JP2003015290A - Photosensitive resin composition and positive type pattern forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition developable with an aqueous alkali solution and having positive type pattern forming ability and to provide a new positive type pattern forming method. SOLUTION: The positive type photosensitive resin composition comprises (A) a photosensitive polymer of formula (1) (where R<1> is a tetravalent aromatic group; R<2> is a divalent aromatic group; and (k), (m) and (n) are each an integer of >=1), (B) a bior higher functional vinyl ether compound, (C) a photo-acid generator which changes into an acidic compound under active light such as UV and (D) a solvent. The positive type pattern forming method uses the composition.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyimide-type heat-resistant resin composition capable of forming a pattern with an alkaline aqueous solution and having positive-type photosensitivity, and a heat-resistant pattern using the photosensitive resin composition. The present invention relates to a forming method.

[0002]

2. Description of the Related Art Conventionally, as a heat-resistant polymer composition having photosensitivity, a type in which a tertiary amine compound having an acryl or methacryl group is introduced by ionic bond to polyamic acid which is a precursor of polyimide ( Kaisho 54-
145794) or a compound having an acryl or methacryl group introduced through an ester bond (Japanese Patent Laid-Open No. Sho 4).
9-115541). All of them have a negative pattern forming ability and are used as a protective film for electronic materials such as semiconductors. However, the photosensitive resin must use an organic solvent having a high polarity at the time of pattern formation, and is not preferable in terms of industrial waste and environmental problems. Furthermore, these resins have a high swelling property with respect to the organic solvent. Therefore, it is impossible to form a fine pattern.

To address these problems, a positive type photosensitive resin has been proposed in which a diazonaphthoquinone compound is added as a photosensitizer to polybenzoxazole having heat resistance equivalent to that of a polyimide resin (JP-A-56-27140). This positive-type photosensitive resin has the advantage that it is possible to form a pattern in an alkaline aqueous solution and therefore does not require the use of an organic solvent. Furthermore, since this resin has a low swelling property in an alkaline aqueous solution, it is relatively A fine pattern can be obtained. However, this positive-type photosensitive resin has a drawback that the dimensional control of the pattern is poor in the pattern on a large wafer because the difference in solubility between the exposed portion and the unexposed portion is low.

However, with the rapid development of semiconductor technology in recent years, the required characteristics of the related materials, especially the pattern forming material, have become severe. As a material for semiconductor protective film, while it has film characteristics equivalent to those of polyimide resin that is already popular, it is required to have a resolution comparable to that of resist materials, and in that sense, high resolution is possible. The development of positive-type photosensitive resin compositions is strongly awaited.

[0005]

The object of the present invention is to solve the above-mentioned conventional drawbacks, to enable pattern formation with an alkaline aqueous solution, and to provide a heat-resistant resin composition having positive photosensitivity, and The present invention provides a method for forming a heat resistant pattern using a photosensitive resin composition.

[0006]

DISCLOSURE OF THE INVENTION As a result of earnest studies to achieve the above object, the present inventor has found a novel positive photosensitive resin composition having a composition described below and a method for forming a positive pattern thereof. The present invention has been completed by finding that the above object can be achieved by adopting the method.

That is, the present invention provides (A) a photosensitive polymer represented by the following general formula:

[Chemical 2] (However, in the formula, R ¹ is a tetravalent aromatic group, R ² is a divalent aromatic group, and k, m, and n each represent an integer of 1 or more.) (B) Bifunctional or more Vinyl ether compound,
A positive-type photosensitive resin composition comprising (C) a photo-acid generator capable of being converted into an acidic compound by actinic rays such as ultraviolet rays and (D) a solvent. In addition, this composition,
An insolubilized coating film forming step of coating on a substrate and drying at 90 to 130 ° C. to form an insolubilized coating film against an alkaline aqueous solution, and the obtained insolubilized coating film is exposed to active ultraviolet rays through a positive mask pattern. After that, 90 ~ 13
An exposure coating film decomposition step of heating only at 0 ° C. to decompose only the exposed portion of the insolubilized coating film, and a positive pattern for dissolving only the exposed decomposition portion of the exposed coating film using an alkaline aqueous solution to develop a positive pattern The positive type pattern forming method is characterized by including a developing step and an imidization heat treatment step of heat-treating the developed positive type pattern to form a polyimide positive type pattern.

The present invention will be described in detail below.

The method for synthesizing the photosensitive polymer composition (A) used in the present invention is carried out by the following procedure.

(1) R ¹ shown in the general formula of the above chemical formula 2
Esterification reaction step of acid dianhydride having a skeleton and a phenol compound, (2) under the addition of a dehydration condensation agent, the esterification reaction product of (1) and R ² skeleton in the general formula of the above Chemical formula ² A polycondensation reaction step with a diamine compound having (1), (3) a purification step of a composition subjected to a polycondensation reaction, and (4) a preparation step of a resin solvent containing a photosensitizer.

First, the above synthesis method will be described in the order of steps (1) to (4).

(1) Step of esterification reaction of acid dianhydride having R ¹ skeleton in the formula (2) with phenolic compound The acid component to be the R ¹ skeleton used in the present invention is, for example, pyromellitic acid, 3,3 ', 4,4'-biphenyltetracarboxylic acid, 2,3,3', 4'-biphenyltetracarboxylic acid, 3,3 ', 4,4'-benzophenonetetracarboxylic acid, 4,4'- Oxydiphthalic acid, 3,
3 ', 4,4'-diphenylsulfone tetracarboxylic acid, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane, 2,3,6,7-naphthalene tetracarboxylic acid, 1,2,5 , 6-naphthalene tetracarboxylic acid, 1,4,5,8-naphthalene tetracarboxylic acid, 1,2,3,4-cyclobutane tetracarboxylic acid,
1,2,3,4-butanetetracarboxylic acid, 1,2,
4,5-cyclopentane tetracarboxylic acid, 1,2,
4,5-cyclohexanetetracarboxylic acid, 3,3 ',
4,4'-bicyclohexyl tetracarboxylic acid, 2,
3,5-tricarboxycyclopentyl acetic acid, 3,4-
Examples thereof include dicarboxy-1,2,3,4-tetrahydronaphthalene-1-succinic acid and the anhydrides thereof, and these can be used alone or in combination.

Further, examples of the phenol compound introduced into the above-mentioned R ¹ skeleton acid component by an ester bond include:

[Chemical 3] Etc.

The esterification reaction between the above-mentioned R ¹ skeleton acid component and the above-mentioned phenol compound is carried out, for example, with an acid dihydrate having an R ¹ skeleton and an alcohol having a phenol skeleton. It is preferable to carry out the reaction at room temperature in the presence of a basic aprotic polar solvent such as N-methyl-2-pyrrolidone or the like and a basic catalyst such as triethylamine, pyridine or triethanolamine to facilitate the reaction. This basic catalyst is used in an amount of 1.5 to 3.0 times, preferably 2.0 times that of the acid component.
It can be used in the range of up to 2.5 times mol.

Further, m and n in the above formula (2) can be combined in any ratio, but m / n
It is desirable to use n in the range of 0.1 to 1.0. m
When / n is less than 0.1, the number of polymers dissolved in an alkaline aqueous solution decreases, and as a result, the sensitivity to ultraviolet rays decreases. Further, when m / n exceeds 1.0, the storage stability of the composition is deteriorated, which is not preferable.

[0016] (2) as the diamine component comprising a R ² backbone of the polycondensation reaction used in the present invention (A) polymer composition of the esterified diamine compound comprising a R ² backbone reactants and of 2 where the , For example, m-phenylenediamine, p-phenylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 2,6-diaminotoluene, 3,5-diaminotoluene, 1-methoxy-2,
4-diaminobenzene, 1,4-diamino-2-methoxy-5-methylbenzene, 1,3-diamino-4,6-
Dimethylbenzene, 3,5-diaminobenzoic acid, 2,5
-Diaminobenzoic acid, 1,2-diaminonaphthalene,
1,4-diaminonaphthalene, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene, 1,8-diaminonaphthalene, 2,3-diaminonaphthalene, 2,6-diaminonaphthalene, 1 ，
4-diamino-2-methylnaphthalene, 1,5-diamino-2-methylnaphthalene, 1,3-diamino-2-phenylnaphthalene, 2,2-bis (4-aminophenyl) propane, 1,1-bis ( 4-aminophenyl) ethane, 4,4'-diaminodiphenylmethane, 3,3 '
-Dimethyl-4,4'-diaminodiphenylmethane,
3,3 ', 5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-5,5'-
Diethyl-4,4'-diaminodiphenylmethane, 3,
3 ', 5,5'-tetraethyl-4,4'-diaminodiphenylmethane, 4,4'-methylenebis (cyclohexylamine), 4,4'-methylenebis (3,3-dimethyl-cyclohexylamine), 2,4' -Diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfone,
4,4'-diaminodiphenyl sulfone, 4,4'-
Diaminobenzanilide, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether,
4,4'-diaminodiphenyl ether, bis (4-aminophenyl) diethylsilane, bis (4-aminophenyl) diphenylsilane, bis (4-aminophenyl)
-N-methylamine, bis (4-aminophenyl) -N
-Phenylamine, 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 2,6-diaminopyridine, 3,5-diaminopyridine, 4,4'-
Diaminobiphenyl, 3,3'-diaminobiphenyl,
3,3'-dimethyl-4,4'-diaminobiphenyl,
3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, o-toluidine sulfone, 4,4'-bis (4-aminophenoxy) biphenyl, 2 , 2-bis [4- (4-aminophenoxy) phenyl] propane,
Bis [4- (4-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 1,4-bis (4- Aminophenoxy) benzene, 1,3-bis (4-aminophenoxy)
Benzene, 9,10-bis (4-aminophenyl) anthracene, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis (3 -Aminophenyl) hexafluoropropane, 1,1-bis (4-aminophenyl) -1-phenyl-2,2,2-trifluoroethane, 2,2-bis (3-amino-4-hydroxyphenyl) hexa Fluoropropane, 2,2-bis (3-amino-4-methylphenyl) hexafluoropropane,
2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane and the like can be mentioned, and these can be used alone or in combination of two or more. Also,
These compounds are preferably used in an equimolar amount with respect to the above ester compound, but can be used in a range of 0.5 to 1.5 times the molar amount depending on the purpose of use, final viscosity and molecular weight.

Next, in the present invention, n in the above formula 2
The dehydration condensing agent of the ester compound and the diamine component, which has the structure shown in, will be described.

When the above-mentioned ester compound and diamine component are reacted by a polycondensation method, usually an acid chloride is used, but in the electric and electronic fields including semiconductor devices, the released chlorine ion is product reliability. In the case of carrying out the polymerization by the acid chloride method, it is necessary to sufficiently wash with pure water after polycondensation because it causes a defect. In addition, carbodiimide derivatives such as DCC (dicyclohexylcarbodiimide) used as a dehydration condensing agent are accompanied by side reactions, gelation of a polyimide precursor,
There are problems such as toxicity, and it is difficult to completely remove urea generated as a by-product. Therefore, it is used by cooling the reaction system, adding the dehydration condensing agent in several times, breaking the molar balance of the acid component and the diamine component, and the like. As another method, diphenyl (2,2) has been recently used as a dehydration condensing agent for which the present inventors have applied for a patent.
3-dihydro-2-thioxo-3-benzoxazole) phosphonate and its derivatives, diphenyl (2,
3-dihydro-2-thioxo-3-benzothiazole)
A polycondensation method using phosphonate and a derivative thereof can be mentioned. In this method, stable production can be performed under mild conditions, so that a polyimide precursor having high resolution and high film characteristics can be obtained. These may be used alone or in combination of two or more. These can be used in an amount of 1 to 3 times, preferably 2 to 2.5 times the molar amount of the above ester compound.

In the polycondensation reaction having a structure represented by m in the above formula 2, the polycondensation reaction of the acid component shown in step (1) is carried out after the dehydration condensation reaction of the ester compound and the diamine component described above is completed. It is possible to react by mixing an anhydride with the above diamine compound.

Examples of the polymerization solvent for the resin composition used in the present invention include aprotic polar solvents such as N-methylpyrrolidone, N, N'-dimethylacetamide and N, N'-dimethylformamide, cyclohexanone and cyclohexanone. Pentanone and the like are used, and these can be used alone or in combination of two or more.

(3) Purification of composition subjected to polycondensation reaction The obtained slurry is stirred and washed in a poor solvent such as methanol, ethanol, isopropyl alcohol and water, and the deposited product is dried under reduced pressure to form a solid. A compound having a resin skeleton represented by 2 is obtained.

(4) Preparation of Resin Solvent Containing Photosensitizer The polymer composition produced as described above has N-methyl-2-pyrrolidone, dimethylacetamide, dimethylformamide, γ-butyrolactone,
It is dissolved in a polar solvent such as γ-valerolactone, cyclohexanone, cyclopentanone, tetrahydrofuran, dioxane and used in the form of varnish.

The (B) bifunctional or higher functional vinyl ether compound used in the present invention is a compound for causing a cross-linking reaction with the polymer composition represented by the chemical formula 2 through an acetal bond. Therefore, it is necessary to have a bifunctional or higher functional vinyl ether group. Examples of the bifunctional or higher vinyl ether compound include:

[Chemical 4]

[Chemical 5] These may be used alone or in admixture of two or more. The amount of addition is the polymer resin composition 10
1 to 30 parts by weight is preferable with respect to 0 parts by weight. If the addition amount is less than 1 part by weight, the effect is not obtained, and if it exceeds 30 parts by weight, the properties of the obtained coating film deteriorate.

The photoacid generator (C) used in the present invention is a substance which produces a Lewis acid or a cation species by an actinic ray such as ultraviolet rays, and in recent years, it is a resist for forming a fine pattern of a semiconductor integrated circuit (commonly called a chemically amplified resist). Is often used in. Examples of the photo-acid generator include the following chemical formulas 6 to 1.
The compound shown in 3 is mentioned.

[0025]

[Chemical 6]

[Chemical 7]

[Chemical 8]

[Chemical 9]

[Chemical 10]

[Chemical 11]

[Chemical 12]

[Chemical 13] These compounds are more preferable in the present invention, but are not limited to the above structure as long as they are decomposed by irradiation with active ultraviolet rays and efficiently generate an acid. These can be used alone or in combination,
The addition amount is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the photosensitive resin composition. If it is less than 0.1 parts by weight, the sensitivity to ultraviolet rays is low, and if it exceeds 20 parts by weight, the properties of the coating film obtained are deteriorated, so this range is preferable. Also,
The photoacid generator is not limited to the above compounds as long as it can efficiently generate a Lewis acid or a cationic species. Furthermore, when using the photoacid generator,
It is preferably selected according to the light wavelength of the exposure light source used.

The resin composition obtained according to the present invention is used in a state of being dissolved in a solvent. Examples of the solvent (D) to be used include N-methylpyrrolidone,
Aprotic polar solvents such as N, N'-dimethylacetamide, N, N'-dimethylformamide, cyclohexanone, cyclopentanone, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, Butyl lactate and the like can be mentioned, and these can be used alone or in admixture of two or more.

Next, a method for forming a positive pattern using the photosensitive resin composition obtained according to the present invention will be described.

Considering application to a semiconductor device, first, this resin composition is coated on a target wafer using a spin coater, and then the coating film is dried at 90 to 130 ° C. A mask having a pattern drawn on the obtained coating film is transmitted to irradiate active ultraviolet rays of 365 nm and 436 nm. Next, the coating film is heated again at 90 to 130 ° C., and subsequently the coating film is treated with an alkaline aqueous solution, for example, an inorganic alkaline aqueous solution such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate or ammonia, ethylamine or n-propyl. Primary amines such as amines,
Secondary amines such as diethylamine and di-n-propylamine, tertiary amines such as triethylamine and methyldimethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide and the like. Only the portion irradiated with actinic light is dissolved and developed using an aqueous solution of a primary amine, and rinsed with pure water. As a developing method, a method such as spraying, paddle, dipping, and ultrasonic wave can be considered. As a result, a desired positive pattern can be obtained on the target wafer. further,
By heat-treating this coating film at 150 ° C. for 1 hour, at 250 ° C. for 1 hour, and at 350 ° C. for 1 hour, the resin composition can be imidized to form a polyimide film having excellent film characteristics.

That is, the greatest feature of the present invention is that, as a result of intensive research conducted by the present inventor, a positive pattern formation mechanism described below was discovered. In the positive pattern forming method, the resin composition has a carboxylic acid moiety of the polyimide precursor of Chemical formula 3 having R ¹ and R ² skeletons in the insolubilizing coating film drying step of drying after spin coating on the substrate. It chemically reacts with a vinyloxy group-containing compound having an R ³ skeleton and becomes insoluble in an alkaline aqueous solution. Then, by irradiating the insolubilized coating film with an actinic ray such as an ultraviolet ray, the photoacid generating photosensitizer in the actinic ray exposed portion is decomposed to generate an acid. Further, in the subsequent exposure coating decomposition step of heating, the generated acid decomposes the chemical bond between the polyimide precursor and the vinyloxy group-containing compound, and R
Return to the polymer of the polyimide precursor having the ¹ , R ² skeleton to regenerate the carboxylic acid. The carboxylic acid of this polymer has a high solubility in an alkaline aqueous solution,
As a result, only a portion irradiated with an actinic ray such as an ultraviolet ray has a high solubility in an alkaline aqueous solution, and a non-irradiated portion is insolubilized and is not dissolved at all. Due to this high contrast, the photosensitive resin composition of the present invention can form a positive pattern having high resolution and good dimensional controllability.

Further, in the resin compositions containing the diazonaphthoquinone compound proposed so far, low sensitivity to actinic rays has been a problem. The main cause is derived from the diazonaphthoquinone compound. In other words, the diazonaphthoquinone compound reduces the transmittance of actinic rays when added in a large amount, resulting in a decrease in sensitivity. In the photosensitive resin composition of the present invention, since a positive type pattern is formed without using a diazonaphthoquinone compound, not only has a good actinic ray transmittance, but also an acid generated from a photoacid generating photosensitizer is repeatedly used. Therefore, a sufficient pattern forming ability can be exhibited even with a low amount of actinic rays. Since this reaction mechanism is capable of causing a chemical reaction in an amplified manner,
In the present invention, it has become possible to provide a highly sensitive photosensitive resin composition.

[0031]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below based on Examples.

Example 1 First, a reaction flask equipped with a nitrogen introducing tube and a stirring blade was placed in a 4-
Hydroxybenzyl alcohol and triethylamine (1.0 mol each) are added to 2.0 L of N-methyl-2-pyrrolidone and stirred to dissolve. Continue 3,3 ', 4,4'
-Bezophenone tetracarboxylic acid dianhydride 0.5mo
1, and stirred for 3 hours to carry out an esterification reaction. After completion of the reaction, 4,4'-diaminodiphenyl ether 1.0mo
Then, 1.0 mol of diphenyl (2,3-dihydro-2-thioxo-3-benzoxazole) phosphonate is added and stirred for 3 hours.
Further, 0.5 mol of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride is added to this reaction solution, and the mixture is stirred and reacted for 3 hours. The obtained slurry-like mixture is put into a large amount of methanol for washing, and the precipitated solid resin is dried by a vacuum dryer for 12 hours. 20 g of dried solid resin, 10 g of triethylene glycol divinyl ether, and 2.0 of 1,8-naphthalimidyl triflate.
g in 80 g of N-methyl-2-pyrrolidone,
The photosensitive resin composition thus obtained was filtered through a 1 μm Teflon filter to obtain Sample 1.

A 6-inch silicon wafer was coated with this sample 1 by using a spin coater, and dried on a bake plate at 120 ° C. for 4 minutes to obtain a film thickness of 10
A coating film of μm was obtained. This coating film was irradiated with a test pattern with an energy of 10 to 1000 mj / cm ² by an ultraviolet exposure device using a bandpass filter that transmits only 365 nm, and subsequently heated at 120 ° C. for 1 minute. Next, static paddle development was performed for 60 seconds with a 2.38% TMAH (tetramethylammonium hydride) aqueous solution.

At this time, in the coating film exposed at 100 mJ / cm ² or more, the coating film was completely dissolved, and the obtained relief pattern had a sharp line and space pattern of 3.0 μm. I was able to confirm that Further, this relief pattern is applied at 150 ° C. for 1 hour, 2
Heat treatment at 50 ℃ for 1 hour, 350 ℃ for 1 hour,
The imidization of the coating film was completed. This imide pattern is
No resin pattern collapse, peeling, or the like was observed in the heat treatment.

Example 2 First, a reaction flask equipped with a nitrogen inlet tube and a stirring blade was placed in a 3-
Hydroxybenzyl alcohol and triethylamine (1.0 mol each) are added to 2.0 L of N-methyl-2-pyrrolidone and stirred to dissolve. Continue 3,3 ', 4,4'
-Bezophenone tetracarboxylic acid dianhydride 0.5mo
1, and stirred for 3 hours to carry out an esterification reaction. After completion of the reaction, 4,4'-diaminodiphenyl ether 1.0mo
Then, 1.0 mol of diphenyl (2,3-dihydro-2-thioxo-3-benzoxazole) phosphonate is added and stirred for 3 hours.
Further, 0.5 mol of 3,3 ', 4,4'-bezophenone tetracarboxylic acid dianhydride was added to this reaction solution, and the mixture was stirred and reacted for 3 hours. The obtained slurry-like mixture is put into a large amount of methanol for washing, and the precipitated solid resin is dried by a vacuum dryer for 12 hours. 20 g of dried solid resin, 10 g of triethylene glycol divinyl ether and 2.0 g of 1,8-naphthalimidyl triflate.
Was dissolved in 80 g of N-methyl-2-pyrrolidone, and the obtained photosensitive resin composition was filtered through a 1 μm Teflon filter to obtain Sample 2.

A 6-inch silicon wafer was coated with this sample 2 using a spin coater, and dried on a bake plate at 120 ° C. for 4 minutes to give a film thickness of 10
A coating film of μm was obtained. This coating film was irradiated with a test pattern with an energy of 10 to 1000 mJ / cm ² by an ultraviolet exposure device using a bandpass filter that transmits only 365 nm, and subsequently heated at 120 ° C. for 1 minute. Next, static paddle development was performed for 60 seconds with a 2.38% TMAH (tetramethylammonium hydride) aqueous solution.

At this time, in the coating film exposed at 200 mJ / cm ² or more, the coating film was completely dissolved, and the obtained relief pattern had 3.0 μm line and space pattern sharply formed. I was able to confirm that Further, this relief pattern is applied at 150 ° C. for 1 hour, 2
Heat treatment at 50 ℃ for 1 hour, 350 ℃ for 1 hour,
The imidization of the coating film was completed. This imide pattern is
No resin pattern collapse, peeling, or the like was observed in the heat treatment.

Example 3 First, a reaction flask equipped with a nitrogen inlet tube and a stirring blade was placed in a 2-
Hydroxybenzyl alcohol and triethylamine (1.0 mol each) are added to 2.0 L of N-methyl-2-pyrrolidone and stirred to dissolve. Continue 3,3 ', 4,4'
-Bezophenone tetracarboxylic acid dianhydride 0.5mo
1, and stirred for 3 hours to carry out an esterification reaction. After completion of the reaction, 4,4'-diaminodiphenyl ether 1.0mo
Then, 1.0 mol of diphenyl (2,3-dihydro-2-thioxo-3-benzoxazole) phosphonate is added and stirred for 3 hours.
Further, 0.5 mol of 3,3 ', 4,4'-bezophenone tetracarboxylic acid dianhydride was added to this reaction solution, and the mixture was stirred and reacted for 3 hours. The obtained slurry-like mixture is put into a large amount of methanol for washing, and the precipitated solid resin is dried by a vacuum dryer for 12 hours. 20 g of dried solid resin, 10 g of triethylene glycol divinyl ether and 2.0 g of 1,8-naphthalimidyl triflate.
Was dissolved in 80 g of N-methyl-2-pyrrolidone, and the obtained photosensitive resin composition was filtered through a 1 μm Teflon filter to obtain Sample 3.

A 6-inch silicon wafer was coated with this sample 3 using a spin coater, and was heated and dried at 120 ° C. for 4 minutes on a bake plate to obtain a film thickness of 10
A coating film of μm was obtained. This coating film was irradiated with a test pattern with an energy of 10 to 1000 mJ / cm ² by an ultraviolet exposure device using a bandpass filter that transmits only 365 nm, and subsequently heated at 120 ° C. for 1 minute. Next, static paddle development was performed for 60 seconds with a 2.38% TMAH (tetramethylammonium hydride) aqueous solution.

At this time, in the coating film exposed at 140 mJ / cm ² or more, the coating film was completely dissolved, and the obtained relief pattern had a sharp line and space pattern of 3.0 μm. I was able to confirm that Further, this relief pattern is applied at 150 ° C. for 1 hour, 2
Heat treatment at 50 ℃ for 1 hour, 350 ℃ for 1 hour,
The imidization of the coating film was completed. This imide pattern is
No resin pattern collapse, peeling, or the like was observed in the heat treatment.

Example 4 First, a reaction flask equipped with a nitrogen inlet tube and a stirring blade was placed in a 4-
Hydroxybenzyl alcohol and triethylamine (1.0 mol each) are added to 2.0 L of N-methyl-2-pyrrolidone and stirred to dissolve. Then, 0.5 mol of hexafluoropropylidene-2,2-bisphthalic anhydride was added.
Addition is continued for 3 hours with esterification reaction. After completion of the reaction, 4,4'-diaminodiphenyl ether 1.0mo
Then, 1.0 mol of diphenyl (2,3-dihydro-2-thioxo-3-benzoxazole) phosphonate is added and stirred for 3 hours.
Furthermore, hexafluoropropylidene- was added to this reaction solution.
0.5 mol of 2,2-bisphthalic anhydride is added and stirred and reacted for 3 hours. The obtained slurry-like mixture is put into a large amount of methanol for washing, and the precipitated solid resin is dried by a vacuum dryer for 12 hours. 20 g of dried solid resin and triethylene glycol divinyl ether 1
0 g and 2.0 g of 1,8-naphthalimidyl triflate were dissolved in 80 g of N-methyl-2-pyrrolidone, and the resulting photosensitive resin composition was mixed with 1 μm of Teflon (registered trademark).
It filtered with the property filter and obtained sample 4.

A 6-inch silicon wafer was coated with this sample 4 using a spin coater, and dried on a bake plate at 120 ° C. for 4 minutes to give a film thickness of 10
A coating film of μm was obtained. This coating film was irradiated with a test pattern with an energy of 10 to 1000 mJ / cm ² by an ultraviolet exposure device using a bandpass filter that transmits only 365 nm, and subsequently heated at 120 ° C. for 1 minute. Next, static paddle development was performed for 60 seconds with a 2.38% TMAH (tetramethylammonium hydride) aqueous solution.

At this time, in the coating film exposed at 100 mJ / cm ² or more, the coating film was completely dissolved, and the obtained relief pattern had a sharp line and space pattern of 3.0 μm. I was able to confirm that Further, this relief pattern is applied at 150 ° C. for 1 hour, 2
Heat treatment at 50 ℃ for 1 hour, 350 ℃ for 1 hour,
The imidization of the coating film was completed. This imide pattern is
No resin pattern collapse, peeling, or the like was observed in the heat treatment.

[0044]

EFFECT OF THE INVENTION The photosensitive polymer composition of the present invention can be used as a moisture resistant protective film of a semiconductor device and can obtain a high resolution positive pattern,
Not only has it become possible to put the device into practical use, which has been difficult to develop in the past, but it is also possible to eliminate the organic solvent, which has been used enormously, because it is possible to form a pattern with an alkaline aqueous solution. . In addition, the photosensitive polymer resin composition of the present invention can achieve higher resolution and higher contrast than ever by using a novel photosensitive system.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) H01L 21/027 H01L 21/30 502R F term (reference) 2H025 AA02 AA04 AA10 AB16 AB17 AC08 AD03 BG00 CB25 CB41 CB45 CC17 CC20 FA17 2H096 AA25 BA11 DA01 EA05 FA01 GA08 4J043 PA02 PA04 PA19 QB15 QB24 QB25 QB31 QB34 RA35 RA39 SA06 SA42 SA43 SA44 SA47 SA62 SA71 SA72 SB01 SB02 TA01 TA02 TA12 TA32 TA71 TB01 TB02 UA022 UA032 UA041 UA042 UA121 UA122 UA131 UA132 UA141 UA151 UA221 UA231 UA251 UA261 UA262 UA361 UA662 UA672 UA762 UB011 UB021 UB061 UB062 UB121 UB122 UB131 UB141 UB151 UB152 UB211 UB221 UB281 UB301 UB302 UB311 UB401 UB402 VA011 VA012 VA021 VA022 VA031 VA041 VA061 VA062 VA081 VA091 VA092 XA16 XA19 YA23 ZB22

Claims (2)

[Claims] 1. A photosensitive polymer represented by the following general formula (A): (However, in the formula, R ¹ is a tetravalent aromatic group, R ² is a divalent aromatic group, and k, m, and n each represent an integer of 1 or more.) (B) Bifunctional or more Vinyl ether compound,
A positive photosensitive resin composition comprising (C) a photo-acid generator which is converted into an acidic compound by actinic rays such as ultraviolet rays and (D) a solvent. 2. An insolubilized coating film forming step of coating the positive photosensitive resin composition according to claim 1 on a substrate and drying at 90 to 130 ° C. to form an insolubilized coating film in an alkaline aqueous solution. After exposing the insolubilized coating film through a positive mask pattern with active ultraviolet rays, 90 to 1
An exposed coating film decomposition step of heating only at 30 ° C. to decompose only the exposed portion of the insolubilized coating film, and a positive pattern for dissolving only the exposed and decomposed portion of the exposed coating film using an alkaline aqueous solution to develop into a positive pattern A positive pattern forming method comprising: a developing step; and an imidization heat treatment step of heat-treating the developed positive pattern to form a polyimide positive pattern.