JPS61185932A - Semiconductor device - Google Patents

Abstract

PURPOSE:To improve the reliability upon moisture resistance by a method wherein a polyimide resin film comprising polyimide precursive resin composition dehydrated for ring closure is formed on a conductor layer. CONSTITUTION:The titled semiconductor contains polyamide acid containing siloxane coupling produced from reacted aromatic diamine, diaminosiloxane and aromatic tetracarbon acid as well as aminosiloxane represented by the structural formula 1. Then polyimide resin film comprising polyimide precurcive resin composition with compounding ratio of diaminosiloxane specified for 0.1-10mol of total mole quantity of aromatic diamine and diaminosiloxane as well as mixing ratio of aminosilane group specified for 0.1-2.0wt% of polyamide acid dehydrated for closing ring is formed on a conductor layer. At this time, if the weight of aminosilane group does not exceed 0.1% of polyamide acid, acceptable adhesive property will not be provided while if it exceed 2.0%, the stability of resin composition will be unacceptable.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention is applicable to hybrid ICs, monolithic ICs, L8
This relates to semiconductor devices such as I.

(Prior Art) In recent years, polyimide resins have been widely used as glabellar insulating films or surface protective films (sometimes referred to as passivation films) of semiconductor devices. This is the AI of polyimide resin! This is because of its moisture-resistant protection against wiring materials such as (aluminum) and ease of forming a thin film.

A general example in which the above polyimide resin is used as a surface protective film of a semiconductor device will be described with reference to the drawings.

In FIG. 2, the semiconductor chip includes the following configuration. 1 is a single-crystal silicon (Si) semiconductor substrate in which elements such as diodes and transistors are implanted; 2.3 and 4 are silicon oxide films with a thickness of 0.4 to 0.6 μm that cover the main surface of the semiconductor substrate 1; 9. SiOz) or phosphorus glass film. Photoetching was performed to open a portion. 5,
6 and 7 are the first conductor layers (lower layers) which are in resistive contact with the emitter, paste and collector regions, respectively, and which extend over the silicon oxide films 2, 3 and 4, respectively. This is a wiring layer. AI! After the wiring layer is formed by vacuum evaporation or sputtering, unnecessary portions are removed by photoetching to form a pattern. This AI! For example, the wiring layer is 1
．． It has a thickness of 5 μm and a width of 7 μm.

Next, generally the silicon oxide film or phosphorus glass shown in FIG. 2 and the AI! Spread a solution of an aluminum chelate compound onto the wiring layer using a spinner or the like.

As shown in FIG. 3, an aluminum oxide film 8 having a thickness of approximately 100 to 200 A is formed by heat treatment at a temperature of about 350° C. for 30 minutes. A polyimide resin film 9 is formed by spin coating and heat curing to form a semiconductor device.

This is because polyimide resin film is generally silicon oxide film,
AI! This is due to poor adhesion to wiring layers, etc.

By applying aluminum chelate treatment, the adhesion strength with these materials is improved. This adhesive strength has a great relationship with the moisture resistance reliability of the semiconductor device, and increasing the adhesive strength improves the moisture resistance of the semiconductor device.

In general, methods for improving the adhesion of polyimide resin include (1) a method of treating the substrate surface with a solution containing a primer such as aluminum chelate or a silane coupling agent before coating the polyamic acid as described above; 2) A method in which a silane coupling agent is added to a polyamic acid solution immediately before use, and (3) a method in which a siloxane bond is introduced into a polyamic acid by copolymerizing diaminosiloxane are known.

However, method (1) has the disadvantage that the steps in the Queha process are complicated. In addition, in the case of method (2), in order to impart sufficient adhesiveness to the polyimide resin film, a weight ratio of at least 5 to 9 of the polyamic acid solution is required.
% or more of the silane coupling agent must be added, and adding such a large amount of silane coupling agent will significantly reduce the viscosity stability of the polyamic acid solution, exhibit extreme thickening, and cause gelation. In some cases, it is impossible to store a polyamic acid solution with a silane coupling agent added thereto. Therefore, in method (2),
In the case of applications such as the electronic industry where contamination of foreign matter is extremely disliked, a silane coupling agent must be added immediately before use, and then foreign matter filtration must be performed, which is a major drawback in the process. Also, method (3).

Adhesion strength at room temperature is sufficiently improved, but at 120"C.

When a pressure tack test of 22 atmospheres is performed, this adhesive strength rapidly decreases, and the moisture resistance reliability of the semiconductor device also decreases.

Further, semiconductor devices are usually used after being sealed with thermosetting resin. The first reason for using resin sealing is that the material cost is low. Second, it is easy to rationalize manufacturing and reduce costs. However, when the present inventors investigated the moisture resistance of the above-mentioned resin-sealed semiconductor device, they found that since the resin itself has the property of allowing moisture to pass through from the outside, if it is left under adverse conditions for a long time, the AI of the conductor layer will deteriorate! It was found that corrosion of the wiring occurred. For this reason, it has been found that there is a problem in reliability when using the above-mentioned semiconductor device in the industrial field, which is 9% of fields where a high degree of reliability is required.

Therefore, in order to improve the reliability of semiconductor devices, the conductor layer is
I! AI containing several silicones! Some efforts have been made, such as changing the However, in this case, there is a problem that the cost increases.

Taking a semiconductor device with a two-layer wiring structure as an example to explain why the above defects occur, in a resin-sealed semiconductor device, moisture that has entered from the outside through the resin encapsulation may cause damage to the conductor layer. AI! Corrosion is thought to occur due to reaction with wiring.

And AI! Polyimide resin films usually have no cranks, which causes corrosion of wiring, so no moisture can enter through cracks, but on the other hand, since they are organic materials, they inherently absorb moisture inside. It is said that The inventors.

We investigated a semiconductor device that uses Al for the conductor layer and polyimide resin for the insulating layer. In the case of two-layer wiring, the corrosion of A/ is caused by the Al! The AI of the conductor layer that is not in contact with this is better! It was found that it is much more susceptible to corrosion.

From this, AI! The occurrence of corrosion in the conductor layer is related not only to the hygroscopicity of the polyimide resin film, but also to the adhesive strength t4 at the interface between the conductor layer and the interlayer polyimide resin film, or the adhesive strength at the interface between the polyimide resin films between the eyebrows. If this is small, absorbed moisture will exist at the interface, which is thought to cause corrosion of the kl conductor layer. In particular, in the case of the above-mentioned two-layer wiring, the strength of the interface between the polyimide resin that is the insulating film between the eyebrows and the conductor layer or polyimide resin film is small, so the conductor layer that is in contact with the polyimide resin film is more likely to corrode than the conductor layer that is not in contact with it. It's getting easier.

(Problems to be Solved by the Invention) An object of the present invention is to provide a highly reliable semiconductor device using a polyimide resin film with excellent adhesive properties on a conductor layer.

(Means for solving problems) The present invention is.

(a) a polyamic acid containing a siloxane bond obtained by reacting an aromatic diamine, a diaminosiloxane, and an aromatic tetracarboxylic dianhydride; and (b) a general formula (%) (in which R1 is a hydrogen atom or a monovalent hydrocarbon residues.

& means a divalent hydrocarbon residue, all means a monovalent hydrocarbon residue),
and the blending ratio of the diaminosiloxane.

A polyimide precursor resin composition with a mixing ratio of 0.1 to 10 mole based on the total molar amount of aromatic diamine and diaminosiloxane and a mixing ratio of the aminosilanes of 0.1 to 20% by weight based on the polyamic acid is dehydrated. The present invention relates to a semiconductor device formed on a ring-closed polyimide resin film gold conductor layer.

Examples of aromatic diamines used in producing polyamic acids containing siloxane bonds include 1, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 44'-diaminodiphenyl sulfone, 4,
．． 4'-diaminodiphenyl sulfide, benzidine, metaphenylenediamine.

Para-phenylene diamine, 1,5-naphthalene diamine, λ6-naphthalene diamine and the like can be mentioned.

These compounds may be used alone or in combination of two or more.

Further, this aromatic diamine is represented by the general formula (where Ar is aromatic and Y means Box or CO gold.

One amino group and Y -NH! It is also possible to use a diaminoamide compound represented by the group (located in the ortho position with respect to the group). These diaminoamide compounds include 1
For example, 4,4'-diaminodiphenyl ether-3-sulfonamide, 3,4'-diaminodiphenyl ether-4-sulfonamide, 3,4'-diaminodiphenyl ether-3'-sulfonamide, 3,3'-diaminodiphenyl ether- 4-sulfonamide, 4.4'
-diaminodiphenylmethane-3-sulfonamide, &
4'-diaminodiphenylmethane-4-sulfonamide, 4'-diaminodiphenylmethane-1-sulfonamide, &3'-diaminodiphenylmethane-4-sulfonamide, 44'-diaminodiphenylsulfone-3-sulfonamide, 3.4 '-Diaminodiphenylsulfone-4-sulfonamide, &4'-diaminodiphenylsulfone-3'-sulfonamide, 3.3'-
Diaminodiphenylsulfone-4-sulfonamide.

4.4'-diaminodiphenylsulfide-3-sulfonamide, &4'-diaminodiphenylsulfide-4-sulfonamide, &3'-diaminodiphenylsulfide-4-sulfonamide, tome 4'-diaminodiphenylsulfide-J-sulfonamide , 1.4-
Diaminobenzene-2-sulfonamide, 44'-diaminodiphenyl ether-3-carbonamide, λ4'
-diaminodiphenyl ether-4-carbonamide,
3.4'-Diami" fudiphenyl ether-3'-carbonamide, λ3'-diaminodiphenyl ether-4
-carbonamide, 4'-diaminodiphenylmethane-3-carbonamide, &4'-diaminodiphenylmethane-4-carbonamide, 4'-diaminodiphenylmethane-3'-carbonamide, and 3'-diaminodiphenylmethane-4- Carbonamide, 4,4'-diaminodiphenylsulfone-3-carbonamide, Kame 4
'-Diaminodiphenylsulfone-4-carbonamide, tome 4'-diaminodiphenylsulfone-J-carbonamide, 43'-diaminodiphenylsulfone-4-carbonamide, 4,4'-diaminodiphenylsulfide-3-carbonamide, 4'-diaminodiphenyl sulfide-4-carbonamide, 3,3'-diaminodiphenyl sulfide-4-carbon azide, 4'-diaminodiphenyl sulfide-J-sulfonamide, 1,4-diaminobenzene-2-carbonamide Amides and the like can be mentioned.

Diaminosiloxane used to introduce a siloxane bond into polyamic acid has the general formula 2, for example (R4 and Rs are divalent hydrocarbon residues I R'l #
R71 and R9 are monovalent hydrocarbon residues, Ram
~R9 may be the same or different (m means an integer of 1 or more), and examples thereof include compounds represented by the following formula. These compounds may be used alone or in combination of two or more.

CHs CHa CHs CHs C6H5Cs Hs CaHIICsHs CHs CHs CsHs C@Hs Examples of aromatic tetracarboxylic dianhydrides include 9, for example, pyromellitic dianhydride, 3.3:4.4'-diphenyltetracarboxylic dianhydride, 3 .3:4.4'-benzophenonetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, 1,2,5,6-su, phthalenethtracarboxylic dianhydride, 2. : 17-naphthalenetetracarboxylic dianhydride, 23,5.6-pyrylenetetracarboxylic dianhydride, 1,4,5.8-naphthalenetetracarboxylic dianhydride, &49゜10-perylenetetracarboxylic dianhydride Examples thereof include acid dianhydride, 4,4'-sulfonylsiphthalic dianhydride, and the like.

These compounds may be used alone or in combination of two or more.

To produce a polyamic acid containing siloxane bonds, the total amount of the aromatic diamine and diaminosiloxane is
It is reacted in a solvent in approximately equimolar amounts with the aromatic tetracarboxylic dianhydride.

As a solvent, 1 such as N-methyl-2-pyrrolidone, N
, N-dimethylacetamide, N,N-dimethylformamide, N,N,N-diethylformamide, dimethylsulfoxide, hexamethylphosphoramide9. Examples include tetramethylene sulfone. These compounds may be used alone or in combination.

The aminosilanes used in the present invention have the general formula HN-R
It is represented by z 8i (ORs)s (in the formula, R1 to R3 have the above-mentioned meanings).

Examples of aminosilanes include r-aminopropyltrimethoxysilane, r-aminopropyltriethoxysilane, r-aminobutyl-triethoxysilane, N-phenyl-r-aminopropyltriethoxysilane, N-
Examples include β(aminoethyl)γ-aminopropyltrimethoxysilane and γ-ureidopropyltriethoxysilane 7. These compounds may be used alone or in combination for 2s or more.

When using the polyimide precursor resin in the present invention, a solvent is used, and the solvent is one that dissolves both the above-mentioned siloxane bond-containing boriamic acid and the above-mentioned aminosilanes9. The used solvent is used to produce polyamic acid containing siloxane bonds. The solvents may be used alone or in combination of two or more solvents. The amount of solvent is preferably in a range such that the concentration of polyamic acid containing siloxane bonds is 5 to 25% by weight.

In the resin composition used in the present invention, there are certain limitations on the proportion of siloxane bonds in the polyamic acid containing siloxane bonds. That is, the blending ratio of diaminosiloxane is 0.1 to 10 mol, preferably 0.5 to 5 mol, based on the total molar amount of aromatic diamine and diamino siloxane. When the amount of diaminosiloxane is 0.1 mole, the effect of imparting adhesiveness is poor, and when it exceeds 10 mole, the inherent heat resistance of polyimide is impaired.

The mixing ratio of aminosilanes is 0.1 to zO weight %, preferably 0.3 to 1.0 weight %, based on the polyamic acid containing siloxane bonds. When the amount of aminosilanes is less than 0.1% by weight, the effect of imparting adhesiveness is poor, and when it exceeds 20% by weight.

The stability of the resin composition is impaired.

When producing the resin composition of the present invention, first a polyamic acid containing a siloxane bond is produced.

A polyamic acid containing a siloxane bond can be prepared by a known method, for example, by dissolving an aromatic diamine and diaminosiloxane in the above-mentioned solvent, and adding an aromatic tetracarbo/acid dianhydride to the solution at 80°C or lower.

Particularly preferably, it is obtained by reacting with stirring at a temperature around room temperature or lower.

Next, after adjusting the viscosity to an appropriate viscosity for use, aminosilanes diluted in advance with the solvent to a concentration of 10 weight St+ or less are added at room temperature or lower, and mixed with stirring to form a resin composition. It is said that

The resin composition is applied onto the conductor layer using a spinner or the like, dried preferably at 100 to 250°C for 10 to 60 minutes, and then preferably heated at 250 to 400°C for 30 to 90 minutes to perform dehydration and ring closure. It is considered to be a polyimide resin.

The polyimide resin film in the present invention is a resin film that spreads over an inorganic insulating film and a conductor layer for wiring provided on the surface of a semiconductor substrate having at least one semiconductor element, and a resin film that spreads over an inorganic insulating film and a conductor layer for wiring provided on the surface of a semiconductor substrate having at least one semiconductor element. A first conductor layer for wiring is provided through an insulating film of silicon oxide or silicon nitride provided on the first conductor layer, and a second conductor layer is provided on this through an insulating film of an organic resin. It has a plurality of wiring conductor layers such as a third layer.

Further, it is used as the organic resin insulating film of a multilayer wiring structure having an organic resin insulating film on the uppermost wiring conductor layer.

In the present invention, the polyimide resin film is formed on the conductor layer, but in the case of a semiconductor device having multiple conductor layers, the polyimide resin film is formed under the uppermost conductor layer. It may also be a conductor layer. This resin film may be formed both on the top conductor layer and the conductor layer formed below it, or it may be formed only on the top conductor layer or only on the conductor layer formed below it. Good too. Formation of polyimide resin film on the conductor layer, even on the top conductor layer.

This also takes place by known means on the conductor layer formed below.

The present invention will be explained by examples.

(Example) The present invention will be explained with reference to comparative examples and examples.

Comparative Example 1 4.42-diaminodiphenyl ether 6.035g
, i,3-bis(aminopropyl)tetramethyldisiloxane 0.3949. Pyromellitic dianhydride
3.4609 and λ■4.4'-benzophenonetetracarboxylic dianhydride 5.1109T-,N-methyl-2-pyrrolidone 85.09 were reacted at room temperature to obtain 100 g of a polyamic acid solution containing siloxane bonds. Ta.

This material had a viscosity of 2001)S, so 80
The viscosity was lowered while stirring at °C to adjust to 101)81C.

This is combined with silicon oxide (Sigh) and AI! The semiconductor substrate on which the wiring layer was formed was coated with a spinner at 2000 rpm for 30 seconds, and then heated at 200°C for 30 minutes in an N3 gas atmosphere.
This was then heated and cured at 350° C. for 60 minutes to form a surface retaining film made of polyimide resin with a thickness of 2 μm. next,
A hole was made in the bonding butt portion, and a semiconductor device was fabricated by packaging it in an epoxy sealing material.

Example 1 To the polyamic acid solution containing siloxane bonds obtained in Comparative Example 1, a solution of r-aminopropyltriethoxysilane, which is an aminosilane, dissolved in 79 g of 1st N-methyl 2-pyrrolid was added, and the mixture was stirred at room temperature for 1 hour. After melting, a polyimide precursor resin composition having a nonvolatile content of 14.3% by weight after heat treatment at 200°C for 2 hours and a viscosity of 10.5 pS at 25°C was obtained. A polyimide resin film was formed using this resin composition under the same conditions as in Comparative Example 1.

A moisture resistance reliability test was conducted on the semiconductor device samples prepared in Comparative Example 1 and Example 1 above. In this test, a pressure tack test was performed on the semiconductor device at 121°C.
℃ and vapor pressure of 22 atmospheres, AI! We investigated changes in the resistance value of the wiring layer.

The comparative values are shown in FIG.

This shows that the semiconductor device of Example 10 using the polyimide precursor resin composition of the present invention has superior moisture resistance reliability compared to the semiconductor device of Comparative Example 10.

Example 2 FIG. 5 shows a cross-sectional view of a semiconductor chip, and FIG. 6 shows a schematic cross-sectional view of a semiconductor device completed by sealing the semiconductor chip with resin. The embodiment shown in FIG. 5 is applied to a bipolar IC with a two-layer wiring structure, and in order to simplify the explanation, FIG. Only the structure of the bipolar transistor is shown.

In FIG. 5, the semiconductor chip 31 includes the following configuration. 11 is a P- type single crystal silicon (Si) semiconductor substrate, 12 is an N+ type semiconductor buried layer, 13 is an N'''' type silicon semiconductor layer formed on the substrate 1 by epitaxial growth technology, and 14 is a semiconductor layer. 4 covering the main surface of 13
000X~s o o o! A silicon dioxide (SiOx) film or a phosphor glass film having a thickness of 100 mL is used, and a portion thereof is opened by photoetching. In order to electrically isolate the semiconductor layer 13 into a plurality of element formation regions (islands), 15 is a Pfj& isolation region created by diffusion technology, which is formed so as to surround the element formation region to be separated by one. There is. 7 is a second base region formed by diffusion technology, and 19 is an N''ll emitter region.

36 is N''ll collector extraction area (contact area)
''' is 6.

23, 24 and 25 are in resistive contact to the emitter, base and collector regions, respectively, and.

A first conductor layer (lower layer) extending on the silicon oxide film 14
A/wiring layer. AI! After the wiring 1 is formed by vapor deposition or sputtering, unnecessary portions are removed by photoetching to form a pattern.

This wiring layer has a thickness of, for example, 1.5 μm and a width of 7 μm.

26 is a polyimide resin film obtained from the polyimide precursor resin composition of the present invention, and has a thickness of, for example, 2 to 5 μm.

This resin film was formed by the following method.

4.4'-silminodiphenyl ether 6.035g
(95 mol ts) l 1,3-bis(aminopropyl)
Tetramethyldisiloxane 0.3949 (5 molti)
and pyromellitic dianhydride 3.4609 (50 mol%), 3.3:44'-penzophenonetetracarboxylic dianhydride 5.1109 (50 mol%), N-methyl-2-pyrrolidone 7a09 react at room temperature in
A polyamic acid solution 909 containing siloxane bonds was obtained.

This one had a viscosity of 200 pS, 80℃
While stirring, the viscosity was lowered to 10 pSKi14.

Next, r-aminopropyltriethoxysilane 19tN
A solution dissolved in 9 g of -methyl-2-pyrrolidone was prepared, and 0.759 of the solution was added to the above polyamic acid solution 909 containing a siloxane bond which had been cooled to room temperature, and the solution was stirred and dissolved at room temperature for 1 hour. The resin composition thus obtained was 200%
The nonvolatile content concentration measured at °C/2 hours was 16.3% by weight, and the viscosity at 25 °C was 10.5 pS.

This resin composition was applied onto the A/wiring layer at zsoorpm for 3
A polyimide resin film was formed by coating with a spinner for 0 seconds and then heat-treating at 100° C. for 30 minutes, then at 200° C. for 30 minutes, and at 350° C. for 60 minutes in a N2 gas atmosphere.

Next, a photoresist film is selectively formed on this resin film, and using this as a mask, the polyimide resin film 26 is etched to form a contact hole for the A/wiring layer.

After this, the photoresist mask is removed. next.

An At interconnection layer 27, which is a second conductor layer, is formed by a vapor deposition technique.

AI! The wiring layer 27 has a thickness of, for example, 1.5 μm and 7 μm.
has a width of 28 is the second AI! This is a polyimide resin film that is the final protective film that covers the wiring layer, and is made of the same material as the resin film of the second insulating layer, and is formed by the same process.

What is the thickness of this final protective film?

For example, it is set to 25 μm. The resin film of this final protective film is 1
Although not shown, the bonding butt part is through-hole etched using a photo-etching method, and the AI!
A plurality of bonding pad portions connected to the wiring layer of the wiring layer 27 are exposed. This exposed bonding pad portion has an area of, for example, 130 μm×130 μm.

This semiconductor chip is sealed with resin, as shown in FIG. That is, in FIG. 6, numeral 31 is the above-mentioned semiconductor chip, in which a predetermined circuit is integrated. The semiconductor chip 31 is fixed to a fixed electrode (tab electrode) 32 using a gold-silicon eutectic alloy or the like, and is electrically connected to another external lead 33 by a connector wire 34 . The fixing of the semiconductor chip 31 to the fixed electrode 32 and the connection of connector wires (for example, made of gold wire) between the semiconductor chip 31 and the external leads are accomplished by a well-known technique. As is well known, this
Connections between the semiconductor chip and the connector wires are made in the lead frame state. Reference numeral 35 denotes a sealing body made of epoxy resin, which is formed by a well-known transfer molding technique. This sealing body 35 is formed to surround the semiconductor chip 31 and the connector wire 34.

In the semiconductor device of the present invention thus obtained, the lower surface of the At wiring layer 27, which is the second conductor layer, is covered by the polyimide resin film 26, which is the second insulating layer. Its upper surface is covered with a polyimide resin film 28 as a third insulating layer. Of course, the upper wiring layer is exposed from the polyimide resin film 2B of the third insulating layer at the connection portion of the connector wire 34 shown in FIG. 6, that is, at the bonding pad portion (not shown). has been done. Then, the polyimide resin film 2 of the third insulating layer
8 and is surrounded by a sealing resin body 35.

The At wiring layer 27 is a polyimide resin film 26 of the second insulating layer.
and the polyimide resin film 28 of the third insulating layer, and the polyimide resin film 28 is
It has superior adhesion to the A/wiring layer, which is the second conductor layer, and adhesion at the interface between the resin films, compared to conventional polyimide resin films. Therefore, AI! prevents moisture that may enter from the outside through the resin sealing body 35! The wiring layer 27 is strongly protected by polyimide resin films 26 and 28.

As a result, using the polyimide resin film of the present invention has better AI than using the conventional polyimide resin film! The ability to prevent the conductor layer from being corroded by moisture that has entered the wiring layer 271C from the outside has become stronger.

At this time, the bonding pad exposed from the polyimide resin 18 has a large area, for example, 130 μm x 130 μm, and the connector wire connection portion is present on this pad so as to cover the pad portion. 2. AI in the part exposed from the old resin film 28! Corrosion of the wiring layer 27 does not substantially pose a problem.

Furthermore, since the polyimide resin of the present invention has excellent adhesive strength with the silicon dioxide film 4, which is the first insulating layer, it has excellent adhesive strength with the pyrotechnic film, which was necessary when using conventional polyimide resin. The process of forming a coupling agent layer for ensuring the stability is unnecessary.

To confirm the effects of the invention, the present inventors used the polyimide resin of the present invention and the conventional polyimide resin for the final protective coating consisting of the interlayer insulating film, which is the second insulating film, and the third insulating film in the above structure. A semiconductor device using this was fabricated and a moisture resistance test was conducted, with the following results obtained.

The bipolar IC obtained in the above example was used in the test. Both the first conductor layer and the second conductor layer were made of aluminum and had a film thickness of 1.5 μm. In the semiconductor device used in the test, the second conductive layer was not exposed because the bonding pad portion was not etched, which is normally performed after forming the final protective film, which is the third insulating film. Further, no resin sealing was performed after that.

Test Example 1 A semiconductor device was created using the resin composition obtained in the example for both the glabella insulating film and the final protective film. The formation and processing methods were the same as those described in the examples.

Test Example 2 A semiconductor device was fabricated using a polyimide resin containing siloxane bonds for both the interlayer insulating film and the final protective film.

This polyimide resin film containing siloxane bonds is 4.4'
-diaminodiphenylmethane.

35 mol%, 4.4'-diaminodiphenyl ether-
3-Carbonamide, 10 mol%, 1,3-bis(aminopropyl)-tetramethyldisiloxane.

5 mol thiopyromellitic dianhydride, 50 mol t-N
- A polyamic acid solution containing siloxane bonds (resin concentration 15 weight - 1 viscosity 1200 CpS) was prepared by placing it in methyl-2-pyrrolidone solvent and reacting at room temperature for 5 hours,
Apply this with a spinner for 30 seconds at 300 Orpm, and
2. After heat treatment at 200℃ for 30 minutes in an atmosphere of 3.
A heat treatment was performed at 50° C. for 60 minutes to form a polyimide resin film containing siloxane bonds.

Test Example 3 A semiconductor device was created using a polyimide resin film as both the glabella insulating film and the final protective film. This polyimide resin film is made of PI-2545 (Dup
ont Co., Ltd.) under the same formation conditions as Test Example 2.

Test Example 4' A semiconductor device was fabricated using polyimide resin films as both the interlayer insulating film and the final protective film. This polyimide resin film was formed by processing under the same formation conditions as Test Example 2 using commercially available Pyre-ML (product of DuPont).

A moisture resistance test was conducted on the semiconductor device samples prepared in Test Examples 1 to 4 above. In this test, each sample was left at a temperature of 121°C and a vapor pressure of 22 atmospheres, and the AI of the second conductive layer was measured for each sample. The progress of corrosion in the wiring layer was observed using a microscope over the time of the humidity test. The results are shown in the table below. Here, A indicates that there is no corrosion of the aluminum wiring layer within the chip, and B indicates that corrosion is approximately 5 to 10%.
C: 30-50%; D: Corrosion is observed throughout the chip.
E indicates that the wiring layer is partially dissolved.

From this, the sample of Test Example 1 using the polyimide resin of the present invention was 3 to 5% compared with the conventional polyimide resin.
O which has been shown to have twice the moisture resistance
Below are the margin moisture resistance test results (121
℃, 2.2 atm) (Effects of the Invention) The semiconductor device of the present invention in which a polyimide resin film formed by dehydrating and ring-closing the polyimide precursor resin composition is formed on a conductor layer has extremely excellent moisture resistance and reliability, and especially , useful for electronic components that require high reliability.

[Brief explanation of drawings]

Fig. 1 is a cross-sectional view of a semiconductor chip according to an embodiment of the present invention, Fig. 2 is a cross-sectional view of the semiconductor chip before being covered with a polyimide resin film, and Fig. 3 is a cross-sectional view of a semiconductor chip using a conventional primer. , and FIG. 4 are graphs showing changes in resistance values in pressure tack tests conducted in Examples and Comparative Examples. FIG. 5 is a partial sectional view of a semiconductor chip in a semiconductor device according to an embodiment of the present invention, and FIG. 6 is a schematic sectional view of a semiconductor device obtained by resin-sealing the semiconductor chip. Explanation of symbols 1...Single crystal silicon semiconductor substrate 2...Silicon oxide film or phosphorus glass film 3...Silicon oxide film or phosphorus glass film 4...Silicon oxide film or phosphorus glass film 5...Al ! Wiring layer 6
...Al! Wiring layer 7...AJ wiring layer 8...Aluminum oxide film 9...Polyimide resin film 10...Polyimide resin film 11...P- type single crystal Si semiconductor substrate 12...N+
type semiconductor buried layer 13...N- type Si semiconductor layer 14...5iOz film 15...P type isolation region 17...P type base region 19...N+ type emitter region 20. -・N+ type collector extraction area 23, 24.25...AJ wiring layer 26, 28...Polyimide resin film 27...AJ wiring layer 31...Semiconductor chip 3
2...Fixed electrode 33...External drawer lead 34...Connector wire 35...Sealing body rod 1 diagram V2 Iku rod 3ro No. 5121 Kaya 4 diagram

Claims (1)

[Claims] 1. (a) Polyamic acid containing a siloxane bond obtained by reacting aromatic diamine, diaminosiloxane, and aromatic tetracarboxylic dianhydride; and (b) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (R_1 in the formula is a hydrogen atom or a monovalent hydrocarbon residue, R
_2 means a divalent hydrocarbon residue, R_3 means a monovalent hydrocarbon residue),
And, the blending ratio of the diaminosiloxane is 0.0% relative to the total molar amount of the aromatic diamine and diaminosiloxane.
A polyimide resin film is formed on the conductor layer by dehydrating and ring-closing a polyimide precursor resin composition with a mixing ratio of 1 to 10 mol% and the aminosilanes being 0.1 to 2.0% by weight relative to the polyamic acid. semiconductor device.