JPH0540337A - Photosensitive resin composition - Google Patents

Abstract

PURPOSE:To obtain the photosensitive resin composition superior in adhesion to a substrate subjected to fluoric acid treatment and inorganic passivation and further even after humidity treatment by incorporating a specified aminoacrylate compound and a specified sensitizer in a specified polyamic acid solution. CONSTITUTION:This photosensitive resin composition is prepared by allowing an aromatic diamine compound represented by formula I to react with tetracarboxylic dianhydride represented by formula II in an amido compound having a C=C double bond polymerizable by chemically active rays to prepare the polyamic acid solution dissolved in the polyamido compound, and incorporating the aminoacrylate compound represented by formula III and the sensitizer having a maximum absorption wavelength of 330-500nm in the polyamic acid solution in the amido compound solvent. In formulae I-III, R1 is an aliphatic or aromatic group; X is H or methyl; and Y is methyl or ethyl. As the aromatic diamine, 1,3 bis(3-aminophenoxy)benzene and the like are enumerated, thus permitting adhesion with semiconductor chips to be enhanced by using these diamines and therefore a semiconductor manufacture process to be shortened.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a highly sensitive photosensitive polyimide resin composition having excellent adhesion after hydrofluoric acid treatment and also excellent adhesion after humidity treatment.

[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. Due to high integration of elements, large size, thinning and miniaturization of encapsulation resin package, transition to surface mounting method by solder reflow, heat cycle resistance, heat shock resistance, etc. are required to be significantly improved. There is a growing need for new polyimide resins. However, the conventional polyimide resin peels off when it is immersed in a hydrofluoric acid-based chemical solution that etches a protective material such as glass.Therefore, the protective material is first etched using a resist, and then the polyimide resin is applied and etched. It has taken complicated steps.

On the other hand, a technique for imparting photosensitivity to the polyimide resin itself has recently attracted attention. The use of these photosensitized polyimide resins not only has the effect of simplifying the pattern creation process compared to non-added polyimide resins, but it also saves the use of highly toxic etching liquids, so it is safe. It is also excellent in terms of pollution, and it is expected that the photosensitization of polyimide resin will be an important technology. As the photosensitive polyimide resin, for example, the following formula (A)

[0004]

[Chemical 4]

A polyimide precursor composition having a photosensitive group with an ester group having a structure shown by
55-41422, JP-A-60-228537) or the following formula (B)

[0006]

[Chemical 5]

A composition obtained by adding a compound containing a carbon-carbon double bond and an amino group or a quaternized salt thereof which is dimerizable or actinic by actinic radiation to a polyamic acid having a structure as shown in (for example, Japanese Patent Publication No. 59-52822) is known. All of these are dissolved in a suitable organic solvent, applied in a varnish state, dried, irradiated with ultraviolet rays through a photomask, developed, rinsed to obtain a desired pattern, and further heated to form a polyimide. It is a film.

However, such a conventional composition has the following drawbacks. That is, in the composition shown in (A), a tetracarboxylic dianhydride and an alcohol having a photosensitive group are first subjected to an esterification reaction, and then a diamine is subjected to an amidation reaction to produce a remarkably complicated process. However, only those having a low molecular weight and a large amount of ionic impurities were obtained. However, the ester bond has a strong bond strength, and thus has an advantage that it can be spray-developed (a method of rapidly spraying a developing solution to develop rapidly). On the contrary, since the binding force was too strong, the photosensitive groups could not be completely removed even at a high temperature of 400 ° C or higher, and the polyimide film became black and the physical properties (strength, elongation, etc.) of the film were deteriorated. .. On the other hand, in the composition shown in (B), since it is only necessary to add and mix the photosensitizer to the polyamic acid, the manufacturing process is remarkably simple, but the ionic bond strength between the polyamic acid and the photosensitizer is extremely weak, Paddle development (a method of dropping a developing solution on a stationary film to be developed for development) has to be performed, which requires a little time. Further, there are drawbacks such that cracks and film loss are likely to occur during development and the resolution is low. On the other hand, since the bonding strength is weak, the photosensitive group is easily removed by heating, which is advantageous in that the film properties of the polyimide film are excellent. However, (A), (B)
The exposure sensitivity of each of these is 200 to 400 mJ / cm ² (ultra high pressure mercury lamp, polyimide thickness 10 μm), and it has become insufficient to meet the demand for higher sensitivity due to recent technological progress. Further, when applied to a semiconductor, it was insufficient in terms of adhesion to the semiconductor.

[0009]

DISCLOSURE OF THE INVENTION The present invention is intended to obtain a photosensitive resin composition having excellent adhesion to inorganic passivation after hydrofluoric acid treatment and excellent adhesion even after humidity treatment. ..

[0010]

DISCLOSURE OF THE INVENTION The present invention provides a carbon-containing compound capable of polymerizing an aromatic diamine represented by the formula (1) and a tetracarboxylic dianhydride represented by the general formula (2) by actinic radiation. The reaction is carried out in an amide compound containing a carbon double bond, and the polyamic acid solution using the amide compound as a solvent is mixed with the amino acrylate compound represented by the general formula (3) and an absorption maximum wavelength (λ max) of 330 to 500 nm. A photosensitive resin composition comprising a certain sensitizer.

[0011]

In the present invention, the polyimide resin or its precursor polyamic acid is obtained by polymerizing a diamine represented by the formula (1) and a tetracarboxylic dianhydride represented by the general formula (2) by actinic radiation. Obtained by a method of reacting in an amide compound containing possible carbon-carbon double bonds. Then, the hydrofluoric acid-resistant treatment when applied to the semiconductor device by the specific combination as described above, the adhesion to the semiconductor after the treatment, the same excellent adhesion after the humidity treatment,
Moreover, a polyimide resin having excellent characteristics as a photosensitive resin can be obtained.

The polyimide resin preferably has a high molecular weight, and therefore the reaction temperature is preferably -20 ° C to 50 ° C, more preferably -10 ° C to 30 ° C. The molar ratio of tetracarboxylic dianhydride and diamine is 0.8 to 1.1.
Is preferred.

As the aromatic diamine used in the present invention,
1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-
Examples thereof include aminophenoxy) benzene and 1,4-bis (3-aminophenoxy) benzene. By using these diamines, the adhesiveness with the semiconductor chip is improved.

In the present invention, a siloxane bond is introduced in order to further improve the adhesiveness with the semiconductor chip. Examples of such diaminosiloxane include compounds represented by the following formula. These compounds may be used alone or in combination of two or more.

[0015]

[Chemical 6]

Further, the following generally known diamines other than those mentioned above may be used in combination so long as the adhesiveness does not deteriorate so much. For example, p-phenylenediamine,
Examples include m-phenylenediamine, 4,4-diaminophenyl ether, 4,4-diaminodiphenylmethane and 4,4-diaminophenyl sulfone.

Examples of the aliphatic tetracarboxylic acid anhydride used in the present invention include cis, cis, cis, cis-1,2,3,4-anhydrocyclopentanetetracarboxylic acid and bicyclo [2,2,2] oct-
7-ene-2,3,5,6-tetracarboxylic dianhydride, cyclobutanetetracarboxylic dianhydride and the like can be mentioned.

Examples of the aromatic tetracarboxylic dianhydride used in the present invention include the following acid anhydrides. Pyromellitic dianhydride, 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 3,3,4,4-diphenyl Tetracarboxylic dianhydride, 2,2 ', 3,3'-diphenyltetracarboxylic dianhydride, 2,3,3', 4'-diphenyltetracarboxylic dianhydride, 3,3 ', 4, 4'-p-terphenyl tetracarboxylic dianhydride, 1,2,5,6-naphthalene tetracarboxylic dianhydride, 2,
2-bis (3,4-dicarboxydiphenyl) ether dianhydride, naphthalene-1,2,4,5-tetracarboxylic dianhydride,
Naphthalene-1,4,5,8-tetracarboxylic dianhydride, 4,8-
Dimethyl-1,2,3,5,6,7-hexahydronaphthalene-1,2,5,
6-tetracarboxylic dianhydride, 2,6-dichloronaphthalene
-1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, phenanthrene-1,2,9,10-tetracarboxylic Acid dianhydride, pyrrolidine-2,3,4,5-tetracarboxylic acid dianhydride, pyrazine-2,
3,5,6-Tetracarboxylic acid dianhydride, 2,2-bis (2,5-dicarboxyphenyl) propane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride , 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, Examples thereof include benzene-1,2,3,4-butanetetracarboxylic dianhydride and thiophene-2,3,4,5-tetracarboxylic dianhydride. In addition to the above-mentioned aromatic tetracarboxylic dianhydride, a silicone-based tetracarboxylic dianhydride or an aliphatic tetracarboxylic dianhydride can of course be used together in order to impart various properties.

Examples of the amide compound containing a carbon-carbon double bond polymerizable by actinic radiation used in the present invention include, for example,
N-methyl acrylamide, N-ethyl acrylamide, N-
Methyl methacrylamide, N-ethyl methacrylamide,
N, N-dimethylacrylamide, N, N-diethylacrylamide, N, N-dibutylacrylamide, N-acryloylpiperidine, N-acryloylmorpholine, N, N-dimethylmethacrylamide, N, N-diethylmethacrylamide, N, N
-Dimethylaminoethyl methacrylamide, N, N-dimethylaminopropyl methacrylamide, N-vinylpyrrolidone and the like can be mentioned, but not limited to these. In addition, one kind or a mixture of two or more kinds may be used.

The polyamic acid according to the present invention is characterized by being produced in an amide compound containing a carbon-carbon double bond which can be polymerized by actinic radiation. Conventionally, the use of the amide compound as a reaction system solvent has not been performed at all. The conventional reaction system solvent has been an organic polar solvent having a dipole moment whose functional group does not react with acid anhydrides and diamines. Besides being inert to the system and being a solvent for the product, the organic polar solvent had to be a solvent for at least one of the reaction components, preferably both.

Typical solvents of this type are N, N-
Dimethylformamide, N, N-dimethylacetamide, N,
N-diethylformamide, N, N-diethylacetamide,
N, N-dimethylmethoxyacetamide, dimethylsulfoxide, hexamethylphosphamide, N-methyl-2-pyrrolidone, pyridine, dimethylsulfone, tetramethylenesulfone, dimethyltetramethylenesulfone, methylformamide, N-acetyl-2-pyrrolidone, There are diethylene glycol monomethyl ether, diethylene glycol dimethyl ether and the like, and these solvents are used alone or in combination. In addition to these, as those used in combination as a solvent, benzene, benzonitrile, dioxane, butyrolactone, methyl cellosolve, ethyl cellosolve, butyl cellosolve, xylene, toluene, non-solvents such as cyclohexane, a dispersion medium of the raw material, a reaction modifier, It was also used as a film smoothing agent. Conventional reaction system solvents have not been sensitive to light. for that reason,
In manufacturing a conventional photosensitive resin, a photosensitive component to light is particularly added. However, since it is diluted with a large amount of the reaction system solvent, there is a limit in improving the concentration of the photosensitive group.

Since the amide compound according to the present invention contains an amide bond, it has excellent solubility in polyamic acid. Further, according to the method using the amide composition as a solvent,
Since the solvent itself is 100% photosensitive, the concentration of the photosensitive group is remarkably high, and thus the photosensitivity can be remarkably increased. In addition, the method for producing a photosensitive resin according to the present invention is very simple because each component is simply added and mixed, and the variation in quality is extremely small.

The amino acrylate compound used in the present invention is added to accelerate the photoreaction, and examples thereof include N, N-dimethylaminoethyl methacrylate,
Examples thereof include N, N-dimethylaminoethyl acrylate, N, N-diethylaminoethyl methacrylate and N, N-diethylaminoethyl acrylate. When using it,
It may be one kind or a mixture of two or more kinds. Further, in order to further promote the photoreaction, an acrylate (methacrylate) compound having no amino group can be used together.

The sensitizer used in the present invention is a compound having an absorption maximum wavelength (λ max) at 330 to 500 nm. λ max is 3
When the thickness is 30 nm or less, light is absorbed by the polyamic acid itself and a photoreaction cannot be performed, which is not preferable. Also, if it is 500 nm or more, it reacts with visible light and it is necessary to make the work place a shield room,
It is not preferable because its handleability is reduced. The sensitizer of the present invention is, for example,

[0025]

[Chemical 7]

Examples thereof include, but are not limited to: In addition, one kind or a mixture of two or more kinds may be used.

To the photosensitive resin composition according to the present invention, an adhesion aid, a leveling agent and other various fillers may be added.

In the method of using the photosensitive resin composition according to the present invention, first, the composition is applied to a suitable support such as a silicon wafer, a ceramic or an aluminum substrate. The coating method is spin coating using a spinner, spray coating using a spray coater, dipping, printing, roll coating, or the like. Next, after prebaking at a low temperature of 60 to 80 ° C. to dry the coating film, a desired pattern shape is irradiated with actinic rays. As actinic rays, X-rays, electron rays, ultraviolet rays, visible rays and the like can be used, but those having a wavelength of 200 to 500 nm are preferable.

Next, the unirradiated portion is dissolved and removed with a developing solution to obtain a relief pattern. As a developing solution, N-
Methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N
-Use dimethylformamide, etc., methanol, isopropyl alcohol, 2-ethoxyethanol, water, etc. alone or as a mixture. As the developing method, methods such as spraying, paddle, dipping, and ultrasonic wave can be used.

Next, the relief pattern formed by development is rinsed. As the rinse liquid, methanol, ethanol, isopropyl alcohol, butyl acetate or the like is used. Next, heat treatment is performed to form an imide ring,
A final pattern with high heat resistance is obtained. Then, the glass inorganic passivation is etched with a hydrofluoric acid-based etching solution, and is molded by casting, transfer molding, or the like with a molding material such as epoxy resin, phenol resin, or silicone resin.

The polyimide resin film obtained as described above has excellent adhesion after hydrofluoric acid treatment and humidity treatment.
Since a polyimide resin film can be used in place of the resist instead of the conventional etching of the protective material using a photoresist, the semiconductor manufacturing process can be shortened and a semiconductor device having excellent moisture resistance can be obtained.

[0032]

EXAMPLES The present invention will be described in more detail with reference to examples, but the present invention is not limited to these.

Example 1 29.23 g (0.1 mol) of 1,3-bis (3-aminophenoxy) benzene and formula (4)

[0034]

[Chemical 8]

Silicone diamine represented by 0.74 g (0.
003 mol) and 32.23 g (0.1 mol) of 3,3,4,4-benzophenone tetracarboxylic acid dianhydride are reacted in 270 ml of N, N-dimethylacrylamide at 20 ° C. for 5 hours,
A viscous varnish was obtained. Obtained polyamic acid solution 500
20 parts by weight of N, N-dimethylaminoethyl methacrylate and Michler's ketone (λ ma)
x 365nm) 5 parts by weight was added and dissolved at room temperature. The obtained composition was coated on a silicon wafer on which phosphorus glass (PSG) was formed with a spinner and dried at 60 ° C. for 1 hour with a dryer.
It was dried for an hour to obtain a film of about 10 μm.

Photographic step tablet No. 2 and 21 steps manufactured by Kodak Co., Ltd. in this film (in this gray scale, the amount of transmitted light decreases to 1/2 of the previous step as the number of steps increases, so the remaining step after development is large. , And then irradiate it with 1000 mJ / cm ² of ultraviolet light, then develop with a developer consisting of 60 parts by weight of N-methyl-2-pyrrolidone and 40 parts by weight of methanol, and rinse with isopropyl alcohol. As a result, the pattern remained up to 18 steps, and it was found to have high sensitivity. In addition, no cracks were generated and almost no decrease in film thickness was observed.

Further, it was heat-cured at 150, 250 and 350 ° C. for 30 minutes to obtain a film. The wafer was immersed in a 2% hydrofluoric acid aqueous solution for 20 minutes, but no peeling was observed. Further, a moisture resistance treatment at 125 ° C./100% was performed for 500 hours, and a crepe test was conducted, but no peeling was observed.

(Comparative Example 1) 3,3-dimethyl-4-methoxybenzophenone was used in place of the Michler's ketone used in Example 1. However, since the λmax of this sensitizer was 296 nm, photoinitiation was efficiently performed. It was found that there was no practical use because the reaction was not possible and all the patterns flowed during development.

(Comparative Example 2) A tetraphenylporphyrin zinc complex was used in place of the Michler's ketone used in Example 1, but the λ max of this sensitizer was 650 nm.
A photoreaction occurred during the work, and a pattern could not be obtained by the development.

(Comparative Example 3) N-methyl-2-pyrrolidone was used in place of N, N-dimethylacrylamide used in Example 1, and all other components were blended in the same manner and evaluated in the same manner. The number of stages was only 8, and the sensitivity was low, and the occurrence of cracks was confirmed, which proved to be impractical.

Comparative Example 4 Tetraethylene glycol dimethacrylate was used in place of the N, N-dimethylaminoethyl methacrylate used in Example 1, and all other components were compounded in the same manner and evaluated in the same manner. The number of steps was only 9, and the sensitivity was low, and the occurrence of cracks was confirmed, which proved to be low in practicality.

(Comparative Example 5) 1,3-bis (3) used in Example 1
-Aminophenoxy) benzene was used in place of 4,4-diaminodiphenyl ether, and all other components were blended in the same manner and evaluated in the same manner, but when treated with hydrofluoric acid, peeling occurred in 5 minutes.

[0043]

EFFECT OF THE INVENTION The photosensitive resin composition according to the present invention is prepared by a special method in which an amide compound having a carbon-carbon double bond polymerizable with actinic radiation and having an excellent ability to dissolve polyamic acid is used as a solvent. Since the solvent itself is 100% photosensitive, the concentration of the photosensitive group is extremely high, so that the exposure sensitivity can be improved 10 times or more as compared with the conventional type photosensitive resin composition. became. Further, since the adhesiveness after the hydrofluoric acid treatment, which was a defect of the conventional polyimide resin, is significantly improved, not only the semiconductor manufacturing process can be shortened, but also the adhesiveness after the humidity treatment is good, so that the semiconductor element protecting composition Is suitable as

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Claims (1)

[Claims] 1. An aromatic diamine represented by the formula (1), and The tetracarboxylic acid dianhydride represented by the general formula (2) is converted into An amino acrylate compound represented by the general formula (3) is prepared by reacting in an amide compound containing a carbon-carbon double bond that can be polymerized by actinic radiation and using a solution of the amide compound in a polyamic acid solution. And a sensitizer having an absorption maximum wavelength (λ max) of 330 to 500 nm.