JP2000241640A - Optical element, its manufacture, and optical module - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve the reliability of an optical element by increasing the adhesion of a polyimide resin film containing fluorine used as a material for an optical device to a substrate. SOLUTION: An optical element is obtained by forming a coating of an organic zirconium compound on a substrate surface, forming a polyimide resin coating not containing fluorine, and forming a polyimide resin coating containing fluorine.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an optical element using a polyimide resin containing fluorine, a method of manufacturing the same, and an optical module.

[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 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 than a device using an inorganic material such as glass. However, the polyimide containing fluorine is glass, quartz, silicon,
Adhesion to silicon oxide, silicon nitride, aluminum, aluminum oxide, aluminum nitride, tantalum oxide, gallium arsenide, and the like was low, and there was a problem in reliability in long-term use.

As an attempt to solve the above problem, Japanese Patent Application Laid-Open No. 174930/1995 discloses an optical device in which a coating of an organic zirconium compound is formed on the surface of a substrate and then a polyimide resin coating containing fluorine is formed. The manufacturing method is shown.

[0005]

However, the formation of only a film of an organic zirconium compound results in insufficient adhesiveness. In particular, in applications that require long-term reliability, such as optical devices used in optical communication equipment, it is necessary to prevent peeling for more than 200 hours in accelerated tests such as a pressure cooker test (121 ° C, 2 atm). In this case, the adhesiveness is insufficient. The adhesiveness depends on the type of substrate,
It also depends on the type of resin of the fluorine-containing polyimide resin film. For example, when the difference in thermal expansion coefficient between the substrate and the fluorine-containing polyimide resin film is large, when a resin film containing a large amount of fluorine is used, Adhesion is insufficient when the overall thickness of the coating is large. An object of the present invention is to provide an optical element whose reliability is improved by improving the adhesion of a polyimide-based resin film containing fluorine used as a material for an optical device to a substrate, a method of manufacturing the same, and an optical module. .

[0006]

An optical element according to the present invention comprises a substrate, on which a coating of an organic zirconium compound, a coating of a resin containing no fluorine, and a coating of a polyimide resin containing fluorine are sequentially formed. . The method for producing an optical element of the present invention comprises forming a coating of an organic zirconium compound on a substrate surface, and then forming a fluorine-free resin coating.
A step of forming a polyimide resin film containing fluorine. The thickness of the resin containing no fluorine is preferably 10 μm or less, more preferably 1.0 μm or less. The optical module of the present invention
An organic zirconium compound layer, a fluorine-free resin layer and a fluorine-containing polyimide-based resin layer are sequentially formed on a substrate, and a polymer optical waveguide is formed, and a laser light source, a light receiving element or at one or both ends of the polymer optical waveguide It is characterized in that one of the optical fibers is arranged.

According to the present invention, a substrate, a film of an organic zirconium compound, a resin film containing no fluorine, and a polyimide resin film containing fluorine are sequentially arranged.
An object of the present invention is to provide an optical element which solves the above problems, has excellent adhesiveness, and is stable even when used for a long time.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, an optical element refers to a substrate made of an inorganic material such as glass or quartz, a semiconductor or 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 may be formed on the above-described substrate, and silicon oxide, silicon nitride, oxidized silicon, or the like may be formed on the substrate to further protect the substrate and adjust the refractive index. A coating such as aluminum, aluminum nitride, and tantalum oxide may be formed.

The organic zirconium compound used in the present invention is preferably a zirconium ester or a zirconium chelate compound.

Examples of the zirconium ester include tetrapropyl zirconate and tetrabutyl zirconate. Examples of the zirconium chelate compound include tetrakis (acetylacetonate) zirconium, monobutoxytris (acetylacetonate) zirconium, and the like.
Zirconium dibutoxybis (acetylacetonate), zirconium tributoxyacetylacetonate,
Tetra (ethyl acetyl acetate) zirconium, monobutoxy tris (ethyl acetyl acetate) zirconium, dibutoxy bis (ethyl acetyl acetate)
Zirconium, tributoxyethyl acetyl acetate, tetrakis (ethyl lactonate) zirconium,
Bis (bisacetylacetonate) bis (ethylacetylacetonate) zirconium, monoacetylacetonate tris (ethylacetylacetonate) zirconium, monobutoxymonoacetylacetonatebis (ethylacetylacetonate) zirconium and the like can be mentioned. In any case of the zirconium ester and the zirconium chelate compound, those containing zirconium oxide at the time of film formation are not limited to those exemplified above. The above compounds can be used alone or in combination.

The organic zirconium compound includes methanol,
Ethanol, butanol, benzene, toluene, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, organic solvents such as γ-butyrolactone, dissolved in water, etc., and applied as a solution on the substrate surface by spin coating etc. At 70 to 400 ° C. to form a film. When the thickness of the organic zirconium compound is too large, the film becomes brittle, so that the thickness is preferably 3000 Å or less.

The fluorine-free resin used in the present invention includes various resins such as a polyimide resin, a silicone resin, an acrylic resin, a polycarbonate resin, an epoxy resin, a polyamide resin, a polyester resin, and a phenol resin. Resin can be used. What is necessary is just to select according to the board | substrate using the resin with good adhesiveness with a board | substrate. In applications where heat resistance is required in the manufacturing process of the element or the use environment, a polyimide resin, a polyquinoline resin, or the like is preferable. As the resin containing no fluorine, a resin containing nitrogen is preferable.

The fluorine-free polyimide resin used in the present invention includes polyimide resin, poly (imide / isoindoloquinazolinedionimide) resin, polyetherimide resin, polyamideimide resin and polyesterimide resin. . As the resin containing no fluorine used in the present invention, a resin whose fluorine content is sufficiently lower than the fluorine content of the polyimide resin containing fluorine can be selected instead of the resin containing no fluorine atom. In this case, the fluorine content is preferably not more than half of that of the core formed of the polyimide resin containing fluorine. Specifically, it is preferable that the fluorine content is 10 wt% or less. Further, it is preferable that the content be 2 wt% or less.

The polyimide resin containing fluorine used in the present invention includes a polyimide resin having fluorine, a poly (imide / isoindoloquinazolinedionimide) resin having fluorine, a polyetherimide resin having fluorine, and a fluorine-containing polyimide resin. Polyamide imide resin and the like can be mentioned. When a polyamideimide resin is obtained, trimellitic anhydride chloride or the like is used. The precursor solution of the polyimide resin is N-methyl-2-pyrrolidone, N, N
-It is obtained by reacting tetracarboxylic dianhydride with diamine in a polar solvent such as dimethylacetamide, γ-butyrolactone, dimethylsulfoxide and the like. By reacting the fluorine-containing tetracarboxylic dianhydride with the diamine, a fluorine-containing polyimide resin precursor solution can be produced. By reacting tetracarboxylic dianhydride with a diamine having fluorine, a precursor solution of a polyimide resin containing fluorine can be produced. When neither the tetracarboxylic dianhydride nor the diamine has fluorine, a precursor solution of a fluorine-free polyimide resin can be produced.

Examples of tetracarboxylic dianhydrides having fluorine include (trifluoromethyl) pyromellitic dianhydride, di (trifluoromethyl) pyromellitic dianhydride, and di (heptafluoropropyl) pyromellitic Acid dianhydride, pentafluoroethyl pyromellitic dianhydride, bis {3,5-di (trifluoromethyl) phenoxy} pyromellitic dianhydride, 2,2-bis (3,4-
Dicarboxyphenyl) hexafluoropropane dianhydride, 5,5'-bis (trifluoromethyl) -3,
3 ', 4,4'-tetracarboxybiphenyl dianhydride, 2,2', 5,5'-tetrakis (trifluoromethyl) -3,3 ', 4,4'-tetracarboxybiphenyl dianhydride, , 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-dicarboxy) Phenoxy) 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 1,4-bis (2-hydroxyhexafluoroisopropyl) benzenebis (trimellitic anhydride), 1,3
-Bis (2-hydroxyhexafluoroisopropyl)
Benzene bis (trimellitic anhydride) and the like may be used, and two or more kinds may be used as a mixture.

Examples of tetracarboxylic dianhydrides having no fluorine include pyromellitic dianhydride, benzene-
1,2,3,4-tetracarboxylic dianhydride, 3,
3 ', 4,4'-diphenyltetracarboxylic dianhydride, 2,2', 3,3'-diphenyltetracarboxylic dianhydride, 2,3,3 ', 4'-diphenyltetracarboxylic Acid dianhydride, p-terphenyl-3,4,3 ″,
4 "-tetracarboxylic dianhydride, m-terphenyl-
3,4,3 ", 4" -tetracarboxylic dianhydride, 1,
2,5,6-naphthalenetetracarboxylic dianhydride,
2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2, 6-dichloronaphthalene-1,4,5,8
-Tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8, tetracarboxylic dianhydride,
2,3,6,7-tetrachloronaphthalene-1,4
5,8-tetracarboxylic dianhydride, 2,3,5,6-
Pyridinetetracarboxylic dianhydride, 3,4,9,10
-Perylenetetracarboxylic dianhydride, 3,3 ',
4,4'-benzophenonetetracarboxylic dianhydride,
2,2 ', 3,3'-benzophenonetetracarboxylic dianhydride, 2,3,3', 4'-benzophenonetetracarboxylic dianhydride, 3,3 ', 4,4'- Biphenyl ether tetracarboxylic dianhydride, 4,4'-sulfonyl diphthalic dianhydride, 3,3 ', 4,4'-tetraphenylsilanetetracarboxylic 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, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2 3-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) Methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, phenanthrene-1,
8,9,10-tetracarboxylic dianhydride, pyrazine-
2,3,5,6-tetracarboxylic dianhydride, thiophene-2,3,4,5-tetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) dimethylsilane dianhydride, bis (3,4-dicarboxyphenyl) methylphenylsilane dianhydride, bis (3,4-dicarboxyphenyl) diphenylsilane dianhydride, 1,4-bis (3,4-dicarboxyphenyldimethylsilyl) ) Benzene dianhydride, 1,3-bis (3,4-dicarboxyphenyl) -1,1,3,3-tetramethyldicyclohexane dianhydride, p-phenylbis (trimellitic acid monoester acid anhydride) Ethylene glycol bis (trimellitic anhydride), propanediol bis (trimellitic anhydride), butanediol bis (trimellitic anhydride), pentanedio Rubis (trimellitic anhydride), hexanediol bis (trimellitic anhydride), octanediol bis (trimellitic anhydride), decanediol bis (trimellitic anhydride), ethylene tetracarboxylic dianhydride, 1, 2, 3,4-butanetetracarboxylic dianhydride, decahydronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,
5,6,7-hexahydronaphthalene-1,2,5,6
Tetracarboxylic dianhydride, cyclopentane-1,
2,3,4-tetracarboxylic dianhydride,

Pyrrolidine-2,3,4,5-tetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, bis (exo-bicyclo [2
2,1] heptane-2,3-dicarboxylic anhydride) sulfone bicyclo- (2,2,2) -oct (7) -ene-2,
3,5,6-tetracarboxylic dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 5- (2,5-dioxotetrahydrofuryl) ) -3-Methyl-3-cyclohexene-1,2-
Dicarboxylic anhydride, tetrahydrofuran-2,3
4,5-tetracarboxylic dianhydride, and the like,
Two or more types may be used as a mixture.

Examples of diamines having fluorine include 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, diamino Tetra (trifluoromethyl) benzene, diamino (pentafluoroethyl) benzene, 2,5-diamino (perfluorohexyl) benzene, 2,5-diamino (perfluorobutyl) benzene, 1,4-bis (4-
Aminophenyl) benzene, p-bis (4-amino-2)
-Trifluoromethylphenoxy) benzene, bis (aminophenoxy) bis (trifluoromethyl) benzene, bis (aminophenoxy) tetrakis (trifluoromethyl) benzene, bis {2-[(aminophenoxy) phenyl] hexafluoroisopropyl} benzene 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 3,3'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, octafluorobenzidine, bis {(trifluoromethyl) ) Aminophenoxydibiphenyl, 4,4'-bis (4-amino-2
-Trifluoromethylphenoxy) biphenyl, 4,
4'-bis (4-amino-3-trifluoromethylphenoxy) biphenyl, 1,4-bis (anilino) octafluorobutane, 1,5-bis (anilino) decafluoropentane, 1,7-bis (anilino) Tetradecafluoroheptane, 3,3'-difluoro-4,4'-diaminodiphenyl ether, 3,3 ', 5,5'-tetofluoro-4,4'-diaminodiphenyl ether, 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'-difluoro-4,4'-diaminodiphenylmethane, 3,3'-di ( Trifluoromethyl)-
4,4'-diaminodiphenylmethane, 3,3 ', 5
5'-tetrafluoro-4,4'-diaminodiphenylmethane, 3,3 ', 5,5'-tetrakis (trifluoromethyl) -4,4'-diaminodiphenylmethane,
3,3'-difluoro-4,4'-diaminodiphenylpropane, 3,3 ', 5,5'-tetrafluoro-4,
4'-diaminodiphenylpropane, 3,3'-bis (trifluoromethyl) -4,4'-diaminodiphenylpropane, 3,3 ', 5,5'-tetra (trifluoromethyl) -4,4'- Diaminodiphenylpropane,
3,3'-difluoro-4,4'-diaminodiphenylsulfone, 3,3 ', 5,5'-tetrafluoro-4,
4'-diaminodiphenylsulfone, 3,3'-bis (trifluoromethyl) -4,4'-diaminodiphenylsulfone, 3,3 ', 5,5'-tetrakis (trifluoromethyl) -4,4'- Diaminodiphenylsulfone, 4,4'-bis (4-amino-2-trifluoromethylphenoxy) diphenylsulfone, 4,4'-bis (3-amino-5-trifluoromethylphenoxy) diphenylsulfone, 3,3 '-Difluoro-4,4'-
Diaminodiphenyl sulfide, 3,3 ', 5,5'-
Tetrafluoro-4,4'-diaminodiphenyl sulfide, 3,3'-bis (trifluoromethyl) -4,
4'-diaminodiphenyl sulfide,

3,3 ', 5,5'-tetrakis (trifluoromethyl) -4,4'-diaminodiphenyl sulfide, 3,3'-difluoro-4,4'-diaminobenzophenone, 3,3', 5 , 5'-Tetrafluoro-
4,4'-diaminobenzophenone, 3,3'-bis (trifluoromethyl) -4,4'-diaminobenzophenone, 3,3 ', 5,5'-tetra (trifluoromethyl) -4,4'- Diaminobenzophenone, 4,4 '
-Diamino-p-terphenyl, 3,3'-dimethyl-
4,4'-diaminodiphenylhexafluoropropane, 3,3'-dimethoxy-4,4'-diaminodiphenylhexafluoropropane, 3,3'-diethoxy-
4,4'-diaminodiphenylhexafluoropropane, 3,3'-difluoro-4,4'-diaminodiphenylhexafluoropropane, 3,3'-dichloro-
4,4'-diaminodiphenylhexafluoropropane, 3,3'-dibromo-4,4'-diaminodiphenylhexafluoropropane, 3,3 ', 5,5'-tetramethyl-4,4'-diaminodiphenylhexa Fluoropropane, 3,3 ', 5,5'-tetramethoxy-
4,4'-diaminodiphenylhexafluoropropane, 3,3 ', 5,5'-tetraethoxy-4,4'-
Diaminodiphenylhexafluoropropane, 3,
3 ', 5,5'-tetrafluoro-4,4'-diaminodiphenylhexafluoropropane, 3,3', 5
5'-tetrachloro-4,4'-diaminodiphenylhexafluoropropane, 3,3 ', 5,5'-tetrabromo-4,4'-diaminodiphenylhexafluoropropane, 3,3', 5,5'- Tetrakis (trifluoromethyl) -4,4'-diaminodiphenylhexafluoropropane,

3,3'-bis (trifluoromethyl)-
4,4'-diaminodiphenylhexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 1,3-bis (anilino) hexafluoropropane, 2,2-bis {4- (4-amino Phenoxy) 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, 2,2-bis {4- (4-amino-3-trifluoromethylphenoxy) phenyl} hexafluoropropane, bis [{ (Trifluoromethyl) aminophenoxydiphenyl] hexafluoropropane, 1,3-diamino-5-
(Perfluorononenyloxy) benzene, 1,3-diamino-4-methyl-5- (perfluorononenyloxy) benzene, 1,3-diamino-4-methoxy-5
(Perfluorononenyloxy) benzene, 1,3-diamino-2,4,6-trifluoro-5- (perfluorononenyloxy) benzene, 1,3-diamino-4-
Chloro-5- (perfluorononenyloxy) benzene, 1,3-diamino-4-bromo-5- (perfluorononenyloxy) benzene, 1,2-diamino-4-
(Perfluorononenyloxy) benzene,

1,2-diamino-4-methyl-5- (perfluorononenyloxy) benzene, 1,2-diamino-4-methoxy-5- (perfluorononenyloxy) benzene, 1,2-diamino -3,4,6-trifluoro-5- (perfluorononenyloxy) benzene, 1,2-diamino-4-chloro-5- (perfluorononenyloxy) benzene, 1,2-diamino-4-
Bromo-5- (perfluorononenyloxy) benzene, 1,4-diamino-3- (perfluorononenyloxy) benzene, 1,4-diamino-2-methyl-5-
(Perfluorononenyloxy) benzene, 1,4-diamino-2-methoxy-5- (perfluorononenyloxy) benzene, 1,4-diamino-2,3,6-trifluoro-5- (perfluoro Nonenyloxy) benzene, 1,4-diamino-2-chloro-5- (perfluorononenyloxy) benzene, 1,4-diamino-2-
Bromo-5- (perfluorononenyloxy) benzene, 1,3-diamino-5- (perfluorohexenyloxy) benzene, 1,3-diamino-4-methyl-5
-(Perfluorohexenyloxy) benzene, 1,3
-Diamino-4-methoxy-5- (perfluorohexenyloxy) benzene, 1,3-diamino-2,4,6
-Trifluoro-5- (perfluorohexenyloxy) benzene, 1,3-diamino-4-chloro-5-
(Perfluorohexenyloxy) benzene, 1,3-
Diamino-4-bromo-5- (perfluorohexenyloxy) benzene, 1,2-diamino-4- (perfluorohexenyloxy) benzene, 1,2-diamino-
4-methyl-5- (perfluorohexenyloxy) benzene,

1,2-diamino-4-methoxy-5
(Perfluorohexenyloxy) benzene, 1,2-
Diamino-3,4,6-trifluoro-5- (perfluorohexenyloxy) benzene, 1,2-diamino-
4-chloro-5- (perfluorohexenyloxy) benzene, 1,2-diamino-4-bromo-5- (perfluorohexenyloxy) benzene, 1,4-diamino-3- (perfluorohexenyloxy) benzene,
1,4-diamino-2-methyl-5- (perfluorohexenyloxy) benzene, 1,4-diamino-2-methoxy-5- (perfluorohexenyloxy) benzene, 1,4-diamino-2,3 6-trifluoro-5
-(Perfluorohexenyloxy) benzene, 1,4
-Diamino-2-chloro-5- (perfluorohexenyloxy) benzene, 1,4-diamino-2-bromo-
5- (perfluorohexenyloxy) benzene and the like may be mentioned, and two or more kinds may be used as a mixture.

Examples of diamines having no fluorine include:
p-phenylenediamine, m-phenylenediamine,
2,6-diaminopyridine, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene, benzidine, 3,
3'-dimethylbenzidine, 3,3'-dimethoxybenzidine, 3,3'-diaminobenzophenone, 3,3 '
-Dimethyl-4,4'-diaminobenzophenone, 3,
3'-dimethoxy-4,4'-diaminobenzophenone, 3,3'-diethoxy-4,4'-diaminobenzophenone, 3,3'-dichloro-4,4'-diaminobenzophenone, 3,3'-dibromo- 4,4'-diaminobenzophenone, 3,3 ', 5,5'-tetramethyl-4,4'-diaminobenzophenone, 3,3', 5
5'-tetramethoxy-4,4'-diaminobenzophenone, 3,3 ', 5,5'-tetraethoxy-4,4'
-Diaminobenzophenone, 3,3 ', 5,5'-tetrachloro-4,4'-diaminobenzophenone, 3,
3 ', 5,5'-tetrabromo-4,4'-diaminobenzophenone, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'
-Diaminodiphenyl ether, 3,3'-dimethyl-
4,4'-diaminodiphenyl ether, 3,3'-diisopropyl-4,4'-diaminodiphenyl ether, 3,3'-dimethoxy-4,4'-diaminodiphenyl ether, 3,3'-diethoxy-4,4'- Diaminodiphenyl ether, 3,3'-dichloro-4,
4'-diaminodiphenyl ether, 3,3'-dibromo-4,4'-diaminodiphenyl ether, 3,
3 ', 5,5'-tetramethyl-4,4'-diaminodiphenyl ether, 3,3', 5,5'-tetraethyl-4,4'-diaminodiphenyl ether, 3,3 ',
5,5'-tetramethoxy-4,4'-diaminodiphenyl ether, 3,3 ', 5,5'-tetraethoxy-
4,4'-diaminodiphenyl ether, 3,3 ',
5,5'-tetrachloro-4,4'-diaminodiphenyl ether, 3,3 ', 5,5'-tetrabromo-4,
4'-diaminodiphenyl ether, 3,3'-diisopropyl-5,5'-dimethyl-4,4'-diaminodiphenyl ether,

3,3'-diisopropyl-5,5'-diethyl-4,4'-diaminodiphenyl ether, 4,
4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-4,
4'-diaminodiphenylmethane, 3,3'-dimethoxy-4,4'-diaminodiphenylmethane, 3,3'-
Diethoxy-4,4'-diaminodiphenylmethane,
3,3'-dichloro-4,4'-diaminodiphenylmethane, 3,3'-dibromo-4,4'-diaminodiphenylmethane, 3,3 ', 5,5'-tetramethyl-4,
4'-diaminodiphenylmethane, 3,3 ', 5,5'
-Tetraisopropyl-4,4'-diaminodiphenylmethane, 3,3 ', 5,5'-tetramethoxy-4,
4'-diaminodiphenylmethane, 3,3 ', 5,5'
-Tetraethoxy-4,4'-diaminodiphenylmethane, 3,3 ', 5,5'-tetrachloro-4,4'-diaminodiphenylmethane, 3,3', 5,5'-tetrabromo-4,4'- Diaminodiphenylmethane, 3,
3 ', 5,5'-tetraisopropyl-4,4'-diaminodiphenylmethane, 3,3'-diisopropyl-
5,5'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-diisopropyl-5,5'-diethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 3,3 ' -Diaminodiphenylpropane, 3,3'-dimethyl-4,4'-diaminodiphenylpropane,

3,3'-dimethoxy-4,4'-diaminodiphenylpropane, 3,3'-diethoxy-4,
4'-diaminodiphenylpropane, 3,3'-dichloro-4,4'-diaminodiphenylpropane, 3,3 '
-Dibromo-4,4'-diaminodiphenylpropane,
3,3 ', 5,5'-tetramethyl-4,4'-diaminodiphenylpropane, 3,3', 5,5'-tetramethoxy-4,4'-diaminodiphenylpropane,
3 ', 5,5'-tetraethoxy-4,4'-diaminodiphenylpropane, 3,3', 5,5'-tetrachloro-4,4'-diaminodiphenylpropane, 3,
3 ', 5,5'-tetrabromo-4,4'-diaminodiphenylpropane, 3,3'-diisopropyl-5,
5'-dimethyl-4,4'-diaminodiphenylpropane, 3,3'-diisopropyl-5,5'-diethyl-
4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 3,3'-dimethyl-4,4'-diaminodiphenylsulfone, 3,3'-dimethoxy- 4,
4'-diaminodiphenyl sulfone, 3,3'-diethoxy-4,4'-diaminodiphenyl sulfone, 3,
3'-dichloro-4,4'-diaminodiphenylsulfone, 3,3'-dibromo-4,4'-diaminodiphenylsulfone, 3,3 ', 5,5'-tetramethyl-4,
4'-diaminodiphenyl sulfone, 3,3 ', 5
5'-tetramethoxy-4,4'-diaminodiphenylsulfone, 3,3 ', 5,5'-tetraethoxy-4,
4'-diaminodiphenyl sulfone, 3,3 ', 5
5'-tetrachloro-4,4'-diaminodiphenylsulfone, 3,3 ', 5,5'-tetrabromo-4,4'
-Diaminodiphenylsulfone, 3,3'-diisopropyl-5,5'-dimethyl-4,4'-diaminodiphenylsulfone, 3,3'-diisopropyl-5,5'-
Diethyl-4,4'-diaminodiphenylsulfone,

4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 3,
3'-dimethyl-4,4'-diaminodiphenyl sulfide, 3,3'-dimethoxy-4,4'-diaminodiphenyl sulfide, 3,3'-diethoxy-4,4'-
Diaminodiphenyl sulfide, 3,3'-dichloro-
4,4'-diaminodiphenyl sulfide, 3,3'-
Dibromo-4,4'-diaminodiphenyl sulfide,
3,3 ', 5,5'-tetramethyl-4,4'-diaminodiphenyl sulfide, 3,3', 5,5'-tetramethoxy-4,4'-diaminodiphenyl sulfide,
3,3 ', 5,5'-tetraethoxy-4,4'-diaminodiphenyl sulfide, 3,3', 5,5'-tetrachloro-4,4'-diaminodiphenyl sulfide,
3,3 ', 5,5'-tetrabromo-4,4'-diaminodiphenylsulfide, 1,4-bis- (4-aminophenoxy) benzene, 1,3-bis- (4-aminophenoxy) benzene, , 2-bis- (4-aminophenoxyphenyl) propane, bis- (4-aminophenoxyphenyl) sulfone, bis- (4-aminophenoxyphenyl) sulfide, bis- (4-aminophenoxyphenyl) biphenyl, 4,4 '-Diaminodiphenyl ether-3-sulfonamide, 3,4'-diaminodiphenyl ether-4-sulfonamide, 3,4'-
Diaminodiphenyl ether-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'-
Diaminodiphenyl sulfide-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'-diaminodiphenylsulfide-3-carbonamide, 3,4'-diaminodiphenylsulfide-
4-carbonamide, 3,3'-diaminodiphenylsulfide-4-carbonamide, 3,4'-diaminodiphenylsulfide-3'-carbonamide, 1,
4-diaminobenzene-2-carbonamide, 4-aminophenyl-3-aminobenzoic acid,

2,2-bis (4-aminophenyl) propane, bis- (4-aminophenyl) diethylsilane,
Bis- (4-aminophenyl) diphenylsilane, bis- (4-aminophenyl) ethylphosphine oxide, bis- (4-aminophenyl) -N-butylamine, bis- (4-aminophenyl) -N-methylamine, N- (3 -Aminophenyl) -4-aminobenzamide, 2,4-bis- (β-amino-t-butyl) toluene, bis- (p-β-amino-t-butyl-phenyl) ether, bis- (p-β- Methyl-γ-amino-
Pentyl) benzene, bis-p- (1,1-dimethyl-
5-aminopentyl) benzene, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, tetramethylenediamine, propylenediamine, 3-methylheptamethylenediamine, 4,4'-dimethylheptamethylenediamine , 2,11-diaminododecane, 1,
2-bis- (3-aminopropoxy) ethane, 2,2-
Dimethylpropylenediamine, 3-methoxy-hexamethylenediamine, 2,5-dimethylhexamethylenediamine, 2,5-dimethylheptamethylenediamine, 5-
Methylnonamethylenediamine, 2,17-diaminoicosadecane, 1,4-diaminocyclohexane, 1,1
0-diamino-1,10-dimethyldecane, 1,12-
Diaminooctadecane, etc., and two or more kinds may be used as a mixture.

As a part of the diamine, silicon diamine may be used. As silicon diamine, 1,
3-bis (3-aminopropyl) -1,1,1-tetraphenyldisiloxane, 1,3-bis (3-aminopropyl) -1,1,1-tetramethyldisiloxane, 1,
3-bis (4-aminobutyl) -1,1,1-tetramethyldisiloxane and the like. When silicon diamines are used, they may be present in an amount of 0.
It is preferable to use 1 to 10 mol%. 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 fluorine-free polyimide resin film. The thickness of the polyimide resin film containing no fluorine is controlled to a predetermined thickness by changing the concentration, viscosity, rotation speed of the spinner, and the like of the polyimide precursor solution.

The thickness of the polyimide resin film containing no fluorine is preferably 10 μm or less. 10 μm
When the value exceeds, the entire thickness of the resin film containing no fluorine and the polyimide-based resin film containing fluorine becomes large, and warpage due to stress based on the difference in expansion coefficient from the substrate is likely to occur. In addition, uniformity of the thickness of the entire resin film is hardly achieved. More preferably, the thickness of the fluorine-containing polyimide resin film is 1.0 μm or less. The thickness of the fluorine-containing polyimide resin coating is
It must be optimally selected depending on the configuration of the optical waveguide manufactured using the fluorine-containing polyimide resin film formed thereon. That is, when an optical waveguide is formed such that a core (optical waveguide layer) is directly formed on a polyimide resin film containing no fluorine, or when the polyimide resin film containing no fluorine and the core are arranged close to each other. In the case of forming an optical waveguide (when the thickness of the cladding layer located between the fluorine-free polyimide resin coating and the core is small), the fluorine-free polyimide resin coating may cause an increase in light loss. Therefore, it is preferable to reduce the thickness of the polyimide resin film containing no fluorine. The specific thickness is determined in consideration of the substrate, the polyimide resin film containing no fluorine, the cladding formed of the polyimide resin film containing fluorine, the refractive index of the core, and the height and width of each. In general, the size of the core of an optical waveguide made of a polyimide-based resin film containing fluorine is often about 10 μm in consideration of compatibility with an optical fiber as a transmission line. In order to sufficiently reduce the loss to light propagating through the core layer, the thickness of the polyimide-based resin film containing no fluorine should be 1/1 of the core layer.
It is desirable to set it to 10 or less, and in the case of the above example, 1.
More preferably, it is 0 μm or less. Even more preferably, it is 0.5 μm.

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 obtain a fluorine-containing polyimide resin film. The polyimide-based resin film containing fluorine can form an optical waveguide by etching or irradiation of a particle beam including an electron beam or an electromagnetic wave including light by a known method as necessary.
In forming an optical waveguide, a known method is used.
An optical waveguide in which a polyimide-based resin film containing fluorine is composed of a plurality of films having different refractive indices can be provided.

[0036]

EXAMPLES The present invention will now be described specifically with reference to examples, but the present invention is not limited to these examples. Example 1 (Preparation of an organic zirconium compound solution) As an organic zirconium compound solution, tributoxyacetylacetonate zirconium was dissolved in butanol to prepare a 1% by weight solution. (Preparation of Fluorine-Free Polyimide Precursor Solution) A fluorine-free polyimide precursor solution was prepared by preparing 35.33 g of 4,4'-diaminodiphenyl ether and 4.7 of 4,4'-diaminodiphenyl ether-3-carbonamide.
After dissolving 7 g in 528.3 g of N-methyl-2-pyrrolidone, 31.69 g of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride and 21.44 g of pyromellitic dianhydride were added, and the mixture was added at room temperature. Obtained by stirring for 6 hours. (Preparation of Polyimide Precursor Solution Containing Fluorine) A polyimide precursor solution containing fluorine was prepared by dissolving 21.47 g of 2,2-bis (4-aminophenyl) hexafluoropropane in 450 g of N, N-dimethylacetamide. 28.53 g of 2,2'-bis (3,4-dicarboxyphenylhexafluoropropanoic acid dianhydride was added thereto, and the mixture was stirred at room temperature for 20 hours to obtain an organic zirconium compound. The silicon zirconium compound solution was dropped on the substrate and spin-coated (3000 rpm / 30 rpm).
Second) and dried on a hot plate (200 ° C./5 minutes) to form a film of an organic zirconium compound (film thickness of about 200
Å) formed. (Formation of a polyimide-based resin film containing no fluorine) The above-mentioned polyimide precursor solution containing no fluorine was dropped and spin-coated (2000 rpm / 30 seconds), and then oven (100 ° C./30 minutes + 200 ° C./30). Min + 35
(0 ° C./60 minutes) to form a fluorine-free polyimide film. (Formation of Fluorine-Containing Polyimide Resin Coating) Next, the above-mentioned fluorine-containing polyimide precursor solution was dropped thereon, spin-coated (2000 rpm / 30 seconds), and then oven (100 ° C./30 minutes + 200 ° C./200° C.) 30 minutes + 350
(° C./60 minutes) to form a polyimide film containing fluorine.

Comparative Example 1 As a comparative example, an organic zirconium compound film and a fluorine-free polyimide resin film were not formed.
A sample in which a polyimide film containing fluorine was directly formed on a substrate under the same conditions was produced (FIG. 9).

Comparative Example 2 As a comparative example, only a polyimide-based resin film containing no fluorine was formed on a substrate without forming a film of an organic zirconium compound, and then a polyimide film containing fluorine was formed under the same conditions. A sample was prepared (FIG. 10).

COMPARATIVE EXAMPLE 3 As a comparative example, after forming only a coating of an organic zirconium compound on a substrate, a polyimide coating containing fluorine was directly formed under the same conditions without forming a polyimide resin coating containing no fluorine. A sample was prepared (FIG. 11).

(Evaluation of Adhesion) The adhesion test was performed according to JISK.
According to the cross-cut test method of 5400, the polyimide film was cut into 100 1 × 1 mm squares with a cutter knife, and a cellophane tape was adhered to the portion, and then peeled off.
Evaluation was made based on the number of remaining adhesives after the tape was 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 any of the comparative examples.

FIG. 2 shows a buried polymer optical waveguide according to another embodiment of the present invention. The optical waveguide of the present invention has an organic zirconium compound coating 4 and a fluorine-free resin layer 5 between a substrate 1 and a cladding layer 2. For the resin layer 5 not containing fluorine, any polymer having high adhesion to the substrate can be used. For example, when a fluorinated polyimide resin is used for the cladding layer 2, the adhesion to the substrate is improved by using a fluorine-free polyimide for the resin layer 5 containing no fluorine. A polyimide silicone resin having Si atoms in the molecular structure and having a strong self-adhesive property to silicon or SiO ₂ may be used for the fluorine-free resin layer 5. Alternatively, an acrylic resin containing no fluorine or a polycarbonate resin containing no fluorine may be used for the resin layer 5 containing no fluorine.

Next, a specific embodiment of the present invention will be described with reference to FIG. First, a coating 4 of an organic zirconium compound is formed on a silicon substrate 1, and then N and N of polyamic acid, which is a precursor of a polyimide silicone resin, are formed.
An N-dimethylacetamide solution is applied and baked with a spinner to form a fluorine-free resin layer 5 (1.5 μm thick) made of a polyimide silicone resin. As polyimide silicone resin, here the structural formula

[0043]

Embedded image Benzophenonetetracarboxylic dianhydride (BTDA), methylene dianiline (MDA) and bis-γ-aminopropyltetramethyldisiloxane (GA)
Polymerized product with PD) was used. Further, two kinds of precursors of fluorinated polyimide resins A and B are used to form N,
An N-dimethylacetamide solution was applied and baked to form a cladding layer 2 made of polyimide A (with a thickness of 10 μm).
m) and a core layer 3 (7 μm in thickness). Fluorinated polyimide A has the structural formula

[0044]

Embedded image 2,2'-bis (trifluoromethyl)-represented by
4,4'-diaminobiphenyl (TFDB) and 2,2 '
-A polymerization product with bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA). The fluorinated polyimide resin B has the structural formula

[0045]

Embedded image Is a polymerization product of TFDB, 6FDA and pyromellitic dianhydride (PMDA) represented by the following formula: 6FDA and 6FDA such that the refractive index of the core layer 3 is about 0.3% larger than that of the cladding layer 2. The ratio of PMDA (that is, the ratio of m and n) was 4: 1. Next, a part of the core layer 3 is removed by reactive ion etching of oxygen to form a waveguide pattern, and an N, N-dimethylacetamide solution of polyamic acid, which is a precursor of the fluorinated polyimide resin A, is applied. Baking was performed to further provide a clad layer (thickness: 10 μm). The propagation loss of the manufactured optical waveguide was 0.3 dB / cm at a wavelength of 1.3 μm. This is a small value equivalent to the conventional optical waveguide (FIG. 9) manufactured using the same fluorinated polyimide resin. When a pressure cooker test was performed on the manufactured optical waveguide, a conventional optical waveguide (FIG. 9), an optical waveguide having only a resin layer containing no fluorine (FIG. 10), and an optical waveguide having only an organic zirconium compound coating were used. (FIG. 11) shows the clad layer 2
Although peeling occurred between the substrate and the substrate 1, no peeling was observed in the element having the organic zirconium compound coating film of the present invention and the fluorine-free resin layer, and the adhesion was improved and the long-term reliability was improved. Improvement was confirmed. In the above description, the case where a buried optical waveguide is manufactured by etching is particularly described. However, the present invention is similarly applied to a ridge optical waveguide having no upper cladding layer as shown in FIG. be able to. Also, a buried optical waveguide manufactured by using a photosensitive polymer for the core layer and irradiating a part thereof with light to reduce the refractive index can be similarly implemented as shown in FIG. . FIG. 5 also shows a buried optical waveguide manufactured by using a photosensitive polymer different from the above for the core layer and irradiating a part thereof with light to increase the refractive index. Can be similarly implemented. Further, the material of the substrate and the surface of the substrate is SiO ₂ , quartz, Si
It is any other inorganic material such as N _x the same effect can be expected.

FIGS. 6A and 6B show an optical switch as an example of a polymer optical integrated circuit according to an embodiment of the present invention. This 1 × 4 optical switch has a thin film heater electrode 10 on a waveguide, and switches the optical path by heating the waveguide by the heater to change the refractive index. This optical switch was manufactured by the following process. First, a coating film 4 of an organic zirconium compound is formed on a silicon substrate 1 in the same manner as in the previous embodiment, and then a N, N-dimethylacetamide solution of a polyamic acid as a polyimide silicone resin precursor, and
A fluorine-free resin layer 5 (1.5 μm thick) made of a polyimide silicone resin is formed by sequentially applying and baking N, N-dimethylacetamide solutions of the precursor polyamic acid of the fluorinated polyimide resins A and B, respectively. A lower clad layer 2 (thickness 10 μm) made of fluorinated polyimide resin A and a core layer 3 (thickness 7 μm) made of fluorinated polyimide resin B are laminated. Next, a part of the core layer is removed by using oxygen reactive ion etching to form a waveguide pattern (including a branch structure). Next, an amide acid solution, which is a precursor of the fluorinated polyimide resin A, is applied and baked to form an upper clad layer 2 'made of the fluorinated polyimide resin A, and a Cr thin film heater 10 is provided.
Finally, an optical fiber 11 for inputting and outputting light to and from the element end face
(Total of 5) were adhered. The insertion loss of the manufactured optical switch was about 4 dB, and switching was performed at an extinction ratio of 20 dB or more by supplying about 40 mW of power to each heater. Further, even when the heater current was repeatedly turned ON / OFF 10,000 times or more, the polymer did not peel off from the substrate. On the other hand, in a conventional device having no organic zirconium compound coating and no fluorine-containing resin layer, the polymer waveguide was separated from the substrate by turning on / off the heater current. A 4 × 4 optical switch (FIG. 7) was configured by combining the produced 1 × 4 optical switches.

An optical communication device was constructed by installing the 4 × 4 optical switches in each station (FIG. 8). In the present optical communication apparatus, the stations A and B, the stations B and C, and the stations C and A usually communicate with each other using one short-distance optical fiber. However, for example, when the optical fiber is disconnected between the stations A and B, the station A is switched by switching the optical switch of each station.
Communication between station A and station B, fiber between station A and station C, station C
, An optical switch between stations C and B. Originally, the optical communication device operated normally for a long time.

According to the above embodiments, it is possible to provide a polymer optical waveguide, an optical integrated circuit, and an optical module having high adhesion to a substrate and high reliability. In addition, a highly reliable optical communication device can be provided by forming an optical communication device using them. According to the embodiment of the present invention, it is possible to provide a polymer optical waveguide, an optical integrated circuit, and an optical module having high adhesion to a substrate and high reliability. Further, since a highly reliable optical communication device can be provided by configuring the optical communication device using them, the industrial use value is extremely large.

[0049]

According to the present invention, the adhesion of a polyimide film containing fluorine to a substrate can be improved, the reliability of an optical element can be improved, and a polymer optical waveguide having high adhesion to a substrate and high reliability can be obtained. , An optical integrated circuit, and an optical module. By configuring an optical communication device using them, a highly reliable optical communication device can be provided.

[Brief description of the drawings]

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

FIG. 2 is a perspective view of a buried polymer optical waveguide according to another embodiment of the present invention.

FIG. 3 is a perspective view of a ridge-type optical waveguide without an upper cladding layer.

FIG. 4 is a perspective view of a buried optical waveguide.

FIG. 5 is a perspective view of another embedded optical waveguide.

6A and 6B are a plan view and an AA ′ cross-sectional view of an optical switch which is an example of a polymer optical integrated circuit.

FIG. 7 is a plan view illustrating a configuration of an optical switch.

FIG. 8 is a plan view illustrating a configuration of an optical communication device.

FIG. 9 is a perspective view of a conventional optical waveguide.

FIG. 10 is a perspective view of an optical waveguide having only a resin layer containing no fluorine.

FIG. 11 is a perspective view of an optical waveguide having only a coating of an organic zirconium compound.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Tohru Takahashi 48 Wadai, Tsukuba, Ibaraki Prefecture Within Hitachi Chemical Co., Ltd. In-house (72) Inventor Shigeru Koibuchi 4-3-1-1, Higashicho, Hitachi City, Ibaraki Pref.Hitachi Chemical Industry Co., Ltd. In-house (72) Inventor Shinji Tsuji 1-280 Higashi Koikekubo, Kokubunji-shi, Tokyo Inside the Hitachi, Ltd.Central Research Laboratory Co., Ltd. Reference) 2H047 KA04 KA05 KA12 LA00 LA12 PA02 PA21 PA24 PA28 QA05 QA07 RA00 TA 00 2K002 AA02 AB04 BA13 CA06 CA30 DA08 EA04 GA10 HA11 2K009 BB01 CC32 DD01 EE00

Claims (5)

[Claims] An organic zirconium compound coating on a substrate,
An optical element, wherein a film of a resin containing no fluorine and a film of a polyimide-based resin containing fluorine are sequentially formed. 2. An optical element comprising the steps of: forming a fluorine-containing resin coating on a surface of an organic zirconium compound on a substrate surface; and forming a fluorine-containing polyimide resin coating. Manufacturing method. 3. The optical element or the method for producing an optical element according to claim 1, wherein the film thickness of the resin containing no fluorine is 10 μm or less. 4. The film thickness of the resin containing no fluorine is 1.0 μm.
The optical element or the method for manufacturing an optical element according to claim 1, wherein: 5. A polymer optical waveguide in which an organic zirconium compound layer, a fluorine-free resin layer and a fluorine-containing polyimide resin layer are sequentially formed on a substrate, and a laser is provided at one or both ends of the polymer optical waveguide. An optical module comprising any one of a light source, a light receiving element, and an optical fiber.