JP2001066775A - Positive chemical amplification type photosensitive resin composition, production of resist pattern and production of electronic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a positive type chemical amplification type photosensitive resin composition of superior sensitivity, resolution and pattern shape, a method for producing a resist pattern of superior resolution, pattern shape, work efficiency and productivity and a method for producing an electronic device of superior resolution, pattern shape, work efficiency and productivity. SOLUTION: This photosensitive resin composition contains (a) an alkali water-soluble resin, (b) at least two polyphenol compounds, (c) a compound which generates acid when irradiated with active actinic rays and (d) a compound having an acid decomposable group which increases solubility in the aqueous alkali solution by an acid catalyzed reaction in a side chain. A coating film of the photosensitive resin composition is irradiated with active actinic rays and developed to produce the object resist pattern. The photosensitive resin composition is applied and dried on the circuit forming face or protective film forming face of an electronic circuit and the resulting coating film is irradiated with active actinic rays and developed to produce the object electronic device.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a positive-working chemically amplified photosensitive resin composition, a method for producing a resist pattern, and a method for producing an electronic device.

[0002]

2. Description of the Related Art In recent years, the miniaturization of integrated circuits has been advanced in accordance with the high integration, and the formation of patterns of sub-half micron or less has been required in 256M DRAMs and the like, and resist materials having excellent resolution have been demanded. ing.
In particular, in recent years, the tendency to advance the miniaturization has become remarkable, and competition for establishing lithography techniques for forming finer patterns has been intensifying for device manufacturers.

At present, lithography technology using light as a light source is the mainstream, and the wavelength of light as a light source has been shortened for fine processing, and KrF excimer laser (248 nm) has been applied to mass production for processing of advanced devices. Therefore, application of a shorter wavelength ArF excimer laser (193 nm) is being studied. However, it is difficult to achieve fine processing at the 100 nm level with light, and exposure using X-rays, electron beams, or the like is the lithography technique closest to practical use. In particular, although exposure by an electron beam has been established on the apparatus and is regarded as promising, the throughput in wafer processing is a major problem. As a means to improve this 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, a chemically amplified photosensitive resin composition containing a compound which generates an acid catalyst by active actinic radiation and a compound whose solubility in a developing solution is changed by an acid ( US Patent 3,77
9,778, JP-A-59-45439,
JP-A-2-25850) is known. These known examples disclose compounds containing an acetal group and compounds containing a t-butyl group as compounds whose solubility in a developer is changed by an acid. In the conductive resin composition, the difference in the dissolution rate in the developer between the irradiated part and the unirradiated part, which is necessary to obtain a fine pattern with good shape, cannot be sufficiently obtained,
The resolution is not enough. Further, when a mixture of an alkali-soluble resin and a compound whose solubility in a developing solution is changed by an acid is used, a hardly-solubilized layer is formed on the resist surface by separation into two heterogeneous layers or by micro-layer separation, There is a very serious problem that the pattern shape is deteriorated.

Further, a chemically amplified photosensitive resin composition containing a compound which generates an acid catalyst by actinic actinic radiation and a compound whose solubility in a developing solution is changed by an acid is generated by an acid-catalyzed reaction as a resist reaction mechanism. Since the diffusion of acid is used, the efficiency of acid generation during irradiation with actinic radiation and the diffusion distance of generated acid greatly affect resist characteristics. That is, when the acid generation efficiency is low, the sensitivity becomes low, and when the acid generation efficiency is high, the sensitivity becomes high. When the diffusion distance of the acid is short, the sensitivity tends to be low, and when the diffusion distance is long, the sensitivity tends to be high. Furthermore, the diffusion distance of the acid also affects the resolution. If the diffusion distance of the acid is short, the resolution is faithful to the design pattern, and high resolution is easily obtained. And the resolution often deteriorates. Therefore, sensitivity and resolution tend to be in a trade-off relationship.

[0006]

The object of the present invention is to provide a positive chemically amplified photosensitive resin composition having excellent sensitivity, resolution and pattern shape. The invention according to claim 2 provides the effect of the invention according to claim 1 and provides a positive chemically amplified photosensitive resin composition having excellent resolution. The third aspect of the invention provides the positive chemically amplified photosensitive resin composition having the effects of the first or the second aspect of the invention and further having excellent resolution.

A fourth aspect of the present invention is to provide a positive chemically amplified photosensitive resin composition having the effects of the first, second or third aspect of the present invention, and further having excellent resolution and pattern shape. The invention according to claim 5 is based on claim 1,
An object of the present invention is to provide a positive chemically amplified photosensitive resin composition having the effects of the invention described in 2, 3 or 4, and further having excellent resolution and pattern shape. The invention of claim 6 provides the effects of the invention of claims 1, 2, 3, 4, or 5, and further provides a positive chemically amplified photosensitive resin composition having excellent sensitivity, resolution and pattern shape. It is.

The present invention provides a method of manufacturing a resist pattern having excellent resolution, pattern shape, workability and productivity. The invention described in claim 8 provides a method for manufacturing an electronic device having excellent resolution, pattern shape, workability, and productivity.

[0009]

The present invention comprises (a) a resin soluble in an aqueous alkali solution, (b) at least two kinds of polyphenol compounds, (c) a compound which generates an acid upon irradiation with active actinic radiation, and (d) a side compound. The present invention relates to 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. The present invention relates to the positive chemically amplified photosensitive resin composition wherein the polyphenol compound (b) has 2 to 8 phenolic hydroxyl groups. Also, the present invention
(B) a polyphenol compound, (b1) a polyphenol compound having 2 or 3 hydroxyl groups in the molecule, and (b2)
The present invention relates to the positive chemically amplified photosensitive resin composition, wherein the hydroxyl group in the molecule is a polyphenol compound having 4 to 8 hydroxyl groups.

[0010] The present invention also provides the positive type chemically amplified photosensitizer, wherein (a) the alkaline aqueous solution-soluble resin is a novolak resin obtained by polycondensing a cresol compound or a xylenol compound with an aldehyde compound in the presence of an acid catalyst. The present invention relates to a water-soluble resin composition. Further, the present invention provides (a) an aqueous alkali solution soluble resin having a molecular weight of 2,000 in terms of polystyrene.
The present invention relates to the positive chemically amplified photosensitive resin composition, wherein the low molecular weight component of 0 or less is 0 to 10% by weight. In the present invention, the amount of the component (a), the component (b), the component (c) and the component (d) may be 2 parts per 100 parts by weight of the total amount of the component (a). ５０50 parts by weight, component (c) is 2-3
The present invention relates to the positive chemically amplified photosensitive resin composition wherein 0 parts by weight and the component (d) are 3 to 300 parts by weight.

[0011] The present invention also relates to a method for producing a resist pattern, which comprises irradiating a coating film of the positive-type chemically amplified photosensitive resin composition with active actinic radiation and then developing the same. Further, the present invention provides a method for applying the positive-type chemically amplified photosensitive resin composition to a circuit forming surface or a protective film forming surface of an electronic circuit, drying and irradiating the obtained coating film with active actinic radiation, and then developing. And a method of manufacturing an electronic device.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The positive type chemically amplified photosensitive resin composition of the present invention comprises (a) an alkali aqueous solution-soluble resin, and (b)
Contains at least two kinds of polyphenol compounds, (c) a compound that generates an acid upon irradiation with actinic radiation, and (d) a compound having an acid-decomposable group in a side chain whose solubility in an aqueous alkali solution is increased by an acid-catalyzed reaction. Must be done.

The above-mentioned (a) alkali aqueous solution-soluble resin is not particularly limited. For example, a novolak resin obtained by polycondensing a cresol compound or a xylenol compound with an aldehyde compound in the presence of an acid catalyst may be used. preferable. These are used alone or in combination of two or more.

The cresol compound includes, for example,
o-cresol, m-cresol, p-cresol and the like. Examples of the xylenol compound include 2,3-xylenol, 2,4-xylenol,
2,5-xylenol, 3,4-xylenol, 3,5
-These include xylenol and the like, used alone or in combination of two or more.

As the aldehyde compound, for example,
Formaldehyde, paraformaldehyde and the like can be mentioned, and the amount of use is preferably 0.5 to 1 mol, more preferably 0.6 to 0.9 mol, per 1 mol of the cresol compound or the xylenol compound. preferable. When the amount is less than 0.5 mol, a sufficient molecular weight cannot be obtained, and as a result, a base resin having an appropriate dissolution rate tends not to be obtained. Tend not to be obtained.

Examples of the acid catalyst for polycondensing the cresol compound or xylenol compound with an aldehyde compound include inorganic acids such as hydrochloric acid, nitric acid and sulfuric acid, formic acid, and the like.
Organic acids such as oxalic acid and acetic acid can be exemplified. The amount of the acid catalyst to be used is preferably 1 × 10 ⁻⁵ to 1 × 10 ⁻¹ mol, preferably 1 × 10 ⁻⁴ to 1 × 10 ⁻² mol, per 1 mol of the cresol compound or xylenol compound. More preferably, there is. If the amount is less than 1 × 10 ^-5 mol, a base resin having a sufficient molecular weight tends not to be obtained. If the amount exceeds 1 × 10 ^-1 mol, the synthesis reaction cannot be controlled and the variation in the synthesis tends to be large. There is.

The reaction temperature and 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 about 70 to 130 ° C. and the reaction time is 1 to 12 hours. It is preferred that it is about. Examples of the polycondensation method include, for example, a method of charging a cresol compound or a xylenol compound and an aldehyde and a catalyst at once,
A method in which a cresol compound or a xylenol compound and an aldehyde are added together with the progress of the reaction in the presence of an acid catalyst is exemplified. After the completion of the polycondensation, for example, 2 ×
After reducing the pressure to about 0 to 50 mmHg, the temperature in the reaction system was raised to 150 to
It is preferable to raise the temperature to 200 ° C. to remove unreacted raw materials, condensed water, catalyst and the like present in the reaction system, and then recover the resin.

The resin (a) soluble in an aqueous alkali solution is as follows:
It is preferable to use one obtained by reducing or removing low molecular weight components. As a method for reducing or removing such low molecular weight components, for example, (a) an aqueous alkali solution-soluble resin is dissolved in a good solvent such as acetone, ethyl cellosolve acetate, tetrahydrofuran, methyl ethyl ketone, methanol, etc. to form a varnish, and the varnish is prepared in toluene. , Hexane, pentane, xylene, water, etc. by adding it to a poor layer containing many low molecular weight components and a thick layer containing many high molecular weight components, or by forming a precipitation layer containing many high molecular weight components. , A method of reducing or removing low molecular weight components. As disclosed in JP-A-64-14229, (a) an aqueous alkaline solution-soluble resin is pulverized and dispersed in an aromatic solvent such as toluene or xylene to extract low-molecular-weight components to reduce low-molecular-weight components. A method for removing the resin, and a method of mixing a (a) alkali aqueous solution-soluble resin with a good solvent and a poor solvent with respect to an ordinary aqueous polycondensation as described in JP-A-2-222409. A method in which a synthetic reaction is carried out to obtain a resin soluble in an aqueous alkali solution having a small amount of low molecular weight components is exemplified.

According to the above method, the low molecular weight component having a molecular weight of 2,000 or less in terms of polystyrene of the resin (a) soluble in an aqueous alkali solution can be in the range of 0 to 10% by weight.
Such an alkaline aqueous solution-soluble resin may be used.
The low molecular weight component having a molecular weight of 2,000 or less in terms of polystyrene of the (a) alkali aqueous solution-soluble resin is preferably 0 to 10% by weight, more preferably 0 to 9% by weight, and 0 to 8% by weight. It is particularly preferred that there is.
In the present invention, the ratio of the low molecular weight component is determined by a gel permeation chromatograph (GPC) method calibrated using standard polystyrene and has a molecular weight of 2,000.
It is calculated from the following area ratio to the whole.

It is preferable that (b) at least two kinds of polyphenol compounds have 2 to 8 phenolic hydroxyl groups in the molecule. More preferably, (b1) a polyphenol compound having 2 or 3 hydroxyl groups in the molecule and (b2) a polyphenol compound having 4 to 8 hydroxyl groups in the molecule.

(B1) two or three hydroxyl groups in the molecule
Examples of polyphenol compounds include bis (2
-Hydroxyphenyl) methane, 2-hydroxyphenyl- (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxy Phenyl) propane, tris (2-hydroxyphenyl) methane, tris (4-hydroxyphenyl) methane, bis (2-hydroxyphenyl)-(4-hydroxyphenyl) methane, bis (4-hydroxyphenyl)
-(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, bis (4-hydroxyphenyl) -phenylmethane, bis (2 -Hydroxyphenyl) -phenylmethane, 4,4'-dihydroxy-3,3'-dimethyl-biphenyl and the like, and tris (4-hydroxyphenyl) methane, 1,1,1-tris (2-hydroxyphenyl) Ethane is preferred. These are used alone or in combination of two or more.

Examples of (b2) polyphenol compounds having 4 to 8 hydroxyl groups in the molecule include 4,6-bis [(4-hydroxyphenyl) methyl] -1,3-benzenediol, 4,6-tris [(4-hydroxyphenyl) methyl] -1,3-benzenediol, 4,
4 '-[(3,4-dihydroxyphenyl) methylene]
Bis [2-methylphenol], 4,4 '-[(3,4
-Dihydroxyphenyl) methylene] bis [2,6-dimethylphenol], 4,4 '-[(3,4-dihydroxyphenyl) methylene] bis [2,3,6-trimethylphenol], 4,6-bis [ (3,5-dimethyl-4-hydroxyphenyl) methyl] -1,2,3-benzenetriol, 4,4 ′, 4 ″,-4 ′ ″-(1,2
—Ethanediylidene) tetrakisphenol, 4,
4 ', 4 ",-4"'-(1,2-ethanediylidene)
Tetrakis [2-methylphenol], 2,2'-methylenebis [6-[(2-hydroxy-5-methylphenyl) methyl] -4-methylphenol], 4,4 ',
4 ",-4 '''-(1,4-phenylenedimethylidene)
4,6-bis [(4
-Hydroxyphenyl) methyl] -1,3-benzenediol and 2,4,6-tris [(4-hydroxyphenyl) methyl] -1,3-benzenediol are preferred.
These are used alone or in combination of two or more.

The blending amount of the polyphenol compound (b) is preferably 2 to 50 parts by weight, more preferably 5 to 30 parts by weight, based on 100 parts by weight of the (a) aqueous alkali soluble resin. If the amount is less than 2 parts by weight, it tends to be difficult to obtain a sufficient resolution, and if it exceeds 50 parts by weight, it tends to be difficult to achieve both sensitivity and resolution.

Also, in the polyphenol compound (b),
(B2) The compounding amount of the polyphenol compound having 4 to 8 hydroxyl groups in the molecule is preferably 5 to 90% by weight, preferably 2 to 90% by weight.
It is preferably from 0 to 80% by weight. This compounding amount is 5
If the content is less than 90% by weight, good contrast cannot be obtained, and the compatibility between sensitivity and resolution tends to be difficult. If the content is more than 90% by weight, the unexposed part dissolves in an alkali developing solution at a high rate, and the amount of development film loss is large. Resolution tends to decrease.

Examples of the compound (c) that generates an acid upon irradiation with actinic radiation include onium salts, halogen-containing compounds, quinonediazide compounds, and sulfonic acid ester compounds. These are used alone or in combination of two or more.

Examples of the onium salt include an iodonium salt, a sulfonium salt, a phosphonium salt, an ammonium salt, a diazonium salt, and the like. A diaryliodonium salt, a triarylsulfonium salt, a C1 to C4 salt
There is a trialkylsulfonium salt of, the counter anion of the onium salt, for example, tetrafluoroboric acid, hexafluoroantimonic acid, trifluoromethanesulfonic acid,
Trifluoroacetic acid, toluenesulfonic acid and the like are preferred.
Examples of the halogen-containing compound include a haloalkyl group-containing hydrocarbon compound, a haloalkyl group-containing heterocyclic compound, and the like, and trichloromethyltriazine, bromoacetylbenzene, and the like are preferable.

Examples of the quinonediazide compound include a diazobenzoquinone compound and a diazonaphthoquinone compound. Examples of the sulfonic acid ester compound include, for example, an ester compound of an aromatic compound having a phenolic hydroxyl group and an alkyl sulfonic acid or an aromatic sulfonic acid. As the aromatic compound having a phenolic hydroxyl group, for example, Phenol, resorcinol, pyrogallol, 1,2 naphthalenediol, and the like. Examples of the alkylsulfonic acid include methanesulfonic acid, ethanesulfonic acid,
Examples of the aromatic sulfonic acid include benzenesulfonic acid and the like.

The compounding amount of the component (c), which generates an acid upon irradiation with actinic actinic radiation, is from 100 parts by weight of the total amount of the resin (a) soluble in an aqueous alkali solution from the viewpoint of providing sufficient sensitivity to actinic radiation. On the other hand, it is preferably 1 to 30 parts by weight, more preferably 2 to 20 parts by weight. If the amount is less than 1 part by weight, sufficient sensitivity tends not to be obtained, and if it exceeds 30 parts by weight, the solubility in a solvent tends to decrease.

In the compound (d) having an acid-decomposable group whose solubility in an aqueous alkali solution is increased by an acid-catalyzed reaction in the side chain, the acid-decomposable group of the side chain is efficiently dissociated by an acid. The solubility of the product in aqueous alkali is significantly different from that of the compound before dissociation. (D) above
Examples of the compound having an acid-decomposable group whose solubility in an aqueous alkali solution is increased by an acid-catalyzed reaction in a side chain include, for example, an acrylic resin, a copolymer of styrene and acrylic acid, and a polymer of hydroxystyrene (polyvinyl phenol) And the like. Compounds in which a hydrogen atom such as a phenolic hydroxyl group and a carboxyl group of an alkali aqueous solution-soluble resin such as those described above are substituted with a group capable of dissociating in the presence of an acid (an acid-decomposable group).

In the compound having an acid-decomposable group, it is not necessary that all of the hydroxyl groups or carboxyl groups are protected by the acid-decomposable group. Regarding the molecular weight of the vinyl polymer having an acid-decomposable group, the weight-average molecular weight (Mw) [weight average measured by gel permeation chromatography using a standard polystyrene calibration curve from the viewpoint of compatibility with an aqueous alkali-soluble resin] Molecular weight, the same applies hereinafter) is 1,5
It is preferably from 00 to 3,000, and from 1,800 to
More preferably, it is 2,500.

Examples of the acid-decomposable group include a methoxymethyl group, a methoxyethoxymethyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, a benzyloxymethyl group, a 1-methoxyethyl group, a 1-ethoxyethyl group and a methoxybenzyl group. Group, t-butyl group, methoxycarbonyl group, ethoxycarbonyl group, t-butoxycarbonyl group, trimethylsilyl group, triethylsilyl group, phenyldimethylsilyl group and the like. Among them, a tetrahydropyranyl group, a tetrahydrofuranyl group, a t-butoxycarbonyl group, a 1-ethoxyethyl group, a triethylsilyl group and the like can be mentioned. These are used alone or in combination of two or more.

The rate of substitution of phenolic hydroxyl groups or carboxyl groups by hydrogen by acid-decomposable groups (that is, the ratio of acid-decomposable groups to hydrogen of phenolic hydroxyl groups or carboxyl groups and the total number of acid-decomposable groups in component (d)). Is 15)
It is preferably from 100 to 100 mol%, more preferably from 30 to 100 mol%.

The compound having an acid-decomposable group whose solubility in an aqueous alkali solution is increased by an acid-catalyzed reaction in the side chain as the component (d) is, for example, a phenolic hydroxyl group of a compound having a phenolic hydroxyl group or a carboxyl group. Alternatively, it can be produced by substituting a carboxyl group hydrogen atom with the acid-decomposable group. As this method, a conventionally well-known method can be adopted.For example, when an acetal group such as a tetrahydropyranyl group or a 1-ethoxyethyl group is introduced as an acid-decomposable group,
As a reactant in the presence of an acid catalyst, 3,4-dihydro-
A vinyl ether compound such as 2H-pyran, ethyl vinyl ether or poly (p-vinylphenol) is reacted in a suitable reaction solvent.

(D) 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 3 to 300 parts by weight based on 100 parts by weight of the (a) aqueous alkali soluble resin. Preferably, 5
More preferably, it is 200 parts by weight. If the blending amount is less than 3 parts by weight, the film loss of the unirradiated portion tends to be large in a system in which the irradiated portion has increased solubility in an alkaline aqueous solution due to an acid catalyzed reaction. In a system in which solubility in an aqueous alkali solution is increased by an acid catalyzed reaction, the dissolution rate of the irradiated portion in a developer tends to decrease.

Usually, the component (a) of the present invention is a soluble resin in an aqueous alkali solution, (b) a polyphenol compound, (c) a compound capable of generating an acid upon irradiation with active actinic radiation, and (d) an aqueous alkali solution by an acid-catalyzed reaction on the side chain. The compound having an acid-decomposable group whose solubility in the compound is increased is dissolved in a suitable solvent and provided as a resist solution. 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 such as propylene glycol monomethyl ether acetate. Examples include alkyl ether acetates, ketones such as methyl amyl ketone, aromatic hydrocarbons such as toluene, and nonesters such as 2-hydroxypropionic acid. These are used alone or in combination of two or more.

The amount of the solvent is preferably 50 to 95% by weight, more preferably 60 to 90% by weight, based on the total amount of the photosensitive resin composition containing the solvent. If the amount is less than 50% by weight, the solvent tends not to have sufficient solubility in the resist material,
If it exceeds, a sufficient thickness tends not to be obtained when a resist film is used.

The photosensitive resin composition of the present invention may contain a surfactant in an amount of 100% in total for the component (a) in order to improve coatability and developability such as prevention of striation (unevenness of film thickness).
It is preferable to add about 1 × 10 ⁻⁶ to 1 × 10 ⁻³ parts by weight based on parts by weight. Examples of the surfactant include polyoxyethylene uraryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, and polyoxyethylene octyl phenol ether. Commercially available products include Megafax F171 and F171.
173 (trade name, manufactured by Dainippon Ink and Chemicals, Inc.), Florado FC430, FC431 (trade name, manufactured by Sumitomo 3M Limited), and organosiloxane polymer KP341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.). . These are used alone or in combination of two or more.

Further, the photosensitive resin composition of the present invention includes:
If necessary, about 1 × 10 ⁻⁶ to 1 × 10 ⁻² parts by weight of a storage stabilizer, a dissolution inhibitor and the like can be added to 100 parts by weight of the total amount of the component (a).

The resist pattern in the present invention is obtained by applying the photosensitive resin composition of the present invention on a circuit-forming surface or a protective film-forming surface of a substrate such as a wafer or glass and drying it to form a coating film. It can be manufactured by irradiation and development. Further, by using the resist pattern as a mask, for example, an electronic device can be obtained by etching or ion-implanting the substrate.

There are no particular restrictions on the conditions for the irradiation with the actinic radiation, 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 are used. . The development can be performed, for example, with a developer. Examples of the developer include inorganic alkalis such as sodium hydroxide, primary amines such as ethylamine, secondary amines such as diethylamine, and triethylamine. And quaternary ammonium salts such as tetramethylammonium hydroxide and choline, or alkaline aqueous solutions in which cyclic amines such as piperidine are dissolved.

[0041]

The present invention will be described below with reference to examples.

Synthesis Example 1 328.1 g of m-cresol and p-cresol 4 in a separable flask equipped with a stirrer, a cooling tube and a thermometer
Then, 00.9 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, and a polycondensation reaction was performed for 3 hours while stirring at an internal temperature of 97 ° C. Thereafter, the internal temperature was raised to 180 ° C., and at the same time, the pressure in the reaction vessel was reduced to 10 to 20 mmHg, and unreacted cresol, formaldehyde, water and oxalic acid were recovered. Next, the molten resin was poured into a metal vat to collect the cresol novolak resin. This resin is referred to as resin 1-1.

Next, 550 g of Resin 1-1 was dissolved in 1,100 g of ethyl cellosolve acetate to form a resin varnish.
000 g was mixed and stirred for 30 minutes and then allowed to stand. As a result, a dense layer having a high molecular weight component was obtained in the lower part. The concentrated layer was separated and dried under reduced pressure to obtain an alkali aqueous solution-soluble resin having a reduced low molecular weight component (hereinafter, this resin is referred to as resin 1-).
2). When resin 1-2 was analyzed by GPC, the ratio of low molecular weight components having a polystyrene molecular weight of 2,000 or less was 5% by weight.

Synthesis Example 2 In the same separable flask as in Synthesis Example 1, 260.0 g of m-cresol, 195.0 g of p-cresol,
220.3 g of 3,5-xylenol, 339.0 g of 37% by weight formalin and 2.2 g of oxalic acid were charged, and a novolak resin was synthesized in the same manner as in Synthesis Example 1 (hereinafter, this resin is referred to as 2-1). . Then, resin 2-
1 550 g of ethyl cellosolve acetate 825 g
Into a resin varnish, and methanol 1,1
After mixing and stirring for 30 minutes, 00 g and 825 g of distilled water were allowed to stand, and a dense layer having a high molecular weight component was obtained in the lower layer. The concentrated layer 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 2-2). When resin 2-2 was analyzed by GPC, the ratio of low molecular weight components having a polystyrene equivalent molecular weight of 2,000 or less was 5% 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 g) and 300 ml of ethyl acetate were charged and dissolved by stirring at room temperature (25 ° C.). Then, 3,4-dihydro-2H-pyran 105 was placed in the flask.
g, 12 ml of hydrochloric acid (12N) was added, and the mixture was stirred at room temperature for 1 hour and then left at room temperature for 3 days. Then, the reaction solution was added with 2.
After adding 160 ml of a 38% by weight aqueous solution and stirring well, the organic layer was taken out. After the organic layer solution obtained here was washed three times with 300 ml of distilled water, the organic layer was dried and concentrated by an evaporator. Concentrated solution 50 ml petroleum ether 50
Reprecipitation was performed using 0 ml. After repeating the reprecipitation operation twice, the product was dried under reduced pressure (3 mmHg, 40 mmHg).
C.) for 8 hours to obtain 22 g of poly (p-vinylphenol) in which 95% of the hydroxyl groups of the hydroxyl groups in the polymer were replaced with tetrahydropyranyl groups.

Synthesis Example 4 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.). Was. Next, the flask was immersed in an ice bath to adjust the temperature in the reaction system to 5 ° C., and then 15 g of ethanesulfonyl chloride was added dropwise using a dropping funnel over 20 minutes. 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. Next, the reaction solution was placed in 300 ml of distilled water,
The deposited precipitate was separated by filtration. This precipitation was repeated several times using acetone and ethanol to obtain 32 g of ethanesulfonic acid ester of pyrogallol.

Example 1 In a separable flask equipped with a stirrer, 274 g of the resin 1-2 obtained in Synthesis Example 1 and 4,6-bis [(4hydroxyphenyl) methyl] -1,3-benzenediol 9
g, 9 g of 1,1,1-tris (4-hydroxyphenyl) methane, poly (p-vinylphenol) obtained by substituting the hydrogen of the hydroxyl group obtained in Synthesis Example 3 with a tetrahydropyranyl group
10.1 g, 4 g of ethanesulfonic acid ester of pyrogallol obtained in Synthesis Example 4 and 432 g of 2-heptanone
Was charged and dissolved to visually confirm that a uniform solution was obtained. Then, 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 resulting 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 0.7 μm. An acceleration voltage of 50k is applied to this substrate.
After writing a hole pattern on the resist film at an irradiation dose of ³ μC / cm ² using an electron beam
A heat treatment for a minute promotes a reaction that increases the solubility of the latent image portion of the resist in an aqueous alkaline solution. After this heat treatment, the resist film on which the latent image was formed was developed for 60 seconds using a 2.38% by weight aqueous solution of tetramethylammonium hydroxide to obtain a positive resist pattern. 0.15μm
As a result of observing the cross-sectional shape of the hole pattern with an electron microscope, the resist pattern was rectangular and good. Also,
The film loss after development was 0.02 μm, which was good.

Example 2 In Example 1, 64.4 g of resin 2-2 and 10 g of 4,6-bis [(4hydroxyphenyl) methyl] -1,3-benzenediol were used instead of 74 g of resin 1-2.
g, a resist solution was prepared in the same manner as in Example 1 except that the blending amount of 1,1,1-tris (4-hydroxyphenyl) methane was changed to 17.6 g, and the resist solution was irradiated at a dose of 3.5 μC / cm ^2. An electron beam lithography experiment was performed. As a result of observing the cross-sectional shape of the hole pattern of 0.15 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.

Example 3 A resist solution was prepared in the same manner as in Example 1 except that the resin 1-292 g was used instead of the resin 1-274 g, and irradiation was performed at 5.5 μC / cm ² . Electron beam lithography experiments were performed with the amount. As a result of observing the cross-sectional shape of the 0.20 μm hole pattern with an electron microscope, the resist pattern was rectangular and good. Further, the amount of film reduction after development is 0.1.
03 μm, which was good.

Comparative Example 1 In Example 1, 4,6-bis [(4-hydroxyphenyl) methyl] -1,3-benzenediol was replaced with 18
g, a resist solution was prepared in the same manner as in Example 1 except that 1,1,1-tris (4-hydroxyphenyl) methane was not blended, and an electron beam lithography experiment was conducted at an irradiation dose of 8.5 μC / cm ^2. Was done. As a result of observing the cross-sectional shape of the 0.20 μm hole pattern with an electron microscope, the resist pattern had an inverted tapered shape, and the pattern shape was deteriorated as compared with Example 1. The amount of film reduction after development was 0.03 μm, which was good.

Comparative Example 2 In Example 1, 18 g of 1,1,1-tris (4-hydroxyphenyl) methane and 4,6-bis [(4hydroxyphenyl) methyl] -1,3-benzenediol were mixed. A resist solution was prepared in the same manner as in Example 1 except that it was not performed, and an electron beam lithography experiment was performed at an irradiation dose of 8.5 μC / cm ² . As a result of observing the cross-sectional shape of the 0.20 μm hole pattern with an electron microscope, the resist pattern had a forward tapered shape, and the pattern shape was deteriorated as compared with Example 1. The amount of film reduction after development was 0.03 μm, which was good.

[0053]

The positive type chemically amplified photosensitive resin composition according to the first aspect is excellent in sensitivity, resolution and pattern shape. The positive type chemically amplified photosensitive resin composition according to the second aspect has the effects of the first aspect, and further has excellent resolution. The positive type chemically amplified photosensitive resin composition according to the third aspect has the effects of the first or second aspect of the invention, and is further excellent in resolution.

The positive type chemically amplified photosensitive resin composition according to the fourth aspect has the effects of the inventions according to the first, second or third aspects, and is further excellent in resolution and pattern shape. Claim 5
The positive-type chemically amplified photosensitive resin composition described above has the effects of the invention described in the first, second, third, or fourth aspects, and is further excellent in resolution and pattern shape. The positive type chemically amplified photosensitive resin composition according to the sixth aspect has the effects of the inventions according to the first, second, third, fourth or fifth aspect, and is further excellent in sensitivity, resolution and pattern shape.

The method for manufacturing a resist pattern according to claim 7 is excellent in resolution, pattern shape, workability and productivity. The method of manufacturing an electronic device according to claim 8 provides excellent resolution, pattern shape, workability, and productivity.

 ──────────────────────────────────────────────────の Continuing on the front page (72) Koji Kato, Inventor 4-1-1, Higashi-cho, Hitachi City, Ibaraki Prefecture Hitachi Chemical Co., Ltd. Yamazaki Office (72) Inventor, Masahiro Hashimoto 4--13, Higashi-machi, Hitachi City, Ibaraki Prefecture No. 1 Inside Hitachi Chemical Co., Ltd.Yamazaki Plant (72) Inventor Yui Arai 1-280 Higashi Koigakubo, Kokubunji City, Tokyo, Japan Inside (72) Inventor Toshio Sakami 1-280 Higashi Koigabo, Kokubunji City, Tokyo F-term in Hitachi Central Research Laboratory, Inc. (reference) 2H025 AA01 AA02 AA03 AB16 AC04 AC05 AC06 AC07 AC08 AD03 BE00 BG00 CB29 CB41 CB52 CB56 CC20 2H096 AA25 BA10 BA11 BA16 BA20 EA03 EA04 EA05 EA06 EA07 EA07

Claims (8)

[Claims] (1) an aqueous alkali-soluble resin,
(B) at least two types of polyphenol compounds,
(C) Positive chemical amplification system photosensitization comprising a compound that generates an acid upon irradiation with actinic radiation and (d) a compound having an acid-decomposable group whose side chain has increased solubility in an aqueous alkali solution by an acid-catalyzed reaction. Resin composition. 2. The positive chemically amplified photosensitive resin composition according to claim 1, wherein the polyphenol compound (b) has 2 to 8 phenolic hydroxyl groups. 3. The method according to claim 2, wherein (b) the polyphenol compound is (b)
3. A positive chemical amplification system according to claim 1, wherein 1) a polyphenol compound having 2 or 3 hydroxyl groups in the molecule and (b2) a polyphenol compound having 4 to 8 hydroxyl groups in the molecule. Resin composition. 4. The positive mold according to claim 1, wherein the (a) alkali-soluble resin is a novolak resin obtained by polycondensing a cresol compound or a xylenol compound with an aldehyde compound in the presence of an acid catalyst. Chemically amplified photosensitive resin composition. 5. A low-molecular-weight component having a polystyrene-equivalent molecular weight of 2,000 or less of (a) an alkali aqueous solution-soluble resin,
The positive type chemically amplified photosensitive resin composition according to claim 1, wherein the content is 10 to 10% by weight. 6. The compounding amount of component (a), component (b), component (c) and component (d) is such that component (b) is 2 to 2 parts by weight based on 100 parts by weight of the total amount of component (a). The positive chemically amplified photosensitive resin composition according to claim 1, 2, 3, 4, or 5, wherein 50 parts by weight, 2 to 30 parts by weight of the component (c) and 3 to 300 parts by weight of the component (d). . 7. A resist comprising irradiating a coating film of the positive-type chemically amplified photosensitive resin composition according to claim 1, 2, 3, 4, 5 or 6 with actinic radiation and then developing the resist. The method of manufacturing the pattern. 8. The positive-type chemically amplified photosensitive resin composition according to claim 1, 2, 3, 4, 5, or 6 is applied to a circuit forming surface or a protective film forming surface of an electronic circuit and dried. A method for manufacturing an electronic device, comprising irradiating a coating film with actinic radiation and then developing.