in the range of 30,000. This weight average molecular weight is 3,
If it is less than 000, the coating properties are inferior, and if it exceeds 30,000, the solubility in an aqueous alkali solution tends to decrease.

In the coating solution of the present invention, the component (A) is generally added in a proportion of 1 to 20 parts by weight, preferably 2 to 10 parts by weight, based on 100 parts by weight of the component (B). If the amount is less than 1 part by weight, the amount of acid generated upon irradiation with radiation is insufficient, and sufficient action is not exhibited. If the amount is more than 20 parts by weight, it is difficult to dissolve in a solvent and (A) ) It becomes difficult to mix with the components.

Next, in the basic components of the coating solution of the present invention,
As the amine component used as the component (C), any one can be selected from those used in the conventionally known basic components. Examples of such an amine component include an aliphatic amine, an aromatic amine, and a heterocyclic amine. Here, examples of the aliphatic amine include methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, n-propylamine, di-n-propylamine, tri-n-propylamine, and isopropylamine. Examples of the aromatic amine include benzylamine, aniline, N-methylaniline,
N, N-dimethylaniline, o-methylaniline, m-
Examples include methylaniline, p-methylaniline, N, N-diethylaniline, diphenylamine, di-p-tolylamine and the like. Further, as a heterocyclic amine,
Examples thereof include pyridine, o-methylpyridine, o-ethylpyridine, 2,3-dimethylpyridine, 4-ethyl-2-methylpyridine, and 3-ethyl-4-methylpyridine. Those having a boiling point, for example, aliphatic amines such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine and triethylamine are preferred.

These may be used alone or in combination of two or more. Among them, triethylamine alone is particularly preferred because of its excellent resist pattern shape and stability over time. .

In the coating liquid of the present invention, the component (C) is used in an amount of 0.01 to 1% by weight, preferably 0.05 to 0.5% by weight based on the weight of the component (B). Be blended. Accordingly, unnecessary diffusion of the acid generated by the irradiation of the radiation can be prevented, and a resist pattern faithful to the mask pattern can be obtained, and the resolution and the stability over time can be improved. If the compounding amount of the component (C) is less than 0.01% by weight, sufficient resolution cannot be obtained,
If it exceeds 1% by weight, the sensitivity is deteriorated.

The coating liquid of the present invention is prepared by adding an organic solvent solution containing the above components (A), (B) and (C) as a basic composition,
(D) An organic carboxylic acid is added as a component. Examples of the organic solvent used for preparing the organic solvent solution include ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, and 2-heptanone; Glycol, ethyl glycol monoacetate, diethylene glycol, diethylene glycol monoacetate, propylene glycol, propylene glycol monoacetate, dipropylene glycol or dipropylene glycol monoacetate monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether or monophenyl ether Polyhydric alcohols and their derivatives, cyclic ethers such as dioxane, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate Le, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate,
Esters such as ethyl ethoxypropionate can be mentioned. These may be used alone or as a mixture of two or more.

The organic carboxylic acid of the component (D) is not particularly limited, and may be, for example, a saturated or unsaturated aliphatic carboxylic acid, alicyclic carboxylic acid, oxycarboxylic acid, alkoxycarboxylic acid, ketocarboxylic acid, or aromatic carboxylic acid. Acids and the like can be mentioned. Here, as the saturated aliphatic carboxylic acid, for example, formic acid, acetic acid, propionic acid, butyric acid,
Mono- or polyvalent carboxylic acids such as isobutyric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid and the like can be mentioned. As unsaturated aliphatic carboxylic acids, for example, acrylic acid, crotonic acid, isocrotonic acid, 3-butenoic acid, methacrylic acid, 4-pentenoic acid, propionic acid, 2-butyric acid, maleic acid, fumaric acid, acetylene carboxylic acid, etc. Is mentioned. Examples of the alicyclic carboxylic acid include 1,1-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid,
1,1-cyclohexyldiacetic acid and the like can be mentioned.

Further, as the oxycarboxylic acid, for example, oxyacetic acid and the like, and as the alkoxycarboxylic acid, for example,
For example, methoxyacetic acid, ethoxyacetic acid and the like, and as the ketocarboxylic acid, for example, pyruvic acid and the like can be mentioned. On the other hand, examples of the aromatic carboxylic acid include p-hydroxybenzoic acid, o-hydroxybenzoic acid, and 2-hydroxy-3
-Nitrobenzoic acid, 3,5-dinitrobenzoic acid, 2-nitrobenzoic acid, 2,4-dihydroxybenzoic acid, 2,5
-Dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 2-vinylbenzoic acid, 4-vinylbenzoic acid, phthalic acid, terephthalic acid, isophthalic acid, etc. And aromatic carboxylic acids having a substituent such as a hydroxyl group, a nitro group, a carboxyl group, and a vinyl group.

Among these organic carboxylic acids, aromatic carboxylic acids are preferable because of their characteristics of having an appropriate acidity and being non-volatile. Of these, salicylic acid is particularly preferred because of its solubility in resist solvents and good resist patterns for various substrates.

In the coating solution of the present invention, the component (D) is used in an amount of 0.01 to 5% by weight, preferably 0.05 to 2.0% by weight, based on the weight of the component (B). It is compounded by. Moreover, 2 to 2 of the amine of the component (C)
It is advantageous to use 20 times the weight. Thereby, (C)
The sensitivity can be prevented from deteriorating due to the components, the resolution can be further improved, and a good resist pattern can be formed on various substrates. If the compounding amount of the component (D) is less than the above range, a good resist pattern cannot be formed on various substrates, and if it is too large, the film loss of an unexposed portion during development becomes large.

In the present invention, the reason why the improvement of the resist properties is achieved by adding a specific amount of an organic carboxylic acid is not always clear, but it is probably not due to the buffering action by a weak acid and a strong base. It is thought.

The coating solution for forming a positive resist film of the present invention may further contain, if desired, additives that are miscible, for example, an additional resin for improving the performance of the resist film, a plasticizer, a stabilizer, a coloring agent, A commonly used substance such as a surfactant can be added and contained.

As a method of using the coating solution for forming a positive resist film of the present invention, a conventional method of forming a resist pattern by a photoresist technique is used. A preferred example thereof will be described below. First, a coating solution obtained by dissolving, in a solvent, the above-mentioned components (A), (B), (C) and (D) and various additives, if necessary, on a support such as a silicon wafer. Is coated with a spinner or the like, and dried to form a photosensitive layer.
-Irradiation with UV and excimer laser light through a desired mask pattern is performed, followed by development processing using a developing solution, for example, an alkaline aqueous solution such as a 1 to 10% by weight aqueous solution of tetramethylammonium hydroxide. With this forming method, an image faithful to the mask pattern can be obtained.

[0032]

The coating solution for forming a positive resist film according to the present invention is of a chemically amplified type and is faithful to a mask pattern, and can be subjected to PEB (POST EXPO) from image forming exposure.
It can provide a resist pattern with good stability up to SURE BAKE, that is, stable stability over time, and has high resolution and sensitivity, and is suitable for microfabrication in the manufacture of VLSI. Used for

[0033]

Next, the present invention will be described in more detail with reference to examples. The physical properties of the coating solution for forming a positive resist film were determined as follows. (1) Sensitivity: A sample was applied on a silicon wafer using a spinner, and this was applied on a hot plate at 90 ° C. and 90 ° C.
After drying for a second, a resist film having a thickness of 0.7 μm was obtained. The film was exposed using a reduction projection exposure apparatus NSR-2005EX8A (manufactured by Nikon Corporation) at a dose of 1 mJ / cm ² and then exposed to PEB (POST) at 110 ° C. for 90 seconds.
(EXPOSURE BAKE) and 23.38% by weight aqueous solution of tetramethylammonium hydroxide.
When the film was developed at 60 ° C. for 60 seconds, washed with water for 30 seconds, and dried, the minimum exposure time at which the film thickness of the exposed portion after development became 0 was measured as sensitivity in mJ (energy amount) per unit area.

(2) Resolution: The resolution is shown by the limit resolution at the exposure dose for reproducing a mask pattern of 0.25 μm. (3) Mask pattern fidelity: O when the resist pattern was obtained according to the mask pattern, O when the resist pattern was slightly thinner than the mask pattern, and the resist pattern was extremely thinner than the mask pattern The case was evaluated as x.

(4) Pattern shape for various substrates: a substrate (substrate) in which a silicon nitride film (SiN) is formed on a silicon wafer, titanium nitride (Ti)
0.25 μm instead of the substrate (substrate) on which N) was formed and the substrate (substrate) on which the BPSG insulating film was formed, respectively.
The cross-sectional shape of the resist pattern was observed by an SEM (scanning electron microscope) photograph, and a rectangular shape was designated as A, and a skirted shape was designated as B.

(5) Stability of Deposition with Time In (1), after performing the operations up to the exposure, leave the device for 60 minutes, and then perform the same operation to change the cross-sectional shape of the 0.25 μm resist pattern to SEM (scanning type). electronic microscope)
Observation was carried out by a photograph, and the case where the resist pattern was obtained in accordance with the mask pattern was evaluated as ○, and the case where the resist pattern became thinner than the mask pattern was evaluated as ×.

Example 1 Polyhydroxystyrene having a weight-average molecular weight of 10,000 in which 39 mol% of hydroxyl groups were substituted by a tert-butyloxycarbonyloxy group and a weight-average molecular weight in which 39 mol% of hydroxyl groups were substituted by an ethoxyethoxy group 10,000
Mixture 1 with polyhydroxystyrene in a weight ratio of 3: 7
After dissolving 00 parts by weight, 7 parts by weight of bis (cyclohexylsulfonyl) diazomethane, 0.1 part by weight of triethylamine, and 0.5 part by weight of salicylic acid in 490 parts by weight of propylene glycol monomethyl ether acetate,
This was filtered using a membrane filter having a pore size of 0.2 μm to prepare a coating solution for forming a positive resist film.

Table 1 shows the results of evaluation of the above characteristics.

Examples 2 to 5 The same procedures as in Example 1 were carried out except that triethylamine and the amount thereof were changed to the amines and amounts shown in Table 1, and salicylic acid and the amount were changed to the organic carboxylic acids and amounts shown in Table 1. In the same manner as in Example 1, a coating solution for forming a positive resist film was obtained. Table 1 shows the results of the evaluation of the above characteristics.
Shown in

Comparative Example 1 A coating solution for forming a positive resist film was obtained in the same manner as in Example 1 except that salicylic acid was omitted.
Table 1 shows the results of evaluation of the above-mentioned characteristics.

Comparative Example 2 A coating solution for forming a positive resist film was obtained in the same manner as in Example 1 except that triethylamine was omitted. Table 1 shows the results of the evaluation of the above characteristics.
Shown in

Comparative Example 3 A coating solution for forming a positive resist film was obtained in the same manner as in Example 1, except that the amount of salicylic acid was changed as shown in Table 1. Table 1 shows the results of evaluation of the above-mentioned characteristics.

[0043]

[Table 1]

In Comparative Example 3, the film loss of the unexposed portion was large.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Akiyoshi Yamazaki 150 Nakamurako Nakahara-ku, Kawasaki City, Kanagawa Prefecture Inside Tokyo Ohka Kogyo Co., Ltd. (72) Inventor Toshiaki Nakayama 150 Nakamurako, Nakahara-ku, Kawasaki-shi, Kanagawa Prefecture Tokyo Ohka Kogyo Co., Ltd.

Claims (6)

[Claims] 1. An organic solvent solution containing (A) a component that generates an acid upon irradiation with radiation, (B) a resin component whose solubility in an aqueous alkali solution increases by the action of an acid, and (C) an amine component as basic components. , An organic carboxylic acid (D) is added thereto, and the content of the component (C) is 0.01 to 1% by weight based on the weight of the component (B), and the content of the component (D) is 0.01 to 1% by weight. A coating solution for forming a positive resist film, wherein the coating solution is contained in an amount of about 5% by weight. 2. The composition according to claim 2, wherein the component (D) is 2 to 2 parts.
The coating solution for forming a positive resist film according to claim 1, which is 0 times the weight. 3. The coating solution for forming a positive resist film according to claim 1, wherein the component (C) is an aliphatic amine. 4. The coating solution for forming a positive resist film according to claim 3, wherein the aliphatic amine is triethylamine. 5. The coating solution for forming a positive resist film according to claim 1, wherein the organic carboxylic acid is an aromatic carboxylic acid. 6. The coating solution for forming a positive resist film according to claim 5, wherein the aromatic carboxylic acid is salicylic acid.