JPH088243A - Semiconductor device - Google Patents

Abstract

PURPOSE:To obtain a semiconductor device whose manufacturing process is simple and safe where the insulation layer of a photosensitive resin composition with a high sensitivity and improved resolution in that a relief pattern can be formed by applying light or radioactive rays is provided by providing the insulation layer which is formed by a specific photosensitive resin composition on the surface of a semiconductor element. CONSTITUTION:An insulation layer 6 formed by a photosensitive resin composition with a solution of polyamic acid indicated by a shown general formula (A), a compound with activated aromatic ring and tertiary amino group (B), a photodecomposable proton generation agent (C), and a polyfunctional latent electrophilic agent (D) as necessary constituents is provided on the surface of a semiconductor element 1 directly or via another insulation layer 5, where R<1>, R<2>, and n in the formula indicate a quadrivalent organic acid residue, a divalent diamine residue, and one or larger integer, respectively. For example, a compound as the constituent (B) is m-hydroxybenzoic acid 2- dimethylaminoethyl ester.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a semiconductor device having a photosensitive polyimide resin insulating layer which is highly sensitive to irradiation with light or radiation and has excellent resolution.

[0002]

2. Description of the Related Art Since an element portion formed on the surface of a substrate of a semiconductor device is easily affected by an external environment, a protective film is provided on the element surface to maintain reliability and the like. Conventionally,
As such an organic protective film, a polyimide resin has come to be used in terms of film-forming properties, electric characteristics, reliability, etc., and in recent years, an inorganic protective film and a polyimide resin film have come to be used in combination. Is coming.

A semiconductor element having a protective film must be patterned on its surface, such as a through hole, or must be padded to establish electrical continuity with external leads. Conventionally, the processing of the polyimide resin film has been performed with a strong alkali by a photo-etching process using a photoresist. This processing step is very complicated and takes a long time, and there is a problem in the toxicity of the etching solution. Therefore, in recent years, studies have been made to impart photosensitivity to the polyimide resin itself. Since the polyimide resin with photosensitivity does not need to use a photoresist like the polyimide resin having no photosensitivity, the pattern forming process can be simplified and rationalized,
Further, since it is possible to perform patterning without using a highly toxic etching solution, it is excellent in safety and pollution, and a polyimide resin having photosensitivity is expected to become more important in the future.

As the photosensitive polyimide resin, for example, a photosensitive resin composition [R. E. Kerwin, et al. , Polymer Eng. &
Sci. , 11 (5), 426 pp (1971)] are known.
However, this system has the drawback that the electrical properties and reliability are reduced due to the presence of dichromate in the final polyimide resin film obtained, and that the polyamic acid gels during storage due to a dark reaction, and further, There was a drawback that hexavalent chromium was contained in the waste liquid discharged in the manufacturing process.

Further, Japanese Patent Publication No. 55-30207 and Japanese Patent Publication No. 55-4
1422 discloses a polyimide precursor composition having a structure represented by the following formula, in which a photosensitive group is introduced into an ester group.

[0006]

Embedded image (However, in the formula, n represents an integer of 1 or more.) The photosensitive polyimide resin of this system not only has a complicated manufacturing process of the resin itself but also involves a dehydrochlorination reaction at the stage of introducing a photosensitive group. However, there is a drawback that chlorine ions remain in the obtained polyimide resin, and the electrical characteristics and the reliability of the element using this resin film are poor.

Further, Japanese Patent Publication No. 54-145794 discloses a polyamic acid having a structure represented by the following formula:

[0008]

[Chemical 3] (In the formula, R ^a represents a tetravalent organic group, R ^b represents a divalent organic group, and R ^c represents an ester group.) A carbon-carbon double bond dimerizable or polymerizable by actinic radiation, Also, a composition added with a compound containing an amino group or a quaternized salt thereof is shown. Although the photosensitive polyimide resin of such a system does not have a problem of impurity ions, it has a sensitivity of several hundred to several thousand mJ / cm ² which is low for practical use, and the viscosity change during storage and the above There was a defect such as precipitation of the added compound.

[0009]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned drawbacks, and it is possible to form a relief pattern on the surface of a semiconductor device by irradiation with light or radiation with high sensitivity and resolution. It is an object of the present invention to provide a semiconductor device provided with an insulating layer of a photosensitive resin composition, which is possible, and which has a simple manufacturing process and is safe in terms of environmental protection.

[0010]

Means for Solving the Problems The present inventor has conducted extensive studies to achieve the above-mentioned object, and as a result of studying various chemical structures of polymers, as a result of providing an insulating layer of the composition described below, The present invention has been completed by discovering that the above object can be achieved.

That is, the present invention provides (A) a solution of a polyamic acid represented by the following general formula on the surface of a semiconductor element directly or through another insulating layer:

[0012]

[Chemical 4] (In the formula, R ¹ represents a tetravalent organic acid residue, R ² represents a divalent diamine residue, and n represents an integer of 1 or more.) (B) Activated aromatic ring and 3 An insulating layer formed from a photosensitive resin composition containing a compound having a primary amino group, (C) a photodecomposable proton generator and (D) a polyfunctional latent electrophilic agent as essential components. It is a semiconductor device.

The present invention will be described in detail below.

The polyamic acid (A), which is one component of the photosensitive resin composition used in the present invention, is obtained by the reaction of an acid component and a diamine component. As a specific compound of the acid component used here, for example, pyromellitic acid,
1,2,3,4-benzenetetracarboxylic acid, 1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,4,5-cyclopentanetetracarboxylic acid, 1,2,4,5-cyclohexanetetra Carboxylic acid, 3,3 ', 4,4'-bicyclohexyltetracarboxylic acid, 2,3,5-tricarboxycyclopentyl acetic acid, 3,4-dicarboxy-1,2,3,4-tetrahydronaphthalene-1- Succinic acid, 3,3 ', 4,4'-biphenyltetracarboxylic acid,
2,3,3 ', 4'-biphenyltetracarboxylic acid, 3,3', 4,
4'-benzophenone tetracarboxylic acid, 2,3,3 ', 4'
-Benzophenone tetracarboxylic acid, 3,3 ', 4,4'-biphenyl ether tetracarboxylic acid (4,4'-oxydiphthalic acid), 2,3,3', 4'-biphenyl ether tetracarboxylic acid, 2,2 -Bis (3,4-dicarboxyphenyl) propane, 2,2-bis (2,3-dicarboxyphenyl) propane, bis (3,4-dicarboxyphenyl) methane, bis (2,3-dicarboxyphenyl) ) Methane, 1,1-bis (2,3-
Dicarboxyphenyl) ethane, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane, 3,3 ′,
4,4'-diphenylsulfone tetracarboxylic acid, 2,3,
3 ', 4'-diphenylsulfone tetracarboxylic acid, 2,3,
6,7-naphthalene tetracarboxylic acid, 1,4,5,8-naphthalene tetracarboxylic acid, 1,2,5,6-naphthalene tetracarboxylic acid, 3,4,9,10-tetracarboxyperylene, 2,2 -Anhydrides such as bis [4- (3,4-dicarboxyphenoxy) phenyl] propane and 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] hexafluoropropane or lower alkyl esters thereof These may be used alone or in combination.

Specific examples of the diamine component include, as specific compounds, 4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane and 3,3 ', 5,5'. -Tetramethyl-4,4'-diaminodiphenylmethane, 3,3 ', 5,5'-tetraethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-5,5'-diethyl-4,4' -Diaminodiphenylmethane, 4,4'-methylenebis (cyclohexylamine), 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, 3,3'-
Dimethoxy-4,4'-diaminodiphenylmethane, 3,3 '
-Diethoxy-4,4'-diaminodiphenylmethane, bis (3-aminophenyl) ether, bis (4-aminophenyl) ether, 3,4'-diaminodiphenylether,
3,3'-diethyl-4,4'-diaminodiphenyl ether, 3,3'-dimethoxy-4,4'-diaminodiphenyl ether, bis [4- (4-aminophenoxy) phenyl] ether, 3,3'-dimethyl -4,4'-diaminodiphenyl sulfone, 3,3'-diethyl-4,4'-diaminodiphenyl sulfone, 3,3'-dimethoxy-4,4'-diaminodiphenyl sulfone, 3,3'-diethoxy-4 , 4'-diaminodiphenyl sulfone, 3,3'-dimethyl-4,4'-diaminodiphenylpropane, 3,3'-diethyl-4,4'-diaminodiphenylpropane, 3,3'-dimethoxy-4,4 ′-
Diaminodiphenylpropane, 3,3'-diethoxy-4,
4'-diaminodiphenylpropane, 2,2-bis [4- (4-
Aminophenoxy) phenyl] propane, 1,3-bis (4-
Aminophenyl) propane, 2,2-bis (4-aminophenyl) propane, 4,4'-diaminodiphenylsulfide, 3,3'-dimethyl-4,4'-diaminodiphenylsulfide, 3,3'-diethyl- 4,4'-diaminodiphenyl sulfide, 3,3'-dimethoxy-4,4'-diaminodiphenyl sulfide, 3,3'-diethoxy-4,4'-diaminodiphenyl sulfide, 2,2'-diaminodiethyl sulfide, 2,4'-diaminodiphenyl sulfide, m-
Phenylenediamine, p-phenylenediamine, 1,3-bis (4-aminophenoxy) benzene, 1,2-bis (4-aminophenyl) ethane, 1,1-bis (4-aminophenyl) ethane, bis (3 -Aminophenyl) sulfone, bis (4-aminophenyl) sulfone, o-toluidine sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 4,
4'-diaminodibenzyl sulfoxide, bis (4-aminophenyl) diethylsilane, bis (4-aminophenyl) diphenylsilane, bis (4-aminophenyl) ethylphosphine oxide, bis (4-aminophenyl) phenylphosphine oxide, Bis (4-aminophenyl)-
N-phenylamine, bis (4-aminophenyl) -N-
Methylamine, 1,2-diaminonaphthalene, 1,4-diaminonaphthalene, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene, 1,8-diaminonaphthalene, 2,3-diamino Naphthalene, 2,6-diaminonaphthalene, 1,4-diamino-2-methylnaphthalene, 1,5-diamino-2-methylnaphthalene, 1,3-diamino-2-phenylnaphthalene, 9,9-bis (4- Aminophenyl) fluorene,
4,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl,
3,3'-Dimethyl-4,4'-diaminobiphenyl, 3,4 '
-Dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 4,4'-bis (4-
Aminophenoxy) biphenyl, 2,4-diaminotoluene, 2,5-diaminotoluene, 2,6-diaminotoluene, 3,
5-diaminotoluene, 1,3-diamino-2,5-dichlorobenzene, 1,4-diamino-2,5-dichlorobenzene, 1-methoxy-2,4-diaminobenzene, 1,3-diamino-4, 6-dimethylbenzene, 1,4-diamino-2,5-dimethylbenzene, 1,
4-diamino-2-methoxy-5-methylbenzene, 1,4-diamino-2,3,5,6-tetramethylbenzene, 1,4-bis (2-methoxy-4-aminopentyl) benzene, 1, 4-bis (1,1-
Dimethyl-5-aminopentyl) benzene, 1,4-bis (4-
Aminophenoxy) benzene, 3,5-diaminobenzoic acid,
2,5-diaminobenzoic acid, o-xylenediamine, m-xylenediamine, p-xylenediamine, 9,10-bis (4-aminophenyl) anthracene, 3,3′-diaminobenzophenone, 4,4′-diamino Benzophenone, 2,6-diaminopyridine, 3,5-diaminopyridine, 1,3-diaminoadamantane, 3,3′-diamino-1,1,1′-diadamantane, N- (3-aminophenyl) -4 -Aminobenzamide, 4,4'-diaminobenzanilide, 4-aminophenyl-3-aminobenzoate, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis (3-aminophenyl) hexa Fluoropropane, 2- (3-aminophenyl) -2- (4-aminophenyl) hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [ 4- (2-chloro-4-aminophenyl Phenoxy) phenyl] hexafluoropropane,
1,1-bis (4-aminophenyl) -1-phenyl-2,2,2-trifluoroethane, 1,1-bis [4- (4-aminophenoxy) phenyl] -1-phenyl-2,2 , 2-Trifluoroethane, 1,3-bis (3-aminophenyl) hexafluoropropane, 1,3-bis (3-aminophenyl) decafluoropropane, 2,2-bis (3-amino-4-hydroxy) Phenyl) hexafluoropropane, 2,2-bis (3-amino-4-methylphenyl) hexafluoropropane, 2,2-bis (5-amino-4-methylphenyl) hexafluoropropane, 1,4-
Examples thereof include bis (3-aminophenyl) but-1-en-3-yne, which may be used alone or in combination of two or more.

The polyamic acid has a logarithmic viscosity in the range of 0.2 to 4.0 at 30 ° C. as a solution of a concentration of 0.5 g / 100 ml of N-methyl-2-pyrrolidone, and more preferably,
It is in the range of 0.3 to 2.0. Such a polyamic acid is obtained by subjecting an acid component and a diamine component of approximately equimolar amounts to an addition polymerization reaction in an organic solvent at a reaction temperature of 30 ° C. or lower, preferably 20 ° C. or lower for 3 to 12 hours. As the organic solvent in this polymerization reaction, for example, N, N-dimethylsulfoxide, N,
Examples thereof include N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N-methyl-2-pyrrolidone and hexamethylenephosphoamide, which may be used alone or in combination with 2
A mixture of two or more species can be used. Depending on the acid component and diamine component used, it is also possible to synthesize a general-purpose organic solvent-soluble polyamic acid, in such a case,
The polyamic acid obtained as described above is put into a poor solvent such as water or methanol to precipitate a polymer, and after sufficiently drying, an operation of dissolving in a desired organic solvent is performed to obtain a polyamic acid solution. The concentration of the polyamic acid solution is not particularly limited, as it may be appropriately determined depending on the purpose of use of the present invention and the method of use, but is usually 1 to
Use at a concentration of 30%.

Component (B), which is one component of the photosensitive resin composition used in the present invention, is a compound having an aromatic ring and a tertiary amino group, in which the aromatic ring is electronically activated. Used, the tertiary amino group is defined as an amino group in which a hydrogen atom is not directly bonded to a nitrogen atom. For example, a compound represented by the following general formula is used.

[0018]

[Chemical 5] (However, in the formula, Ar is an aromatic ring, and R ³ and R ⁴ are each a carbon number of 1 to
6 is a lower alkyl group, R ⁵ is a divalent organic group, and R ⁶ is an OH, NHCOR, OC that electronically activates an aromatic ring.
OR, O, and each represent an alkyl group or an aryl group.) As this specific compound, p-hydroxybenzoic acid-
2-Dimethylaminoethyl ester, m-hydroxybenzoic acid-2-dimethylaminoethyl ester, o-hydroxybenzoic acid-2-dimethylaminoethyl ester, p-hydroxybenzoic acid-2-diethylaminoethyl ester, m-hydroxybenzoic acid -2-diethylaminoethyl ester, o-
Hydroxybenzoic acid-2-diethylaminoethyl ester, p-hydroxy-N, N-dimethylbenzylamine,
m-hydroxy-N, N-dimethylbenzylamine, o-hydroxy-N, N-dimethylbenzylamine, p-hydroxy-N, N-diethylbenzylamine, m-hydroxy-N, N-diethylbenzylamine, o- Hydroxy-
N, N-diethylbenzylamine etc. can be mentioned. However, the compound is not limited to these, and is a compound containing a tertiary amino group capable of ionically binding to a carboxylic acid of an amic acid, and a carbocation and an aromatic ring that causes an electrophilic substitution reaction in one molecule. I wish I had it. These compounds can be used alone or in combination. The compounding ratio of this compound is preferably 30 to 300 mol% with respect to the carbonyl group of the polyamic acid described above, and more preferably 50 to 200 mol%. If the blending amount is less than 30% by mole, the photosensitivity is inferior, and if it exceeds 300% by mole, the storage stability of the resin composition and the physical properties of the polyimide film are inferior.

As the photodecomposable proton-generating agent (C) which is one component of the photosensitive resin composition used in the present invention, allyl diazonium salt (Ar N ₂ ⁺ X ⁻ ) and diallyl iodonium salt (Ar ₂ I ⁺ X) are used. ^- ), Triallyl sulfonium salt (Ar ₃ S ⁺ X ⁻ ), aromatic sulfonic acid ester and the like, and these can be used alone or in combination of two or more kinds. The mixing ratio of the photodegradable proton generating agent is 1 to the solid content of the polyamic acid solution described above.
It is desirable to add 50% by weight, more preferably 5
Within the range of up to 20% by weight. If the content is less than 1% by weight, the acid generation rate will be slow and sufficient sensitivity cannot be obtained, and if it exceeds 50% by weight, the storage stability of the resin composition will be poor, such being undesirable.

The polyfunctional latent electrophilic agent (D), which is one component of the photosensitive resin composition used in the present invention, is an electrophilic substitution such as carbocation with an acid generated from the photodegradable proton generator described above. The functional group capable of reacting is not particularly limited as long as it produces two or more functional groups in one molecule, but preferably the blocking acid is liberated when the carbocation is produced. Those are preferable. Specific compounds include, for example, 1,4-bis (acetoxymethyl) benzene, 1,3,5-tri (acetoxymethyl) benzene, 3,4-bis (acetoxymethyl) furan,
Examples include 1,4-bis (sulfoxymethyl) benzene, 1,3,5-tri (sulfoxymethyl) benzene, and 3,4-bis (sulfoxymethyl) furan, which may be used alone or
A mixture of two or more species can be used. The compounding ratio of the polyfunctional latent electrophilic agent is preferably 30 to 300 mol% and more preferably 50 to 200 mol% based on the carbonyl group of the polyamic acid. Compounding amount 30
If it is less than mol%, the cross-linking density between molecules becomes small, and sufficient sensitivity and resolution cannot be obtained, and if it exceeds 300 mol%, the storage stability of the resin composition and the physical properties of the polyimide film are poor, which is not preferable.

The photosensitive resin composition used in the present invention comprises the above-mentioned polyamic acid solution, activated aromatic ring and 3
A compound having a primary amino group, a photodegradable proton generator,
It can be easily produced by blending a polyfunctional latent electrophilic agent. Further, although each of the above-mentioned components is an essential component, other additives can be blended within a range not deviating from the object of the present invention. The photosensitive resin composition thus obtained,
In addition to the surface protection film for IC and LSI, it can be preferably used for an interlayer insulating film, an alignment film for liquid crystal, and the like.

Next, using the photosensitive resin composition of the present invention,
An example of manufacturing a semiconductor device by forming a relief pattern on the surface of a semiconductor element will be described. First, a photosensitive resin composition is prepared by mixing a polyamic acid solution, a compound having an activated aromatic ring and a tertiary amino group, a photodegradable proton generator and a polyfunctional latent electrophilic agent. This composition is applied on a semiconductor substrate by a conventional method such as spin coating or printing and dried to remove the organic solvent. Next, the obtained coating film is exposed to X-rays, electron beams, ultraviolet rays, visible rays, and preferably ultraviolet rays through a negative photomask. After exposure, spray a developing solution to remove the unexposed areas, or
Development is performed by immersing the substrate in a developing solution. This developing solution is preferably an organic solvent capable of dissolving and removing the unexposed portion in the coating film within an appropriate time, and examples thereof include N, N-dimethylsulfoxide, N, N-dimethylformamide,
N, N-diethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N-methyl-2-pyrrolidone, hexamethylenephosphoamide, etc. may be used alone or in a mixture, and methanol may be added to these good solvents. , Ethanol, isopropanol, ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, acetic acid isoamyl ester and the like can be mixed and used by adjusting the solubility. After development,
The relief pattern can be formed by washing the substrate with an appropriate rinse solution. As the rinse liquid used here, methanol, ethanol, isopropanol, ethyl cellosolve, butyl cellosolve,
Ethyl carbitol, butyl carbitol, acetic acid isoamyl ester and the like can be used alone or in combination. The substrate on which the relief pattern was obtained is 100 to 400.
The polyamic acid is cured into a polyimide by heat treatment at 60 ° C. for 60 to 90 minutes at 200 ° C., preferably 200 to 350 ° C. In this way, a relief pattern having heat resistance, insulation, etc. can be obtained.

After that, the semiconductor is sealed with epoxy resin, diallyl phthalate resin, phenol resin, unsaturated polyester resin, silicone resin or the like by casting, transfer molding, injection molding or the like to a thickness of about 0.5 to 5 mm to form a semiconductor. The device can be manufactured.

Next, the semiconductor device of the present invention will be described with reference to the drawings.

FIG. 1 is a schematic sectional view for explaining a semiconductor device. In FIG. 1, for example, a pnp type transistor is formed on the surface of a semiconductor element 1 such as silicon. A silicon dioxide film 2 for protecting the junction between the emitter and the base is formed on the surface of the semiconductor element 1, and a base electrode 3 and an emitter electrode 4 are formed by an aluminum vapor deposition film. A silicon nitride vapor deposition film 5 which is an inorganic protective film is formed on the surface of this semiconductor element, and a photosensitive resin composition is further patterned on the upper surface thereof by the above-described method so that holes are formed on the emitter electrode 4. The protective film layer 6 is formed. Then, the silicon nitride vapor deposition film 5 is etched with strong hydrofluoric acid to form a bonding pad on the emitter electrode 4. After that, the electrode of the semiconductor element and the lead wire,
Bonding is performed with a gold or aluminum bonding wire 7. When the planar type transistor is sealed, the semiconductor element 1 is fixed to the tip of the tab lead 8 and the semiconductor element 1 including the tip of the tab lead 8 is sealed in order to provide mechanical strength and to protect it from the outside air. Seal with resin 9. In this way, a semiconductor device can be manufactured.

[0026]

In the semiconductor device of the present invention, by using the specific photosensitive resin composition as the insulating protective film, the insulating protective film of the relief pattern is formed on the semiconductor element without using the conventional photoetching process with the photoresist. Is what you get. A specific photosensitive resin composition is a carbocation in one molecule for a benzene ring in a specific molecule that is mixed with a polyamic acid and ionically bonded.
By subjecting a cross-linking agent capable of generating one or more to an electrophilic substitution reaction, a difference in solubility between the exposed portion and the unexposed portion in the developing solution appears. As a result, conventional double radicals polymerize double bonds such as acrylic, which is a photosensitive group,
It is possible to form a relief pattern with high sensitivity and high resolution, as compared with a photosensitive polyimide in which a solubility difference between an exposed portion and an unexposed portion appears. Furthermore, since a relief pattern can be obtained in the state of polyamic acid and then converted into a polyimide film by thermal conversion, there is an advantage that a pattern with high adhesion can be obtained. Further, the manufacturing process of the semiconductor device has been shortened, and the highly reliable semiconductor device can be manufactured by the manufacturing process of the process which is advantageous for pollution and environmental problems.

[0027]

EXAMPLES Next, the present invention will be described with reference to examples, but the present invention is not limited to these examples.

Example 1 Dry nitrogen was passed through a flask equipped with a stirrer, a condenser and a nitrogen inlet tube to replace the inside of the flask, and then 20.02 g of 4,4'-diaminodiphenyl ether and 424.9 g of N-methyl-2-pyrrolidone were added. Dissolved. To this solution, a mixture of 10.91 g of pyromellitic dianhydride and 16.11 g of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride as a powder,
While paying attention to heat generation, it was added in several portions. While suppressing the heat generated by the reaction in an ice bath, stirring was continued for 8 hours to prepare a polyamic acid solution. A part of this polyamic acid solution was put into a mixed solvent of water and methanol and reprecipitated to obtain a polyamic acid powder. This powder is N
-Methyl-2-pyrrolidone 0.5 g / 100 ml Dissolved to a concentration of 30 ° C and measured logarithmic viscosity 1.32 dl / g
Met. M-Hydroxybenzoic acid-2-dimethylaminoethyl ester 4.82 g in 100 g of this polyamic acid solution
Then, 1.0 g of triphenylsulfonium trifluoromethanesulfonate and 5.0 g of 1,4-bis (acetoxymethyl) benzene were dissolved, and pressure filtration was performed with a 1.0 μm filter to produce a photosensitive resin composition.

Example 2 Dry nitrogen was passed through a flask equipped with a stirrer, a condenser and a nitrogen inlet tube to replace the inside of the flask, and then 2,2'-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane 51.84 g and N-methyl-2-pyrrolidone 294.7 g were added and dissolved. Add pyromellitic dianhydride 2 to this solution.
1.81 g was added as a powder in several divided portions while paying attention to heat generation. While suppressing the heat generated by the reaction in an ice bath, stirring was continued for 6 hours to prepare a polyamic acid solution. A part of this polyamic acid solution was put into a mixed solvent of water and methanol and reprecipitated to obtain a polyamic acid powder. This powder was added to N-methyl-2-pyrrolidone 0.5 g /
It was dissolved so as to have a concentration of 100 ml, and the logarithmic viscosity at 30 ° C. was measured to be 0.95 dl / g. The polyamic acid powder was dissolved in cyclohexanone so that the solid content was 10% to obtain a polyamic acid solution. P-Hydroxybenzoic acid-2-dimethylaminoethyl ester 2.99 g, diphenyliodonium trifluoromethanesulfonate 1.0 g and 1,4-bis (acetoxymethyl) benzene 3.11 g were dissolved in 100 g of this polyamic acid solution, and 1.0 μm A photosensitive resin composition was manufactured by performing pressure filtration with a filter.

Comparative Example 1 To 100 g of the polyamic acid solution obtained in Example 1,
2- (N, N-dimethylamino) ethyl methacrylate
8.23g and IRGACURE907 which is a radical generator
(Ciba Geigy, trade name) 1.0g
A photosensitive resin composition was manufactured by performing pressure filtration with a 1.0 μm filter.

Comparative Example 2 100 g of the polyamic acid solution obtained in Example 1 was used as it was.

Using the photosensitive resin composition and the polyamic acid solution (Comparative Example 2) produced in the Examples and Comparative Examples, an insulating protective film was formed on the surface of the semiconductor element by using a process compatible with each of them, and sealing was performed. A semiconductor device sealed with a resin was manufactured. With respect to these semiconductor devices, a simple manufacturing process and a moisture resistance test were conducted, and electrical characteristics of the polyimide resin film were measured. The results are shown in Table 1. In any case, the present invention is excellent,
The effect of the present invention could be confirmed.

[0033]

[Table 1]

[0034]

As is clear from the above description, the semiconductor device of the present invention is a highly reliable device manufactured by a simple and safe process by using a specific photosensitive resin composition as an insulating film. Is what you can do.

[Brief description of drawings]

FIG. 1 is a schematic sectional view for explaining a semiconductor device of the present invention.

[Explanation of reference numerals] 1 semiconductor element 2 silicon dioxide film 3 base electrode 4 emitter electrode 5 silicon nitride vapor deposition film 6 organic protective film 7 bonding wire 8 tab lead 9 sealing resin

Claims (1)

[Claims] 1. A solution of (A) a polyamic acid represented by the following general formula, directly on the surface of a semiconductor element or through another insulating layer: (In the formula, R ¹ represents a tetravalent organic acid residue, R ² represents a divalent diamine residue, and n represents an integer of 1 or more.) (B) Activated aromatic ring and 3 An insulating layer formed from a photosensitive resin composition containing a compound having a primary amino group, (C) a photodecomposable proton generator and (D) a polyfunctional latent electrophilic agent as essential components. Semiconductor device.