JPH11337753A - Production of optical device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a producing method of an optical device having excellent adhesion property which can be stably used for a long time by forming a zirconium alkoxide compd. film on a substrate surface and forming a polyimide resin film containing fluorine thereon. SOLUTION: First, a zirconium alkoxide compd. film is formed on a substrate surface, and then a polyimide resin coating film containing fluorine is formed thereon. As for the zirconium alkoxide compd., for example, zirconium tetraethoxide, and zirconium n-propoxide are used, and these may be used as a single material or a combination of two or more kinds. Moreover, other org. zirconium compds. such as zirconium esters can be used with the zirconium alkoxide compd. As for the polyimide resin containing fluorine, a polyimide resin containing fluorine, poly(imideisoindoquinazolinedion imide) resin containing fluorine or the like can be used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing an optical device using a polyimide resin containing fluorine.

[0002]

2. Description of the Related Art Polyimide resins have excellent properties such as high heat resistance, resistance to soldering, film flexibility and film strength, and are used in printed circuit boards, semiconductor devices, multi-chip module substrates, and the like. Widely used in electric and electronic fields. In addition, a polyimide resin containing fluorine has characteristics such as a high light transmittance and a low refractive index due to containing fluorine, and thus is suitable for an optical material and an optical component. For example, Japanese Patent Application Laid-Open No. 4-235506 discloses an optical waveguide produced by forming a polyimide film containing two kinds of fluorine having different refractive indexes on a silicon substrate whose surface is covered with a silicon oxide film. A method for manufacturing the device is shown. Polyimide containing fluorine will be used in the future because it has excellent optical properties as described above and can easily form a coating film by coating method etc. compared to optical parts using inorganic materials such as quartz glass. Can be expected to expand. However, fluorine-containing polyimide has low adhesion to a support substrate, for example, glass, quartz, silicon, silicon oxide, silicon nitride, aluminum, aluminum oxide, tantalum oxide, gallium arsenide, etc. There was a problem.

[0003]

An object of the present invention is to provide a method for producing an optical device which has excellent adhesiveness and is stable even after long-term use.

[0004]

SUMMARY OF THE INVENTION The present invention relates to a method for manufacturing an optical device, comprising forming a zirconium alkoxide compound film on a substrate surface and then forming a fluorine-containing polyimide resin film.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION An optical device according to the present invention includes, as a substrate, an inorganic material such as glass or quartz; a semiconductor or a metal material such as silicon, gallium arsenide, aluminum or titanium; a polymer material such as polyimide or polyamide; Alternatively, using a material obtained by combining these materials, an optical waveguide, an optical multiplexer, an optical demultiplexer, an optical attenuator, an optical diffractor, an optical amplifier, an optical interferometer, an optical filter, an optical switch are formed on these substrates. , A wavelength converter, a light-emitting element, a light-receiving element, or a combination thereof. A semiconductor device such as a light emitting diode or a photodiode or a metal film for an electrode may be formed on the substrate, and silicon oxide, nitride, or the like may be formed on the substrate to protect the substrate or adjust the refractive index. A film of silicon, aluminum oxide, aluminum nitride, tantalum oxide, or the like may be formed.

Examples of the zirconium alkoxide compound used in the present invention include zirconium tetraethoxide, zirconium n-propoxide, zirconium isopropoxide, zirconium tetra n-butoxide, zirconium tetra tert-butoxide and the like. May be used alone or in combination of two or more. Further, these zirconium alkoxide compounds can be used in combination with other organic zirconium compounds. Examples of the organic zirconium compound include a zirconium ester and a zirconium chelate compound.

As zirconium esters, for example,
Examples include zirconium chelate compounds such as tetrakis (acetylacetonate) zirconium, monobutoxytris (acetylacetonate) zirconium, dibutoxybis (acetylacetonate) zirconium, and tributoxy. Zirconium acetylacetonate, tetra (ethyl acetylacetate)
Zirconium, zirconium monobutoxytris (ethyl acetylacetate), zirconium dibutoxybis (ethyl acetylacetate), tributoxyethyl acetyl acetate, tetrakis (ethyl lactonate)
Zirconium, bis (bisacetylacetonate) bis (ethylacetylacetonate) zirconium, monoacetylacetonate tris (ethylacetylacetonate) zirconium, monobutoxymonoacetylacetonate bis (ethylacetylacetonate) zirconium and the like can be mentioned. The zirconium ester or zirconium chelate compound is not limited to those exemplified as long as it contains zirconium oxide at the time of film formation, and can be used in combination with the zirconium alkoxide compound.

When the zirconium alkoxide compound and another organic zirconium compound are used in combination, the amount of the zirconium alkoxide compound is based on 100 parts by weight of the zirconium alkoxide compound as an essential component.
It is preferably not more than 00 parts by weight.

The zirconium alkoxide compound includes alcohol solvents such as methanol, ethanol and butanol, aromatic solvents such as benzene, toluene and xylene;
It can be used by dissolving in an organic solvent such as a polar solvent such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-formamide, and γ-butyrolactone, or in water. The obtained solution is applied on the substrate surface by a spin coating method, a method of dipping the substrate, a method of printing with a roll or the like, and then dried at a temperature of 70 to 400 ° C. to obtain a coating. If the zirconium alkoxide compound coating is too thick, the film becomes brittle.
It is preferably at most 000 °, more preferably at most 500 °.

The fluorine-containing polyimide resin used in the present invention includes a fluorine-containing polyimide resin, a fluorine-containing poly (imide / isoindoloquinazolinedionimide) resin, a fluorine-containing polyetherimide resin, and a fluorine-containing polyimide resin. Polyamide imide resin and the like can be mentioned.

A precursor solution of a polyimide resin is prepared by reacting a tetracarboxylic dianhydride with a diamine in a polar solvent such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, γ-butyrolactone, and dimethyl sulfoxide. Can be obtained by Fluorine may be contained in both the tetracarboxylic dianhydride and the diamine, or may be contained only in either of them.

The acid dianhydride having fluorine includes, for example, (trifluoromethyl) pyromellitic dianhydride,
Di (trifluoromethyl) pyromellitic dianhydride, di (heptafluoropropyl) pyromellitic dianhydride,
Pentafluoroethyl pyromellitic dianhydride, bis {3,5-di (trifluoromethyl) phenoxy} pyromellitic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride Thing, 5,
5'-bis (trifluoromethyl) -3,3 ', 4
4'-tetracarboxybiphenyl dianhydride, 2,
2 ', 5,5'-tetrakis (trifluoromethyl)-
3,3 ', 4,4'-tetracarboxybiphenyl dianhydride, 5,5'-bis (trifluoromethyl) -3,
3 ', 4,4'-tetracarboxydiphenyl ether dianhydride, 5,5'-bis (trifluoromethyl)-
3,3 ', 4,4'-tetracarboxybenzophenone dianhydride, bis {(trifluoromethyl) dicarboxyphenoxy} benzene dianhydride, bis {(trifluoromethyl) dicarboxyphenoxy} (trifluoromethyl) benzene Dianhydride, bis (dicarboxyphenoxy) (trifluoromethyl) benzene dianhydride, bis (dicarboxyphenoxy) bis (trifluoromethyl) benzene dianhydride, bis (dicarboxyphenoxy) tetrakis (trifluoromethyl) benzene Dianhydride, 2,2-bis {(4- (3,4-dicarboxyphenoxy) phenyl} hexafluoropropane dianhydride,
Bis {(trifluoromethyl) dicarboxyphenoxy} biphenyl dianhydride, bis {(trifluoromethyl) dicarboxyphenoxy} bis (trifluoromethyl) biphenyl dianhydride, bis {(trifluoromethyl) dicarboxyphenoxy} diphenyl ether Dianhydride, bis (dicarboxyphenoxy) bis (trifluoromethyl) biphenyl dianhydride and the like.

As the diamine having fluorine, for example, 4- (1H, 1H, 11H-eicosafluoroundecanooxy) -1,3-diaminobenzene, 4- (1
H, 1H-perfluoro-1-butanoxy) -1,3-
Diaminobenzene, 4- (1H, 1H-perfluoro-
1-heptanoxy) -1,3-diaminobenzene, 4-
(1H, 1H-perfluoro-1-octanoxy)-
1,3-diaminobenzene, 4-pentafluorophenoxy-1,3-diaminobenzene, 4- (2,3,5
6-tetrafluorophenoxy) -1,3-diaminobenzene, 4- (4-fluorophenoxy) -1,3-diaminobenzene, 4- (1H, 1H, 2H, 2H-perfluoro-1-hexanoxy) -1 , 3-Diaminobenzene, 4- (1H, 1H, 2H, 2H-perfluoro-
1-dodecanoxy) -1,3-diaminobenzene,
(2,5-) diaminobenzotrifluoride, bis (trifluoromethyl) phenylenediamine, diaminotetra (trifluoromethyl) benzene, diamino (pentafluoroethyl) benzene, 2,5-diamino (perfluorohexyl) benzene, 2 , 5-diamino (perfluorobutyl) benzene, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 3,
3'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, octafluorobenzidine, 4,4'-
Diaminodiphenyl ether, 2,2-bis (p-aminophenyl) hexafluoropropane, 1,3-bis (anilino) hexafluoropropane, 1,4-bis (anilino) octafluorobutane, 1,5-bis (anilino) Decafluoropentane, 1,7-bis (anilino) tetradecafluoroheptane, 2,2'-bis (trifluoromethyl) -4,4'-diaminodiphenyl ether, 3,3'-bis (trifluoromethyl) -4 ,
4'-diaminodiphenyl ether, 3,3 ', 5
5'-tetrakis (trifluoromethyl) -4,4'-
Diaminodiphenyl ether, 3,3'-bis (trifluoromethyl) -4,4'-diaminobenzophenone,
4,4'-diamino-p-terphenyl, 1,4-bis (p-aminophenyl) benzene, p-bis (4-amino-2-trifluoromethylphenoxy) benzene, bis (aminophenoxy) bis (tri Fluoromethyl) benzene, bis (aminophenoxy) tetrakis (trifluoromethyl) benzene, 2,2-bis {4- (4-aminophenoxy) phenyl} hexafluoropropane,
2,2-bis {4- (3-aminophenoxy) phenyl} hexafluoropropane, 2,2-bis {4- (2
-Aminophenoxy) phenyl} hexafluoropropane, 2,2-bis {4- (4-aminophenoxy)-
3,5-dimethylphenyl @ hexafluoropropane,
2,2-bis {4- (4-aminophenoxy) -3,5
-Ditrifluoromethylphenyl {hexafluoropropane, 4,4'-bis (4-amino-2-trifluoromethylphenoxy) biphenyl, 4,4'-bis (4-
Amino-3-trifluoromethylphenoxy) biphenyl, 4,4'-bis (4-amino-2-trifluoromethylphenoxy) diphenylsulfone, 4,4'-bis (3-amino-5-trifluoromethylphenoxy) Diphenylsulfone, 2,2-bis {4- (4-amino-
3-trifluoromethylphenoxy) phenyl} hexafluoropropane, bis {(trifluoromethyl) aminophenoxybiphenyl, bis [{(trifluoromethyl) aminophenoxy} phenyl] hexafluoropropane, bis {2-[(aminophenoxy ) Phenyl] hexafluoroisopropyl-benzene and the like.

Examples of the tetracarboxylic dianhydride having no fluorine include p-terphenyl-3,4,3 ″, 4 ″ -tetracarboxylic dianhydride as an acid anhydride.
Pyromellitic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3'-4,
4'-biphenyltetracarboxylic dianhydride, 3,
3 ', 4,4'-biphenyl ether tetracarboxylic dianhydride, 1,2,5,6-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 2 1,3,5,6-pyridinetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 4,4 '-Sulfonyldiphthalic dianhydride, 3,3', 4,4'-tetraphenylsilanetetracarboxylic dianhydride, meta-terphenyl 3,4
3 ", 4" -tetracarboxylic dianhydride, 3,3'-
4,4'-diphenylethertetracarboxylic dianhydride, 1,3-bis (3,4-dicarboxyphenyl)-
1,1,3,3-tetramethyldisiloxane dianhydride,
1- (2,3-dicarboxyphenyl) -3- (3,4
-Dicarboxyphenyl) -1,1,3,3-tetramethyldisiloxane dianhydride. When a polyamideimide resin is obtained, trimellitic anhydride chloride or the like is used.

Examples of the diamine having no fluorine include 4,4'-diaminodiphenyl ether and 4,4 '
-Diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfide, benzidine, metaphenylenediamine, paraphenylenediamine, 2,2-bis- (4-aminophenoxyphenyl) propane, 1,5 -Naphthalenediamine,
2,6-naphthalenediamine, bis- (4-aminophenoxyphenyl) sulfone, bis- (4-aminophenoxyphenyl) sulfide, bis- (4-aminophenoxyphenyl) biphenyl, 1,4-bis- (4-amino Phenoxy) benzene, 1,3-bis- (4-aminophenoxy) benzene, 3,4′-diaminodiphenyl ether, 3,3′-dimethyl-4,4′-diaminobiphenyl, 3,3′-dimethoxy-4, 4'-diaminobiphenyl, 4,4'-diaminodiphenyl ether-
3-sulfonamide, 3,4'-diaminodiphenylether-4-sulfonamide, 3,4'-diaminodiphenylether-3'-sulfonamide, 3,3'-diaminodiphenylether-4-sulfonamide, 4,
4'-diaminodiphenylmethane-3-sulfonamide, 3,4'-diaminodiphenylmethane-4-sulfonamide, 3,4'-diaminodiphenylmethane-3 '
-Sulfonamide 3,3'-diaminodiphenylmethane-4-sulfonamide, 4,4'-diaminodiphenylsulfone-3-sulfonamide, 3,4'-diaminodiphenylsulfone-4-sulfonamide, 3,4'-diamino Diphenylsulfone-3'-sulfonamide,
3,3'-diaminodiphenylsulfone-4-sulfonamide, 4,4'-diaminodiphenylsulfide-
3-sulfonamide, 3,4'-diaminodiphenylsulfide-4-sulfonamide, 3,3'-diaminodiphenylsulfide-4-sulfonamide, 3,
4'-diaminodiphenylsulfide-3'-sulfonamide, 1,4-diaminobenzene-2-sulfonamide, 4,4'-diaminodiphenylether-3-carbonamide, 3,4'-diaminodiphenylether-4-carbonamide 3,4'-diaminodiphenyl ether-3'-carbonamide, 3,3'-diaminodiphenyl ether-4-carbonamide, 4,4'-
Diaminodiphenylmethane-3-carbonamide, 3,
4'-diaminodiphenylmethane-4-carbonamide, 3,4'-diaminodiphenylmethane-3'-carbonamide, 3,3'-diaminodiphenylmethane-4
-Carbonamide, 4,4'-diaminodiphenylsulfone-3-carbonamide, 3,4'-diaminodiphenylsulfone-4-carbonamide, 3,4'-diaminodiphenylsulfone-3'-carbonamide, 3,
3'-diaminodiphenylsulfone-4-carbonamide, 4,4'-diaminodiphenylsulfide-3-
Carbonamide, 3,4'-diaminodiphenylsulfide-4-carbonamide, 3,3'-diaminodiphenylsulfide-4-carbonamide, 3,4'-
Examples thereof include diaminodiphenyl sulfide-3'-sulfonamide, 1,4-diaminobenzene-2-carbonamide and the like.

The above tetracarboxylic dianhydride or diamine may be used in combination of two or more. Further, a photosensitive solution may be used as the precursor solution of the polyimide resin.

The weight average molecular weight of the polyimide precursor (measured by gel permeation chromatography,
The value converted using the standard polystyrene calibration curve) is 1 to
500,000 is preferable in terms of mechanical strength, coatability and the like. The polyimide precursor solution is applied on the substrate surface by a method such as spinner, roll, printing, or the like, and is heat-treated at a final temperature of 200 to 400 ° C. and cured to form a polyimide resin film.

[0018]

Embodiments of the present invention will be described below. Example 1 As a zirconium alkoxide compound solution, zirconium tetra-n-butoxide was dissolved in butanol to prepare a 1% by weight solution. A polyimide precursor solution containing fluorine is prepared by dissolving 21.47 g of 2,2-bis (4-aminophenyl) hexafluoropropane in 450 g of N, N-dimethylacetamide and then adding 2,2′-bis (3,2
It was obtained by adding 28.53 g of 4-dicarboxyphenylhexafluoropropanoic acid dianhydride and stirring at room temperature for 20 hours. The weight average molecular weight of the polyimide precursor was 300,000. The substrate is made of a 2 μm thick SiO 2 on the surface.
A 5-inch silicon wafer on which _two films were formed was used.

The above organic zirconium compound solution is dropped on the substrate, spin-coated (3000 rpm / 30 seconds), dried on a hot plate (200 ° C./5 minutes), and coated with a film of the organic zirconium compound (about 200 μm thick). ) Formed. The above-mentioned polyimide precursor solution containing fluorine is dropped thereon, spin-coated (2000 rpm / 30 seconds), and then oven (100 ° C./30 minutes + 200 ° C./30 minutes +
(350 ° C./60 minutes) to form a fluorine-containing polyimide film.

COMPARATIVE EXAMPLE Without forming a zirconium alkoxide compound coating film, the above-mentioned polyimide precursor solution containing fluorine was directly dropped on the substrate and subjected to spin coating (2000 rpm / 30 seconds), followed by an oven (100 ° C./30 minutes). + 200 ° C / 30
(Min. + 350 ° C./60 min.) To form a polyimide film containing fluorine.

The polyimide films obtained in the above Examples and Comparative Examples were subjected to a pressure cooker test (121 ° C., 2 atm) for 0 hour, 20 hours and 30 hours in order to examine the decrease in adhesion due to moisture. Each polyimide film was cut into 100 squares of 1 mm x 1 mm using a cutter knife according to the cross-cut test method of JIS K5400, and a cellophane tape was adhered to the square, and then peeled off. The adhesiveness was evaluated based on the number of remaining adhesives. Table 1 shows the evaluation results of the adhesiveness. The example shows that the adhesiveness is better than the comparative example.

[0022]

[Table 1]

[0023]

According to the method for manufacturing an optical device according to the first aspect of the present invention, the adhesion of the fluorine-containing polyimide film to the substrate is excellent.
An optical device that is stable even when used for a long time and has high reliability can be obtained.

Claims (1)

[Claims] 1. A method for manufacturing an optical device, comprising: forming a zirconium alkoxide compound film on a substrate surface; and forming a fluorine-containing polyimide resin film.