JPH02180961A - Composition for interlaminar insulation film and/or surface protection film of semiconductor substrate and semiconductor device - Google Patents

Abstract

PURPOSE:To provide a composition fully curable by heat treatment at a relatively low temperature, capable of wet etching and desirable for an interlaminar insulation film and/or surface protection film of a semiconductor substrate by using a specified polyamic acid silicone intermediate. CONSTITUTION:A tetracarboxylic acid dianhydride (A) containing at least an acid dianhydride of formula I (wherein n is 2-16) is reacted with a diamine (B) (e.g. 4,4'-diaminodiphenyl ether) and a diaminosiloxane (C) (e.g. formula II) in an organic polar solvent (e.g. N-methyl-2-pyrrolidone) to produce a polyamic acid silicone intermediate. This intermediate is heat-treated to remove the solvent thereform and to cyclize it through dehydration to produce a polyimide resin film. This resin film is used as an interlaminar insulation film and/or surface protection film of a semiconductor substrate.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a polyimide resin suitable for use as an interlayer insulating film and/or surface protection composition for semiconductor substrates and as an interlayer insulating film and/or surface protection film between conductor layers. The present invention relates to a semiconductor device having a multilayer wiring structure using a film.

(Prior Art) Conventionally, polyimide resins have been used as interlayer insulating films and semiconductors with multilayer wiring structures because they have higher flatness than inorganic insulating films such as silicon dioxide formed by chemical vapor deposition. Widely used for surface protection films. Its usage is as follows. First of all, Ueno.
A solution of polyamic acid, which is a precursor of polyimide resin, is applied onto a semiconductor substrate on which circuit elements are formed on a glass plate, metal, etc., and a predetermined portion thereof is exposed. Imidize part or all of it. Next, the photoresist is formed into a desired turn, immersed in an etching solution to dissolve and remove unnecessary portions, and the photoresist is peeled off. If a portion of the photoresist is imidized and etched, heat treatment is performed again to completely harden it. To completely cure conventional polyimide resins, a temperature of 250°C or higher is required.

However, in image sensors made of a-8i (amorphous silicon) or semiconductor substrates containing compound semiconductors, nine-layer insulation is used to prevent reactions between the electrode materials used and the semiconductor elements, or to prevent the heat resistance of the semiconductor elements themselves. Since the forming treatment temperature of the materials used for the film and the surface protective film must be approximately 250° C. or lower, conventional polyimide resin films are used at a heat treatment temperature of 250° C. or lower, at which point they are not completely imidized. Therefore, unreacted polyamic acid remains in the glabella insulating film and the surface protective film, and corrosion of the conductive layer is likely to occur, resulting in poor moisture resistance reliability.

In addition, as a method that can be completely cured at 250°C or less, polyimide that has been completely imidized or polyamide-imide that has been partially imidized is cured with N-methylpyrrolidone, r
- Etching is not possible after curing in any method using a solution dissolved in a polar solvent such as butyllactone.

It is not practical because it requires a special etching solution or etching process.

Further, when a polyimide resin is used as a glabellar insulation or surface protection coating material for a semiconductor device, silicon oxide, silicon nitride, etc. are present in the base of the semiconductor substrate. General polyimide resins do not have good adhesion with these inorganic coatings, so in order to ensure adhesion, it is essential to use coupling agents such as silanes and organic chelates of metals.
There is a problem that a step of forming a coupling agent layer is required, making the process complicated.

(Problems to be Solved by the Invention) An object of the present invention is to solve the problems of the prior art,
Glabella insulating film and/or surface protection for semiconductor substrates that produces polyimide resin films that can be completely cured at temperatures below 0°C, can be wet-etched, and have excellent adhesion to the base (inorganic film) of semiconductor substrates. It is an object of the present invention to provide a film composition and a semiconductor device using the same that has excellent moisture resistance and reliability, mainly adhesion and corrosion resistance.

(Means for Solving the Problems) The present invention provides at least (a) a tetracarboxylic dianhydride containing an acid dianhydride represented by a large amount (in the formula, n is an integer of 2 to 16); ) diamine, and a composition for an interlayer insulating film and/or surface protective film of a semiconductor substrate, which contains a polyamic acid silicon type intermediate obtained by reacting (cl diaminosiloxane) in an organic polar solvent, and this polyamic acid silicone The present invention relates to a semiconductor device in which a polyimide resin film obtained by dehydrating and ring-closing a mold intermediate is used as an F-interval insulating film and/or a surface protective film of a semiconductor substrate.

Furthermore, the present invention provides a composition for an interlayer insulating film and/or surface protective film of a semiconductor device, wherein the above-mentioned polyamic acid silicon type intermediate is a polyamic acid silicon type intermediate obtained by reacting a diaminoamide compound as a part of diamine. The present invention also relates to a semiconductor device using a polyimide resin film obtained by dehydrating and ring-closing this polyamic acid silicon type intermediate as an in-layer insulating film and/or a surface protective film of a semiconductor substrate.

Examples of the tetracarboxylic dianhydride (indicated by a large amount of al) used in the present invention include hebutamethylene bistrimelitate dianhydride, octamethylene bistrimelitate dianhydride, and decamethylene bistrimelitate dianhydride. Examples include things.

Two or more of these can also be used in combination. These acid dianhydrides can be synthesized from trimellitic anhydride monochloride and the corresponding diol.

The acid dianhydride indicated by [al-amount] may be used alone, or may be used in combination with other acid dianhydrides.

Other acid dianhydrides include pyromellitic dianhydride, 31-4,4'-diphenyltetracarboxylic dianhydride, 3. a: 4,4'-benzophenonetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, 1,2,5.6-naphthalenetetracarboxylic dianhydride, 2,3,6.7-naphthalene Tetracarboxylic dianhydride, 2,3,5.6-pyridinetetracarboxylic dianhydride, 1,4,5.8-naphthalenetetracarboxylic dianhydride, 3,4,9.10-perylenetetracarboxylic dianhydride Examples include acid dianhydride and 4,4'-sulfonylsiphthalic dianhydride, and 28 or more of these can also be used in combination. It is preferable to use these other acid dianhydrides in an amount of less than 50 molti based on the total amount of acid dianhydrides, from the viewpoint of the curing temperature (imidization completion temperature) of the polyamic acid.

The bl diamine used in the present invention is 4.4'
- Diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide.

Examples include benzidine, meta-phenylene diamine, para-phenylene diamine, 1,5-naphthalenediamine, and sloth-7tale diamine, and two or more of these can also be used in combination.

The diaminosiloxane (c) used in the present invention is 2, for example, in a large amount (R represents a divalent hydrocarbon group, R' represents a monovalent hydrocarbon group, and R and R' may be the same or different. y<, n is an integer of 1 or more) 9 For example, CH3CH3 CH3CH3 CHs ClCaHs CgHs CH3CH3, etc., and one type or 281 or more of these can be used.

Further, if necessary, a diaminoamide compound represented by the following formula may be used as a part of the diamine (in the formula, Y is 5
Ozt or CO, X'ri O, CH2, Soz.

means S or CO, and one amino group and Y-M
The Hz group and the Hz group are positioned ortho to each other. ) Specific examples of these compounds include 4,4'-diaminodiphenyl ether-3-sulfonamide.

Tortoise 4'-diaminodiphenyl ether-4-sulfonamide, 3.4'-diaminodiphenyl ether-3'-
Sulfonamide, 3.3'-diaminodiphenyl ether-4-sulfonamide, 4.4'-diaminodiphenylmethane-3-sulfonamide, 3.4'-diaminodiphenylmethane-4-sulfonamide.

λ4'-diaminodiphenylmethane-3'-sulfonamide, 3.3'-diaminodiphenylmethane-4-sulfonamide, 4.4'-diaminodiphenylsulfone-3-sulfonamide, 3.4'-diaminodiphenylsulfone-4- Sulfonamide, 3,4'-diaminodiphenylsulfone-3'-sulfonamide.

3.3'-diaminodiphenylsulfone-4-sulfonamide, 4.4'-diaminodiphenylsulfide-
3-sulfonamide, tome 4'-diaminodiphenyl sulfide-4-sulfonamide, 3.3'-diaminodiphenyl sulfide-4-sulfonamide, 3.4'
-Diaminodiphenyl sulfide-3'-sulfonamide, 1,4-diaminobenzene-2-sulfonamide, 4,4'-diaminodiphenyl ether-3-carbonamide, 3,4'-diaminodiphenyl ether-4
-carbonamide, 3゜4'-diaminodiphenyl ether-3'-carbonamide, 3.3'-diaminodiphenyl ether-4 carbonamide, 4.4'-diaminodiphenylmethane-3-carbonamide, 3.4'-
Diaminodiphenylmethane-4-carbonamide, λ4
'-Diamino diphenylmethane-3'-carbonamide, 3゜3'-diaminodiphenylmethane-4-carbonamide, 4.4'-diaminodiphenyl sulfone-3=
Carbonamide, 3,4'-diaminodiphenylsulfone-4-carbonamide, λ4'-diaminodiphenylsulfone-3'-carbonamide, 3,3'-diaminodiphenylsulfone-4-carbonamide.

4.4'-diaminodiphenyl sulfide-3-carbonamide, 4'-diaminodiphenyl sulfide-4-carbonamide, λ3'-diaminodiphenyl sulfide-4-carbonamide, 3+4'-diaminodiphenyl sulfide-3'-sulfone Amide, 1.
Examples include 4-diaminobenzene-2-carbonamide. Two or more types of these diaminoamide compounds can also be used in combination.

The polyamic acid silicon type intermediate used in the present invention is obtained by reacting the above-mentioned diamine and diaminosiloxane in approximately equimolar amounts with the above-mentioned tetracarboxylic dianhydride. From the viewpoint of adhesion to the semiconductor element surface of the cured product of the polyamic acid silicon type intermediate and heat resistance, it is preferable that diaminosiloxane is contained in the diamine component in an amount of 0.1 to 50 mol. When using a diaminoamide compound, it is preferable to use 5 to 30 moles of the diamine component.

To obtain a polyamic acid silicon type intermediate which is a precursor of a polyimide resin film from the above-mentioned tetracarboxylic dianhydride, diamine and diaminosiloxane, 1% - Kosho 5
A known method such as that disclosed in Japanese Patent No. 7-5407 is used. For example, the polyamic acid silicon type intermediate is prepared by reacting the total amount of the above-mentioned tetracarboxylic dianhydride with the total amount of diamine, diaminosiloxane, and the diaminoamide compound used as necessary in an organic polar solvent using approximately equal moles of the total amount. First, the diamine and diaminosiloxane, which are optionally added, are thoroughly dissolved in the organic polar solvent.Next, the acid dianhydride is added, and the reaction system is heated preferably at about 80°C or below. More preferably, it is obtained by stirring for 3 to 6 hours while maintaining the temperature at around room temperature or lower.

The organic polar solvent is preferably one that dissolves the polyamic acid produced. For example, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-diethylformamide, dimethylsulfoxide. , hexamethylphosphoramide, tetramethylene sulfone, etc., or two or more thereof may be used.

The polyimide resin film in the present invention is prepared by heating the polyamic acid silicon intermediate at 150 to 250°C.

Preferably, it is obtained by heat treatment at a temperature of 180 to 230°C to remove the solvent, followed by dehydration and ring closure.

An example of the manufacturing process of the semiconductor device of the present invention will be described below.

FIG. 1 is a manufacturing process diagram of a semiconductor device having a multilayer wiring structure. In the figure, a semiconductor substrate 1 such as an 8i substrate, a glass plate, a metal plate, etc. having nine circuit elements is covered with a protective film 2 such as a silicon oxide film except for predetermined parts of two circuit elements, and a first layer is placed on the exposed circuit elements. A conductor layer 3 is formed. The aforementioned polyamic acid silicon type intermediate is coated on the semiconductor substrate by a spinner method or the like, and the solvent is removed and the polyamic acid silicon type intermediate is dehydrated and ring-closed by heat treatment to form a polyimide resin film 4 as an interlayer insulating film. is formed (step (a)).

Next, a cyclized rubber-based or phenol novolac-based photosensitive resin layer 5 is formed on the interlayer insulating film 4 by a spinner method, and a window is formed using a known photolithography technique so that a predetermined portion of the glabellar insulating film 4 is exposed. 6A is provided (step (b)
)).

The interlayer insulating film 4 of the window 6A is selectively etched by a chemical etching means using an organic alkaline solution such as hydrazine, a mixture of hydrazine and polyamine, or a tetramethylammonium hydroxide solution as an etching solution, and the window 6B is etched. It can be opened. Next, the photosensitive resin layer 5 is completely removed using an etching solution that corrodes only the photosensitive resin layer 5 without corroding the first conductor layer 3 exposed through the window 6B (
Step (C)).

Furthermore, the second conductor layer 7 is formed using a known metal film forming method and photolithography technique, and the electrical connection with the first conductor layer 3 is completed (step (d)).

When forming a multilayer wiring structure having three or more layers, the above steps are repeated to form each layer. That is, a step (a) of forming an interlayer insulating film to serve as an insulating layer on the conductor layer;
Steps (bl, (cl,
and a step (dl is repeated) of forming an upper conductor extending over the coating and connected to a predetermined portion of the underlying conductor layer.

Next, a surface protection [8] is formed. The protective film 8 is.

The aforementioned polyamic acid silicon type intermediate is similarly coated on the uppermost conductor layer of a semiconductor device having a multilayer wiring structure, and then windows 6C are formed in predetermined portions (step (e)).
. This surface protection film 8 protects the conductor layer from moisture from the outside.
It can be protected from foreign objects.

In the semiconductor device of the present invention, the polyimide resin film described above may be used only for interlayer insulation or surface protection of the semiconductor device, or for both interlayer insulation and surface protection of the semiconductor device.

(Example) EXAMPLES The present invention will be specifically explained below using examples.

Example 1 500c equipped with thermometer, stirrer and calcium chloride tube
27.09 (0,135 mol) of 4,4'-diaminodiphenyl ether (hereinafter referred to as DDE) and 3.73 g (0,015 mol) of 1,3-bis(aminopropyl)tetramethyldisiloxane were placed in a three-necked flask of c. ) and N, N
- Add dimethylacetamide 31z8q and stir until DDE is dissolved. The contents are ice-cooled, and 74.19 (0.15 mol) of octamethylene pistrimellitate dianhydride is added little by little so that the temperature does not exceed 5°C. After the addition, stirring was continued for 5 hours at 5°C. Thereafter, the reaction was carried out at 80°C for 4 hours.

A polyamic acid silicon type intermediate solution having a resin concentration of 25% by weight and a viscosity of 20 poise was obtained.

This solution was coated with a spinner at a rotational speed of 400° rpm on a glass plate semiconductor substrate 1 using aluminum as the silicon oxide film 2 and the first conductor layer 3 in the process shown in FIG. 130-1 in oven
A heat treatment was performed at 40° C. for 30 minutes to form an interlayer insulating film N4. Next, in order to selectively remove only a predetermined portion of the insulating film layer 4, a layer 5 of a phenol novolac resin-based photosensitive resin (positive photoresist, AZ-1350J manufactured by Hoechst) was applied on the layer 4 at a rotation speed of 3000. After coating with a spinner of rprn and exposing it to light using a known photolithography technique, a developer solution based on an aqueous tetramethylammonium hydroxide solution (
NMD-3, manufactured by Tokyo Ohka) was used to develop the resist, and this solution was used as an etching solution for etching at 25° C. for 2 minutes to selectively etch the insulating film layer 4 and open the window 6B. The first conductor layer 3 was exposed at this portion. Thereafter, the photosensitive resin layer 5 was completely removed by immersion treatment at room temperature for 2 minutes using a resist stripping solution (acetone) that etched only the photosensitive resin layer 5 without corroding the first conductor layer 3.

Next, the interlayer insulating layer 4 was subjected to post-heat treatment at 230° C. for 60 minutes to obtain a completely cured polyimide resin film having a thickness of 3 μm. Further, a second conductor layer 7 of aluminum was formed using known vacuum evaporation, sputtering, and photolithography techniques, and electrical connection with the first conductor layer 3 was completed.

Further, on the obtained multilayer wiring structure, a surface protective film layer 8 is formed by applying a polyamic acid solution onto the second conductor layer 7 using a spinner at a rotation speed of 400 Orpm in the same manner as in forming the interlayer insulating film layer 4. Then, a semiconductor device was fabricated. Note that the first surface protective layer 8 is formed by opening a window (as shown in step (e) in FIG.
Since the polyimide resin film is not subjected to selective etching, the second conductor layer 7 is not exposed. Furthermore, no subsequent sealing (packaging) treatment of the semiconductor substrate was performed.

Example 2 A polyamic acid silicon type intermediate solution was prepared in the same manner as in Example 1 except that the acid dianhydride was replaced with 78.39 (0.15 mol) of tecamethylene bistrimelitate dianhydride. This was synthesized and used to form an interlayer insulating film and a surface protection film on a semiconductor substrate in the same manner as in Example 1, thereby producing a semiconductor device.

Example 3 In Example 1, the acid dianhydride was added to a mixture of 52.2 g (0.10 mol) of decamethylene bistrimelitate dianhydride and 10.99 (0.05 mol) of pyromellitic dianhydride. A polyamic acid silicon type intermediate solution was synthesized in the same manner as in Example 1 except for the following changes, and this was used for heat treatment after etching of polyimide resin for 60 minutes at 230°C.
Example 1 except that the time was changed to 60 minutes at 250°C.
In the same manner as above, an interlayer insulating film and a surface protection film are formed,
A semiconductor device was fabricated.

Example 4 In Example 1, the diamine was replaced with 3.65 g of 4,4'-diaminodiphenyl ether-3-carbonamide (o,
ots mol), DDE24.0 g (0.12 mol)
A polyamic acid silicon type intermediate solution was synthesized in the same manner as in Example 1 except that 3.739 (0,015 mol) of 1,3-bis(aminopropyl)-tetramethyldisiloxane was used. A glabellar insulating film and a surface protective film were formed on the semiconductor substrate in the same manner as in Example 1,
A semiconductor device was fabricated.

Comparative Example 1 A polyamic acid silicon type intermediate solution was synthesized in the same manner as in Example 1 except that 23.98 g (0.11 mol) of pyromellitic dianhydride was used as the acid dianhydride. A semiconductor device was manufactured using this.

Comparative Example 2 In Example 1, 1,3- which is diaminosiloxane
A polyamic acid solution was synthesized using the same diamine and acid dianhydride as in Example 1 except that bis(aminopropyl)-tetramethyldisiloxane was not used. Using this, a glabellar insulation film and a surface protection film were formed in the same manner as in Example 1.

A semiconductor device was fabricated.

<Test Example> Moisture resistance tests were conducted using two methods using the semiconductor devices manufactured in Examples 1 to 3 and Comparative Examples 1 to 2 as samples. One was a moisture-resistant adhesion test using a board test, and the other was a corrosion-resistance test under a humidity test of an aluminum wiring layer, which is a conductor layer.

The substrate test was conducted based on JIS K 5400, and scratches were made horizontally and vertically at fan intervals of 1 mm at a depth from the surface of the polyimide resin film to the surface of the semiconductor substrate using a knife.
I made 100 squares using the corners. Next, first apply cellophane tape (manufactured by Block Chemical Co., Ltd.) to the surface of the polyimide resin film on which the eyes have been formed. The number of resin films was counted. If the adhesive strength between the polyimide resin film and the semiconductor substrate is weak, the polyimide resin film will be peeled off from the semiconductor substrate while remaining attached to the cellophane tape side. The test was an initial test and a humidity test (121℃).

The test was carried out later (after being left under a vapor pressure of 2 atmospheres).

Corrosion resistance was determined by testing the fabricated semiconductor devices with humidity resistance (121°C).
The progress of corrosion of the aluminum wiring layer, which is a conductive layer, of each semiconductor device was observed using a microscope at the time intervals shown in Table 1.

The results of the moisture resistant adhesive strength and corrosion resistance tests are shown in Table 1.

Table 1) Moisture resistant adhesive strength Number remaining in base grain test (n/100)
shows.

Roof 2) Corrosion resistance The degree of corrosion was expressed in stages A-E.

A: There was no corrosion of aluminum wiring within the semiconductor device.

B: Corrosion was reduced by about 5 to 10 inches.

C: Corrosion was approximately 30-50%.

D Corrosion was observed throughout the second conductor device.

E: The aluminum wiring layer was dissolved.

These results show that the semiconductor devices of the present invention in Examples 1 to 3 have superior moisture resistance reliability compared to the semiconductor devices of Comparative Examples 1 and 2.

This is because the polyamic acid silicon type intermediate used in Examples 1 to 3 was completely imidized at 230 to 250°C to form a polyimide resin film.

The polyamide silicon type intermediate used in Comparative Example 1 was 250
The heat treatment at ℃ did not completely imidize, indicating that unreacted polyamic acid remained.

Note that the polyimide resin used in Comparative Example 1 was used for semiconductor substrates such as 81 wafers of monolithic ICs.
When the heat treatment was performed at .degree. C., the moisture resistance of the semiconductor substrate was comparable to the results of Examples 1 to 3.

In addition, the moisture-resistant adhesive strength of the polyamic acid used in Comparative Example 2 was
Compared to Examples 1 to 3, the corrosion resistance decreased after 100 hours or more under the humidity test (121° C., 2 atm), indicating that the corrosion resistance was also inferior.

Further, in the above embodiments, aluminum was used as the conductor layer of the semiconductor device, but the present invention is not limited to aluminum.

(Effects of the Invention) According to the present invention, a polyimide resin that can be completely cured by heat treatment at 250° C. or lower and can be wet etched is obtained, which has a highly reliable multilayer wiring structure with excellent moisture resistance. A semiconductor device can be obtained, and it can be applied to a semiconductor substrate structured with compound semiconductors such as Sl, Ga, and As for monolithic ICs and LSIs.

[Brief explanation of the drawing]

FIG. 1 is a manufacturing process diagram of a semiconductor device having a multilayer wiring structure. Explanation of symbols 1...Semiconductor substrate 3...First conductor layer 5...Photosensitive resin layer 7...Second conductor layer

Claims (1)

[Scope of Claims] 1. Tetracarboxylic dianhydride including at least (a) general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (in the formula, n is an integer from 2 to 16) 1. A composition for an interlayer insulating film and/or a surface protective film of a semiconductor substrate, the composition comprising a polyamic acid silicon type intermediate obtained by reacting a diamine (b) and a diaminosiloxane (c) in an organic polar solvent. 2. For the interlayer insulating film and/or surface protective film of a semiconductor substrate according to claim 1, wherein the polyamic acid silicon type intermediate is a polyamic acid silicon type intermediate obtained by reacting a diaminoamide compound as a part of diamine. Composition. 3. A semiconductor device using a polyimide resin film obtained by dehydrating and ring-closing the polyamic acid silicon type intermediate according to claim 1 as an interlayer insulating film and/or a surface protective film of a semiconductor substrate. 4. A semiconductor device using a polyimide resin film obtained by dehydrating and ring-closing the polyamic acid silicon type intermediate according to claim 2 as an interlayer insulating film and/or a surface protective film of a semiconductor substrate.