JPH10133379A - Positive chemically amplifying photosensitive resin composition and production of resist image - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain good characteristics of sensitivity, resolution and heat resistance by incorporating a resin soluble with an alkali soln., a specified trihydroxybenzene compd., a compd. which produces acid by irradiation of active chemical rays, and a specified compd. SOLUTION: This positive chemically amplifying photosensitive resin compsn. contains a resin soluble with an alkali soln., a trihydroxybenzene compd. expressed by the formula, a compd. which produces acid by irradiation of active chemical rays, and a compd. having an acid decomposing group in side chains which increases solubility with an alkali soln. by the reaction of acid catalyst. In the formula, R<1> to R<3> are hydrogen atoms, alkyl groups having 1 to 5 carbon atoms, alkoxy groups or phenyl groups having 1 to 5 carbon atoms, and R<1> to R3 may be same or different. As for the resin soluble with an alkali soln., for example, a novolac resin, acryl resin, styrene-acrylic acid copolymer and hydroxystyrene polymer can be used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive chemically amplified photosensitive resin composition and a method for producing a resist image used in microfabrication of semiconductor devices and the like, and more particularly, to ultraviolet rays, far ultraviolet rays, X-rays, and electron beams. An acid is generated in the pattern latent image forming area by pattern irradiation of radiation such as, and a reaction using this acid as a catalyst changes the solubility of the irradiated part and the unirradiated part in the alkali developing solution, and the pattern appears. The present invention relates to a positive chemically amplified photosensitive resin composition and a method for producing a resist image using the same.

[0002]

2. Description of the Related Art In recent years, integrated circuits have been miniaturized in accordance with high integration, and 64M or 256M DRAMs and the like have been required to form patterns of sub-half micron or less, and resist materials having excellent resolution have been developed. Requested. Conventionally, a reduction projection exposure apparatus has been used for producing an integrated circuit. At present, a pattern having an exposure wavelength or less can be resolved by devising a photomask or the like.
However, a resolving power sufficient to support 64M or 256M DRAM has not been obtained.

On the other hand, exposure using X-rays or electron beams can be expected to achieve finer pattern processing than exposure using light. The minimum dimension of the pattern depends on the beam diameter, and a high resolution can be obtained. However, even in an exposure method that can perform fine processing, the throughput of wafer processing poses a problem in terms of LSI mass production. As a method for improving the throughput, it is important to improve the sensitivity of the resist used, as well as to improve the apparatus.

As a resist material for achieving high sensitivity, for example, a composition containing a highly reactive medium in the presence of an acid catalyst and an acid precursor which generates an acid upon irradiation with actinic radiation is disclosed in US Pat. 3,779,778, JP-A-5
JP-A-9-45439 and JP-A-2-25850 have known a chemically amplified photosensitive resin composition. These known examples disclose a compound or polymer containing an acetal group and a compound or polymer containing a t-butyl group as a highly reactive medium. These media contain a group that is decomposed by an acid, and are modified into a compound or a polymer that changes the solubility in a developer using the acid generated by irradiation with actinic radiation as a catalyst.

[0005] It is necessary that the difference in the dissolving rate between the irradiated portion and the non-irradiated portion in the developing solution necessary for obtaining a fine pattern with good shape is large. There is a problem that the so-called γ value decreases (resolution decreases) due to the small size. If an alkali-soluble resin is mixed with a component that reacts under an acid catalyst, the mixture may be separated into two inhomogeneous layers, or a poorly soluble layer may be formed on the resist surface by micro-layer separation, thereby deteriorating the pattern shape. There was a very serious problem.

As described above, the resist material is desired to have high sensitivity and high resolution, but also to be resistant to high temperatures generated during dry etching, that is, high heat resistance. In a photosensitive resin composition containing a quinonediazide compound as a photosensitive agent, improvement of an alkali-soluble resin has been attempted in order to achieve both high sensitivity, high resolution, and high heat resistance. For example, as an aqueous alkali soluble resin, US Pat. No. 4,529,682 discloses o.
Novolak resin obtained by condensing a mixture of cresol, m-cresol and p-cresol with formaldehyde, a mixture of m-cresol, p-cresol and 2,5-xylenol in JP-A-60-158440 Is a novolak resin obtained by condensing the compound with formaldehyde, and JP-A-63-234249 discloses m-lac resin.
Novolak resins obtained by condensing a mixture of cresol, p-cresol and 3,5-xylenol with formaldehyde have been proposed. in this way,
By limiting the raw materials for synthesizing the resin soluble in the aqueous alkali solution, it was possible to provide a resist material having high sensitivity and high resolution. However, it was not possible to provide a material having high heat resistance.

[0007] It has also been proposed to improve the heat resistance of a resist material by improving the molecular weight of a resin soluble in an aqueous alkali solution. For example, JP-A-64-14229 and JP-A-2-60915 propose to improve the heat resistance by removing a low molecular weight portion of an alkali-soluble resin. However, the removal of the low molecular weight component of the resin soluble in an aqueous alkali solution causes a decrease in sensitivity and resolution, and it has been difficult to provide a resist material having well-balanced properties.

In the case of a positive chemically amplified resist utilizing an acid catalyzed reaction, attempts have been made to achieve both sensitivity, resolution and heat resistance characteristics by limiting the synthesis raw materials of the above-mentioned alkaline aqueous solution-soluble resin or improving the molecular weight. However, it has been difficult to provide a resist material having well-balanced properties.

[0009]

According to the first aspect of the present invention, an acid is generated in a pattern latent image forming portion by pattern irradiation of radiation such as ultraviolet rays, far ultraviolet rays, X-rays, and electron beams. The reaction as a catalyst changes the solubility of the irradiated part and the unirradiated part in an alkali developing solution, and provides a high sensitivity, high resolution, and high heat resistance in a positive-type chemically amplified photosensitive resin composition that reveals a pattern. The present invention provides a positive type chemically amplified photosensitive resin composition. The invention according to claim 2 is the invention according to claim 1,
Another object of the present invention is to provide a positive chemically amplified photosensitive resin composition having high heat resistance. The third aspect of the present invention is to provide a method of manufacturing a resist image capable of exhibiting a resist pattern having good resolution.

[0010]

According to the present invention, there are provided (a) an alkali aqueous solution-soluble resin, and (b) a general formula (I)

Embedded image (Wherein, R ¹ , R ² and R ³ represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or a phenyl group, and R ¹ , R ² and R ³ represent (C) a compound which generates an acid upon irradiation with active actinic radiation, and (d) an acid-catalyzed reaction of a side chain with an alkali aqueous solution to increase the solubility in an aqueous alkali solution. The present invention relates to a positive chemically amplified photosensitive resin composition containing a compound having an acid-decomposable group.

[0011] The present invention also provides the positive chemically amplified photosensitive resin composition as described above, wherein the content of the low molecular weight component having a weight average molecular weight of 2,000 or less in terms of polystyrene is 10% by weight or less. About things. Further, the present invention relates to a method for producing a resist image, which comprises irradiating a coating film of the positive-type chemically amplified photosensitive resin composition with active actinic radiation, and then developing the resist film.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Examples of the resin soluble in an aqueous alkali solution used in the present invention include a novolak resin, an acrylic resin, a copolymer of styrene and acrylic acid, and a polymer of hydroxystyrene.

The alkali aqueous solution-soluble resin used in the present invention is preferably a novolak resin obtained by polycondensing a phenol having at least one phenolic hydroxyl group with an aldehyde. For example, phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol,
Examples include phenols having one phenolic hydroxyl group such as 2,3,5-trimethylphenol, phenols having two phenolic hydroxyl groups such as resorcinol and catechol, and phenols having three such as phloroglucin, pyrogallol and hydroxyhydroquinone. Can be These phenols can be used alone or in combination of two or more. Aldehydes include, for example, formaldehyde, paraformaldehyde and the like. The amount of aldehydes used is
The range is preferably 0.5 to 1.5 mol per 1 mol of the phenol.

In the above polycondensation, it is preferable to use an acid catalyst capable of increasing the molecular weight. As the acid catalyst, inorganic acids such as hydrochloric acid, nitric acid and sulfuric acid, and formic acid,
Organic acids such as oxalic acid and acetic acid can be mentioned. The amount of the acid catalyst used is 1 × 10 ⁻⁵ to 1 mol of phenols.
The range is preferably from ¹ to 10 ^-1 mol. The reaction temperature and the reaction time of the polycondensation can be appropriately adjusted according to the reactivity of the raw materials for synthesis, but usually the reaction temperature is 70 to 130 ° C. and the reaction time is 1 to 12 hours. Examples of the method of the polycondensation reaction include a method in which phenols, aldehydes and a catalyst are charged at once, a method in which phenols and aldehydes are added with an acid catalyst as the reaction proceeds. After the completion of the polycondensation, under reduced pressure, for example, 20
At a pressure of ５０50 mmHg, the temperature in the reaction system is raised to 150 to 200 ° C. to remove unreacted raw materials, condensed water, a catalyst and the like present in the reaction system, and then recover the resin.

In the present invention, the alkali aqueous solution-soluble resin is particularly preferably one containing only 10% by weight or less (may be 0%) of a low molecular weight component having a molecular weight of 2,000 or less in terms of polystyrene. As a method for reducing or removing such low molecular weight components in the alkali aqueous solution-soluble resin, a dissolution fractionation method is generally used. That is, an alkaline aqueous solution-soluble resin is dissolved in a good solvent such as acetone, tetrahydrofuran, methyl ethyl ketone, and ethyl cellosolve acetate to form a resin varnish. To separate into a dilute phase with many low molecular weight components and a dense phase with many high molecular weight components, or
By forming a precipitated phase having a high molecular weight component, the low molecular weight component is reduced or removed.

As shown in JP-A-64-14229, a resin soluble in an aqueous alkali solution is pulverized and dispersed in an aromatic solvent such as toluene or xylene to extract and reduce or remove low molecular weight components. May be performed. Also, in the present invention, Japanese Patent Application Laid-Open No. 2-222409
As shown in the publication, when synthesizing an alkali aqueous solution-soluble resin, a normal polycondensation synthesis reaction is performed by mixing a good solvent and a poor solvent similar to those described above for the resin,
A method of obtaining a resin soluble in an aqueous alkaline solution having a low molecular weight component may be used. By such a method, the polystyrene-equivalent molecular weight of the aqueous alkali-soluble resin is 2,000.
The following low molecular weight components can range from 0 to 10% by weight.

Examples of the trihydroxybenzene compound used in the present invention include pyrogallol (1,2,3-trihydroxybenzene) and phloroglucin (1,3,5).
-Trihydroxybenzene) and hydroxyhydroquinone (1,2,4-trihydroxybenzene), all of which can be obtained as commercial products. The trihydroxybenzene compounds may be used alone or in combination of two or more. The blending amount of the trihydroxybenzene compound is 100
It is preferably 2 to 50 parts by weight with respect to parts by weight,
The amount is more preferably 3 to 40 parts by weight, particularly 5 to 3 parts by weight.
It is preferably 0 parts by weight. If the amount of the trihydroxybenzene compound is too small, it is difficult to obtain a sufficient resolution, and if the amount is too large, it tends to be difficult to achieve both sensitivity and resolution.

The compound which generates an acid upon irradiation with active actinic radiation used in the present invention includes an onium salt, a halogen-containing compound, a quinonediazide compound and a sulfonic acid ester compound.

Examples of the onium salt include an iodonium salt, a sulfonium salt, a phosphonium salt, an ammonium salt, a diazonium salt and the like, preferably a diaryliodonium salt, a triarylsulfonium salt,
There is a trialkylsulfonium salt having 1 to 4 carbon atoms, and a counter anion of the onium salt includes, for example, tetrafluoroboric acid, hexafluoroantimonic acid, trifluoromethanesulfonic acid, trifluoroacetic acid, and toluenesulfonic acid.

Examples of the halogen-containing compound include a haloalkyl group-containing hydrocarbon compound and a haloalkyl group-containing heterocyclic compound, and preferably include trichloromethyltriazine and bromoacetylbenzene.

Examples of the quinonediazide compound include a diazobenzoquinone compound and a diazonaphthoquinone compound.

Examples of the sulfonic acid ester compound include an ester compound of an aromatic compound having a phenolic hydroxyl group and an alkyl sulfonic acid or an aromatic sulfonic acid, preferably an aromatic compound having a phenolic hydroxyl group. Include phenol, resorcinol, pyrogallol, 1,2-hydroxynaphthalene, and the like, alkyl sulfonic acids include methanesulfonic acid, ethanesulfonic acid, and propanesulfonic acid; and aromatic sulfonic acids include benzenesulfonic acid and the like. There is.

The amount of the compound that generates an acid upon irradiation with active actinic radiation is preferably 0.5 to 30 parts by weight, more preferably 2 to 15 parts by weight, based on 100 parts by weight of the aqueous alkali-soluble resin. Is preferred. If the amount of the compound that generates an acid by actinic radiation is too large, the solubility in a solvent is reduced. If the amount is too small, sufficient sensitivity is not provided.

The compound having an acid-decomposable group which increases the solubility in an aqueous alkali solution by an acid-catalyzed reaction in the side chain, which is desirable for use in the present invention, is such that the acid-decomposable group on the side chain is efficiently dissociated by an acid. This is a compound in which the solubility of the final product in an aqueous alkaline solution is significantly different from that of the polymer before dissociation. Such compounds are:
For example, a novolak resin obtained by polycondensing a phenol and an aldehyde as described above, an acrylic resin,
A compound in which a hydrogen atom such as a phenolic hydroxyl group or a carboxyl group of an alkaline aqueous solution-soluble resin such as a copolymer of styrene and acrylic acid or a hydroxystyrene polymer is substituted with a group capable of dissociating in the presence of an acid. No.

Specific examples of groups that can be dissociated in the presence of an acid include methoxymethyl, methoxyethoxymethyl, tetrahydropyranyl, tetrahydrofuranyl, benzyloxymethyl, 1-methoxyethyl, 1-ethoxyethyl group, methoxybenzyl group, tert
-Butyl group, methoxycarbonyl group, ethoxycarbonyl group, tert-butoxycarbonyl group, trimethylsilyl group, triethylsilyl group, phenyldimethylsilyl group and the like.

The substitution rate of the phenolic hydroxyl group or carboxyl group of a group which can be dissociated in the presence of an acid with hydrogen is preferably 15 to 100%, and more preferably 30 to 100%. Preferably, there is.

The molecular weight of a compound having an acid-decomposable group whose solubility in an aqueous alkali solution is increased by an acid-catalyzed reaction in the side chain is determined by GPC (gel permeation chromatography) in terms of polystyrene equivalent weight average molecular weight. Those having (Mw) of 1,500 to 3,000 are preferred. Since the compound having this molecular weight range has good compatibility with the resin soluble in the aqueous alkali solution, there is no formation of a layer hardly soluble in the aqueous alkali solution on the resist surface, and a high-resolution resist material can be obtained.

The compound having an acid-decomposable group whose solubility in an aqueous alkali solution is increased by an acid-catalyzed reaction is added in an amount of 3 parts by weight per 100 parts by weight of the resin soluble in an aqueous alkali solution.
To 300 parts by weight, more preferably 5 to 2 parts by weight.
It is preferably 00 parts by weight. If the amount of the compound having an acid-decomposable group that increases the solubility in an aqueous alkali solution by an acid-catalyzed reaction is too large, the dissolution rate of the irradiated portion in a developing solution decreases, and the acid-catalyzed reaction dissolves in an aqueous alkali solution. When the compounding amount of the compound having an acid-decomposable group whose property is increased is too small, the film loss of the unirradiated portion tends to increase.

Examples of the solvent used in the present invention include glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol alkyl ether acetates such as methyl cellosolve acetate, diethylene glycols such as diethylene glycol monomethyl ether, and propylene glycol. Propylene glycol alkyl ether acetates such as methyl ether acetate, aromatic hydrocarbons such as toluene, ketones such as cyclohexanone, and esters such as 2-hydroxypropionate can be used.

The amount of the solvent used is preferably from 50 to 95% by weight, more preferably from 75 to 95% by weight, based on the total amount of the photosensitive resin composition containing the solvent. If the amount of the solvent is too small, the solubility of the solvent in the resist material is insufficient, and if the amount of the solvent is too large, a sufficient film thickness cannot be obtained when a resist coating film is formed.

The photosensitive resin composition of the present invention has coatability,
For example, a surfactant for preventing striation (unevenness in film thickness) and improving developability can be added. Examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, and polyoxyethylene octyl phenol ether. Commercially available products include Megafac F171 (a product of Dainippon Ink and Chemicals, Inc.). Name), Florado FC430, FC431
(Trade name of Sumitomo 3M), and organosiloxane polymer KP341 (trade name of Shin-Etsu Chemical Co., Ltd.). Further, the photosensitive resin composition of the present invention may optionally contain a storage stabilizer, a dissolution inhibitor, and the like.

The photosensitive resin composition of the present invention is prepared in the form of a solution, thereby forming a coating film on a substrate for producing a semiconductor, then irradiating the pattern with active actinic radiation, and developing the resist image to form a resist image. You. The active actinic radiation is not limited, and for example, radiation such as far ultraviolet rays such as excimer lasers, X-rays such as synchrotron radiation, and charged particle beams such as electron beams is used. The conditions for development are not limited, and examples of the developer include inorganic alkalis such as sodium hydroxide, primary amines such as ethylamine, secondary amines such as diethylamine, and tertiary amines such as triethylamine. An alkaline aqueous solution in which alcohol amines such as quaternary amines and dimethylethanolamine, quaternary ammonium salts such as tetramethylammonium hydroxide and choline, or cyclic amines such as piperidine is used.

[0033]

In general, in the positive photosensitive resin composition, increasing the ratio of the dissolution rate of the irradiated portion to the developing solution in the unirradiated portion leads to higher resolution. The trihydroxybenzene compound added in the present invention has an effect of sufficiently lowering the dissolution rate of the non-irradiated portion in the alkali developing solution, whereby high resolution of the positive photosensitive resin composition can be achieved. . In order to evaluate the dissolution inhibiting effect on an aqueous alkali solution produced by blending a compound having an acid-decomposable group whose solubility in an aqueous alkali solution increases by an acid catalyzed reaction in a side chain with the aqueous alkali soluble resin, an alkali aqueous soluble resin 100 was used. For parts by weight,
Resin soluble in aqueous alkali solution with respect to dissolution rate of 2.38 wt% aqueous solution of tetramethylammonium hydroxide when 5 parts by weight of a compound having an acid-decomposable group whose solubility in an aqueous alkali solution increases due to an acid catalyzed reaction in a side chain Was measured. The larger the numerical value of the parameter indicating the dissolution inhibiting effect, the greater the dissolution inhibiting effect, and high resolution of the positive photosensitive resin composition is expected. This ratio is 4 ~
Although it was 10, this ratio can be increased to 30 to 100 by adding a trihydroxybenzene compound.

The heat resistance of the resist material is greatly affected by the molecular weight and molecular weight distribution of the base resin. The higher the molecular weight or the lower the proportion of the low molecular weight component that lowers the heat resistance, the better the heat resistance of the resist material.
In this case, when the molecular weight of the alkali aqueous solution-soluble resin as the base resin is increased, the sensitivity is lowered.
0% by weight. Although the sensitivity and resolution may be reduced by reducing the number of low molecular weight components, the addition of the above-mentioned trihydroxybenzene compound does not reduce the sensitivity and can further improve the resolution.

[0035]

The present invention will be described below with reference to examples. Synthesis Example 1-1 m-cresol 328.1 g, p-cresol 40 in a separable flask equipped with a stirrer, a cooling tube, and a thermometer.
0.9 g, 361.2 g of 37% by weight formalin and 2.2 g of oxalic acid were charged, and the separable flask was immersed in an oil bath.
The polycondensation was carried out for 3 hours while keeping the internal temperature at 97 ° C while stirring. Thereafter, the internal temperature was raised to 180 ° C., and simultaneously the pressure in the reaction vessel was reduced to 10 to 20 mmHg to recover unreacted phenols, formaldehyde, water and oxalic acid. Next, the molten resin was poured into a metal vat to collect the cresol novolak resin. This resin is referred to as a resin 1-1.

Synthesis Example 1-2 550 g of the resin obtained in Synthesis Example 1-1 was dissolved in 1,100 g of ethyl cellosolve acetate to form a resin varnish.
To this, 1,000 g of toluene and 1,000 g of hexane
Was mixed and stirred for 30 minutes, and then allowed to stand. As a result, a dense phase having a high molecular weight component was obtained in the lower layer. The concentrated phase was separated and dried under reduced pressure to obtain an alkali aqueous solution-soluble resin having reduced low molecular weight components (hereinafter, this resin is referred to as resin 1-2). The resin 1-2 was measured using GPC, and from the calculation of the area ratio of the peak having a polystyrene equivalent weight average molecular weight of 2,000 or less, the weight ratio of the low molecular weight component having a polystyrene equivalent weight average molecular weight of 2,000 or less was 5%. %Met.

Synthesis Example 2 Cresol-novolak resin CN-19 (Meiwa Kasei Co., Ltd.)
200 g) was dissolved in 800 g of methyl ethyl ketone to form a resin varnish. The resin varnish was gradually dropped into 1,000 g of hexane, mixed and stirred for 30 minutes, and the precipitate was recovered and dried under reduced pressure to obtain a low molecular weight component. A reduced alkali aqueous solution soluble resin was obtained (hereinafter, this resin is referred to as resin 2). Resin 2 was measured using GPC and found to have a weight average molecular weight in terms of polystyrene of 2,
From the calculation of the area ratio of the peak of 000 or less, the weight ratio of the low molecular weight component having a polystyrene equivalent weight average molecular weight of 2,000 or less was 7% by weight.

Synthesis Example 3 Poly (p-vinylphenol) (trade name: Linker M, Maruzen Petrochemical Co., Ltd.) was placed in a separable flask equipped with a stirrer.
20 ml) and 300 ml of ethyl acetate.
℃) to dissolve. Then, in the flask,
-Dihydro-2H-pyran 105 g, 12N hydrochloric acid 0.5
After stirring for 1 hour at room temperature, the mixture was allowed to stand at room temperature for 3 days. Next, 160 ml of a 2.38% by weight aqueous solution of tetramethylammonium hydroxide was added to the reaction solution, and the mixture was stirred well, and the organic layer was taken out. The obtained organic layer solution was washed three times with 300 ml of distilled water, and then the organic layer was dried and concentrated by an evaporator. Concentrated solution 50
Reprecipitation was carried out using 500 ml of petroleum ether per ml. After the reprecipitation operation was repeated twice, the product was dried in a vacuum dryer (3 mmHg, 40 ° C.) for 8 hours, and poly (95%) of the hydroxyl groups in the polymer were replaced with tetrahydropyranyl groups. 22 g of (p-vinylphenol) were obtained.

Synthesis Example 4 25 g of silver trifluoromethanesulfonate was dissolved in 200 ml of tetrahydrofuran, and 20 g of trimethylsulfonium iodide was added thereto and stirred. After reacting at room temperature for about 1 day, the precipitated silver iodide is removed by filtration. The filtrate was concentrated, and the obtained crude product was recrystallized using ethyl alcohol to obtain 17 g of trimethylsulfoniotrifluoromethanesulfonate.

Example 1 Synthesis Example 1-1 was placed in a separable flask equipped with a stirrer.
82.8 g of resin 1-1 obtained in the above, 9.2 g of pyrogallol (manufactured by Wako Pure Chemical Industries, Ltd.), and poly (p-vinylphenol-) having the hydroxyl group obtained in Synthesis Example 3 protected by a tetrahydropyranyl group. ), 5 g of trimethylsulfoniotrifluoromethanesulfonate and 300 g of methylcellosolve acetate obtained in Synthesis Example 4 as compounds which generate an acid upon irradiation with active actinic radiation, and dissolved to form a uniform solution. After confirming this, the solution was filtered through a membrane filter having a pore size of 0.1 μm to prepare a resist solution.

The resulting resist solution was applied on a silicon wafer and heat-treated at 90 ° C. for 10 minutes to obtain a resist film having a thickness of 1.0 μm. Using an electron beam writing apparatus of an acceleration voltage of 50kV to the substrate, e in dose of 2.5μC / cm ² - after drawing a Rupatan to resist, 110 ° C., and heat-treated for 10 minutes in the latent image portion of the resist alkali Accelerated reactions that increase solubility in aqueous solutions. After this heat treatment,
The resist film on which the latent image was formed was developed for 90 seconds using a 2.38% by weight aqueous solution of tetramethylammonium hydroxide to obtain a positive resist pattern. 0.2 μm
As a result of observing the cross-sectional shape of the lupatan with an electron microscope, the resist pattern was rectangular and good. The amount of film reduction after development was 0.02 μm, which was good. The formed resist pattern is placed on a hot plate at 120 ° C. for 5 hours.
The resist pattern was not deformed even after standing for minutes, and the heat resistance was good.

Example 2 A resist was prepared in the same manner as in Example 1 except that 82.8 g of Resin 1-2 was used instead of Resin 1-1, and a resist was prepared at 4.5 μC / cm ² . An electron beam writing experiment was performed with the irradiation dose. As a result of observing the cross-sectional shape of the hole pattern of 0.2 μm with an electron microscope, the resist pattern was rectangular and good. The amount of film reduction after development was 0.02 μm, which was good. The formed resist pattern is 12
Even when left on a hot plate at 0 ° C. for 5 minutes, the resist pattern was not deformed, and the heat resistance was good.

Example 3 In Example 1, pyrogallol (Wako Pure Chemical Industries, Ltd.)
) Instead of phloroglucin (Wako Pure Chemical Industries, Ltd.)
Was prepared in the same manner as in Example 1 except that 9.2 g of was used, and an electron beam lithography experiment was performed with an irradiation amount of 4.0 μC / cm ² . As a result of observing the cross-sectional shape of the hole pattern of 0.2 μm with an electron microscope, the resist pattern was rectangular and good. The amount of film reduction after development was 0.02 μm, which was good. The formed resist pattern is 12
Even when left on a hot plate at 0 ° C. for 5 minutes, the resist pattern was not deformed, and the heat resistance was good.

Example 4 In Example 1, resin 2 was replaced with resin 8 in place of resin 1-2.
A resist was prepared in the same manner as in Example 1 except that 2.8 g was used, and an electron beam lithography experiment was performed at an irradiation dose of 5.5 μC / cm ² . As a result of observing the cross-sectional shape of the hole pattern of 0.2 μm with an electron microscope, the resist pattern was rectangular and good. The amount of film reduction after development was 0.02 μm, which was good. The formed resist pattern is 120
The resist pattern was not deformed even when left on a hot plate at 5 ° C. for 5 minutes, and the heat resistance was good.

Comparative Example 1 A resist was prepared in the same manner as in Example 1 except that pyrogallol was not added.
An electron beam lithography experiment was performed with an irradiation dose of cm ² . As a result of observing the cross-sectional shape of the hole pattern of 0.4 μm with an electron microscope,
The resist pattern was rectangular and good. However, smaller hole patterns are not resolved and polyphenol
The resolution was inferior to that of the resist to which the compounds were added.

Comparative Example 2 A resist was prepared in the same manner as in Example 2 except that pyrogallol was not added.
An electron beam lithography experiment was performed with an irradiation dose of cm ² . As a result of observing the cross-sectional shape of the hole pattern of 0.4 μm with an electron microscope,
The resist pattern was rectangular and good. However, smaller hole patterns are not resolved and polyphenol
The resolution was inferior to that of the resist to which the compounds were added.

[0047]

The positive type chemically amplified photosensitive resin composition according to the first aspect has excellent sensitivity and resolution to ultraviolet rays, far ultraviolet rays, electron beams, X-rays and other active actinic rays. The positive type chemically amplified photosensitive resin composition according to claim 2 has excellent sensitivity, resolution, and heat resistance to ultraviolet rays, far ultraviolet rays, electron beams, X-rays, and other active actinic rays. According to the method for manufacturing a resist image according to the third aspect, a resist pattern having excellent resolution and excellent resolution and heat resistance can be produced.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Masahiro Hashimoto 4-3-1-1, Higashicho, Hitachi City, Ibaraki Prefecture Inside the Yamazaki Plant of Hitachi Chemical Co., Ltd. (72) Inventor Shigeru Koibuchi 4--13 Higashicho, Hitachi City, Ibaraki Prefecture No. 1 Inside the Yamazaki Plant of Hitachi Chemical Co., Ltd. (72) Inventor Tsuru Hashimoto 4-13-1, Higashicho, Hitachi City, Ibaraki Prefecture Inside the Yamazaki Plant of Hitachi Chemical Co., Ltd.

Claims (3)

[Claims] (1) an aqueous alkali-soluble resin,
(B) General formula (I) (Wherein, R ¹ , R ² and R ³ represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or a phenyl group, and R ¹ , R ² and R ³ represent (C) a compound which generates an acid upon irradiation with active actinic radiation, and (d) an acid-catalyzed reaction of a side chain with an alkali aqueous solution to increase the solubility in an aqueous alkali solution. A positive chemically amplified photosensitive resin composition containing a compound having an acid-decomposable group. 2. The positive-type chemically amplified photosensitive resin composition according to claim 1, wherein the content of the low molecular weight component having a weight average molecular weight of 2,000 or less in terms of polystyrene is 10% by weight or less. Stuff. 3. A method for producing a resist image, comprising irradiating a coating film of the positive-type chemically amplified photosensitive resin composition according to claim 1 with an actinic ray, and then developing the coating film. .