JP3281470B2 - Optical device manufacturing method - Google Patents

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 Fluorine-containing polyimide resins have been applied to optical devices because they have characteristics such as higher light transmittance and lower refractive index than those containing no fluorine. For example, Japanese Patent Application Laid-Open No. Hei 4-235506 discloses that an optical waveguide is manufactured by forming a polyimide film containing two kinds of fluorines having different refractive indexes on a silicon substrate whose surface is covered with a silicon oxide film and performing patterning. A method for manufacturing an optical device is shown.

[0003]

By using a polyimide containing fluorine as described above, an optical device having excellent optical characteristics can be obtained by a simpler process as compared with a device using an inorganic material such as glass. However, polyimide containing fluorine has low adhesion to glass, quartz, silicon, silicon oxide, silicon nitride, aluminum, aluminum oxide, aluminum nitride, tantalum oxide, gallium arsenide, etc. on the substrate surface on which the film is formed, and is used for a long time. Had a problem with reliability. The present invention
An object of the present invention is to provide a method for manufacturing an optical device which solves this problem and has excellent adhesiveness and is stable even when used for a long time.

[0004]

SUMMARY OF THE INVENTION The present invention relates to an inorganic material,
Conductive materials, metallic materials, and composite materials of these materials
A film of tributoxyacetylacetonate zirconium on a substrate surface made of a material selected from the group consisting of
Forming a film having a thickness of not more than 2,000 mm , and on the film,
Including the step of forming a polyimide resin film containing fluorine.
A method for manufacturing an optical device.

The optical device according to the present invention uses an inorganic material such as glass or quartz, a semiconductor or a metal material such as silicon, gallium arsenide, aluminum or titanium, or a composite material of these materials as a substrate. on these substrates, an optical waveguide, an optical multiplexer, an optical demultiplexer, an optical attenuator, optical diffraction device, an optical amplifier, an optical interferometer, an optical filter, an optical switch, wavelength converter, the light-emitting element, a light receiving element or they Indicates a compound formed as a composite. 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.

According to the present invention, tributoxya
Cetyl acetonate zirconium film thickness less than 3000mm
Is formed.

Tributoxyacetylacetonate zircon
Nium is methanol, ethanol, butanol, benzene, toluene, N-methyl-2-pyrrolidone, N, N
-Dissolved in an organic solvent such as dimethylacetamide, γ-butyrolactone, water, or the like, applied as a solution on the substrate surface by a spin coating method or the like, and dried at 70 to 400 ° C. to form a film. Tributoxyacetylacetone
If the zirconium zirconium film is too thick, the film becomes brittle and the thickness is set to 3000 ° or less. Examples of the fluorine-containing polyimide resin used in the present invention include a fluorine-containing polyimide resin, a fluorine-containing poly (imide / isoindoloquinazolinedionimide) resin, a fluorine-containing polyetherimide resin, and a fluorine-containing polyamideimide resin. And the like.

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. Is obtained by Fluorine may be contained in both the tetracarboxylic dianhydride and the diamine, or may be contained only in either of them.

Examples of acid dianhydrides having fluorine include:
(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.

The following are examples of the diamine having fluorine. 4- (1H, 1H, 11H-eicosafluoroundecanooxy) -1,3-diaminobenzene, 4- (1H, 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 (trifluoromethyl) 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 is exemplified.

Examples of tetracarboxylic dianhydrides having no fluorine include p-terphenyl-anhydride as an acid anhydride.
3,4,3 ″, 4 ″ -tetracarboxylic dianhydride, 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-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-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 '
-Diphenyl ether tetracarboxylic 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 and the like. When a polyamideimide resin is obtained, trimellitic anhydride chloride or the like is used.

As the diamine having no fluorine, 4,4
4'-diaminodiphenyl ether, 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-aminophenoxy) benzene, 1,3-bis- (4-aminophenoxy) benzene, 3,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diamino Biphenyl, 4,4'-diaminodiphenylether-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'-diaminodiphenylsulfone-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'-diaminodiphenylether-
3'-carbonamide, 3,3'-diaminodiphenylether-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'-
Diaminodiphenyl sulfide-3-carbonamide, 3,4'-diaminodiphenyl sulfide-4-
Carbonamide, 3,3'-diaminodiphenylsulfide-4-carbonamide, 3,4'-diaminodiphenylsulfide-3'-sulfonamide, 1,4-
And diaminobenzene-2-carbonamide.

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

The polyimide precursor solution is applied on the substrate surface by a method such as spinner or printing, and is heat-treated at a final temperature of 200 to 400 ° C. to be cured to form a polyimide resin film.

An embodiment of the present invention will be described.

【Example】

Example As an organic zirconium compound solution, tributoxyacetylacetonate zirconium was dissolved in butanol to prepare a 1% by weight solution. The polyimide precursor solution containing fluorine is 2,2-bis (4-aminophenyl)
After dissolving 21.47 g of hexafluoropropane in 450 g of N, N-dimethylacetamide, 28.53 g of 2,2'-bis (3,4-dicarboxyphenylhexafluoropropanoic acid dianhydride was added, and the solution was added at room temperature for 20 minutes. The substrate was coated with a 2 μm thick S
A 5-inch silicon wafer on which an iO ₂ film was formed was used. The above organic zirconium compound solution is dropped on the substrate, spin-coated (3000 rpm / 30 seconds), and then dried on a hot plate (200 ° C./5 minutes) to form an organic zirconium compound film (thickness: about 200 °). did. The polyimide precursor solution was dropped thereon and spin-coated (2000 rpm / 30 seconds).
(0 ° C / 30 minutes + 200 ° C / 30 minutes + 350 ° C / 60 minutes)
To form a polyimide film containing fluorine. Further, as a comparative example, a sample was prepared in which the above-mentioned polyimide film directly containing fluorine was formed on a substrate under the same conditions without forming a film of the organic zirconium compound. The adhesion test is performed according to the grid test method of JIS K5400.
The polyimide film was cut into 100 squares of 1 × 1 mm using a cutter knife, and a cellophane tape was adhered to the square, and then peeled off. In addition, a pressure cooker test (121 ° C., 2 atm) was performed to examine a decrease in adhesion due to moisture. FIG. 1 shows the results of the evaluation of the adhesiveness. The examples show that the adhesiveness is improved as compared with the comparative example.

[0016]

According to the present invention, the adhesiveness of the polyimide film containing fluorine to the substrate can be improved, and the reliability of the optical device can be improved.

[Brief description of the drawings]

FIG. 1 is a diagram showing the results of an adhesion test of Examples and Comparative Examples of the present invention.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-4-235506 (JP, A) JP-A-55-99728 (JP, A) JP-A-56-131949 (JP, A) JP-A-57-997 30335 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) G02B 6/12

Claims (1)

(57) [Claims] An inorganic material, a semiconductor material, a metal material, and an inorganic material.
Materials selected from the group consisting of composite materials of these materials
On a substrate surface made of charges, form a thickness 3000Å or less of the coating tri butoxy acetylacetonate zirconium
To process, and on the coating film, method of producing the optical device comprising the steps of forming a polyimide resin coating film containing fluorine.