JPH11125906A - Positive chemical amplifying photosensitive resin composition and production of resist image - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a positive chemical amplifying photosensitive resin compsn. having high sensitivity, high resolution and excellent heat resistance and to provide a producing method of a resist image to develop a resist pattern with good resolution and heat resistance in the positive chemical amplifying photosensitive resin compsn. in which an acid is produced in a pattern latent image forming part by irradiation with a radiation such as UV rays, far UV rays, X-rays and electron beams along the pattern and the solubility with respect to an alkali developer is changed in the irradiated part from an unirradiated part by the reaction using the acid as a catalyst to develop the pattern. SOLUTION: This photosensitive resin compsn. contains an alkali soluble resin prepared by the condensation reaction of 3,5-xylenol and other phenol compd. and aldehyde compd., a compd. which produces an acid by irradiation with actinic rays, and a compd. having an acid-decomposable group which increases the solubility with respect to an alkali soln. by the acid catalytic reaction in side chains. The resist image is produced by irradiating a coating film of the positive chemical amplifying photosensitive resin compsn. above described with actinic rays and then developing.

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 the 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, the miniaturization of integrated circuits has been advanced in accordance with high integration, and in 64M or 256M DRAMs, pattern formation of sub-half micron or less has been required, 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-59-4
Compositions described in JP-A-5439 and JP-A-2-25850 are known. These known examples include compounds or polymers containing an acetal group as a highly reactive medium,
A compound or polymer containing a t-butyl group is disclosed. Since these media contain an acid-decomposable group, they are converted into a compound or a polymer that changes the solubility in a developer by using an acid generated by irradiation with actinic radiation as a catalyst.

However, in the conventional resist material, the so-called γ value is reduced because the difference in the dissolution rate in the developing solution between the irradiated portion and the non-irradiated portion, which is necessary for obtaining a fine pattern with good shape, is reduced. (Reduction in resolution). When an alkali-soluble resin and a component that reacts under an acid catalyst are mixed and used, they are separated into two inhomogeneous layers, or a hardly soluble layer is formed on the resist surface by micro-layer separation, and the pattern shape is deteriorated. There was a very serious problem.

Further, conventional resist materials include resins soluble in an aqueous alkali solution used in a composition and vinyl polymers having an acid-decomposable base in a side chain whose solubility in an aqueous alkali solution is increased by an acid-catalyzed reaction. There is a problem that the heat resistance is low due to the low softening point and the low glass transition temperature, and there is a problem that the resist pattern is deformed by heat generated during dry etching.

[0007]

The present invention according to claims 1 to 3, according to the present invention, is to generate an acid in a pattern latent image forming portion by pattern irradiation of radiation such as ultraviolet rays, far ultraviolet rays, X-rays and electron beams. In a positive-type chemically amplified photosensitive resin composition that changes the solubility of the irradiated part and the non-irradiated part in an alkali developing solution by a reaction using It is intended to provide a positive chemically amplified photosensitive resin composition having excellent properties.
The invention according to claim 4 provides a method for producing a resist image capable of producing a resist pattern having good resolution and heat resistance.

[0008]

The present invention provides (a) 3, 5
An alkali aqueous solution-soluble resin obtained by the condensation reaction of xylenol and other phenolic compounds with an aldehyde compound, (b) a compound capable of generating an acid by irradiation with active actinic radiation, and (c) a side chain having solubility in an aqueous alkali solution by an acid-catalyzed reaction The present invention relates to a positive chemically amplified photosensitive resin composition comprising a compound having an acid-decomposable group in which is increased.
In addition, the present invention provides the positive chemically amplified photosensitive resin composition further comprising (d) a phenolic hydroxyl group of 2 to 8;
A bodily-type chemically amplified photosensitive resin composition containing a polyphenol compound.

The present invention also provides a positive-type chemically amplified photosensitive resin composition in which the aqueous alkali-soluble resin contains 20% by weight or less of a low molecular weight component having a molecular weight of 1,000 or less in terms of polystyrene. The present invention relates to an amplification-type photosensitive resin composition. The present invention also 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.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION 3,5 used in the present invention
An alkali aqueous solution-soluble resin obtained by a condensation reaction of xylenol and another phenol compound with an aldehyde compound is a novolak resin obtained by polycondensation of 3,5-xylenol and a phenol having at least one phenolic hydroxyl group using an aldehyde. Is mentioned. Examples of phenols having one or more phenolic hydroxyl groups include, for example,
Phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 3,4-xylenol, 2,5-xylenol,
Phenols having one phenol such as 2,3,5-trimethylphenol, phenols having two phenolic hydroxyl groups such as resorcinol and catechol, phenols having three phenolic hydroxyl groups such as phloroglucin, pyrogallol and hydroxyhydroquinone And the like. Of these phenols, m-
Cresol, p-cresol and resorcinol are particularly preferred. One or more of these phenols can be used, respectively. The mixing ratio of 3,5-xylenol is preferably from 2 to 95 mol%, more preferably from 10 to 60 mol%, based on other phenols having one or more phenolic hydroxyl groups. If the mixing ratio of 3,5-xylenol is too small, high heat resistance cannot be obtained, and if the mixing ratio of 3,5-xylenol is too large, the dissolution rate during development becomes slow, and high sensitivity cannot be obtained.
Aldehydes include, for example, formaldehyde, paraformaldehyde and the like. The amount of the aldehyde used is 0.5 to 1 mol of the phenol.
A range of .about.1.5 mol is preferred.

In the present invention, other than the above-mentioned alkali aqueous solution-soluble resin, another alkali aqueous solution-soluble resin may be used as long as the effects of the present invention are not impaired. Examples of such an alkali aqueous solution-soluble resin include a novolak resin, an acrylic resin, a copolymer of styrene and acrylic acid, a polymer of hydroxystyrene, and a copolymer of hydroxystyrene and styrene. Novolak resins and phenols having one or more phenolic hydroxyl groups are polycondensed with aldehydes. Phenols include phenols other than the above-mentioned 3,5-xylenol, and can be obtained by reacting in the same manner as the above-mentioned aldehydes. Other alkaline aqueous solution-soluble resin is 0 to the total amount of the alkaline aqueous solution-soluble resin.
It is preferably used in the range of 90% by weight,
%, More preferably 0 to 40% by weight.
Most preferably, it is used in the range of weight%.

As a catalyst for the polycondensation, an acid catalyst capable of increasing the molecular weight is preferable. Examples of the acid catalyst include inorganic acids such as hydrochloric acid, nitric acid, and sulfuric acid, and organic acids such as formic acid, oxalic acid, and acetic acid. The amount of the acid catalyst used is preferably in the range of 1 × 10 ^-5 to 1 × 10 ^-1 mol per 1 mol of phenols. The reaction temperature and reaction time of the polycondensation
The reaction temperature can be appropriately adjusted according to the reactivity of the synthesis raw materials, but usually the reaction temperature is 70 to 130 ° C., and the reaction time is 1 to 12 hours. Examples of the polycondensation method include a method in which phenols, aldehydes and a catalyst are charged all at once, and a method in which phenols and aldehydes are added in the presence of a catalyst as the reaction proceeds. After completion of the polycondensation, unreacted raw materials present in the reaction system,
To remove condensed water, catalyst, etc., under reduced pressure, for example, 2
At 0 to 50 mmHg, the temperature in the reaction system is raised to 150 to 200 ° C., and then the resin is recovered.

In the present invention, it is particularly preferable that the resin soluble in an aqueous alkali solution contains only 20% by weight or less (may be 0%) of a low molecular weight component having a molecular weight of 1,000 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 aqueous alkali solution-soluble resin is dissolved in a good solvent such as acetone, ethyl cellosolve acetate, tetrahydrofuran, and methyl ethyl ketone to form a varnish. Reduction or removal of low molecular weight components is performed by dividing into a dilute phase having many components and a dense phase having many high molecular weight components, or by forming a precipitated phase having many high molecular weight components.

As disclosed in JP-A-64-14229, a resin soluble in an aqueous alkaline solution is pulverized and dispersed in an aromatic solvent such as toluene or xylene to extract and reduce or remove low molecular weight components. You may go. Further, in the present invention, as shown in JP-A-2-222409, when synthesizing a resin, a good solvent and a poor solvent are mixed with the resin and a normal polycondensation synthesis reaction is performed to obtain a low molecular weight resin. You may use the method of obtaining the alkali aqueous solution soluble resin with few components. By such a method, the polystyrene-equivalent molecular weight of the aqueous alkali-soluble resin is 2,
The low molecular weight component of 000 or less can be in the range of 0 to 10% by weight. In the present invention, the molecular weight in terms of polystyrene is determined by gel permeation chromatography (GP).
It is measured by the method C) using standard polystyrene, and is determined by an area ratio to the whole having a molecular weight of 2,000 or less.

The (b) compound which generates an acid upon irradiation with actinic radiation used in the present invention includes onium salts, halogen-containing compounds, quinonediazide compounds, sulfonic acid ester compounds and the like.

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, a trialkylsulfonium salt (an alkyl group). The number of carbon atoms is 1 to 4), and examples of the counter anion of the onium salt include 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.

As the quinonediazide compound, for example,
Examples thereof include a diazobenzoquinone compound and a diazonaphthoquinone compound.

Examples of the sulfonic acid ester compound include an ester of an aromatic compound having a phenolic hydroxyl group and an alkyl sulfonic acid or an aromatic sulfonic acid. For example, as the aromatic compound having a phenolic hydroxyl group, Is phenol, resorcinol, pyrogallo-
Sulfonic acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butylsulfonic acid, and aromatic sulfonic acid, such as benzenesulfonic acid and naphthalenesulfonic acid, and 1,2-dihydroxynaphthalene and 1,3-dihydroxynaphthalene. Acids and the like.

The ester of an aromatic compound having a phenolic hydroxyl group with an alkylsulfonic acid can be synthesized by a usual esterification reaction. For example, an aromatic compound having a phenolic hydroxyl group can be reacted with an alkyl sulfonic acid or a chloride of an aromatic sulfonic acid under an alkaline catalyst. The synthesized product thus obtained can be purified by a recrystallization method or a reprecipitation method using an appropriate solvent.

The amount of the compound that generates an acid upon irradiation with active actinic radiation is 0.5 to 30 parts by weight based on 100 parts by weight of the aqueous alkali soluble resin from the viewpoint of providing sufficient sensitivity to active actinic radiation. And preferably 2
It is preferably from 15 to 15 parts by weight. If the amount of the compound that generates an acid by active actinic radiation is too large, the solubility in a solvent is reduced. If the amount is too small, sufficient sensitivity cannot be obtained.

The compound (c) having an acid-decomposable group whose solubility in an aqueous alkali solution is increased by an acid-catalyzed reaction in the side chain used in the present invention is preferably a compound capable of efficiently decomposing the side chain by an acid. A compound in which the group is dissociated, and the solubility of the final product in an aqueous alkaline solution is significantly different from that of the compound before dissociation. Such compounds include hydrogen atoms such as phenolic hydroxyl groups and carboxyl groups of alkaline aqueous solution-soluble resins such as acrylic resins, copolymers of styrene and acrylic acid, and polymers of hydroxystyrene (including polyvinyl phenol). Compounds substituted with a group that can be dissociated in the presence of an acid are mentioned.

Specific examples of the acid-decomposable group in a compound in which the activation energy required for the decomposition of the acid-decomposable group is relatively large and the decomposition reaction is a reversible reaction include a tetrahydropyranyl group, a tetrahydrofuranyl group, and a t-hydrofuranyl group. A butyl group,
There are a trimethylsilyl group, a triethylsilyl group, a benzyloxymethyl group and the like. Specific examples of the acid-decomposable group of the compound in which the activation energy required for the decomposition of the acid-decomposable group is relatively small and the decomposition reaction is an irreversible reaction include methoxymethyl group, methoxyethoxymethyl group, 1-methoxy Ethyl group, 1-ethoxyethyl group, methoxybenzyl group, methoxycarbonyl group, ethoxycarbonyl group, t
-Butoxycarbonyl group and the like.

The rate of substitution of a phenolic hydroxyl group or a carboxyl group of a group capable of being dissociated in the presence of an acid with hydrogen is preferably 15 to 100%, and more preferably 3 to 100%.
Preferably it is 0 to 100%. In the compound having an acid-decomposable group, it is not necessary that all of the hydroxyl groups are protected by the acid-decomposable group. Regarding the molecular weight of the compound having an acid-decomposable group (particularly, a vinyl polymer), the weight average molecular weight (Mw) in terms of polystyrene determined by GPC is 1,500.
Those having a molecular weight of up to 10,000 are preferred. Since the polymer having the molecular weight in this range has good compatibility with the resin soluble in the aqueous alkali solution, there is no formation of a layer insoluble in the aqueous alkali solution on the resist surface, and a high-resolution resist material can be obtained.

(C) The compound having an acid-decomposable group whose solubility in an aqueous alkali solution is increased by an acid-catalyzed reaction is compounded in an amount of 3 to 300 parts by weight based on 100 parts by weight of (a) an aqueous alkali solution-soluble resin. Preferably, it is more preferably 5 to 200 parts by weight. If the amount of the compound having an acid-decomposable group whose solubility in an aqueous alkali solution is increased by an acid-catalyzed reaction is too large, the dissolution rate of the irradiated portion in a developing solution tends to decrease, and the acid-catalyzed reaction causes an alkaline aqueous solution. If the amount of the compound having an acid-decomposable group that increases the solubility in water is too small, the film loss of the unirradiated portion tends to be large.

Various polyphenol compounds can be added to the composition of the present invention. In particular, when the alkaline aqueous solution-soluble resin of the component (a) does not contain a low molecular weight component, the dissolution rate of tetramethylammonium hydroxide in a 2.38% by weight aqueous solution is reduced. It is preferable to add a polyphenol compound of the formula (1). The polyphenol compound is not limited as long as it has 2 to 8 phenolic hydroxyl groups. Examples of these polyphenol compounds include compounds represented by the following chemical formulas 1 and 2.

[0027]

Embedded image

[0028]

Embedded image (Where a, b and c are each independently an integer of 0 to 3 (however, all are not 0), x, y and z are each independently an integer of 0 to 3; ¹ , R ² and R ³ each independently represent an alkyl group or an alkoxy group having 1 to 5 carbon atoms)

Preferably, 1,1-bis (2-hydroxyphenyl) methane, 1- (2-hydroxyphenyl)
-1- (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4
-Hydroxyphenyl) propane, 1,1,1-tris (2-hydroxyphenyl) methane, 1,1,1-tris (4-hydroxyphenyl) methane, 1,1-bis (2-hydroxyphenyl) -1- (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) -1- (2-hydroxyphenyl) methane, 1,
1,1-tris (2-hydroxyphenyl) ethane,
1,1-bis (2-hydroxyphenyl) -1- (4-
(Hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1- (2-hydroxyphenyl) ethane, 1,1,1-tris (4-hydroxyphenyl)
Ethane, 1,1-bis (4-hydroxyphenyl) -1
-[4- {1- (4-hydroxyphenyl) -1-methylethyl} phenyl] ethane, 1,1-bis (2-hydroxyphenyl) -1-phenylethane, 1,1-bis (4-hydroxyphenyl ) -1-Phenylmethane,
1,1-bis (2-hydroxyphenyl) -1-phenylmethane can be mentioned.

These polyphenol compounds may be used alone or in combination of two or more. The compounding amount of the polyphenol compound is preferably from 1 to 60 parts by weight, particularly preferably from 5 to 40 parts by weight, based on 100 parts by weight of the (a) aqueous alkali solution-soluble resin. If the amount of the polyphenol 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.

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 methyl ether acetate. Propylene glycol alkyl ether acetates, aromatic hydrocarbons such as toluene, ketones such as cyclohexanone, and esters such as 2-hydroxypropionic acid. The amount of the solvent used is preferably from 50 to 95% by weight, more preferably from 70 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 solvent is not sufficiently soluble in the resist material. If the amount of the solvent is too large, a sufficient film thickness cannot be obtained when the resist film is used.

In the present invention, the resin (a) soluble in an aqueous alkali solution or the mixture of the resin (a) soluble in an aqueous alkaline solution and the polyphenol compound (d) obtained as described above are dissolved in the above-mentioned solvent and applied to a substrate. After baking, this was treated with 2.3 of tetramethylammonium hydroxide.
The time during which the coating film is completely dissolved by immersion in an 8% by weight aqueous solution is measured, and the film thickness (nm / second) at which the coating film dissolves per second is calculated, and this is defined as the dissolution rate. In measuring the dissolution rate, the thickness of the coating film is preferably 0.5 to 2 μm. The baking is preferably performed at a temperature of 80 to 120 ° C.,
It is preferred to heat for 20 minutes. The amount of the 2.38% by weight aqueous solution of tetramethylammonium hydroxide may be such that the coating surface on the substrate is sufficiently immersed.

In the present invention, the (a) aqueous alkali-soluble resin or the mixture of (a) the aqueous alkali-soluble resin and (d) the polyphenol compound, which has a dissolution rate of 40 to 1000 nm / sec, is measured. Used. If the dissolution rate is less than 40 nm / sec, component (C)
The decomposition reaction of the acid-decomposable group is easily affected by atmospheres such as temperature and humidity, and the stability and reproducibility of the resolution of the resist are inferior.
If the time exceeds 2 seconds, the amount of the development film of the resist will be excessively large,
The effect of the present invention cannot be obtained.

The photosensitive resin composition of the present invention has coatability,
For example, in order to prevent striation (unevenness in film thickness) and improve developability, a surfactant can be added. As surfactants, for example, polyoxyethylene uraryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenol ether, and as commercial products, Megafax F171, F173 (Dai Nippon Ink Chemical Industry (Trade name), Florard FC430,
FC431 (trade name, manufactured by Sumitomo 3M Limited), and organosiloxane polymer KP341 (trade name, manufactured by 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.

With the photosensitive resin composition of the present invention, a resist film is formed on a substrate such as a wafer or glass, and a resist image is produced by irradiation with active actinic radiation and development. As the method, a conventionally well-known method can be adopted. There are no particular restrictions on the conditions of irradiation with actinic radiation and development. 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 are used.

Examples of the developer for the photosensitive resin composition of the present invention include inorganic alkalis such as sodium hydroxide, primary amines such as ethylamine, secondary amines such as diethylamine, and secondary amines such as triethylamine. Tertiary amines,
Alkaline aqueous solutions in which alcohol amines such as dimethylethanolamine, quaternary ammonium salts such as tetramethylammonium hydroxide and choline, or cyclic amines such as piperidine are used are used.

[0037]

The present invention will be described below with reference to examples. Synthesis Example 1 In a 5-liter separable flask equipped with a stirrer, a condenser and a thermometer, 811 g of 3,5-xylenol, m-
Cresol 1040 g, p-cresol 780 g, 37
1350 g of weight% formalin and 10.8 g of oxalic acid were charged, the separable flask was immersed in an oil bath, and refluxed for 1 hour while stirring at an internal temperature of 97 ° C. Then, the internal temperature was raised to 180 ° C. in 2 hours while removing water at normal pressure,
After keeping the temperature at 0 ° C. for 1 hour, the pressure in the reaction vessel was raised to 20 to 5
While reducing the pressure to 0 mmHg, unreacted xylenol, cresol, formaldehyde, water and oxalic acid were recovered to obtain a resin. This resin is referred to as a resin 1-1.

Synthesis Example 1-2 While stirring an infusion solution prepared by mixing 1,500 g of water and 1,500 g of methanol at 300 rpm, Synthesis Example 1 was added to this solution.
Was dissolved in 2,000 g of 2-ethoxyethyl acetate, a resin varnish was added over 3 minutes, and after mixing and stirring for 20 minutes, the mixture was allowed to stand for 20 minutes. As a result, a dense phase having a high molecular weight component was obtained in the lower layer. Separate this concentrated phase, 1-20mm
By drying at 110 ° C. for 25 hours under reduced pressure of Hg, a resin soluble in an aqueous alkali solution with reduced low molecular weight components was obtained (hereinafter, this resin is referred to as resin 1-2). Resin 1
-2 was analyzed by GPC. As a result, the weight average molecular weight in terms of polystyrene was 5,300, and the weight ratio of low molecular weight components having a molecular weight in terms of polystyrene of 1,000 or less was 1
1.3% by weight. The resin 1-1 was analyzed by GPC and found to have a polystyrene equivalent molecular weight of 1,000.
The weight ratio of the following low molecular weight components was 22.9% by weight.

Synthesis Example 2 700 g of 3,5-xylenol was placed in a 5-lottle separable flask equipped with a stirrer, condenser and thermometer.
Cresol 1,100 g, p-cresol 850 g, 3
1370 g of 7% by weight formalin and 10.8 g of oxalic acid were charged, and the separable flask was immersed in an oil bath.
After refluxing for 1 hour while stirring, polycondensation was carried out.
Thereafter, the internal temperature was raised to 180 ° C. while removing water at normal pressure.
After raising the temperature over time and keeping the temperature at 180 ° C. for 1 hour, the unreacted xylenol, cresol, formaldehyde, water and oxalic acid were recovered while reducing the pressure in the reaction vessel to 20 to 50 mmHg to obtain a resin. . This resin is referred to as resin 2.

Synthesis Example 3 A 5-lot separable flask equipped with a stirrer, condenser and thermometer was charged with 500 g of 3,5-xylenol,
Cresole 1,040 g, p-cresol 780 g, resorcinol 250 g, 37% by weight formalin 1350
g and 10.8 g of oxalic acid, the separable flask was immersed in an oil bath, refluxed for 1 hour with stirring at an internal temperature of 97 ° C., and polycondensation was carried out. Thereafter, the internal temperature was raised to 180 ° C. over 2 hours while removing water at normal pressure,
After keeping the temperature in the reaction vessel for 1 hour, the pressure in the reaction vessel is increased to 20 to 50 mm.
While reducing the pressure to Hg, unreacted xylenol, cresol, formaldehyde, water and oxalic acid were recovered to obtain a resin. This resin is referred to as resin 2.

Synthesis Example 4 A 5-lot separable flask equipped with a stirrer, a condenser and a thermometer was charged with 500 g of 3,5-xylenol,
1,040 g of cresol, 780 g of p-cresol,
250 g of 2,5-xylenol, 1350 g of 37% by weight formalin and 10.8 g of oxalic acid were charged, and the separable flask was immersed in an oil bath. Then, the internal temperature was raised to 180 ° C over 2 hours while removing water at normal pressure,
After keeping the temperature at 180 ° C for 1 hour, the pressure in the reaction vessel was raised to 20
While reducing the pressure to ~ 50 mmHg, unreacted xylenol,
Recover cresol, formaldehyde, water and oxalic acid,
A resin was obtained. This resin is referred to as resin 4.

Synthesis Example 5 30 g of pyrogallol, 3.9 g of 4-dimethylaminopyridine and 300 ml of tetrahydrofuran were charged into a separable flask equipped with a stirrer, a thermometer and a dropping funnel, and dissolved by stirring at room temperature (25 ° C.). . Next, the flask was immersed in an ice bath to adjust the temperature inside the reaction system to 5 ° C., and 115 g of ethanesulfonyl chloride was added dropwise over 20 minutes using a dropping funnel. Next, 95 g of triethylamine was added dropwise over 40 minutes using a dropping funnel, and the mixture was stirred for 6 hours while keeping the temperature in the reaction system at 5 ° C. Then distilled water 2000
The reaction solution was added to ml, and the deposited precipitate was separated by filtration. This precipitation was repeated several times using acetone and ethanol to obtain 32 g of pyrogallol ethanesulfonic acid ester.

Synthesis Example 6 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. 22 g of (p-vinylphenol) were obtained.

Synthesis Example 7 Bol (p-vinylphenol) (trade name: VP-5000, Nippon Soda Co., Ltd.) was placed in a separable flask equipped with a stirrer.
20 g) and 400 ml of tetrahydrofuran were stirred and dissolved at room temperature (25 ° C.). Then p-pyridium toluenesulfonate in a flask. lg was charged, and the mixture was stirred and dissolved at room temperature (25 ° C.). Next, 9.62 g of ethyl vinyl ether was charged into the flask, and the mixture was stirred at room temperature (25 ° C.) for 22 hours. Then, 150 ml of ethyl acetate was added to the reaction solution, 100 ml of a 2.38% by weight aqueous solution of tetramethylammonium hydroxide was added, and the mixture was stirred well, and the organic layer was taken out. The obtained organic layer solution was washed three times with 100 ml of distilled water, and then the organic layer was dried and concentrated by an evaporator. 50 ml of concentrated solution
Then, reprecipitation was carried out by flowing 500 ml of n-hexane. After repeating the reprecipitation operation twice, the product was dried in a vacuum dryer (3 mmHg, 40 ° C.) for 8 hours to obtain 65% of the hydroxyl groups.
Was substituted with 1-ethoxyethyl group to obtain 20 g of poly (p-vinylphenol).

Example 1 In a separable flask equipped with a stirrer, 92 g of the resin 1-1 obtained in Synthesis Example 1, 4 g of ethanesulfonic acid ester of pyrogallol obtained in Synthesis Example 5, and hydroxyl group obtained in Synthesis Example 6 9 g of poly (p-vinylphenol) protected with tetrahydropyranyl group and methyl cellosolve acetate 3
After adding 00 g and visually confirming that a uniform solution was obtained, the solution was filtered through a membrane filter having a pore diameter of 0.1 μm to prepare a resist solution (positive chemically amplified photosensitive resin composition).

The obtained resist solution was applied on a silicon wafer and heat-treated at 120 ° C. for 10 minutes to obtain a resist film having a thickness of 1.0 μm. After drawing a hole pattern on the resist with an irradiation dose of 4.0 μC / cm ² using an electron beam lithography system with an acceleration voltage of 50 kV, the substrate was heat-treated at 110 ° C. for 10 minutes, and an alkaline aqueous solution of a latent image portion of the resist was formed. Accelerated the reaction to increase solubility in After this heat treatment, 2.38% by weight of tetramethylammonium hydroxide
The resist film on which the latent image was formed was developed for 70 seconds using an aqueous solution to obtain a positive resist pattern. As a result of observing the cross-sectional shape of the 0.2 μm hole pattern with an electron microscope, the resist pattern was rectangular and good. Also,
The film loss after development was 0.004 μm, which was good. Even if the formed resist pattern was heat-treated at 115 ° C. for 5 minutes, the resist pattern was not deformed, and the heat resistance was good.

Example 2 The procedure of Example 1 was repeated, except that 1,1,1-tris (4-hydroxyphenyl) methane 25 was used as the polyphenol compound.
A resist solution (positive-type chemically amplified photosensitive resin composition) was prepared, and an electron beam lithography experiment was performed at an irradiation dose of 2.5 μC / cm ² . As a result of observing the cross-sectional shape of the 0.2 μm hole pattern with an electron microscope, the resist pattern was rectangular and good. Further, the film loss after development was 0.004 μm, which was good. 115 on the formed resist pattern
The resist pattern was not deformed even after heat treatment at 5 ° C. for 5 minutes, and the heat resistance was good.

Example 3 In Example 1, poly (p-vinylphenol) in which the hydroxyl group obtained in Synthesis Example 6 was protected with a tetrahydropyranyl group
Was replaced by 1-ethoxyethyl group-substituted poly (p-vinylphenol) obtained in Synthesis Example 7 in place of 9 g.
A resist solution (positive-type chemically amplified photosensitive resin composition) was prepared in the same manner as in Example 1 except that 38 g was used, and an electron beam lithography experiment was performed at an irradiation dose of 3.0 μC / cm ² . As a result of observing the cross-sectional shape of the 0.2 μm hole pattern with an electron microscope, the resist pattern was rectangular and good. Further, the film loss after development was 0.004 μm, which was good.

Example 4 Synthesis Example 1-2 was placed in a separable flask equipped with a stirrer.
92 g of the resin 1-2 obtained in the above, 4 g of ethanesulfonic acid ester of pyrogallol obtained in Synthesis Example 5, 9 g of poly (p-vinylphenol) obtained by synthesizing the hydroxyl group obtained in Synthesis Example 6 with a tetrahydropyranyl group, and bisphenol A 5 g of A and 300 g of 2-heptanone were charged, and after it was visually confirmed that a uniform solution had been obtained, the solution was filtered through a membrane filter having a pore size of 0.1 μm, and the resist solution (positive chemically amplified photosensitive resin composition) was obtained. Prepared. Thereafter, in the same manner as in Example 1, an electron beam drawing experiment was performed at an irradiation dose of 2.5 μC / cm ² . As a result of observing the cross-sectional shape of the hole pattern of 0.18 μm with an electron microscope, the resist pattern was rectangular and good. Further, the film loss after development was 0.004 μm, which was good. 11 in the formed resist pattern
Even after heat treatment at 5 ° C. for 5 minutes, the resist pattern was not deformed, and the heat resistance was good.

Example 5 In a separable flask equipped with a stirrer, 50 g of the resin 1-1 obtained in Synthesis Example 1 and 42 g of the resin 4 obtained in Synthesis Example 4 were added.
g, 4 g of ethanesulfonic acid ester of pyrogallol obtained in Synthesis Example 5, 9 g of poly (p-vinylphenol) having a hydroxyl group protected by a tetrahydropyranyl group obtained in Synthesis Example 6.
g, 1,1,1-tris (4-hydroxy) methane 30
g and methyl cellosolve acetate 300 g,
After visually confirming that a uniform solution was obtained, the pore size was adjusted to 0.
The solution was filtered through a 1 μm membrane filter to prepare a resist solution (positive-type chemically amplified photosensitive resin composition). Thereafter, in the same manner as in Example 1, an electron beam drawing experiment was performed at an irradiation dose of 2.5 μC / cm ² . As a result of observing the cross-sectional shape of the hole pattern of 0.18 μm with an electron microscope, the resist pattern was rectangular and good. Further, the film loss after development was 0.004 μm, which was good. Even if the formed resist pattern was heat-treated at 115 ° C. for 5 minutes, the resist pattern was not deformed, and the heat resistance was good.

Example 6 In a separable flask equipped with a stirrer, 92 g of Resin 4 obtained in Synthesis Example 4, 4 g of ethanesulfonic acid ester of pyrogallol obtained in Synthesis Example 5, and hydroxyl group obtained in Synthesis Example 6 were converted to tetrahydrofuran. 9 g of poly (p-vinylphenol) protected with a pyranyl group, 25 g of 1,1,1-tris (4-hydroxy) methane and 30 g of methyl cellosolve acetate
After adding 0 g and visually confirming that a uniform solution was obtained, the solution was filtered through a membrane filter having a pore size of 0.1 μm.
A resist solution (positive-type chemically amplified photosensitive resin composition) was prepared. Thereafter, in the same manner as in Example 1, 2.5 μC /
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 0.2 μm hole pattern with an electron microscope,
The resist pattern was rectangular and good. Further, the film loss after development was 0.004 μm, which was good.
Even if the formed resist pattern was heat-treated at 115 ° C. for 5 minutes, the resist pattern was not deformed, and the heat resistance was good.

Example 7 In a separable flask equipped with a stirrer, 60 g of the resin 3 obtained in Synthesis Example 3 and cresol novolak resin CN-1 were added.
9 (trade name of Meiwa Kasei Co., Ltd.), 4 g of pyrogallol ethanesulfonic acid ester obtained in Synthesis Example 5, 9 g of poly (p-vinylphenol) obtained in Synthesis Example 6 in which the hydroxyl group was protected with a tetrahydropyranyl group. , Bisphenol A
5 g, 1,1,1-tris (4-hydroxy) methane 2
5 g and 300 g of methyl cellosolve acetate were charged, and after visually confirming that a uniform solution was obtained, the solution was filtered through a membrane filter having a pore diameter of 0.1 μm to prepare a resist solution (positive-type chemically amplified photosensitive resin composition). did.
Thereafter, in the same manner as in Example 1, an electron beam drawing experiment was performed at an irradiation amount of 4.0 μC / cm ² . As a result of observing the cross-sectional shape of the 0.2 μm hole pattern with an electron microscope, the resist pattern was rectangular and good. Further, the film loss after development was 0.004 μm, which was good. Even if the formed resist pattern was heat-treated at 115 ° C. for 5 minutes, the resist pattern was not deformed, and the heat resistance was good.

Comparative Example 1 In Example 1, 92 g of cresol novolak resin CN-19 (trade name of Meiwa Kasei Co., Ltd.) was used instead of Resin 1-1.
Dissolution rate in the same manner as in Example 1 except that
A resist solution was prepared and subjected to an electron beam lithography experiment (however, the irradiation amount was set to 5.0 μC / cm ² ).
As a result of observing the cross-sectional shape of the hole pattern with an electron microscope, the resist pattern was rectangular and good. However, the smaller hole pattern was not developed, and the resist pattern was reverse tapered. The film loss after development was 0.03 μm, which was inferior.

[0054]

The positive type chemically amplified photosensitive resin composition according to claim 1 has excellent sensitivity, resolution and heat resistance 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 the second aspect has a higher resolution than that of the first aspect.
The positive chemically amplified photosensitive resin composition according to claim 3,
The heat resistance is further superior to that of the first or second aspect.
According to the method for producing a resist image according to the fourth aspect, a resist pattern having excellent resolution and heat resistance can be produced.

Continued on the front page. (72) Inventor, Lucky Hashimoto 4-3-1, Higashicho, Hitachi City, Ibaraki Pref. Hitachi Chemical Co., Ltd. Yamazaki Factory

Claims (4)

[Claims] 1. An alkaline aqueous solution-soluble resin obtained by condensation reaction of 3,5-xylenol and another phenol compound with an aldehyde compound, (b) a compound which generates an acid upon irradiation with active actinic radiation, and (c) side A positive chemically amplified photosensitive resin composition containing a compound having an acid-decomposable group whose solubility in an aqueous alkali solution is increased by an acid-catalyzed reaction in a chain. 2. The method according to claim 1, wherein (d) a phenolic hydroxyl group is
A polyphenol compound having from 8 to 8 polyphenol compounds.
The bodied chemically amplified photosensitive resin composition as described in the above. 3. The positive-working chemically amplified photosensitive resin composition according to claim 1, wherein the alkali aqueous solution-soluble resin contains a low molecular weight component having a molecular weight of 1,000 or less in terms of polystyrene of 20% by weight or less. 4. A resist image comprising irradiating a coating film of the positive-type chemically amplified photosensitive resin composition according to claim 1, 2 with an actinic ray and then developing the resist film. Manufacturing method.