JPH11312675A - Semiconductor device and manufacture thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To shorten a coating method, by coating the surface of a semiconductor element with a composition consisting of a specific quantity of specific polyamide and a specific quantity of a photosensitive diazoquinone compound, and heating and curing the composition. SOLUTION: The surface of a semiconductor element 1 is coated with a photosensitive resin composition composed of 1-100 pts.wt. 1,2-benzoquinone diazide or 1,2-naphthoquinone diazide of a photosensitive diazoquinone compound and 100 pts.wt. polyamide in formula 1, and worked in a pattern by exposure and development, and the composition is heated and cured. In formula 1, X represents a tetravalent aromatic group, Y a bivalent aromatic group, E an aliphatic group an alicyclic or a cyclic compound having at least one alkenyl group or an alkinyl group, and (a) and (b) a molar fractions where, a+b=100 mol.%, a=60.0 to 100 mol.%, b=0 to 40 mol.%, and n=2 to 500. In formula II, R1 , R2 of Z represent in dependently a bivalent organic group and R3 , R4 represent in dependentty a monovalent organic group. Since polybenzoxazole is patterned directly and SiN can be etched while the pattern is used as a mask, a process is shortened extremely.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a semiconductor device which is adhered to a surface of a semiconductor element by using a photosensitive resin composition having excellent resolution and excellent adhesion after humidity treatment, and manufacturing the same. It is about the method.

[0002]

2. Description of the Related Art Conventionally, a polyimide resin having excellent heat resistance and excellent electrical and mechanical properties has been used for a surface protective film and an interlayer insulating film of a semiconductor element. There is a demand for remarkable improvements in heat cycle resistance and heat shock resistance due to factors such as higher integration of devices, larger size, thinner and smaller sealing resin package, and transition to surface mounting method by solder reflow. A new polyimide resin has been required. However, conventional polyimide resin has a limitation in pattern accuracy, so first etching the protective material using a resist,
Thereafter, a very complicated process of applying and etching a polyimide resin has been taken.

On the other hand, a technique for imparting photosensitivity to a polyimide resin itself has recently attracted attention. The use of these photosensitive polyimide resins not only has the effect of simplifying the pattern forming process compared to the polyimide resin that has not been provided, but also eliminates the need for a highly toxic etchant, which is safe. It is also excellent in terms of pollution, and it is expected that photosensitization of polyimide resin will be an important technology. As the photosensitive polyimide resin, for example, the following formula (A)

[0004]

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[0005] A polyimide precursor composition having a photosensitive group provided with an ester group having a structure represented by the following formula (for example, Japanese Patent Publication No. Sho 55-41422, Japanese Patent Laid-Open Publication No. Sho 60-28537) or the following formula (B)

[0006]

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[0007] A composition comprising a polyamic acid having a structure represented by the formula (1) added with a compound containing a dimerizable or polymerizable carbon-carbon double bond and an amino group or a quaternized salt thereof by actinic radiation (for example, JP-B-59-52822) is known. These are all dissolved in an appropriate organic solvent, coated and dried in a varnish state, irradiated with ultraviolet rays through a photomask, developed and rinsed to obtain a desired pattern, and further heated to obtain a polyimide. It is a coating.

However, such conventional compositions have the following disadvantages. That is, since such a negative photosensitive resin uses an organic solvent as a developing solution, the exposed portion swells and only a resolution of about 10 μm is obtained, and the opening of a miniaturized semiconductor redundant circuit (fuse portion) is obtained. Was not enough.

[0009]

SUMMARY OF THE INVENTION The present invention relates to a semiconductor device having a polyimide resin having excellent resolution and excellent adhesion even after a humidity treatment, and a simplified and simpler device than the conventional device. It's about getting in the way.

[0010]

According to the present invention, there is provided a compound represented by the general formula (1):
A photosensitive resin composition comprising 100 parts by weight of a polyamide (A) and 1 to 100 parts by weight of a photosensitive diazoquinone compound (B) is applied to the surface of a semiconductor element, exposed, developed, patterned, and then heated. A semiconductor device that is cured

[0011]

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Polyamide (A) represented by the general formula (1)
100 parts by weight and photosensitive diazoquinone compound (B) 1-1
A photosensitive resin composed of 00 parts by weight and 1 to 50 parts by weight of a phenol compound (C) represented by the general formulas (2) and / or (3) was applied to the surface of the semiconductor element, exposed, developed, and patterned. After that, it is a semiconductor device that is cured by heating,

[0013]

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[0014]

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Polyamide (A) represented by the general formula (1)
100 parts by weight and photosensitive diazoquinone compound (B) 1-1
00 parts by weight, 1 to 50 parts by weight of a phenol compound (C) represented by the general formulas (2) and / or (3) and represented by the general formulas (4), (5), (6) and (7) At least one organosilicon compound (D) selected from the group: 0.1 to 2
A semiconductor device obtained by applying a photosensitive resin composition consisting of 0 parts by weight to the surface of a semiconductor element, exposing, developing and pattern-forming, and then heat-curing,

[0016]

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[0017]

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[0018]

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[0019]

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The above-mentioned photosensitive resin composition is applied to the surface of a semiconductor element, exposed, developed and patterned to form a pattern, and then the semiconductor element protective material (passivation) is removed by etching. It is a manufacturing method.

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION The polyamide of the formula (1) comprises bisaminophenol having the structure of X, dicarboxylic acid having the structure of Y, diamine having the structure of Z, and acid anhydride having the structure of W. About 3
When heated at 00 to 400 ° C., the ring closes and changes to a heat-resistant resin called polybenzoxazole. X of the polyamide (1) of the present invention is, for example,

[0022]

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However, the present invention is not limited to these. Among them, the one having particularly high sensitivity is selected from the general formula (8).

[0024]

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Further, Y in the formula (1) is, for example,

[0026]

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However, the present invention is not limited to these. Among these, those having particularly high sensitivity are those selected from the general formula (9).

[0028]

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E is used to modify the amino end groups of the hydroxypolyamide to improve storage stability. E can represent:

[0030]

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Specific examples include maleic anhydride, norbornene dicarboxylic anhydride and 4-vinyl-benzoic acid chloride. The advantage of using derivatives of unsaturated carboxylic acids is that an additional networking reaction occurs during the sintering process. Another advantage of using cyclic carboxylic anhydrides, such as maleic anhydride and norbornene dicarboxylic anhydride, is to produce imides with adjacent hydroxyl groups that can simultaneously crosslink or improve adhesion upon sintering. is there. Further, Z in the formula (1) is, for example,

[0032]

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However, the present invention is not limited to these. Z in the formula (1) is used, for example, when adhesion is particularly required to a substrate such as a silicon wafer.
About the use ratio b, it can be used up to 40.0 mol%. If it exceeds 40.0 mol%, the solubility of the resin is extremely reduced, scum is generated, and pattern processing cannot be performed. When using X, Y, and Z, one type or a mixture of two or more types may be used. In the polyamide of the formula (1), the polyamide of the formula (10) where b = 0 is preferably used.

[0034]

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The photosensitive diazoquinone compound used in the present invention is a compound having a 1,2-benzoquinonediazide or 1,2-naphthoquinonediazide structure, and is disclosed in US Pat. Nos. 2,772,972 and 2,797, 21
No. 3,669,658. For example, the following are mentioned.

[0036]

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[0037]

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Among these, the following are particularly preferable from the viewpoint of a high residual film ratio.

[0039]

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The compounding amount of the photosensitive diazidoquinone compound (B) to the polyamide (A) is 1 to 100 parts by weight with respect to 100 parts by weight of the polyamide. If the compounding amount is less than 1 part by weight, the patterning property of the resin is poor. Conversely, if it exceeds 100 parts by weight, the tensile elongation of the film is significantly reduced.
A semiconductor device in which a film having a low tensile elongation is applied to the element surface is not preferable because reliability such as thermal stress deteriorates.

A dihydropyridine derivative can be added to the positive photosensitive resin composition of the present invention, if necessary, to enhance the photosensitive characteristics. Examples of dihydroxypyridine derivatives include, for example, 2,6-dimethyl-3,5-diacetyl-4- (2'-nitrophenyl) -1,4-dihydropyridine, 4- (2'-nitrophenyl) -2,6-dimethyl -3,5-dicarbethoxy-1,4-dihydropyridine, 4- (2 ', 4'-dinitrophenyl)-
2,6-dimethyl-3,5-carbomethoxy-1,4-
Dihydropyridine and the like can be mentioned.

The positive photosensitive resin composition of the present invention may further contain a phenol compound represented by the general formula (2) and / or (3) in addition to the above components (A) and (B). Is preferred.

Techniques for adding a phenol compound to a positive resist composition include, for example, JP-A-3-2002.
No. 51, JP-A-3-200252, JP-A-3-20052
JP-A-200253, JP-A-3-200254, JP-A-4-1650, JP-A-4-1651, JP-A-4-11260, JP-A-4-123
No. 56, JP-A-4-12357. However, phenol compounds such as those described above have a small effect of improving sensitivity even when used in a positive photosensitive resin containing a polyamide as a base resin in the present invention.

However, when the phenol compound represented by the general formula (2) or (3) in the present invention is used, the dissolution rate in the exposed area is increased, and the sensitivity is improved. In addition, the film loss in the unexposed portion, which is observed when the sensitivity is increased by reducing the molecular weight, is very small and good. Further, in the present invention, as a new property by adding the phenol compound represented by the general formula (2), a positive photosensitive resin composition having improved adhesion to a sealing resin can be obtained. It has been found that the reliability of the semiconductor device applied to the surface is improved.

The compounds represented by the general formula (2) include, but are not limited to, the following.

[0046]

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[0047]

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[0048]

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[0049]

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Among them, those which are particularly preferable in terms of sensitivity and residual film ratio are the chemical formulas (11) and (12), and the compounds represented by the chemical formulas (11) and (12) are used alone or in a mixture. In the total phenolic compound (C) in an amount of 50% by weight or more.

[0051]

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[0052]

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Since the phenol represented by the general formula (2) has low solubility at low temperatures, for example, when the composition containing the phenol of the general formula (2) is stored at a very low temperature, rarely the phenol represented by the general formula (2) Precipitation of the phenol compound of (2) may be observed. In such a case, when a part of the general formula (2) is replaced with a phenol compound represented by the general formula (3), the storage stability at a low temperature is improved.

The compounds represented by the general formula (3) include, but are not limited to, the following.

[0055]

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[0056]

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[0057]

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Among these, the compound represented by the chemical formula (13) or (14) is particularly preferable in terms of sensitivity and residual film ratio.

[0059]

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The organosilicon compounds of the present invention represented by the general formulas (4), (5), (6) and (7) are used for improving the adhesiveness between a photosensitive resin and a sealing resin. It is. One type or a mixture of two or more types may be used, but the addition amount is preferably 0.1 to 20 parts by weight based on 100 parts by weight of the polyamide. If the amount is less than 0.1 part by weight, the effect of improving the adhesiveness is not obtained, so that it is not preferable. If the amount exceeds 20 parts by weight, the mechanical strength of the polybenzoxazole film formed on the semiconductor element is reduced and the effect of reducing the stress is reduced. It is not preferable.

The organosilicon compounds represented by the general formula (4) are disclosed in US Pat. Nos. 3,755,354 and 4,460,739.
In the present invention, this organosilicon compound is added to a photosensitive polybenzoxazole precursor as shown in Japanese Patent Publication No. 1-46862, and is known in the art. On the other hand, it has been found that a high adhesiveness that cannot be obtained with a conventional silane coupling agent or the like can be exhibited.

The organosilicon compound represented by the general formula (5) is a substance described in JP-A-1-215869, and is used as a raw material of a curable composition for forming a protective film such as a transparent substrate or a color filter. Although it is a known substance used as one, in the present invention, when this organosilicon compound is added to a photosensitive polybenzoxazole precursor as shown in Japanese Patent Publication No. Thus, it has been found that high adhesiveness that cannot be obtained with a conventional silane coupling agent or the like can be exhibited.

The organosilicon compounds represented by the general formulas (4) and (5) are obtained by combining an acid anhydride or an acid dianhydride with a silane coupling agent having an amino group in an organic solvent at 20 to 100 ° C. for 30 minutes. It can be easily obtained by reacting for 10 to 10 hours. Examples of the acid anhydride used include maleic anhydride, succinic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylhymic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic acid, and phthalic anhydride. However, there is no particular limitation.

Examples of acid dianhydrides include, for example, pyromellitic dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, 3,3 ', 4,4'-benzophenone Tetracarboxylic dianhydride, 2,2 ', 3,3'
-Benzophenonetetracarboxylic dianhydride, 2,3
3 ', 4'-benzophenonetetracarboxylic dianhydride, naphthalene-2,3,6,7-tetracarboxylic dianhydride, naphthalene-1,2,5,6-tetracarboxylic dianhydride, naphthalene- 1,2,4,5-tetracarboxylic dianhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, naphthalene-1,2,6,7-tetracarboxylic dianhydride, , 8-dimethyl-1,2,2
3,5,6,7-hexahydronaphthalene-1,2,2
5,6, -tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-2,3,6,7-tetracarboxylic dianhydride, 2 , 6
-Dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,
5,8-tetracarboxylic dianhydride, 2,3,6,7-
Tetrachloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 1,4,5,8-tetrachloronaphthalene-2,3,6,7-tetracarboxylic dianhydride,
3,3 ', 4,4'-diphenyltetracarboxylic dianhydride, 2,2', 3,3'-diphenyltetracarboxylic dianhydride, 2,3,3 ', 4'-diphenyltetracarboxylic acid Dianhydride, 3,3 ", 4,4" -p-terphenyltetracarboxylic dianhydride, 2,2 ", 3,3"-
p-terphenyltetracarboxylic dianhydride, 2,3
3 ", 4" -p-terphenyltetracarboxylic dianhydride, 2,2-bis (2,3-dicarboxyphenyl)-
Propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -propane dianhydride, bis (2,3-dicarboxyphenyl) ether dianhydride, bis (3,4-
Dicarboxyphenyl) ether dianhydride, bis (2,
3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (2,3-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) ) Sulfone dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, perylene-2,3
8,9-tetracarboxylic dianhydride, perylene-3,
4,9,10-tetracarboxylic dianhydride, perylene-
4,5,10,11-tetracarboxylic dianhydride, perylene-5,6,11,12-tetracarboxylic dianhydride, phenanthrene-1,2,7,8-tetracarboxylic dianhydride, phenanthrene -1,2,6,7-tetracarboxylic dianhydride, phenanthrene-1,2,9,1
0-tetracarboxylic dianhydride, pyrazine-2,3
5,6-tetracarboxylic dianhydride, pyrrolidine-2,
3,4,5-tetracarboxylic dianhydride, thiophene-
2,3,4,5-tetracarboxylic dianhydride, 4,4 ′
-Hexafluoroisopropylidene diphthalic dianhydride; and the like, but is not limited thereto.

Examples of the silane coupling agent having an amino group include γ-aminopropyltrimethoxysilane,
γ-aminopropyltriethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylethyldimethoxysilane, γ-aminopropylethyldiethoxysilane, γ-aminopropyldimethylmethoxysilane, γ
-Aminopropyldimethylethoxysilane, γ-aminopropylethyldiethoxysilane, γ-aminopropyldiethylmethoxysilane, γ-aminopropyldiethylethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N -(Β-aminoethyl) -γ-aminopropyltriethoxysilane, N-
(Β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, 4-aminobutyldimethylmethoxysilane and the like.

Examples of the organosilicon compounds represented by the general formulas (6) and (7) include, for example, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxytosilane, and γ-glycol. Sidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane and the like.

In the present invention, these components are dissolved in a solvent and used in the form of a varnish. Examples of the solvent include N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-
Dimethylacetamide, dimethylsulfoxide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl-1,3-butylene Glycol acetate, 1,3-butylene glycol-3-monomethyl ether, methyl pyruvate, ethyl pyruvate, methyl-3-methoxypropionate and the like may be used alone or in combination.

In the method of using the positive photosensitive resin composition of the present invention, the composition is first applied to a suitable support, for example, a silicon wafer, ceramic, aluminum substrate or the like. Examples of the coating method include spin coating using a spinner, spray coating using a spray coater, dipping, printing, and roll coating. Next, after pre-baking at 60 to 120 ° C. to dry the coating film, a desired pattern shape is irradiated with actinic radiation. As the actinic radiation, X-rays, electron beams, ultraviolet rays, visible rays and the like can be used, but those having a wavelength of 200 to 500 nm are preferable. Next, a relief pattern is obtained by dissolving and removing the irradiated portion with a developer. Examples of the developer include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia, primary amines such as ethylamine and n-propylamine, diethylamine, and di-n. -Secondary amines such as propylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, and quaternary ammoniums such as tetramethylammonium hydroxide and tetraethylammonium hydroxide. An aqueous solution of an alkali such as a salt or an aqueous solution obtained by adding a suitable amount of a water-soluble organic solvent such as an alcohol such as methanol or ethanol or a surfactant thereto can be suitably used. As a developing method, a system such as spray, paddle, immersion, and ultrasonic wave can be used. Next, the relief pattern formed by development is rinsed. Distilled water is used as the rinsing liquid. Next, heat treatment is performed to form an oxazole ring, and a final pattern having high heat resistance is obtained.

Thereafter, glass inorganic passivation is etched by reactive ion etching (RIE) or the like using the heat-resistant resin as a mask, and is cast using a molding material such as an epoxy resin, a phenol resin or a silicone resin.
Molded by transfer molding or the like.

The polyimide resin film obtained as described above has excellent resolution and excellent adhesion after humidity treatment, so that the semiconductor manufacturing process can be shortened and a semiconductor device having excellent moisture resistance can be obtained.

Hereinafter, the manufacturing process of the present invention will be described in detail with reference to the accompanying drawings in comparison with the prior art. In FIG. 1, reference numeral 1 denotes a semiconductor element such as silicon.
An np-type transistor is formed. An electrode 2 is formed on the surface of the semiconductor substrate 1 by aluminum evaporation.
Further, silicon nitride (SiN) 3 for protection is formed. When packaging this planar transistor, it is necessary to etch the (SiN) 3 on the electrode 2 in order to perform gold or aluminum wire bonding. In the conventional method, a resist is first used to form SiN.
Is etched, and then polyimide coating and patterning are performed.

FIGS. 1A to 1J illustrate this step-by-step, and very complicated steps must be taken.
A: semiconductor element b: resist coating, pre-baking c: resist patterning d: SiN etching (using RIE) e: resist peeling f: photosensitive resin coating, pre-baking g: resist coating, pre-baking h: resist pattern I: etching of photosensitive resin j: resist stripping, curing of photosensitive resin

On the other hand, in the present invention, since polybenzoxazole itself has photosensitivity and resolution, the polybenzoxazole can be directly patterned, and SiN can be etched using this as a mask. That is, the steps are illustrated in FIGS. 2A to 2D, and a predetermined semiconductor device can be obtained by simple steps which are much shorter than the conventional method. a: Semiconductor element b: Application of photosensitive resin composition, pre-bake c: Patterning and curing of photosensitive resin composition d: Etching of SiN (RIE dry etching)

[0074]

The present invention will be described below in detail with reference to examples. Example 1 * Synthesis of polyamide 0.86 mol of terephthalic acid, 0.14 mol of isophthalic acid and 1-hydroxy-1,2,3-benzotriazole 2
Dicarboxylic acid derivative 38 obtained by reacting
0.4 g (0.95 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane 3
66.3 g (1.0 mol) was placed in a 4-neck separable flask equipped with a thermometer, a stirrer material inlet, and a dry nitrogen gas inlet tube, and dissolved in 500 g of N-methyl-2-pyrrolidone. -Norbornene-2,3-dicarboxylic anhydride (32.8 g, 0.2 mol) was added, and the mixture was further stirred for 12 hours to complete the reaction. After the reaction mixture was filtered, the reaction mixture was poured into a solution of water / methanol = 3/1, the precipitate was collected by filtration, washed sufficiently with water, dried under vacuum, and expressed by the desired general formula (1). X was a mixture of the following formulas X-1 and Y was a mixture of the following formulas Y-1 and Y-2 to obtain a polyamide (A-1) consisting of a = 100 and b = 0.

* Preparation of Positive Photosensitive Resin Composition 100 g of the synthesized polyamide (A-1), 25 parts by weight of diazoquinone (Q-1) having the structure of the following formula, and 200 parts by weight of N-methyl-2-pyrrolidone After dissolution, 0.2
Filtration through a μm Teflon filter gave a photosensitive resin composition.

* Characteristic evaluation The positive type photosensitive resin composition was applied to a semiconductor element having a redundant circuit of 5 μm × 15 μm by using a spin coater, and then dried in an oven at 70 ° C. for 1 hour to obtain a film thickness of about 3 μm.
Was obtained. G-stepper exposure line NSR
The exposure from 50 mJ / cm ² through a reticle to 20 mJ / cm ² increments increased by 540mJ / cm ² was performed by -1505G3A (manufactured by Nikon Corporation). Then 0.7
After exposing and dissolving the exposed portion by immersing it in a 9% aqueous solution of tetramethylammonium hydroxide for 30 seconds,
Rinse with pure water for 30 seconds. As a result, the exposure amount was 200 m
It was confirmed that the pattern was formed from the portion irradiated with J / cm ² . (The sensitivity is 200 mJ / cm ² ).
At this time, the remaining film ratio (film thickness after development / film thickness before development) is 9
The value was as high as 1.3%. The wafer having a 3 μm via hole resolved was placed in an oven for 30 minutes /
The resin was cured by heating in the order of 150 ° C., 30 minutes / 250 ° C., and 30 minutes / 350 ° C. Further, the semiconductor protective material (plasma SiN) was etched from the wafer by reactive ion etching (RIE) for 185 seconds in CF4 gas. Then divide by chip size to 16 Pi
n After mounting on the lead frame for DIP (Dual Inline Package) using conductive paste, epoxy resin for semiconductor encapsulation (Sumitomo Bakelite Co., Ltd., EME-63
00H) to obtain 16 Pin DIP. After treating these packages at 85 ° C./85% humidity for 168 hours, they were immersed in a 260 ° C. solder bath for 10 seconds, and then subjected to a high-temperature, high-humidity pressure cooker treatment (125 ° C., 2.
3 atm, 100% RH) to check for open defects in the Al circuit. Table 1 shows the results.

Example 2 In the synthesis of polyamide in Example 1, a dicarboxylic acid derivative obtained by reacting terephthalic acid or isophthalic acid with 2 mol of 1-hydroxy-1,2,3-benzotriazole was used. 1 mole of diphenyl ether-4,4'-dicarboxylic acid and 1 mole of
Dicarboxylic acid derivative 443.2 obtained by reacting 2 mol of -hydroxy-1,2,3-benzotriazole
g (0.9 mol), represented by the general formula (1)
Synthesizes a polyamide (A-2) having the following formula Y-3 and a = 100 and b = 0, further using a diazoquinone (Q-2) having the following formula structure as a diazoquinone, And the other evaluations were the same as in Example 1. Table 1 shows the results.

Example 3 In the synthesis of the polyamide in Example 1, 347.9 g of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was used.
(0.95 mol) and replace with 1,3-bis (3
-Aminopropyl) -1,1,3,3-tetramethyldisiloxane (12.4 parts by weight (0.05 mol)) was added, and the compound was represented by the general formula (1), wherein X was the following formulas X-1 and Y The following formula Y
-1 and Y-2, Z is the following formula Z-1, and a = 9
A polyamide (A-3) composed of 5, b = 5 was synthesized, and the other evaluations were performed in the same manner as in Example 1. Table 1 shows the results.
Shown in

Example 4 A phenol compound (P-1) having a structure represented by the following formula was added to the resin composition in Example 1.
15 parts by weight were added, and the other evaluations were performed in the same manner as in Example 1. Table 1 shows the results.

<< Example 5 >> A phenol compound (P-2) having a structure represented by the following formula was added to the resin composition in Example 1.
15 parts by weight were added, and the other evaluations were performed in the same manner as in Example 1. Table 1 shows the results.

Example 6 An organosilicon compound (S-1) having a structure represented by the following formula was added to the resin composition in the example.
5 parts by weight were added, and the other evaluations were the same as in Example 1. Table 1 shows the results.

Example 7 An organic silicon compound (S-2) having a structure represented by the following formula was added to the resin composition in the example.
5 parts by weight were added, and the other evaluations were the same as in Example 1. Table 1 shows the results.

Comparative Example 1 322.2 g of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride (1.
0 mol) of 2-hydroxyethyl methacrylate 26
0.28 g (2.0 mol) was suspended in N-methyl-2-pyrrolidone, 166.1 g (2.1 mol) of pyridine was added, and the mixture was reacted at 25 ° C. for 10 hours. Next, 270.2 g of 1-hydroxy-1,2,3-benzotriazole (2.
0 mol) and completely dissolved in 1 hour.
N-methyl-2-pyrrolidone 40 while maintaining the temperature at 0 ° C or lower.
Dicyclohexylcarbodiimide 41 dissolved in 0 g
2.6 g (2.0 mol) was added dropwise over about 20 minutes. Thereafter, the reaction was performed at 25 ° C. for 3 hours. 4,4′-Diaminodiphenyl ether 190.2 was added to the reacted reaction solution.
(0.95 mol) and 5.11 g (0.02 mol) of N-phenyl-γ-aminopropyltrimethoxysilane were added and reacted at 30 ° C. for 5 hours. After dicyclohexylurea was filtered off, the reaction mixture was reprecipitated in methanol,
The solid was collected by filtration, washed with methanol, and dried under reduced pressure for 48 hours. The molecular weight measured by GPC was 23,000 as a weight average molecular weight. Further, 100 g of the obtained polymer was dissolved in 200 g of N-methyl-2-pyrrolidone, and 0.1 g of methyl ether hydroquinone and N
-Phenylglycine (5 g), 1-phenyl-5-mercapto-1H-tetrazole (1 g), 3- (2-benzimidazolyl) -7-diethylaminocoumarin (0.5 g), and tetraethylene glycol dimethacrylate (10 g) were added, and the composition was obtained. Was applied to the same semiconductor element as in Example 1 using a spinner and dried at 100 ° C. for 3 minutes to obtain a 9 μm thick film. 50m through reticle through this film
540m from J / cm ² by increasing 20mJ / cm ² at a time
Exposure was performed up to J / cm ² , then developed using cyclopentanone as a developing solution, and rinsed with propylene glycol methyl ether acetate. As a result, the exposure amount 150
It was confirmed that a pattern was formed from a portion irradiated with mJ / cm ² . The residual film ratio at this time was 90.2%. However, the resolution is 7 μm, and 5 μm × 5 μm
Redundant circuit was not resolved.

Comparative Example 2 A four-neck separable flask equipped with a thermometer, a stirrer, a raw material charging port and a dry nitrogen gas inlet was charged with 4,4'-diaminodiphenyl ether.
2 g (0.95 mol), 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane 1
2.4 g (0.05 mol) was added thereto, and anhydrous N-methyl-2-pyrrolidone was added thereto so that the solid content ratio in all the charged materials was 1%.
The solution was added in an amount of 5% by weight and dissolved. Then 0
The flask was immersed in an aqueous solution at 50 ° C., and while suppressing heat generation, 218.1 g of purified pyromellitic dianhydride (18.1 g) was added.
Mol). After the tetracarboxylic dianhydride was dissolved, the reaction was continued for 10 hours while maintaining the temperature of the system at 20 ° C. Note that the dry nitrogen gas was flowed over the entire process from the preparation stage of the reaction to the removal of the product. The obtained product is a pale yellow viscous solution, and the intrinsic viscosity of a 0.5% by weight solution of N-methyl-2-pyrrolidone is 1.10 (30%).
° C). This solution was applied to the same semiconductor element as in Example 1 using a spinner, dried at 145 ° C. for 1 minute, and
An m-thick film was obtained. Further, this film was coated with a positive resist OFPR-800 (manufactured by Tokyo Ohka Kogyo Co., Ltd.) using a spinner, dried at 100 ° C. for 1 minute, and further irradiated with 200 mJ / cm ² ultraviolet light through a reticle. Next, the developer 6 was developed using NMD-3 (manufactured by Tokyo Ohka Kogyo Co., Ltd.).
After dissolving and removing the exposed portion by immersing for 0 second,
Rinse with pure water for 30 seconds. As a result, the resolution is 30μ.
m, and the 5 μm × 15 μm redundant circuit was not resolved.

[0085]

[Table 1]

[0086]

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[0087]

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[0088]

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[0089]

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[0090]

According to the present invention, a pattern of high sensitivity and a high residual film ratio is obtained, and a positive photosensitive resin composition excellent in adhesion to a sealing resin and a substrate; It is possible to obtain a highly reliable semiconductor device in which a pattern of a polybenzoxazole resin having a high residual film ratio is formed on a semiconductor element using a positive photosensitive resin having excellent properties.

[Brief description of the drawings]

FIG. 1 shows a conventional semiconductor device manufacturing process.

FIG. 2 shows a process for manufacturing a semiconductor device according to the present invention.

[Explanation of symbols]

 Reference Signs List 1 semiconductor device 2 electrode 3 nitride film (SiN) 4 resist 5 polyimide 6 resist 7 polybenzoxazole resin

Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03F 7/022 G03F 7/022 H01L 21/027 H01L 21/30 502R

Claims (4)

[Claims] 1. 100 parts by weight of a polyamide (A) represented by the general formula (1) and a photosensitive diazoquinone compound (B)
A semiconductor device in which a photosensitive resin composition comprising 1 to 100 parts by weight is applied to the surface of a semiconductor element, exposed, developed, patterned, and then cured by heating. Embedded image 2. 100 parts by weight of a polyamide (A) represented by the general formula (1) and a photosensitive diazoquinone compound (B)
A photosensitive resin comprising 1 to 100 parts by weight and 1 to 50 parts by weight of a phenol compound (C) represented by the general formula (2) and / or (3) is applied to the surface of the semiconductor element, and exposed and developed to form a pattern. A semiconductor device that is processed and then cured by heating. Embedded image Embedded image 3. 100 parts by weight of a polyamide (A) represented by the general formula (1) and a photosensitive diazoquinone compound (B)
1 to 100 parts by weight, 1 to 50 parts by weight of a phenol compound (C) represented by the general formula (2) and / or (3) and represented by the general formulas (4), (5), (6) and (7) A photosensitive resin composition comprising 0.1 to 20 parts by weight of one or more kinds of organosilicon compounds (D) selected from the group consisting of A semiconductor device that is processed and then cured by heating. Embedded image Embedded image Embedded image Embedded image 4. A method for applying the photosensitive resin composition according to claim 1, 2 or 3 to a surface of a semiconductor element, exposing and developing the pattern, and then removing the semiconductor element protective material (passivation) by etching. A method of manufacturing a semiconductor device.