JPH07181532A - Nonlinear optical material and nonlinear optical waveguide element - Google Patents

Abstract

PURPOSE:To obtain a nonlinear optical material which lessens flocculation, crystallization and orientation relaxation at a high content and has high quadratic and cubic nonlinear optical characteristics by dissolving or dispersing specific compds. consisting of pi electron conjugation-based cyclic compds. into a polymer. CONSTITUTION:This nonlinear optical material contains the nonlinear optical material formed by dissolving or dispersing >=1 kinds of the compds. expressed by formula 1 or their derivatives into a polymer material or this nonlinear optical material contains the conjugated/coordinated polymer of the formula I formed by conjugating or coordinating >=1 kinds of the compds. expressed by the formula 1 or their derivatives with high polymer chains. In the formula, pi1 to pi3 denote the electron conjugation-based cyclic compds.; X, Y respectively denote a pair of combinations consisting of one selected from C, H, N or N to O; n denotes an integer of >=0; D denotes an electron-donating group; R1 to R10 respectively denote hydrogen atoms or alkyl groups ; A1 to A3 respectively denote a hydrogen atom, alkyl group or the substituent (Z is a hydrogen atom, halogen atom, etc.) expressed by formula II.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a non-linear optical material and a non-linear optical waveguide device used for an optical integrated circuit, and more specifically, it contains an organic compound having a large second-order or third-order non-linear optical characteristic. And a non-linear optical waveguide element containing the non-linear optical material.

[0002]

2. Description of the Related Art Non-linear optical characteristics in the present invention mean the polarization of atoms and molecules induced by an external strong electric field.
It refers to the optical properties that result from non-negligible nonlinear polarization. For example, the Pockels effect, parametric oscillation, second harmonic generation (SHG), etc. in the second-order nonlinear optical characteristic, and the Kerr effect, electrostatic induction SHG, third harmonic generation (THG), etc. in the third-order nonlinear optical characteristic. ), And the change of the refractive index depending on the light intensity is known. The second-order nonlinear optical characteristic is
The wavelength conversion (SHG) element, electro-optic modulator, etc. can be applied to wavelength conversion (THG) element, high-speed optical shutter light calculation, optical bistable element, optical switching, etc. is there.

Materials having nonlinear optical characteristics (hereinafter referred to as “nonlinear optical materials”) have been conventionally known as potassium dihydrogen phosphate (KDP) and lithium niobate (LiNbO ₃ ).
Inorganic strong induction electric body such as (Landolt-Bormstein New S
eries, Group III, Crystaland Solid State Physics,
Vol 12 1992), which has been put to practical use as an optical frequency multiplication element (Laser Handbook, New Edition, Nos. 432 to 440).
Page, Asakura Shoten, 1989). However, since 2-methyl-4-nitroalinine (MNA), which exhibits a nonlinear optical response larger than those of inorganic ferroelectrics, was discovered by BF Levine et al. In 1979, research and development of organic nonlinear optical materials have been actively conducted. Has been done.

These organic nonlinear optical materials can be expected to be used as new optical materials in that they have optical characteristics such as nonlinear optical constants larger than inorganic ferroelectrics, fast nonlinear optical response and high breakdown threshold. In addition, it has the advantage of having a variety of molecular designs and devices, and is attracting attention as a key material in the future optoelectronics field.

For example, MNA, 1- (4-nitrophenyl)-
3,5-dimethylpyrazole (DMNP), 2- (2,2- dicyano vinyl) anisole (DIVA) and 4 ^'- Citrobacter benzylidene-3-acetamino-4-methoxyaniline (MN
The bulk single crystal obtained from BA) is used as a wavelength conversion material. These materials are processed into fiber-type or slab-type optical waveguides and prototyped as optical frequency multiplication elements (optical functional materials, pages 41 to 105, Kyoritsu Shuppan).
1991). In addition, it is developed by introducing 4- (4-nitrophenylazo) -N- (2-hydroxyethyl) -N-ethylaniline (DR-1) into the side chain of methacrylic acid ester and orienting it by an applied electric field. A prototype of an electro-optic modulator using the Pockels effect has been reported. Furthermore, there is also shown an example in which polydiacetylene showing a large third-order nonlinear optical characteristic is applied to a slab type optical waveguide and developed into an optical switching element.

[0006]

Generally, when an optical element is made of a material exhibiting nonlinear optical characteristics, it is necessary to construct an optical waveguide. In order to efficiently exhibit the nonlinear optical characteristics in the optical waveguide, it is desired that the material used has a large nonlinear optical constant and excellent light propagation characteristics.

In general, it is known that the nonlinear optical constant increases as the content of the nonlinear optical material increases. When forming an optical element using the materials described above, it is necessary to increase the content of the nonlinear optical material. However, it has been observed that when the content of the nonlinear optical material is increased, aggregation and crystallization of the compound occur, and an optically transparent and uniform waveguide cannot be obtained. As a result, there arises a problem that the optical propagation loss characteristic is extremely deteriorated, and it is very difficult to construct an optical element. Further, it is necessary to develop the non-linear optical characteristics by performing the orientation by using the non-linear optical material, but in general, there is a problem that the orientation is relaxed and the non-linear optical characteristics are lost.

The present invention provides a non-linear optical material having a large degree of second-order and third-order non-linear optical characteristics with less aggregation / crystallization and orientation relaxation at the above-mentioned high content, and a non-linear optical waveguide device using the same. That is the purpose.

[0009]

Means for Solving the Problems The inventors of the present invention have made extensive studies in view of the above-mentioned problems, and as a result, by introducing a fluoroalkylsulfonyl group into a π-electron conjugated cyclic compound, a large secondary and By finding a non-linear optical material using an organic compound exhibiting a third-order non-linear optical characteristic, and further forming the above-mentioned non-linear optical material into a thin film, excellent optical modulation characteristics, optical switching characteristics, and optical bistability are achieved. We have found that a nonlinear optical waveguide device can be obtained.

That is, the present invention provides a nonlinear optical material containing a nonlinear optical material in which one or more compounds represented by the general formula [1] or derivatives thereof are dissolved or dispersed in a polymer substance. Material or 1 represented by the general formula [1]
The present invention is directed to a non-linear optical material containing a general formula [1] bond / coordination polymer in which molecules of one or more compounds or their derivatives are bound or coordinated to a polymer chain, and , And a non-linear optical waveguide device using these non-linear optical materials.

[0011]

[Chemical 2]

(Wherein, π _{1 to} π ₃ are π-electron conjugated cyclic compounds, and X and Y are CH, N, or N, respectively.
→ A combination of one pair selected from O, n is an integer of 0 or more, D is an electron donating group, R _{1 to} R ₁₀ are each a hydrogen atom or an alkyl group, and A ₁ , A ₂ or A ₃ is Each represents a hydrogen atom, an alkyl group or a substituent represented by the general formula [2]. However, when having substituents only one of A _1, A ₂ or A ₃ is represented by the general formula [2], the substituent is located A _1, also, A _1, A ₂ Alternatively, when two of A ₃ have a substituent represented by the general formula [2], the substituents are arranged at A ₁ and A ₂ or A ₁ and A ₃ . Here, Z is a hydrogen atom, a halogen atom, a nitro group, a carboxyl group, a hydroxyl group, a dicyanovinyl group or a tricyanovinyl group, m
Represents an integer of 1 or more, and l represents an integer of 0 or more. )

The present invention will be described in detail below. The nonlinear optical material of the present invention contains a substance containing one or more compounds represented by the general formula [1] or derivatives thereof (hereinafter abbreviated as the general formula [1] compound) as described above ( Hereinafter, abbreviated as general formula [1] substance),
In the compound of the general formula [1], specific examples of each skeleton constituent of π _{1 to} π ₃ which is a π-electron conjugated cyclic compound include a benzene ring, a pyrimidine ring, an oxazole ring, a furan ring, a thiazole ring and a thiadiazole ring. And aromatic compounds such as oxathiazole ring, benzothiazole ring, benzoxazole ring, benzoxathiazole ring, naphthalene ring, anthracene ring and isoquinoline ring.
Among these, particularly preferable constituents are benzene ring, thiazole ring, thiadiazole ring, benzothiazole ring, naphthalene ring and the like.

The substituents R _{1 to} R _{10 in} each of the above-mentioned skeleton constituents are hydrogen atoms or alkyl groups, and the alkyl groups include methyl groups having 1 to 8 carbon atoms, ethyl groups, propyl groups, iso- Propyl group, butyl group, iso-butyl group, ter
Preferred examples include t-butyl group, sec-butyl group, amyl group, iso-amyl group, tert-amyl group, sec-amyl group, hexyl group, heptyl group, cyclohexyl group, octyl group, and 2-ethylhexyl group. .

A connector for connecting the π-electron conjugated cyclic compound which is a part of each skeleton constituent, namely, -X = Y- constituent atomic groups X and Y are selected from CH, N, or N → O, respectively. Represents a combination of another pair of atomic groups. Examples of the connector -X = Y- formed of these specific combinations include -CH = CH-, -CH = N-, -N = N-, -C.
Examples include groups represented by molecular formulas such as H = (N → O)-and -N = (N → O)-.

Specific examples of the electron-donating group D include -SR
₁₁ , -OR ₁₁ , -NR ₁₁ R _{12 and the} like can be mentioned. Where R
₁₁ , R ₁₂ is hydrogen, an alkyl group, — (CH ₂ ) _p OH, —
_{(CH 2) p NH 2,} - a (CH _{2) p} SH group selected from group. p is an integer of 1 or more. Of these, an amino group or an amino group derivative is particularly preferable.

A ₁ , A ₂ and A ₃ each represent a hydrogen atom, an alkyl group or a substituent represented by the general formula [2]. Here, the alkyl group has 1 to 8 carbon atoms.
The groups up to are preferred examples.

The electron donating group Z of the general formula [2] represents a hydrogen atom, an electron withdrawing group or a linking inducing group, and the electron withdrawing group is a halogen atom, a nitro group, a dicyanovinyl group or a tricyanovinyl group. Examples of the halogen atom which is one group selected from the group include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Further, the connectivity-inducing group means a polymer main chain or side chain (or substituent)
To a functional substituent that can be linked to a bond by a covalent bond, an ionic bond, a coordinate bond, or the like, and is a carboxyl group, a carboxyl anion group, a sulfonate anion group, a hydroxyl group, an isocyanate group, an amino group, an ammonium cation group. Suitable examples include functional substituents such as

Preferable examples of the substituent represented by the general formula [2] include F (CF ₂ ) _m SO ₂ group and HO (CH ₂ ) _l (C
F ₂ ) _m SO ₂ group, HOOC (CH ₂ ) _l (CF ₂ ) _m SO ₂
Groups.

As typical examples of the compound of the general formula [1], the following compounds are exemplified. 4- (4- (4-perfluorobutylsulfonylphenylazo) -1-naphthylazo) -N-
Ethyl-N- (2-hydroxyethyl) aniline (Compound
[3]), 4- (4- (2,4-diperfluorobutylsulfonylphenylazo) -1-naphthylazo) -N-ethyl-N- (2-hydroxyethyl) aniline (compound [4]), 4 -(4- (2,4,6-
Triperfluorobutylsulfonylphenylazo) -1-naphthylazo) -N-ethyl-N- (2-hydroxyethyl) aniline (compound [5]), 4- (4- (4-perfluorobutylsulfonylphenylazo) 2 , 6-Diethylphenylazo) -N-ethyl-N- (2-hydroxyethyl) aniline (Compound
[6]), 4- (4- (2,4-diperfluorobutylsulfonylphenylazo) 2,6-diethylphenylazo) -N-ethyl-N
-(2-Hydroxyethyl) aniline (Compound [7]), 4- (4
-(2,4,6-Triperfluorobutylsulfonylphenylazo) 2,6-diethylphenylazo) -N-ethyl-N- (2-hydroxyethyl) aniline (Compound [8]), 4- (4- (4-Perfluorobutylsulfonylphenylazo) phenylazo) -N-ethyl-N- (2-hydroxyethyl) aniline, 4-
(4- (2,4-diperfluorobutylsulfonylphenylazo) phenylazo) -N-ethyl-N- (2-hydroxyethyl)
Aniline, 4- (4- (2,4,6-triperfluorobutylsulfonylphenylazo) phenylazo) -N-ethyl-N- (2-hydroxyethyl) aniline, 4- (4- (4-hydroxymethyleneper) Fluorobutylsulfonylphenylazo) -1-naphthylazo) -N-ethyl-N- (2-hydroxyethyl) aniline, 4- (4- (4-hydroxymethyleneperfluorobutylsulfonylphenylazo) 2,6-diethylphenylazo )-
N-ethyl-N- (2-hydroxyethyl) aniline, 4- (4- (4
-Perfluorobutylsulfonylphenyl vinylene) -1-
Naphthylvinylene) -N-ethyl-N- (2-hydroxyethyl)
Aniline, 4- (4- (2,4-diperfluorobutylsulfonylphenylvinylene) -1-naphthylvinylene) -N-ethyl-N
-(2-Hydroxyethyl) aniline, 4- (4- (2,4,6-triperfluorobutylsulfonylphenylvinylene) -1-
Naphthylvinylene) -N-ethyl-N- (2-hydroxyethyl)
Aniline, 4- (4- (4-perfluorobutylsulfonylphenylazoxy) -1-naphthylazoxy) -N-ethyl-N- (2-
Hydroxyethyl) aniline, 4- (4- (2,4-diperfluorobutylsulfonylphenylazoxy) -1-naphthylazoxy) -N-ethyl-N- (2-hydroxyethyl) aniline,
4- (4- (2,4,6-Triperfluorobutylsulfonylphenylazoxy) naphthylazoxy) -N-ethyl-N- (2-hydroxyethyl) aniline, 4- (4- (4-perfluorobutylsulfonyl) Phenylazomethine) Phenylazomethine) -N-ethyl-N- (2-hydroxyethyl) aniline, 4-
(4- (4-perfluorobutylsulfonylphenylazomethine) -1-naphthylazomethine) -N-ethyl-N- (2-hydroxyethyl) aniline and the like can be mentioned.

[0021]

[Chemical 3]

[0022]

[Chemical 4]

The structure exhibiting the main function of the nonlinear optical material of the present invention is a compound represented by the general formula [1]. The existence form of this compound in the nonlinear optical material is represented by the general formula (1) [1] A single compound represented by the formula [1], a mixture of two or more compounds, or a composition containing a derivative of these compounds in a polymer, (2) the above general formula
[1] A polymer compound containing a compound in the molecule (that is, a general formula [1] bond / coordination polymer), (3) a mixture of two or more kinds of general formula [1] bond / coordination polymers, or One or more general formulas [1] binding / coordinating polymers and other ones
Any of a mixture of two or more kinds of general polymers (polymer blend or polymer alloy) or (4) each polymer composition or an inorganic / organic compound blended composition containing a polymer compound may be used. Each of these substances is generically referred to as the general formula [1] substance as described above.

In the above, the general formula [1] bond / coordination polymer represents a polymer compound in which the compound of the general formula [1] is bonded or coordinated to a polymer chain. Here, “bonded or coordinated to a polymer chain” means that the molecule of the general formula [1] is
A state in which the main chain is constituted as it is or by linking with other skeleton molecules, forms a part of the main chain as a crosslinking unit or a terminal unit, or is linked as a side chain to a main chain composed of another skeleton molecule. , Or a state in which it is bound to a ligand existing in the main chain or side chain composed of another skeletal molecule by a coordination bond. In other words, the polymer is represented by the general formula [] by such a bond or coordination. 1] It means a state functionalized into a binding / coordinating polymer.

The “bond” in the above includes a covalent bond and an ionic bond, and the “coordination” includes a coordinate bond and a coordinated ionic bond. General formula of side chain bond type
[1] Among the binding / coordinating polymers, in addition to the compound of the general formula [1] directly bound to the polymeric compound or its side chain, the compound of the general formula and the general formula
[1] A compound bound thereto is also included.

In the above-mentioned "inorganic / organic compound mixture composition containing each polymer compound", a solution of each polymer compound in an inorganic / organic solvent or a dispersion liquid in an inorganic / organic medium is also included. included.

Further, the "non-linear optical material in which one or more compounds represented by the general formula [1] or their derivatives are dissolved or dispersed in a polymeric substance" of the present invention means
[1] A composition in which a compound is dissolved or dispersed in a polymer substance (hereinafter, abbreviated as a polymer composition containing general formula [1]) is subjected to an electric field orientation treatment to exhibit nonlinear optical characteristics. An optical material that has a general formula
[1] The presence state of the compound in the polymer substance can be varied from the state where the compound of the general formula [1] is uniformly dissolved in the polymer substance, to the state where it is partially dissolved and the state where it is completely dispersed. Up to various dissolved / dispersed states.
Further, in the “dispersion”, a large number of microscopic particles of the compound of the general formula [1] are dispersed in an island / sea state in a matrix of a polymer substance, and thus a powder of the compound of the general formula [1] is obtained. , Various compositions are included, such as those in which the gap between particle aggregates such as microplates is filled with a polymer substance and the compound of the general formula [1] is bound to the grain boundary by the polymer substance.

Examples of the polymer compound as a main agent of the polymer substance in the polymer composition containing the above-mentioned general formula [1] include polyethylene, polypropylene, polyisoprene, polybutadiene, poly-4-methylpentene-1 (PM
P) and other polyolefins; polyacrylate, polymethylmethacrylate, polyglycidylmethylmethacrylate and other acrylic / methacrylic resins; polyvinyl alcohol, polyvinyl butyral, polyvinyl acetate, polyethylene vinyl acetate (EVA), polyvinyl chloride, polyvinyl chloride, poly Vinyl-based polymers such as vinylidene chloride and polyvinylcarbazole; polystyrene, poly (4-
Methylstyrene), poly (2-methylstyrene), poly (4-acetylstyrene), poly (4-chlorostyrene),
Styrene-based polymers such as ABS resin and AS resin; polyethylene terephthalate, polybutylene terephthalate,
Polyesters such as polyethylene naphthalene dicarboxylate, polyethylene adipate; bisphenol A
Polycarbonates such as carbonates (carbonate resins), poly-diethylene glycol bisallyl carbonate (CR-39), polydiethoxycarbonylethylene;
Amorphous polyarylate such as bisphenol tere / isophthalate; polyethylene oxide, polyoxytetramethylene, polyoxymethylene, polyoxy-2,6-dimethyl
Polyether polymer such as -1,4-phenylene (PP0 or modified PPE); polyamide such as nylon 6, nylon 66, nylon 3, nylon 46, nylon 56, nylon 62, nylon 6-12; poly-P- Aramides such as phenylene amide; PVF, PVDF, PFE, FE
Fluorine resins such as P, PFA and ETFE; cellulose-based polymers such as ethyl cellulose, cellulose diacetate and cellulose triacetate, or urethane resins, epoxy resins, unsaturated polyester resins, thermosetting resins such as silicone resins and polyimides, or polymers thereof. Block and / or random copolymers containing one or more structural units of the above, and mixtures (polymer blends or polymer alloys) containing two or more of these polymer compounds.

The molecular weight of the above polymer is M _W 3,000 -1,00
It is recommended that it be around 0,000. Of these, M _W 5,000-
100,000 is particularly preferred. Among the above polymers, highly transparent acrylic / methacrylic resin, polystyrene, carbonate resin, PMP, CR-39, polyvinyl alcohol, polyvinyl butyral, polyvinyl acetate, EV
Particularly preferred are A, epoxy resin, urethane resin and the like. Also, transparent modified engineering plastics such as transparent ABS, transparent nylon, and transparent modified copolyester resin, and photocurable resin / photosensitive resin (radical polymerization type acrylate system, photoaddition polymerization type polyol / polyene system, etc.) ) And transparent functional resins such as ethylenically unsaturated carboxylic acid ionomers can also be suitably applied. The molecular weight in these examples, M _W 5,000 to 100,000 are preferred.

The ratio of the compound of the general formula [1] to the polymer is not particularly limited, but the content of the compound of the general formula [1] is 0.2 to 95% by weight based on the polymer. Is preferred. When the content of the compound of the general formula [1] is less than 0.2% by weight, the absorption coefficient of light becomes small and the problem that the nonlinear optical susceptibility is lowered occurs. When used in a state where at least one surface of the thin film is not protected by a substrate, an electrode plate or the like, the upper limit of the content of the compound of the general formula [1] is preferably 50% by weight. The reason is,
When the content of the compound of the general formula [1] is more than 50% by weight,
This is because there arises a problem that the mechanical strength of the obtained thin film becomes small.

As the compound other than the polymer compound of the polymer substance in the polymer composition containing the general formula [1], various conventionally known polymer additives can be compounded.
Addition of a light stabilizer such as benzotriazole, benzophenone, salicylic acid ester, etc. is extremely effective in improving the light resistance and weather resistance. Generally, the content of these additives is 0.5 to 15% by weight, preferably 2 to 10% by weight, based on the nonlinear optical material.

Suitable examples of the polymer composition containing the general formula [1] include compounds [3] to [8] and polymethyl acrylate, polymethyl methacrylate, polyglycidyl methacrylate, and two or more kinds of these resins. Examples thereof include a composition including a copolymer containing the structural unit of, a polycarbonate, a polymer material such as a transparency-modifying type polyurethane resin or an epoxy resin.

In the case of the binding / coordination polymer of the general formula [1], since the compound of the general formula [1] is contained in a part of the main chain or side chain of the polymer, the content of the non-linear component is It is possible to improve and obtain a system having a large nonlinear optical constant. In this case, the content of the compound of the general formula [1] is preferably 20 to 80% by weight. Examples of preferable skeletal polymers that carry the compound of the general formula [1] include polyacrylate / methacrylate-based, polyester-based, polyamide-based, and polyurethane-based polymers.

The "composition comprising a general formula [1] bond / coordination polymer" of the present invention means a mixture / mixture, a laminate or a composite containing the general formula [1] bond / coordination polymer. It means all compositions such as objects. For example, as a suitable example thereof, (1)
General formula [1] Bond / coordination polymer simple substance, (2) Two or more kinds of general formula [1] Mixture of bond / coordination polymers (polymer blend or polymer alloy), (3) General formula [1] Bond /
Mixture of coordination polymer and ordinary polymer (polymer blend or polymer alloy), or (4) general formula
[1] Compounding of binding / coordinating polymer with general formula [1] compound, general inorganic / organic compound, various polymer compounding agents containing these compounds or various polymer compounding materials such as reinforcing materials and fillers. Mixture / mixture such as mixture or these (1)-
Two or more types of formulations / mixtures of each formulation / mixture such as (4) are included.

As a preferable example of the general formula [1] binding / coordination polymer, a compound 4- (4- (4-perfluorobutylsulfonylphenylazo) phenylazo) -N-ethyl-N- (2-hydroxy) Ethyl) aniline, 4- (4- (2,4-diperfluorobutylsulfonylphenylazo) phenylazo) -N-ethyl-N- (2-hydroxyethyl) aniline or 4- (4-
(2,4,6-Triperfluorobutylsulfonylphenylazo) phenylazo) -N-ethyl-N- (2-hydroxyethyl)
A copolymer represented by the general formula [9], which is a copolymer of methacrylic acid ester in a form in which the hydroxyl group of N-ethyl-N- (2-hydroxyethyl) amino group of aniline is condensed with methacrylic acid, and methyl methacrylate. Polymerized methacrylic resin (wherein the ester side chain group R ₁₃ is a group represented by side chains [10] to [12] respectively), compounds [3], [4] or
[5] N-ethyl-N- (2-hydroxyethyl) is represented by the general formula [13], which is a copolymer of methacrylic acid ester and methyl methacrylate in which the hydroxyl group of amino group is condensed with methacrylic acid. Copolymerized methacrylic resin (wherein the ester side chain group R ₁₄ is a group represented by side chains [14] to [16] respectively), compounds [6], [7] or
[8] N-ethyl-N- (2-hydroxyethyl) is represented by the general formula [17], which is a copolymer of methacrylic acid ester and methyl methacrylate in which the hydroxyl group of the amino group is condensed with methacrylic acid. Copolymerized methacrylic resin (wherein the esterified side chain group R ₁₅ is a group represented by side chains [18] to [20] respectively), compounds [6], [7] or
[8] Copolymerization of methacrylic acid ester in the form of condensation of N-ethyl-N- (2-hydroxyethyl) amino group hydroxyl groups with methacrylic acid in a compound in which each ethyl group is replaced with a methyl group, and methyl methacrylate Generalized formula [2
1] (wherein the ester side chain group R ₁₆ is a group represented by side chains [22] to [24] respectively), 4- (4- (4- Hydroxymethylene perfluorobutyl sulfonyl phenylazo) -1-naphthylazo) -N-ethyl-N- (2-hydroxyethyl) aniline Dimethacrylate ester and trimethylolpropane in the form of condensation of methacrylic acid with hydroxyl groups at both ends Copolymerized acrylic / methacrylic resin represented by the general formula [25], which is a copolymer with triacrylate (wherein ₁ R ₁ is a constituent main chain unit [26] of the copolymer.), 4- ( 4- (4-Hydroxymethylene perfluorobutylsulfonylphenylazo) -1-naphthylazo) -N-ethyl-N- (2-hydroxyethyl) general formula obtained by curing reaction of aniline and isocyanate resin (polyisocyanate) [ 27] Crosslink Polyisocyanate (wherein ₂ R ₂ is a resin crosslinking group [28].) Polymeric substances, such as are exemplified.

[0036]

[Chemical 5]

[0037]

[Chemical 6]

[0038]

[Chemical 7]

[0039]

[Chemical 8]

[0040]

[Chemical 9]

[0041]

[Chemical 10]

The non-linear optical material of the present invention can be used as a non-linear optical waveguide element as it is, or can be formed into a film-like state in which it is coated on a flat surface of a substrate or the like. The expression "made of a non-linear optical material" in the present invention means that the film is formed by using this non-linear optical material. This means a step of forming a film of (1), forming a channel with other materials as necessary, and performing electric field orientation to form a nonlinear optical waveguide device.

The film made of the non-linear optical material thus molded is called a non-linear optical layer. Examples of the substrate of the above-mentioned nonlinear optical waveguide device include a Pyrex substrate, a graphite substrate, a MoS ₂ substrate, a KCl ₂ substrate, a NaCl substrate and the like. Of these, a quartz substrate, a Pyrex substrate, and a silicon substrate are particularly preferable. The thickness of the substrate is not particularly limited, but is preferably 0.1 mm or more. In particular, if the thickness of the substrate is less than 0.1 mm, the flatness of the substrate and desired strength cannot be obtained. The thickness of the nonlinear optical layer varies depending on the refractive index of the substrate, the refractive index of the nonlinear optical layer, the nonlinear susceptibility of the nonlinear optical layer, etc.
It is 0.1 to 5 μm. The thickness of the nonlinear optical layer is 0.1 μm
When the thickness is smaller, a problem that sufficient nonlinear optical characteristics cannot be obtained arises, and when the film thickness of the nonlinear optical layer is larger than 5 μm, there arises a problem that control of guided light becomes difficult. Of these, 0.3 to 2 μm is preferable.

To form a non-linear optical layer by forming the non-linear optical material on the above substrate, a spin coating method, a casting method, a dip coating method, a melt pressing method, a vapor deposition method, an L method
Known techniques such as the B film method and the epitaxial method can be used. When the nonlinear optical material does not contain a polymer, spin coating, casting, dip coating,
A vapor deposition method, an LB film method, or an epitaxial method can be used. Of these, the spin coating method is particularly preferable. General formula for spin coating, casting, and dip coating
[1] In the case of forming a non-linear optical layer of a containing polymer composition, the compound of the general formula [1] is added to acetone, methyl ethyl ketone, chloroform, methylene chloride, dioxane, DMF, DMA, pyridine, toluene, acetic acid. It is dissolved in an organic solvent such as ethyl, and this solution is applied onto a substrate. Of the above solvents, chloroform and methylene chloride are particularly preferable.

Generally, light can be propagated in the nonlinear optical layer of the above-mentioned nonlinear optical waveguide element, but a waveguide (clad) for confining light in the nonlinear optical layer may be further provided. The waveguide is a main medium when light propagates through the element, and it is necessary to select a material having a refractive index much smaller than that of the nonlinear optical layer as a material. Examples are glass, polycarbonate, polymethylmethacrylate, As ₂ S ₃ , As ₂ S ₅ , ZnO, LiTaO ₃ , LiTa.
O ₃ , Nb ₂ O ₅ , Ta ₂ O ₅ , and Si ₃ N ₄ are listed. this house,
Glass, polymethylmethacrylate and ZnO are particularly preferred. This waveguide can have a slab type, a channel type, or a ball type. Of these, the slab type and the channel type are particularly preferable. The cross-sectional shape and length of the above waveguide is not particularly limited because it depends on the propagation loss and the refractive index of the waveguide, but in the case of the slab type, the thickness of the waveguide layer is 0.
The length is from 05 to 3 μm, and the length can be from 1 to 30 mm. In the case of the channel type, the distance between the channels is 2
It can be used at ~ 30 μm. Spin coating, vapor deposition, sputtering, CVD, ion exchange, ion implantation, and epitaxial methods can be used to produce the slab waveguide. An ion exchange method, a photolithography method, an etching method, a sputtering method, an ion implantation method, and an epitaxial method can be used for producing the channel waveguide. Preferably, an etching method, an ion exchange method, and a photolithography method are used.

The nonlinear optical material used in the present invention is formed, for example, on the above-mentioned substrate and waveguide to form a nonlinear optical layer. The nonlinear optical layer is a layer that produces nonlinear optical characteristics when light propagates through the element. In the nonlinear optical waveguide device of the present invention, electrodes are appropriately provided on the upper and lower sides of the nonlinear optical layer for use. Various electric conductors are recommended for the electrode, but ITO, gold, silver, chrome,
Aluminum can be used.

The non-linear optical layer is formed of the non-linear optical material made of the substance of the general formula [1], but may include other known organic non-linear optical materials. Examples of these known organic nonlinear optical materials include polydiacetylene derivatives, polyphenylene vinylene derivatives, polyaniline derivatives, polythiophene derivatives, polydiyne derivatives,
Examples thereof include polypyrrole derivatives and phthalocyanine derivatives.

The nonlinear optical waveguide device of the present invention is a linear type,
Various types of Y-branch type, directional coupling type, Mach-Cendar interference type, Fabry-Perot resonator type, and polarization inversion SHG elements can be used. When the guided light is excited in the nonlinear optical layer of the present invention, methods such as an end face coupling method, a prism coupling method, a grating coupling method, a holographic coupling method, and a taper coupling method can be used.

[0049]

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

Example 1 Compound [3], compound [4] and compound [5] were synthesized. The compound [3] was synthesized as follows. Further, the synthesis of the compound [4] and the compound [5] was in accordance with this. A nonlinear optical layer (thin film) made of a compound of the general formula [1] obtained by dissolving the compound of the general formula [1] in a polymer substance was formed, its nonlinear optical characteristics were measured, and it was used as a nonlinear optical material. A nonlinear optical waveguide device was produced and the device performance was evaluated.

Synthesis of Compound [3] Hydrochloric acid was added to 4- (4-perfluorobutylsulfonylphenylazo) -1-naphthylamine in an acetone-ethanol-water mixed solvent. This solution was cooled to 0 to 5 ° C, an aqueous sodium nitrite solution was added, and the mixture was stirred at the same temperature for 6 hours. Then, an acetone solution of N-ethyl-N-hydroxyaniline was added. The mixture was stirred at room temperature overnight. After the reaction, this reaction mixture was extracted with dichloromethane, the product was purified with a silica gel column, and the compound [3]
Got The synthetic process of this compound is represented by the reaction formula [1].

[0052]

[Chemical 11]

The compound was obtained from the above synthesis in a yield of 10%. When this compound was identified, 19F NM
R absorption spectrum measurement (CDCl ₃ , ext. CF ₃ CO
Than OH), δ - 2.02 (t , J = 9.9 H Z, 3
F), - 32.7 (t, J = 13.7H Z, 2F), - 42.0
(S, 2F), - 47.2 (t, J = 13.7H Z, 2F) results were obtained also from EIMS measurement, (70 eV) m /
_Z (rel intensitiy) 705 (M +, 6), 391 (100
), 196 (30), 133 (76), and it was confirmed that the desired compound [3] was synthesized. This compound [3] had a characteristic band of λ _max of 558 nm in ethanol and a characteristic band of λ _max of 534 nm in hexane as measured by IR absorption spectrum.

Film Formation of Non-Linear Optical Layer The film formation is made of polymethylmethacrylate (PMMA) and a compound.
The chloroform solution of [3] was dropped on a glass substrate to form a thin film by spin coating. As a result, PM
Table 1 shows the molar ratio of MA to the compound [3] and the film thickness of the thin film obtained by measurement with a stylus type film thickness meter (Dectac 3030 manufactured by Sloan).

[0055]

[Table 1]

Measurement of Nonlinear Optical Properties of Nonlinear Optical Layer Using the corona discharge device as shown in FIG.
While heating at 110 ° C., an electric field orientation treatment was performed by applying a critical voltage below the discharge voltage, that is, an electric field of 10 kV / cm 2 for 2 minutes. After that, the heating was stopped and allowed to cool, and the application of the electric field was continued until the temperature reached 30 ° C. After the electric field was cut off, the sample was taken out and the nonlinear optical constant (d ₃₃ ) was measured. In FIG. 1, 1 is a corona discharger (here, used as a tip-shaped voltage load electrode),
Reference numeral 2 is a sample for measurement, 3 is a temperature control sample table having a plate electrode on the surface, and 4 is a high voltage power source. The rotating maker fringe method was used to evaluate the nonlinear optical properties of the obtained thin films. A polarized beam of Q-switched Nd: YAG laser (wavelength: 1.064 μm) was focused on the sample. The resulting second harmonic was spectrally detected and detected by a photomultiplier tube. The average output obtained from the boxcar integrator is
It was calculated by computer as a function of the angle of incidence of the incident beam on the sample.

[0057]

[Table 2]

Production of Nonlinear Optical Waveguide Element (Slab Type Optical Waveguide Element) and Evaluation of Element Performance A Y-cut quartz plate (d ₁₁ = 0.33 pm / V) was used as a reference sample. As a result, the value of the second-order nonlinear optical constant d ₃₃ of Samples 1 to 4 and the wavelength of 1.064 μm in the slab type optical waveguide
Table 2 shows the propagation loss values at. After that, sample 2 in this
Samples prepared under the same conditions as above were left at 50 ° C. and 80 ° C., and the nonlinear optical characteristics were measured by the above-mentioned rotational maker fringe method every arbitrary time. The results are shown in FIGS. 2 and 3, respectively, where the nonlinear optical constant at 0 hours is 1. Figure 2 is a graph showing changes with time of the nonlinear optical constant d ₃₃ at 50 ° C. of the samples, FIG. 3 is a graph showing changes with time of the nonlinear optical constant d ₃₃ at 80 ° C. of the same sample.
In FIG. 2 and FIG. 3, the samples are indicated by using the following symbols. ■; Example 1 sample 2 (compound [3]), ●; Comparative example 1 sample 2 (DR-1) At 50 ° C., the nonlinear optical constant (d ₃₃ ) is about 75% of 0 hours even after 10,000 hours. Indicates. Even at 80 ° C., the nonlinear optical constant (d ₃₃ ) shows 50% of 0 hours after 10,000 hours.

Preparation of Nonlinear Optical Waveguide Element (Channel Type Optical Waveguide Element) Next, the compound [3] and PMMA were mixed at 10: 100 on a silicon substrate provided with a gold electrode and an underclad layer (Si0 ₂ ).
A chloroform solution mixed at a molar ratio of was added dropwise to form a thin film by a spin coating method (film thickness: 4 μm). The surface of this thin film was coated with a thin layer of epoxy resin by spin coating. Further, a gold electrode was provided on a required portion above the gold electrode. Heat the substrate to 110 ° C and place 1 between the upper and lower gold electrodes.
An electric field of MV / cm 2 was applied for 2 minutes to orient the compound [3]. The mixture was allowed to cool to 30 ° C and the electric field was cut off. Then, after removing the upper gold electrode, a positive resist was applied and photolithography was performed using a mask having a required waveguide pattern. After that, RIE was performed using O ₂ using the resist as a mask, and the polymer portion was etched leaving the optical waveguide portion. After that, the resist was removed using a stripping solution. An epoxy resin was applied to the entire surface to form an outer clad. Next, a gold electrode for driving the device was formed on the upper part of the optical waveguide portion by photolithography to form a Mach-Cender interference type optical device including a channel type waveguide. After forming the element, the element was separated and the end face of the optical waveguide was optically polished. The width of the waveguide was 5 μm and the length was 20 mm. The structure of the obtained optical waveguide device is shown in FIG. FIG. 4 is a perspective view of the Mach-Cender interference type optical device.
Reference numeral 5 denotes an outer clad for partitioning the optical waveguide (made of a resin material or the like whose refractive index is distinctly different from that of the waveguide material), 6
Is a flat plate type upper electrode provided on the upper layer of one of the optical waveguide branches (electric field load path), and 7 is a nonlinear optical waveguide made of the nonlinear optical material of the present invention, and has two branches, that is, an electric field load path and a non-electric field path. And are connected to the input optical path and the output optical path at both ends. 8 is input light incident on the input optical path, 9 is a substrate having a lower electrode laminated on the surface, 10
Is a lower electrode laminated between the substrate and the underclad layer, 11 is an underclad layer coated on the upper layer of the lower electrode, and 12 is output light emitted from the output optical path to the outside of the system. By applying an electric field to the upper electrode and the lower electrode of this Mach-Cendar interferometer type optical element and injecting light into the input optical path, a phase difference occurs in the light wave between the electric field load path and the non-electric field path, and the output light Phase modulated light in which interference light is mixed with is obtained.

Evaluation of Device Characteristics of Nonlinear Optical Waveguide Device (Channel Type Optical Waveguide Device) As a result of exciting light having an oscillation wavelength (0.63 μm) of a He—Ne laser by the end face coupling method using this optical waveguide device, about 3 V was obtained. A half-wave voltage of was obtained. The electro-optical constant is
It was a value of 64 pm/V. Moreover, it showed very excellent optical modulation characteristics, and the extinction ratio was 25 dB.

The compound [4] or the compound [5]
Was used in an amount of 10 mol per 100 mol of PMMA, and a Mach-Cendar interferometer type optical device was prepared and measured in the same manner as in the case of using the compound [3]. Optical constants are 60 pm / V and 58 respectively
It was pm / V. Moreover, these devices showed very excellent optical modulation characteristics, and the extinction ratio was 22 dB in all cases.

Comparative Example 1 Film Formation of Nonlinear Optical Layer and Measurement of Its Nonlinear Optical Properties [Preparation of Nonlinear Optical Waveguide Element (Slab Waveguide Element) and Evaluation of Element Performance] As a comparative example of a nonlinear optical material, Aldrich Chmical Compan
Using Disperse Red 1 (DR-1) manufactured by y Inc.
A DR-1 / PMMA chloroform solution was prepared in the same manner as in Example 1, and a thin film was formed on a glass substrate by spin coating. Table 3 shows the molar ratio of PMMA to DR-1 and the thickness of the obtained thin film measured by a stylus type film thickness meter (Dectac 3030 manufactured by Sloan).

[0063]

[Table 3]

These samples were placed in the corona discharge device shown in FIG. 1, the substrate was heated to 110 ° C., and a voltage of 10 kV / cm 2 was applied.
It was applied for a minute. After that, the sample was taken out by cooling to 30 ° C., cutting off the voltage application. Next, the nonlinear optical characteristics of this sample were measured using the rotating maker fringe method. Polarized beam of Q-switched Nd: YAG laser (wavelength: 1.064
μm) was focused on the sample. The resulting second harmonic was spectrally detected and detected by a photomultiplier tube. The average power obtained from the boxcar integrator was calculated by the computer as a function of the angle of incidence of the incident beam on the sample. A Y-cut quartz plate (d ₁₁ = 0.33 pm / V) was used as a reference sample. As a result, the values of the second-order nonlinear optical constants d ₃₃ of Samples 1 and 2 in which the film could be formed and the propagation loss value at the wavelength of 1.064 μm in the slab type optical waveguide are shown in Table 4.
Shown in.

[0065]

[Table 4]

Compared with the first embodiment, the nonlinear optical constant is small and the propagation loss is large. After that, 50 samples prepared under the same conditions as this sample 2
The sample was left at 80 ° C. and 80 ° C., and the non-linear optical characteristics were measured by the rotation maker fringe method every arbitrary time. The results are shown in FIGS. 2 and 3 with the nonlinear optical constant at 0 hours being 1. In the case of 50 ° C., the nonlinear optical constant (d ₃₃ ) became 20% of 0 hours after 10,000 hours, and in the case of 80 ° C., the nonlinear optical characteristic became unmeasurable after 50 hours. In both cases, the degree of decrease is greater than in the case of Example 1.

Fabrication of Nonlinear Optical Waveguide Element (Channel Waveguide Element) Next, DR-1 and PMMA were prepared in a molar ratio of 10: 100 on a silicon substrate provided with a gold electrode and an underclad layer (SiO ₂ ). A chloroform solution of the mixture was spin-coated to form a thin film (film thickness: 4 μm). Next, an epoxy resin was formed on the surface of the polymer film by spin coating. Further, a gold electrode was provided on a required portion above the gold electrode.
The substrate is heated to 110 ℃ and 1MV / c between the upper and lower gold electrodes.
An electric field of m 2 was applied for 2 minutes to perform DR-1 alignment treatment.
It was allowed to cool to 30 ° C and the electric field was cut off. Then, after removing the upper gold electrode, a positive resist was applied and photolithography was performed using a mask having a required waveguide pattern. After that, RIE was performed using O ₂ using the resist as a mask, and the polymer portion was etched leaving the optical waveguide portion. After that, the resist was removed using a stripping solution. An epoxy resin was applied to the entire surface to form an outer clad. Next, a gold electrode for driving the device was formed on the upper part of the optical waveguide portion by photolithography to form a Mach-Cender interference type optical device including a channel type waveguide. This element was separated and the end face of the optical waveguide was optically polished. The width of the waveguide was 5 μm and the length was 20 mm. The obtained optical waveguide device is the structure shown in FIG.

Evaluation of Device Characteristics of Nonlinear Optical Waveguide Device (Channel Waveguide Device) As a result of exciting the light of the oscillation wavelength (0.63 μm) of the He—Ne laser by the end face coupling method, a half-wave voltage of about 3 V was obtained. It was The electro-optic constant was 42 pm / V. Also,
It exhibited light modulation characteristics and the extinction ratio was 5 dB. Each value was inferior to that of Example 1.

Example 2 Compound [6], compound [7] and compound [8] were synthesized. The compound [6] was synthesized as follows. Moreover, the synthesis of the compound [7] and the compound [8] was in accordance with this. A nonlinear optical layer (thin film) made of a compound of the general formula [1] obtained by dissolving the compound of the general formula [1] in a polymer substance was formed, its nonlinear optical characteristics were measured, and it was used as a nonlinear optical material. A nonlinear optical waveguide device was produced and the device performance was evaluated.

Synthesis of Compound [6] Hydrochloric acid was added to 4- (4-perfluorobutylsulfonylphenylazo) -2,6-diethylaniline in an acetone / ethanol / water mixed solvent. This solution was cooled to 0 to 5 ° C, an aqueous sodium nitrite solution was added, and the mixture was stirred at the same temperature for 6 hours. Then, an acetone solution of N-ethyl-N-hydroxyaniline was added. The mixture was stirred at room temperature overnight. After the reaction, this reaction mixture was extracted with dichloromethane, and the product was purified by a silica gel column to obtain the target compound equivalent in a yield of 15%. When this compound was identified, MS (70 eV) m / z (re
l intensity) 711 (M +, 56), 696 (64), 412
The results of (85), 179 (56), 133 (100) and 76 (97) were obtained, and it was confirmed that the desired compound [6] was synthesized. This compound [6] has λ _max in ethanol
426 nm, λ _max in hexane was 413 nm.

Film Formation of Non-Linear Optical Layer and Measurement of Non-Linear Optical Properties [Preparation of Non-Linear Optical Waveguide Element (Slab Waveguide Element) and Evaluation of Element Performance] Film formation of the present compound is a compound of polycarbonate (PC) and compound.
The chloroform solution of [6] was dropped on a glass substrate and a thin film was formed by spin coating. At this time, the molar ratio of PC to the compound [6] and the stylus type film thickness meter (Sloan
Table 5 shows the film thickness of the obtained thin film measured by Dectac 3030 manufactured by the same company.

[0072]

[Table 5]

The sample thus obtained was heated to 150 ° C. using a corona discharge device as shown in FIG. 1, and a critical voltage below the discharge voltage, that is, an electric field of 10 kV / cm 2 was applied for 2 minutes. . After that, the heating was stopped and allowed to cool, and the application of the electric field was continued until the temperature reached 30 ° C. After cutting the electric field, the sample is taken out and the non-linear optical constant (d ₃₃ ) is obtained by using the rotating maker fringe method.
Was measured. A polarized beam of Q-switched Nd: YAG laser (wavelength: 1.064 μm) was focused on the sample. The resulting second harmonic was spectrally detected and detected by a photomultiplier tube.

[0074]

[Table 6]

The average power obtained from the boxcar integrator was calculated by the computer as a function of the angle of incidence of the incident beam on the sample. Y-cut quartz plate (d ₁₁ =
0.33 pm / V) was used as a reference sample. As a result, Table 6 shows the values of the second-order nonlinear optical constants d ₃₃ of Samples 1 to 4 and the propagation loss value at the wavelength of 1.064 μm in the slab type optical waveguide. Then, the sample 2 therein was left at 80 ° C., and the non-linear optical characteristics were measured at every arbitrary time by the rotation maker fringe method. The result is shown in FIG. 5 assuming that the nonlinear optical constant at 0 hours is 1. FIG. 5 is a graph showing the change over time of the nonlinear optical constant d ₃₃ of the above sample at 80 ° C. FIG. 5
In the above, the samples are represented by using the following symbols. ■; Example 2 sample 2 (compound [6]), ●; Comparative example 2 sample 2 (DR-1) When left at 80 ° C., the nonlinear optical constant (d ₃₃ ) after 10,000 hours was approximately 0 hour. Indicates 70%.

Further, the compound [7], the compound [8] and PC
From a mixture of 10: 100 molar ratio of the compound [6]
When the nonlinear optical constant d ₃₃ was measured in the same manner as in the case of using, the values were 67 pm / V and 64 pm / V, respectively, and the propagation losses were 4.0 dB / cm and 3.9 dB / cm, respectively.

Comparative Example 2 Film Formation of Nonlinear Optical Layer and Measurement of Nonlinear Optical Properties [Preparation of Nonlinear Optical Waveguide Device (Slab Waveguide Device) and Evaluation of Device Performance] As a comparative example, Disperse Red 1 manufactured by Aldrich Chmical Company Inc. Using (DR-1), a solution of PC: DR-1 chloroform was prepared in the same manner as in Example 2, and a thin film was formed on the glass substrate by spin coating. At this time P
Table 7 shows the molar ratio of C to DR-1 and the thickness of the obtained thin film measured by a stylus type film thickness meter (Dectac 3030 manufactured by Sloan).

[0078]

[Table 7]

These samples were placed in the corona discharge device shown in FIG. 1, the substrate was heated to 150 ° C., and a voltage of 10 kV / cm 2 was applied.
It was applied for a minute. After that, the sample was taken out by cooling to 30 ° C., cutting off the voltage application. Next, the non-linear optical characteristics of this sample were measured using the rotational maker fringe method. Polarized beam of Q-switched Nd: YAG laser (wavelength: 1.06
4 μm) was focused on the sample. The resulting second harmonic was spectrally detected and detected by a photomultiplier tube. The average power obtained from the boxcar integrator was calculated by the computer as a function of the angle of incidence of the incident beam on the sample. A Y-cut quartz plate (d ₁₁ = 0.33 pm / V) was used as a reference sample. As a result, the value of the second-order nonlinear optical constant d ₃₃ of Samples 1 and 2 and the wavelength of the slab type optical waveguide
Table 8 shows the propagation loss values at 1.064 μm.

[0080]

[Table 8]

At this time, the nonlinear optical constant is smaller than that in the second embodiment. Thereafter, Sample 2 among them was left at 80 ° C., and the non-linear optical characteristic was measured by the rotation maker fringe method every arbitrary time. The result is shown in FIG. 5 assuming that the nonlinear optical constant at 0 hours is 1. When left at 80 ° C, the nonlinear optical characteristic becomes about 5% after 10,000 hours.
Almost no longer observable.

Example 3 Three kinds each having a side chain [10], a side chain [11] and a side chain [12] as a functional side chain R ₁₃ in a methacrylic polymer chain represented by the general formula [9] Polymer compounds (each side chain
Polymer having general formula [9], [10], side chain [11]
The polymer compound having the general formula [9] and having a side chain [12] is referred to as the polymer compound having the general formula [9]. The same applies hereinafter) was synthesized. The polymer compound of the general formula [9] having a side chain [10] was synthesized as follows. The general formula [9] polymer compound having a side chain [11] and the general formula [9] polymer compound having a side chain [12] were synthesized according to this. Nonlinear optical waveguide devices using these general formula [1] binding / coordinating polymers as nonlinear optical materials were fabricated and the device performance was evaluated.

Synthesis of general formula [9] polymer compound having side chain [10] First, methacrylic acid chloride and (N-ethyl) anilino
-2-Ethanol was reacted in dry tetrahydrofuran in the presence of triethylamine at room temperature for 24 hours.
After the reaction, the reaction mixture is mixed with water, the reaction product is extracted with diethyl ether, further purified by a silica gel column,
Compound [29] was obtained. Next, this compound [29] is mixed with methyl methacrylate in a ratio of j: k = 10: 100, and azobisisobutylnitrile corresponding to 0.1 mol% of these is mixed, and dissolved oxygen is frozen-deaerated-dissolved. Was removed by repeating the above procedure, and the mixture was sealed in an ampoule and polymerized at 65 ° C. for 24 hours. After the reaction, the polymer was dissolved in chloroform and purified by reprecipitation with methanol to obtain a compound [30]. 4- (4-perfluorobutylsulfonylphenylazo) -1-aniline is dissolved in acetic acid by heating,
It was cooled below 10 ° C. Next, sodium nitrite was gradually added to sulfuric acid so as not to generate heat and dissolved. This is 4- (4-
It was added dropwise to an acetic acid solution of perfluorobutylsulfonylphenylazo) -1-aniline, taking care that the liquid temperature did not exceed 10 ° C. Then, cool the reaction mixture to below 10 ℃, dissolve potassium hexafluorophosphate in a small amount of water and add.
Stir for about 15 minutes. The deposited precipitate was collected with a glass filter and washed with a small amount of acetic acid to obtain a compound [31]. Further, sodium acetate was added to these compound [30] and compound [31], and they were reacted at room temperature for 24 hours. The reaction mixture was added to methanol, and the target polymer compound equivalent product was obtained by the reprecipitation method. When this compound was identified in the same manner as in Example 1, it was confirmed that the desired polymer compound ([9]: [10]) having a side chain [10] was certainly obtained. This synthetic process is represented by chemical formulas as shown in the following reaction formulas [2] to [5].

[0084]

[Chemical 12]

Preparation of Nonlinear Optical Waveguide Element (Channel Waveguide Element) A chloroform solution of this compound (j: k = 10: 100) was spun on a silicon substrate provided with a gold electrode and an underclad layer (SiO ₂ ). Coated and thinned (film thickness: 4 μm
). Next, an epoxy resin was formed on the surface of the polymer film by spin coating. Further, a gold electrode was provided on a necessary portion above the gold electrode. The substrate was heated to 140 ° C. and an electric field of 1 MV / cm 2 was applied between the upper and lower gold electrodes for 2 minutes to orient the polymer compound. It was allowed to cool to 30 ° C and the electric field was cut off. After removing the upper gold electrode, a positive resist was applied and photolithography was performed using a mask having a required waveguide pattern. After that, RIE was performed using O ₂ using the resist as a mask, and the polymer portion was etched leaving the optical waveguide portion. After that, the resist was removed using a stripping solution. An epoxy resin was applied to the entire surface to form an outer clad. Next, a gold electrode for driving the device was formed on the upper part of the optical waveguide portion by photolithography to form a Mach-Cender interference type optical device including a channel type waveguide. This element was separated and the end face of the optical waveguide was optically polished. The width of the waveguide is 5 μm and the length is 20 m
It was m. The optical waveguide device thus obtained is the structure shown in FIG.

Element Performance Evaluation of Nonlinear Optical Waveguide Element (Channel Waveguide Element) Using this element, the oscillation wavelength of He--Ne laser (0.63 μm
As a result of exciting the light of m) by the end face coupling method, about 3.5 V
A half-wave voltage of was obtained. The electro-optical constant was 61 pm / V. In addition, it showed very good optical modulation characteristics and the erasure ratio was 24 dB. Similarly, the side chain of j: k = 10: 100
A polymer compound having [11] and a polymer compound having a side chain [12] were synthesized to fabricate a Mach-Cender interference type optical device. Oscillation wavelength of He-Ne laser (0.63 μm
The light was excited by the end-face coupling method, and the electro-optic constants were 57 pm / V and 54 pm / V, respectively. The erasing ratios were all excellent at 24 dB.

Comparative Example 3 A polymer compound having a side chain [33] as a functional side chain R ₁₇ on a methacrylic polymer chain represented by the following general formula [32] was synthesized. Nonlinear optical waveguide devices were manufactured using these general formula [1] binding / coordination polymers by using nonlinear optical materials, and the device performance was evaluated.

[0088]

[Chemical 13]

Synthesis of General Formula [32] Polymer Compound Having Side Chain [33] First, a compound [30] was obtained in the same manner as in Example 3. next,
4- (4-Nitrophenylazo) -1-aniline was dissolved in acetic acid by heating and further cooled to 10 ° C or lower. Next, sodium nitrite was gradually added to sulfuric acid so as not to generate heat and dissolved. This was added dropwise to the acetic acid solution of 4- (4-nitrophenylazo) -1-aniline while being careful not to let the liquid temperature exceed 10 ° C. Next, the reaction liquid was cooled to 10 ° C. or lower, potassium hexafluorophosphate was dissolved in a small amount of water and added, and the mixture was stirred for about 15 minutes. The deposited precipitate was collected with a glass filter and washed with a small amount of acetic acid to obtain a compound [34]. Furthermore, sodium acetate was added to the compound [30] and the compound [34], and they were reacted at room temperature for 24 hours. After the reaction, the reaction mixture was added to methanol to obtain a target polymer compound equivalent product by the reprecipitation method. As a result of identifying this compound in the same manner as in Example 1, it was found that a polymer compound of the general formula [32] having a side chain [33] was certainly obtained.

Preparation of Nonlinear Optical Waveguide Element (Channel Type Waveguide Element) On a silicon substrate provided with a gold electrode and an underclad layer (SiO ₂ ), a solution of the above polymer (j: k = 10: 100) in chloroform was added. Is spin coated to form a thin film (film thickness: 4 μm
) Was formed into a film. Next, the surface of this thin film was coated with an epoxy resin by spin coating. Then, a gold electrode was provided on a necessary portion above the gold electrode. The substrate was heated to 140 ° C, an electric field of 1MV / cm was applied between the upper and lower gold electrodes for 2 minutes, the polymer compound was oriented, and allowed to cool to 30 ° C.
The electric field was cut off. Next, after removing the upper gold electrode,
A positive resist was applied, and photolithography was performed using a mask having a required waveguide pattern. After that, RIE was performed using O ₂ using the resist as a mask, and the polymer portion was etched leaving the optical waveguide portion. After that, the resist was removed using a stripping solution. An epoxy resin was applied to the entire surface to form an outer clad. Next, a gold electrode for driving the device was formed on the upper part of the optical waveguide portion by photolithography to form a Mach-Cender interference type optical device including a channel type waveguide. This element was separated and the end face of the optical waveguide was optically polished. The width of the waveguide is 5 μm and the length is
It was 20 mm. The obtained optical waveguide device is the structure shown in FIG.

Evaluation of Device Performance of Nonlinear Optical Waveguide Device (Channel Waveguide Device) As a result of exciting the light of the oscillation wavelength (0.63 μm) of the He—Ne laser by the end-face coupling method, a half-wave voltage of about 3.5 V was obtained. Was given. The electro-optic constant is a value of 40 pm / V.
Of about 2/3 or less. As the optical modulation characteristic, the erasing ratio was 16 dB. All of these values were inferior to those of Example 3.

Example 4 Preparation of Nonlinear Optical Waveguide Device (Channel Waveguide Device) and Evaluation of Device Performance 20 mol% of the compound [3] described in Example 1 was added to PMMA.
Add the mixed chloroform solution to the underclad layer (Si
O ₂ ) was dropped on a silicon substrate and made into a thin film by spin coating (film thickness: 4 μm). Next, the surface of the polymer film was thinly coated with an epoxy resin by a spin coating method. Further, a positive resist was applied on the upper portion, and photolithography was performed using a mask having a required waveguide pattern. After that, RIE was performed using O ₂ using the resist as a mask, and the polymer portion was etched leaving the optical waveguide portion. After that, the resist was removed using a stripping solution. Both end surfaces of the optical waveguide were optically polished, and aluminum was vacuum-deposited to form an optical bistable element structure. The width of the waveguide was 5 μ and the length was 20 mm. Y
Light of the oscillation wavelength of the AG laser (1.064 μm) was incident on the end face using a single-mode optical fiber, and the transmitted light intensity was observed as a function of the incident light intensity. As a result, a history phenomenon showing optical bistability at room temperature was confirmed. .

Comparative Example 4 The following compound [35] was synthesized. This synthesis was performed as follows. A nonlinear optical waveguide device was produced using this compound and the device performance was evaluated.

[0094]

[Chemical 14]

Synthesis of Compound [35] Hydrochloric acid was added to an acetone-ethanol-water solvent of 4- (4-nitrophenylazo) -1-naphthylamine, the solution was cooled to 0 to 5 ° C., and then an aqueous sodium nitrite solution was added. And add
The mixture was stirred at the same temperature for 6 hours. Then N-ethyl-N
-An acetone solution of hydroxyaniline was added. The mixture was stirred at room temperature overnight. After the reaction, this reaction mixture was extracted with dichloromethane, and the product was purified with a silica gel column to obtain the target compound equivalent. When this compound was identified, MS (70 eV) m / z (re
l intensity) 468 (M +, 38), 437 (100), 133
From the results of (54), it was confirmed that compound [35] was indeed synthesized. Also, λ _max is 55 in ethanol.
1 nm, λ _max in hexane was 521 nm.

Preparation of Nonlinear Optical Waveguide Element (Channel Waveguide Element) A chloroform solution prepared by mixing 20 mol% of the compound [35] obtained here into PMMA was used as an underclad layer (SiO ₂ ).
A thin film (film thickness: 4 μm) was formed on the silicon substrate provided with the spin coating method. Next, an epoxy resin was formed on the surface of the polymer film by spin coating. Further, a positive resist was applied on the upper portion, and photolithography was performed using a mask having a required waveguide pattern. After that, RI using 0 ₂ with the resist as a mask
E was performed, and the polymer portion was etched leaving the optical waveguide portion. After that, the resist was removed using a stripping solution.
Both end surfaces of the optical waveguide were optically polished, and aluminum was vacuum-deposited to form a light transmission stabilizing element structure. The width of the waveguide is 5μ
It was 20 m in length and 20 mm in length.

Evaluation of Device Performance of Nonlinear Optical Waveguide Device (Channel Waveguide Device) Light of oscillation wavelength (1.06 μm) of YAG laser is incident from the end face using a single mode optical fiber, and transmitted light intensity is a function of incident light intensity. As a result, although a hysteresis phenomenon showing optical bistability at room temperature was confirmed, the signal intensity was about 20% as compared with Example 4.

Example 5 Three kinds each having a side chain [14], a side chain [15] and a side chain [16] as a functional side chain R ₁₄ in a methacrylic polymer chain represented by the general formula [13] Was synthesized. Side chain
The polymer compound of the general formula [13] having [14] was synthesized as follows. The general formula [13] polymer compound having a side chain [15] and the general formula [13] polymer compound having a side chain [16] were synthesized according to this. Nonlinear optical waveguide devices were manufactured using these general formula [1] binding / coordination polymers as nonlinear optical materials, and the device performance was evaluated.

Synthesis of polymer compound of general formula [13] having side chain [14] First, a compound [30] was obtained in the same manner as in Example 3. Next, compound [30] is mixed with methyl methacrylate at a ratio of j: k = 20: 80, and azobisisobutylnitrile corresponding to 0.1 mol% of these is mixed, and dissolved oxygen is frozen-deaerated-dissolved. It was removed by repeating, and it was enclosed in an ampoule and polymerized at 65 ° C. for 24 hours. After the reaction, the polymer
Dissolved in chloroform, and purified by reprecipitation with methanol, compound ^[30], it was obtained. Next, 4- (4-perfluorobutylsulfonylphenylazo) -1-naphthylamine was dissolved in acetic acid by heating and further cooled to 10 ° C or lower.
Next, sodium nitrite was gradually added to sulfuric acid so as not to generate heat and dissolved. This was added dropwise to the acetic acid solution of 4- (4-perfluorobutylsulfonylphenylazo) -1-naphthylamine while being careful not to let the liquid temperature exceed 10 ° C. Next, the reaction liquid was cooled to 10 ° C. or lower, potassium hexafluorophosphate was dissolved in a small amount of water and added, and the mixture was stirred for about 15 minutes. The deposited precipitate was collected with a glass filter and washed with a small amount of acetic acid to obtain a compound [36]. Further, sodium acetate was added to these compound [30] and compound [36], and they were reacted at room temperature for 24 hours. This reaction mixture was added to methanol, and the target polymer compound equivalent product was obtained by the reprecipitation method.

[0100]

[Chemical 15]

As a result of identification of this compound in the same manner as in Example 1, it was confirmed that a high molecular compound of the general formula [13] having a side chain [14] was obtained.

Fabrication of Nonlinear Optical Waveguide Element (Channel Waveguide Element) The above polymer compound containing 20 mol% of this nonlinear optical material part was dissolved in chloroform and thinned by spin coating on a synthetic quartz substrate having a thickness of 1 mm. did. The film thickness is 3.5 μ
It was m. By subjecting this sample to photolithography and etching, each channel width was 4μ.
A directional coupler having m 2, a length of 10 mm, a distance between two channels of 6 μm, and an optically-polished end face of an optical waveguide was produced.

Element Performance Evaluation of Nonlinear Optical Waveguide Element (Channel Type Waveguide Element) A beam having an oscillation wavelength (1.064 μm) of a Q-switched Nd: YAG laser with mode lock is coupled to one side of the channel by an end face coupling method using an objective lens. It was made incident. When the emitted light intensity of the two channels was monitored with respect to the incident light intensity, a switching phenomenon due to a change in the incident light intensity was confirmed.

Similarly, two kinds of polymer compounds of general formula [13] having side chains [15] and [16] respectively were synthesized to prepare a directional coupler. When the output light intensity of the two channels of this directional coupler was monitored against the input light intensity,
The switching phenomenon due to the change of the incident light intensity was confirmed.
From these results, it was shown that the fabricated directional coupler can be switched by the light intensity dependent refractive index change (third-order nonlinear optical effect).

Comparative Example 5 A polymer compound having a side chain [38] as a functional side chain R ₁₈ in a methacrylic polymer chain represented by the following general formula [37] was synthesized. A nonlinear optical waveguide device was produced using this compound, and the device performance was evaluated.

[0106]

[Chemical 16]

Synthesis of general formula [37] polymer compound having side chain [38] First, a compound [30] was obtained in the same manner as in Example 3. Then 4-
(4-Nitrophenylazo) -1-naphthylamine was dissolved in acetic acid by heating and further cooled to 10 ° C or lower. Next, sodium nitrite was gradually added to sulfuric acid so as not to generate heat and dissolved. This was added dropwise to the acetic acid solution of 4- (4-nitrophenylazo) -1-naphthylamine while being careful not to let the liquid temperature exceed 10 ° C. Next, cool the reaction solution to 10 ° C or lower, dissolve potassium hexafluorophosphate in a small amount of water and add 15
Stir for about a minute. The deposited precipitate was collected with a glass filter and washed with a small amount of acetic acid to obtain a compound [39]. Further, sodium acetate was added to the compound [30] and the compound [39], and they were reacted at room temperature for 24 hours. This reaction mixture was added to methanol, and the target polymer compound equivalent product was obtained by the reprecipitation method. When this compound was identified in the same manner as in Example 1, it was found that the polymer compound of the general formula [37] having a side chain [38] was certainly obtained.

A polymer compound having a side chain [38] containing 20 mol% of this non-linear optical material portion was dissolved in chloroform, and a thin film was formed on a synthetic quartz substrate having a thickness of 1 mm by spin coating. The film thickness was 3.5 μm. By subjecting this sample to photolithography and etching,
Each channel had a width of 4 μm, a length of 10 mm, a distance between two channels of 6 μm, and an optical waveguide end face was optically polished to prepare a directional coupler.

Element Performance Evaluation of Nonlinear Optical Waveguide Element (Channel Type Optical Waveguide Element) A beam having an oscillation wavelength (1.064 μm) of a Q-switched Nd: YAG laser with mode lock is applied to one side of the channel by an end face coupling method using an objective lens. It was made incident. When the emitted light intensity of the two channels was monitored with respect to the incident light intensity, a switching phenomenon due to a change in the incident light intensity was confirmed. However, the intensity of emitted light was about 1/10 of that in the case of Example 5, which was weak.

Example 6 As functional side chains R ₁₅ of the methacrylic polymer chain represented by the general formula [17], side chains [18], [19] and [2]
[0] was synthesized. The polymer compound of the general formula [17] having a side chain [18] was synthesized as follows. General formula [17] polymer compound having side chain [19] and side chain
The general formula [17] polymer compound having [20] was synthesized according to this. Nonlinear optical layers using these general formula [1] binding / coordination polymers as nonlinear optical materials were formed, and their nonlinear optical characteristics were measured.

Synthesis of Polymer Compound of General Formula [17] Having Side Chain [18] Compound [6] was synthesized in the same manner as in Example 2. Next, methacrylic acid chloride and compound [6] were condensed in the presence of trimethylamine to obtain compound [40]. Methyl methacrylate and the compound [40] were mixed at a ratio of j: k shown in Table 9 and radically reacted to synthesize a sample of 5 kinds of target polymer compound equivalents.

[0112]

[Chemical 17]

The obtained compound was identified in the same manner as in Example 1. It was revealed that a polymer compound of the general formula [17] having a side chain [18] was obtained.

Film Formation of Nonlinear Optical Layer [Preparation of Nonlinear Optical Waveguide Element (Slab Type Optical Waveguide Element)] The film formation was performed by dropping a chloroform solution of this polymer compound on a glass substrate to form a thin film by spin coating. .
The film thickness is a stylus type film thickness meter (Dectak 3030 manufactured by sloan)
It was measured by. The sample thus obtained was heated to 140 ° C. using a corona discharge device as shown in FIG. 1, and a critical voltage below the discharge voltage, that is, an electric field of 10 kV / cm 2 was applied for 2 minutes. After that, the heating was stopped and allowed to cool, and the application of the electric field was continued until the temperature reached 30 ° C. After breaking the electric field. The sample was taken out and the nonlinear optical constant (d ₃₃ ) was measured.

Measurement of Nonlinear Optical Properties of Nonlinear Optical Layer [Evaluation of Device Performance of Nonlinear Optical Waveguide Device (Slab Optical Waveguide Device)] The rotation maker fringe method was used to evaluate the nonlinear optical properties of the thin film thus prepared. . Q switch N
Polarized beam of d: YAG laser (wavelength: 1.064 μm)
Was focused on the sample. The resulting second harmonic was spectrally detected and detected by a photomultiplier tube. The average power obtained from the boxcar integrator was calculated by the computer as a function of the angle of incidence of the incident beam on the sample. A Y-cut quartz plate (d ₁₁ = 0.33 pm / V) was used as a reference sample. As a result, the film thickness and the second-order nonlinear optical constant d ₃₃ of Samples 1 to 5 having different ratios of the compound [40] and methyl methacrylate and the propagation loss of the slab type optical waveguide at the wavelength of 1.064 μm were obtained. The values are shown in Table 9.

[0116]

[Table 9]

Then, the sample 3 was left at 80 ° C. and the nonlinear optical characteristics were measured by the above-mentioned rotational maker fringe method every arbitrary time. The result is shown in FIG. 6 assuming that the nonlinear optical constant at 0 hours is 1. FIG. 6 is a graph showing the change over time of the nonlinear optical constant d ₃₃ of the above sample at 80 ° C. In FIG. 6, the samples are represented by using the following symbols. ■; Example 6 sample 3 (polymer of general formula [17] having side chain [18]), ●; Comparative example 6 sample 3 (polymer of general formula [41] having side chain [42]) 80 When left at ℃, the nonlinear optical constant (d
₃₃ ) indicates 90% of 0 hours.

Similar to the above, the side chain of j: k = 20: 100 [1
9] or two general formulas [1] each having a side chain [20]
7] Polymer compounds were synthesized and the nonlinear optical constant (d ₃₃ ) was measured using them. As a result, d ₃₃ is 80pm each
It was / V and 77 pm/V. The propagation loss is 4.8 dB each.
The values were / cm and 5.1 dB / cm.

Comparative Example 6 A polymer compound having a side chain [42] as a functional side chain R ₁₉ of a methacrylic polymer chain represented by the following general formula [41] was synthesized. A non-linear optical layer was formed using this general formula [1] binding / coordination polymer as a non-linear optical material, and its non-linear optical characteristics were measured.

[0120]

[Chemical 18]

Synthesis of Polymer Compound of General Formula [41] Having Side Chain [42] First, hydrochloric acid was added to 4- (4-nitrophenylazo) -1-diethylaniline in a mixed solvent of acetone-ethanol-water. . This solution was cooled to 0 to 5 ° C, an aqueous sodium nitrite solution was added, and the mixture was stirred at the same temperature for 6 hours. Then, an acetone solution of N-ethylhydroxyaniline was added. The mixture was stirred at room temperature overnight. After the reaction, this reaction mixture was extracted with dichloromethane, and the product was purified with a silica gel column to obtain compound [43]. Methacrylic acid chloride and compound [43] were condensed in the presence of trimethylamine to obtain compound [44]. This compound [44] is mixed with methyl methacrylate at the ratio of j: k shown in Table 10 and the radical reaction is carried out to obtain the target polymer compound equivalent 3
Seed was synthesized. Identification of this compound in the same manner as in Example 1 revealed that the obtained compound was a polymer compound of the general formula [41] having a side chain [42].

Film Formation of Nonlinear Optical Layer [Preparation of Nonlinear Optical Waveguide Element (Slab Type Optical Waveguide Element)] The film formation was performed by dropping a chloroform solution of this compound on a glass substrate and forming a thin film by spin coating. The film thickness was measured with a stylus type film thickness meter (Dectac 3030 manufactured by sloan). The sample thus obtained was heated to 140 ° C. using a corona discharge device as shown in FIG. 1, and an electric field of 10 kV / cm 2 was applied for 2 minutes. After that, the heating was stopped and allowed to cool, and the application of the electric field was continued until the temperature reached 30 ° C. After the electric field was cut off, the sample was taken out and the nonlinear optical constant (d ₃₃ ) was measured.

Measurement of Nonlinear Optical Properties of Nonlinear Optical Layer [Evaluation of Device Performance of Nonlinear Optical Waveguide Device (Slab Type Optical Waveguide Device)] The rotation maker fringe method was used to evaluate the nonlinear optical properties of this thin film. A polarized beam of Q-switched Nd: YAG laser (wavelength: 1.064 μm) was focused on the sample. The resulting second harmonic was spectrally detected and detected by a photomultiplier tube. The average power obtained from the boxcar integrator was calculated by the computer as a function of the angle of incidence of the incident beam on the sample. A Y-cut quartz plate (d ₁₁ = 0.33 pm / V) was used as a reference sample. As a result, the film thicknesses of the samples 1 to 3 having different ratios of the compound [44] and methyl methacrylate, the value of the second-order nonlinear optical constant d ₃₃ , and the propagation loss value at the wavelength of 1.064 μm in the slab type optical waveguide. Is shown in Table 10.

[0124]

[Table 10]

The nonlinear optical material having j = 20 or more could not be dissolved. Further, the non-linear optical constant is smaller than that in the case of Example 6 in which the same proportion of the non-linear optical material is introduced. After that, sample 3 in this
Was left at 80 ° C. and the non-linear optical characteristics were measured by the above-mentioned maker fringe method every arbitrary time. The result is shown in FIG. 6 assuming that the nonlinear optical constant at 0 hours is 1. When each is left at 80 ° C., the nonlinear optical constant (d ₃₃ ) shows 80% of 0 hours after 10,000 hours, which is a large decrease in the nonlinear optical constant as compared with Example 6.

Example 7 As a functional side chain R ₁₆ of a methacrylic polymer chain represented by the general formula [21], a side chain [22], a side chain [23] and a side chain [2]
4] was synthesized. The polymer compound of the general formula [21] having a side chain [22] was synthesized as follows. The general formula [21] polymer compound having a side chain [23] and the general formula [21] polymer compound having a side chain [24] were synthesized according to this. A non-linear optical waveguide device using these general formula [1] binding / coordination polymers as a non-linear optical material was produced and the device performance was evaluated.

Polymeric compound of general formula [21] having side chain [22] Hydrochloric acid was added to 4- (4-perfluorobutylsulfonylphenylazo) -2,6-dimethylaniline in a mixed solvent of acetone-ethanol-water. It was This solution was cooled to 0 to 5 ° C, an aqueous sodium nitrite solution was added, and the mixture was stirred at the same temperature for 6 hours. Then, an acetone solution of N-ethylhydroxyaniline was added. The mixture was stirred at room temperature overnight. After the reaction was completed, this reaction mixture was extracted with dichloromethane, and the product was purified with a silica gel column to give the compound
I got [45]. Next, methacrylic acid chloride and compound [4
5] was condensed in the presence of trimethylamine to obtain compound [46]. This compound [46] and methyl methacrylate were mixed with j: k = 1
The target polymer compound equivalents were synthesized by mixing at a ratio of 0: 100 and performing a radical reaction.

[0128]

[Chemical 19]

As a result of the same identification as in Example 1, it was revealed that this compound is indeed a polymer compound of the general formula [21] having a side chain [22].

Preparation of Nonlinear Optical Waveguide Element (Channel Type Optical Waveguide Element) A chloroform solution of the polymer compound (j: k = 10: 100) on a silicon substrate provided with a gold electrode and an underclad layer (SiO ₂ ). Was spin-coated to form a thin film (film thickness:
4 μm). Next, the surface of this thin film was coated with a thin layer of epoxy resin by a spin coating method. Further, a gold electrode was provided on a required portion above the gold electrode. The substrate was heated to 140 ° C. and an electric field of 1 MV / cm 2 was applied between the upper and lower gold electrodes for 2 minutes to orient the polymer compound. This was allowed to cool to 30 ° C and the electric field was cut off. Next, after removing the upper gold electrode, a positive resist was applied and photolithography was performed using a mask having a required waveguide pattern. After that, RIE using O ₂ with the resist as a mask
Then, the polymer portion was etched leaving the optical waveguide portion. Then the resist was removed using a stripping solution.
An epoxy resin was applied to the entire surface to form an outer clad.
Further, a gold electrode for driving the device was formed on the upper portion of the optical waveguide portion by using photolithography, and a Mach-Cendar interference type optical device including a channel type waveguide was formed. This element was separated and the end face of the optical waveguide was optically polished. The width of the waveguide was 5 μm and the length was 20 mm. The obtained optical waveguide device is the structure shown in FIG.

Evaluation of Device Performance of Nonlinear Optical Waveguide Device (Channel Type Optical Waveguide Device) As a result of exciting the light of He-Ne laser oscillation wavelength (0.63 μm) by the end-face coupling method, a half-wave voltage of about 4 V was obtained. It was The electro-optic constant was 66 pm / V. Also,
It showed excellent optical modulation characteristics, and the erasure ratio was 25 dB.

As in the above, a general formula [21] having a side chain [23]
A Mach-Cender interference type optical device was prepared by synthesizing a polymer compound and a polymer compound of the general formula [21] having a side chain [24] (j: k = 10: 100). As in the above case, a He--Ne laser oscillation wavelength (0.63 .mu.m) was excited by the end face coupling method, and as a result, a half-wave voltage of about 4 V was obtained. The electro-optic constants were all 62 pm / V. Also, the erase ratio is 25
The values are dB and 26 dB, which show excellent optical modulation characteristics.

Comparative Example 7 A polymer compound having a side chain [48] as a functional side chain R ₂₀ of a methacrylic polymer chain represented by the following general formula [47] was synthesized. A non-linear optical waveguide device using this general formula [1] bond / coordination polymer as a non-linear optical material was produced and the device performance was evaluated.

[0134]

[Chemical 20]

Synthesis of Polymer of General Formula [47] Having Side Chain [48] First, hydrochloric acid was added to 4- (4-nitrophenylazo) -2,6-dimethylaniline in an acetone-ethanol-water mixed solvent. added. This solution was cooled to 0 to 5 ° C, an aqueous sodium nitrite solution was added, and the mixture was stirred at the same temperature for 6 hours. Then, an acetone solution of N-ethylhydroxyaniline was added. The mixture was stirred at room temperature overnight. After completion of the reaction, this reaction mixture was extracted with dichloromethane, and the product was purified by silica gel column to obtain compound [49]. Next, methacrylic acid chloride and compound [49] were condensed in the presence of trimethylamine to obtain compound [50]. This compound [5
[0] and methyl methacrylate were mixed at a ratio of j: k = 10: 100 and a radical reaction was performed to synthesize the target polymer compound equivalent. From the same identification as in Example 1, the obtained compound was found to be a high molecular compound of the general formula [47] having a side chain [48].

Preparation of Nonlinear Optical Waveguide Element (Channel Type Optical Waveguide Element) On a silicon substrate provided with a gold electrode and an underclad layer (SiO ₂ ), a chloroform solution of the polymer compound (j: k = 10: 100). Was spin-coated to form a thin film (film thickness:
4 μm). Next, the surface of this thin film was coated with a thin layer of epoxy resin by a spin coating method. Further, a gold electrode was provided on a required portion above the gold electrode. The substrate was heated to 140 ° C. and an electric field of 1 MV / cm 2 was applied between the upper and lower gold electrodes for 2 minutes to orient the polymer compound. It was allowed to cool to 30 ° C and the electric field was cut off. Next, after removing the upper gold electrode, a positive resist was applied and photolithography was performed using a mask having a required waveguide pattern. After that, RIE was performed using O ₂ using the resist as a mask, and the polymer portion was etched leaving the optical waveguide portion. After that, the resist was removed using a stripping solution. An epoxy resin was applied to the entire surface to form an outer clad. Next, a gold electrode for driving the device was formed on the upper part of the optical waveguide portion by photolithography to form a Mach-Cender interference type optical device including a channel type waveguide. This element was separated and the end face of the optical waveguide was optically polished. The width of the waveguide is 5 μm
And the length was 20mm. The obtained optical waveguide device is shown in FIG.
It is the structure shown in.

Evaluation of Device Performance of Nonlinear Optical Waveguide Device (Channel Type Optical Waveguide Device) Light having an oscillation wavelength (0.63 μm) of a He—Ne laser was excited by the end face coupling method. As a result, a half-wave voltage of about 4V was obtained, the electro-optic constant was 49 pm/V, and the propagation loss was 20dB.
And all were inferior to Example 7.

Example 8 A polymer compound having a main chain unit [26] as a functional main chain unit ₁ R ₁ of an acrylic / methacrylic copolymerization type polymer chain represented by the general formula [25] was synthesized. (Mao, general formula [25]
Shows the structure before the crosslinking reaction described later of this compound. ) A non-linear optical layer was formed using this general formula [1] binding / coordination polymer as a non-linear optical material, and its non-linear optical characteristics were measured.

Synthesis of general formula [25] polymer compound having main chain unit [26] and film formation of non-linear optical layer [Preparation of non-linear optical waveguide device (slab type optical waveguide device)] Acetone-ethanol-water mixed solvent Hydrochloric acid was added to 4- (4-hydroxymethyleneperfluorobutylsulfonylphenylazo) -1-naphthylamine. 0 to this solution
After cooling to 5 ° C, an aqueous sodium nitrite solution was added,
The mixture was stirred at the same temperature for time. Then, an acetone solution of N-ethylhydroxyaniline was added. The mixture was stirred at room temperature overnight. After the reaction, this reaction mixture was extracted with dichloromethane, and the product was purified with a silica gel column to obtain compound [51]. Next, methacrylic acid chloride and compound [51] are condensed in the presence of trimethylamine to give the compound
I got [52].

For the film formation, a solution prepared by mixing this compound [52] and trimethyl roll propane triacrylate (trade name: Biscoat # 295, manufactured by Osaka Organic Chemical Co., Ltd.) at a molar ratio of 10: 100 was dropped on a glass substrate. Was formed into a thin film by spin coating. After that, using a corona discharge device as shown in FIG. 1, this substrate was kept at 10 ° C.
After applying an electric field of 10 kV / cm 2 for 2 minutes, light was irradiated with a high-pressure mercury lamp of 350 W for 15 minutes. The electric field was cut off after stopping the light irradiation. Then, the sample was taken out. By photoreaction, a film in which the nonlinear optical material was oriented was obtained, and at the same time, the target polymer compound equivalent was synthesized. This synthetic process is represented by chemical formulas as shown in reaction formulas [6] to [8].

[0141]

[Chemical 21]

As a result of the same identification as in Example 1, it was revealed that the obtained compound was a polymer compound of the general formula [25] having a main chain unit [26]. In this polymer compound, unreacted acrylate groups or methacrylate groups that do not participate in the main chain connection are crosslinked by reacting double bonds with each other,
The whole thing was cross-linked.

Measurement of Non-Linear Optical Properties of Non-Linear Optical Layer [Evaluation of Device Performance of Non-Linear Optical Waveguide Device (Slab Type Optical Waveguide Device)] After the electric field is cut off, the film thickness immediately after taking out the sample is measured by a stylus type film thickness meter (sloan Measured by the company's Dectak 3030),
Then, the nonlinear optical constant (d ₃₃ ) was measured. The rotating maker fringe method was used to evaluate the nonlinear optical properties of the obtained thin films. A polarized beam of Q-switched Nd: YAG laser (wavelength: 1.064 μm) was focused on the sample. The resulting second harmonic was spectrally detected and detected by a photomultiplier tube. The average power obtained from the boxcar integrator was calculated by the computer as a function of the angle of incidence of the incident beam on the sample. A Y-cut quartz plate (d ₁₁ = 0.33 pm / V) was used as a reference sample. The second-order nonlinear optical constant d ₃₃ value of the sample is 55 pm / V, and the propagation loss value at the wavelength of 1.064 μm is 1.3 dB / V in the slab type optical waveguide.
It was cm. Then, this sample was left at 100 ° C., and the nonlinear optical characteristics were measured by the rotating maker fringe method every arbitrary time. The result is shown in FIG. 7 in which the nonlinear optical constant at 0 hours is 1. FIG. 7 is a graph showing the change with time of the nonlinear optical constant d ₃₃ of the above sample at 100 ° C. In FIG. 6, the samples are represented by using the following symbols. ■; Example 8 (general formula [25] polymer compound having side chain [26]), ●; Comparative Example 8 (general formula [53] polymer compound having side chain [38]) Left at 100 ° C Even in this case, the nonlinear optical constant (d ₃₃ ) shows 93% of 0 hours after 10,000 hours.

Comparative Example 8 A polymer compound having a side chain [38] as a functional side chain R ₂₁ of an acrylic / methacrylic polymer chain represented by the following general formula [53] was synthesized. (Oh, the general formula [53] shows the structure of the present compound before proceeding with the crosslinking reaction.) The general formula [1] nonlinear optics using the bond / coordination polymer as a nonlinear optical material. The layers were deposited and their nonlinear optical properties were measured.

[0145]

[Chemical formula 22]

Synthesis of Polymer Compound of General Formula [53] Having Side Chain [38] and Film Formation of Nonlinear Optical Layer [Preparation of Nonlinear Optical Waveguide Element (Slab Optical Waveguide Element)] Compound [35] was compared with Comparative Example 4 It was synthesized in the same manner as in the inside. Next, methacrylic acid chloride and compound [35] were condensed in the presence of trimethylamine to obtain compound [55]. This compound [55] was mixed with trimethylolpropane triacrylate (trade name: Biscoat # 295, manufactured by Osaka Organic Chemical Co., Ltd.) at a molar ratio of 10: 100, and a film was formed on a glass substrate by spin coating. After that, the sample was continuously kept at 10 ° C. using a corona discharge device as shown in FIG. 1, an electric field of 10 kV / cm 2 was applied for 2 minutes, and then light was irradiated for 15 minutes by a high-pressure mercury lamp of 350 W. The heating was stopped 5 minutes after the start of light irradiation, and the electric field was cut off after stopping the light irradiation. By photoreacting, a film in which the nonlinear optical material was oriented was obtained, and at the same time, the target polymer compound equivalent product was obtained. The same identification as in Example 1 revealed that the obtained compound was a polymer compound of the general formula [53] having a side chain [38]. The polymer compound was cross-linked as a whole by cross-linking the acrylate group with other acrylate groups by double-bonding with each other.

Measurement of Non-Linear Optical Properties of Non-Linear Optical Layer [Evaluation of Device Performance of Non-Linear Optical Waveguide Device (Slab Type Optical Waveguide Device)] After the electric field is cut off, the film thickness immediately after the sample is taken out is the stylus type film thickness meter Dectak 3030 Then, the nonlinear optical constant (d ₃₃ ) was measured. The rotating maker fringe method was used to evaluate the nonlinear optical properties of the obtained thin films. A polarized beam of Q-switched Nd: YAG laser (wavelength: 1.064 μm) was focused on the sample. The resulting second harmonic was spectrally detected and detected by a photomultiplier tube. The average output obtained from the boxcar integrator is
It was calculated by computer as a function of the angle of incidence of the incident beam on the sample. Y-cut quartz plate (d ₁₁ = 0.33
pm / V) was used as a reference sample. The second-order nonlinear optical constant d ₃₃ value of the sample was 38 pm / V, and the propagation loss value at the wavelength of 1.064 μm was 1.8 dB / cm in the slab type optical waveguide. Then, this sample was left at 100 ° C., and the nonlinear optical characteristics were measured by the rotating maker fringe method every arbitrary time. The result is shown in FIG.
Shown in. When left at 100 ° C., the nonlinear optical constant (d ₃₃ ) shows 50% of 0 hours after 10,000 hours.

Example 9 A polymer compound having a crosslinking group [28] as the functional crosslinking group ₂ R ₂ of the polyisocyanate polymer chain represented by the general formula [27] was synthesized. A non-linear optical waveguide device using this general formula [1] bond / coordination polymer as a non-linear optical material was produced and the device performance was evaluated.

Synthesis of Polymer Compound of General Formula [27] Having Crosslinking Group [28] The compound [51] was obtained by the same synthesis as in Example 8. This compound [51] and polymethylene polyphenyl isocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name Millionate MR) were mixed at a molar ratio of 10: 100 on a silicon substrate provided with a gold electrode and an underclad layer (SiO ₂ ). The solution was dropped, and a thin film was formed by spin coating (film thickness: 4 μm
). After that, the substrate was kept at 10 ° C. using a corona discharge device as shown in FIG. 1, and an electric field of 10 kV / cm 2 was applied.
After the voltage was applied for a minute, light was irradiated with a high-pressure mercury lamp of 350 W for 15 minutes. The electric field was cut off after stopping the light irradiation. By photoreacting, the nonlinear optical material was oriented, and at the same time, the target polymer compound equivalent was synthesized. According to the same identification as in Example 1, the obtained compound was represented by the general formula [2] having a bridging group [28].
7] It became clear that it was a polymer compound. The polymer compound was crosslinked as a whole by the reaction of an isocyanate group with another isocyanate group and crosslinking.

Preparation of Nonlinear Optical Waveguide Element (Channel Type Optical Waveguide Element) The surface of the thus obtained thin film was coated with an epoxy resin in a thin layer by spin coating. A positive resist was applied thereon and photolithography was performed using a mask having a required waveguide pattern. After that, RIE was performed using O ₂ using the resist as a mask, and the polymer portion was etched leaving the optical waveguide portion. After that, the resist was removed using a stripping solution. An epoxy resin was applied to the entire surface to form an outer clad. Next, a gold electrode for driving the device was formed on the upper part of the optical waveguide portion by photolithography to form a Mach-Cender interference type optical device including a channel type waveguide. This element was separated and the end face of the optical waveguide was optically polished. The width of the waveguide was 5 μm and the length was 20 mm. The produced optical waveguide device is the structure shown in FIG.

Evaluation of Device Performance of Nonlinear Optical Waveguide Device (Channel Type Optical Waveguide Device) As a result of exciting light of oscillation wavelength (0.63 μm) of He—Ne laser by the end-face coupling method, a half-wave voltage of about 3.5 V was obtained. Was given. The electro-optical constant was a value of 62 pm / V. In addition, it showed very excellent optical modulation characteristics, and the extinction ratio was 24 dB. After leaving this device in an atmosphere of 80 ° C for 10,000 hours, the same measurement was performed, and as a result, the electro-optic constant was 60 pm / V.
No change was observed in the characteristics except for a slight decrease.

Comparative Example 9 A polymer compound having a side chain [38] as a functional side chain R ₂₂ of a polyisocyanate polymer chain represented by the following general formula [55] was synthesized. A non-linear optical waveguide device using this general formula [1] bond / coordination polymer as a non-linear optical material was produced and the device performance was evaluated.

[0153]

[Chemical formula 23]

Synthesis of Polymer Compound of General Formula [55] Having Side Chain [38] Compound [35] was synthesized by the same method as shown in Comparative Example 4. Here, compound [35] and polymethylene polyphenyl isocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name Millionate MR) were mixed at a molar ratio of 10: 100 on a silicon substrate provided with a gold electrode and an underclad layer (SiO ₂ ). Solution was added dropwise to form a thin film by spin coating (film thickness: 4
μm). After that, the substrate was kept at 10 ° C. by using a corona discharge device as shown in FIG. 1, and an electric field of 10 kV / cm 2 was applied.
After the voltage was applied for a minute, light was irradiated with a high-pressure mercury lamp of 350 W for 15 minutes. The electric field was cut off after stopping the light irradiation. By photoreaction, the nonlinear optical material was oriented, and at the same time, the target polymer compound equivalent was prepared. As a result of the same identification as in Example 1, the obtained compound was found to be a polymer compound of the general formula [55] having a side chain [38]. The polymer compound was cross-linked as a whole by crosslinking the isocyanate group with other isocyanate groups.

Preparation of Nonlinear Optical Waveguide Element (Channel Type Optical Waveguide Element) Next, a thin layer of epoxy resin was coated on the surface of the thus obtained thin film by spin coating. A positive resist was applied thereon and photolithography was performed using a mask having a required waveguide pattern. After that, RIE was performed using O ₂ using the resist as a mask, and the polymer portion was etched leaving the optical waveguide portion. After that, the resist was removed using a stripping solution. An epoxy resin was applied to the entire surface to form an outer clad. Next, a gold electrode for driving the device was formed on the upper part of the optical waveguide portion by photolithography to form a Mach-Cender interference type optical device including a channel type waveguide. This element was separated and the end face of the optical waveguide was optically polished. The width of the waveguide was 5 μm and the length was 20 mm. The produced optical waveguide device is the structure shown in FIG.

Evaluation of Device Performance of Nonlinear Optical Waveguide Device (Channel Type Optical Waveguide Device) As a result of exciting the light of He-Ne laser oscillation wavelength (0.63 μm) by the end-face coupling method, a half-wave voltage of about 3.5 V was obtained. Was given. The electro-optical constant was 46 pm / V, which was inferior to that of Example 9. . Moreover, it showed very excellent optical modulation characteristics, and the extinction ratio was 21 dB. After leaving this element in an atmosphere of 80 ° C. for 10,000 hours, the same measurement was performed.
Half-wave voltage rises to about 4.5 V and electro-optic constant is 32 pm / V
It was observed that the extinction ratio was 18 dB and the characteristics deteriorated.

As is clear from the comparison between the above-mentioned Examples and Comparative Examples, the nonlinear optical constant (d ₃₃ ) of the nonlinear optical layer made of the nonlinear optical material of the present invention is 1.2.
It was more than twice as large and its change with time was extremely small. In addition, the nonlinear optical waveguide device obtained from this nonlinear optical material had very excellent characteristics with an electro-optical constant of 55 pm / V or more. Further, in the nonlinear optical waveguide device (channel type optical waveguide device) of the present invention, the extinction ratio represented by the ratio of the maximum value and the minimum value of the light intensity due to modulation is 20 dB or more, and it can be practically used as an optical device. Met.

[0158]

INDUSTRIAL APPLICABILITY The non-linear optical material of the present invention exhibits large second-order and third-order non-linear optical effects and is excellent in light propagation characteristics.
Furthermore, it has excellent mechanical strength. By using the material of the present invention, the content of the non-linear optical material can be increased, and a large non-linear optical effect can be easily expressed. Therefore, an optical waveguide device superior to conventional materials can be prepared. You can Furthermore, by using the nonlinear optical material of the present invention, the nonlinear optical effect after orientation can be stably maintained for a long period of time. Further, the nonlinear optical waveguide element of the present invention is excellent in optical modulation characteristics, optical switching characteristics, and optical bistability. Furthermore, since the nonlinear optical waveguide element of the present invention can be made into a thin film, it can be used as an optical integrated circuit capable of high integration. Applicable.

[Brief description of drawings]

FIG. 1 is a conceptual diagram showing a corona discharge device.

FIG. 2 is a graph showing the change over time of the nonlinear optical constant (d ₃₃ ) at 50 ° C. for a nonlinear optical material in which the compound of the general formula [1] is dispersed and oriented in PMMA.

FIG. 3 is a graph showing a change with time of a nonlinear optical constant (d ₃₃ ) at 80 ° C. regarding a nonlinear optical material in which a compound of the general formula [1] is dispersed and oriented in PMMA.

FIG. 4 is a perspective view of a Mach-Zehnder interference type optical element.

FIG. 5 is a graph showing the change over time in the nonlinear optical constant (d ₃₃ ) at 80 ° C. of a nonlinear optical material in which the compound of the general formula [1] is dispersed and oriented in PC.

FIG. 6 is a graph showing the change with time in the nonlinear optical constant (d ₃₃ ) at 80 ° C. for a nonlinear optical material in which a general formula [1] bond / coordination polymer compound is oriented.

FIG. 7 is a graph showing the change over time of the nonlinear optical constant (d ₃₃ ) at 100 ° C. for a nonlinear optical material in which a bonding / coordinating polymer compound of the general formula [1] is oriented.

[Explanation of symbols]

 1 Corona Discharger 2 Sample 3 Temperature Control Sample Stand 4 High Voltage Power Supply 5 Outer Clad 6 Upper Electrode 7 Nonlinear Optical Waveguide 8 Input Light 9 Substrate 10 Lower Electrode 11 Underclad Layer 12 Output Light

Continuation of front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical indication location C09K 9/02 Z (72) Inventor Hiroshige Muramatsu 2-31, Moritakahito, Moriyama-ku, Nagoya, Aichi 416 (72) Inventor Masaki Matsui 2-2-35 Toyooka-cho, Seki City, Gifu Prefecture (72) Inventor Barathie Jogreker 835-1 Yanagido, Gifu City, Gifu Prefecture Cosmopolis 101

Claims (3)

[Claims] 1. A nonlinear optical material comprising one or more compounds represented by the general formula [1] or a derivative thereof dissolved or dispersed in a polymer substance. [Chemical 1] (In the above formula, π _{1 to} π ₃ are π-electron conjugated cyclic compounds, X
And Y are each a pair combination consisting of one selected from CH, N, or N → O, n is an integer of 0 or more, D is an electron-donating group, and R _{1 to} R ₁₀ are each a hydrogen atom or an alkyl group. , A ₁ , A ₂ or A ₃ is a hydrogen atom,
It represents an alkyl group or a substituent represented by the general formula [2]. However, when having substituents only one of A _1, A ₂ or A ₃ is represented by the general formula [2], the substituent is located A _1, also, A _1, A ₂ Alternatively, when two of A ₃ have a substituent represented by the general formula [2], the substituents are arranged at A ₁ and A ₂ or A ₁ and A ₃ . Here, Z represents a hydrogen atom, a halogen atom, a nitro group, a carboxyl group, a hydroxyl group, a dicyanovinyl group or a tricyanovinyl group, m represents an integer of 1 or more, and l represents an integer of 0 or more. ) 2. Containing a general formula [1] bond / coordination polymer in which molecules of one or more compounds represented by the general formula [1] or derivatives thereof are bonded or coordinated to a polymer chain. Non-linear optical material characterized by 3. A non-linear optical waveguide device comprising the non-linear optical material according to claim 1.