JPH07318991A - Photorefractive polymer - Google Patents

Abstract

PURPOSE:To obtain a polymer having electro-optical and photoconductive molecules in a single state and acting as a photorefractive medium having a significant electro-optical effect and high photoconductivity by introducing photoconductive groups into a structure. CONSTITUTION:This photorefractive polymer is a polymer represented by the formula, wherein A is C or Si, B is O, alkyl, fluoroalkyl, etc., D is H, halogen, CF3, cyano, etc., R is H, halogen or a group having nonlinear optical characteristics such as optionally substd. benzene, pyridine, stilbene, azobenzene, tolan or triazine and X is H, halogen or a photoconductive group such as optionally substd. carbazole, phthalocyanine, porphyrin, porphyrazine, metallocene, squalene, azo pigment or naphthalene. A sensitizer such as trinitrofluorenone may further be used.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel photorefractive polymer and photorefractive device applicable to the fields of electronics and photonics.

[0002]

Photorefractive materials are non-linear optical materials that combine the three properties of electro-optical properties, photoconductivity, and photo-ionizable lattice defects, and photo-ionizable defects in their lattice. There is. Empirically, the required characteristics of photorefractive materials are:
There are two points: (1) lack of central symmetry that causes the Pockels linear EO effect, and (2) existence of a deep level density sufficient to generate space charge. This causes a current to be generated by the laser light, and the presence of an electric field changes the refractive index. The electric field modulates the refractive index by the linear electro-optic effect. The movement of ionized charges occurs due to diffusion, movement of electric field excitation, or photovoltaic effect. The diffraction grating having a refractive index generated in the photorefractive crystal can be erased by using light in an appropriate wavelength range. These are, for example, P. Gunther Jay P. Heinard, "Photorefractive Materials and There Applications".
(P.Gunter JP Huignard "Photorefractive Materials
and Their Applications I & II ", Springer-Verl
Ag Company (1988, 1989)). Photorefractive effects have been observed in a wide variety of electro-optic crystals. The most well-known ones are barium titanate (BaTiO ₃ ), lithium niobate (LiN
bO ₃ ), lithium tantalate (LiTaO ₃ ), potassium niobate (KNbO ₃ ), Sr _x Ba _1-x Nb ₂ O ₆ (S
BN), Bi ₁₂ SiO ₂₀ (BSO), Bi ₁₂ GeO ₂₀ (BG
O), Bi ₁₂ TaO ₂₀ (BTO), KTa _1-x Nb _x O ₃ (K
TN), GaAs, InP and the like. These inorganic EO
Crystals have been considered suitable for holographic techniques. Regarding these, for example, Aloy Roy Kashin "Attitude Fondo Gee Roche" (A.Roy
K. Singh, Atti. Fond. G. Rochi, 48, 327 (1993)). The factors that select photorefractive materials for different applications are photorefractive sensitivity, operating range (maximum refractive index change), photorefractive recording and erasing time, spectral sensitivity, spatial frequency, external electric field dependence and resolution.

Photorefractive materials can be classified into three types. (1) BaTiO ₃ , LiNbO ₃ , LiT
Oxygen octahedral ferroelectrics such as aO ₃ , KNbO ₃ , SBN, and KTN. The storage time of the recorded hologram or the disappearance time of the diffraction grating is in the range of milliseconds for KNbO ₃ to several years for several hours of KTN and the fixing process of LiNbO ₃ . Generally, SBN is used in the blue-green wavelength range. The response time of these materials can be improved and it can be applied as a holographic recording medium. These types of materials are also used in other applications such as optical bistability, phase conjugation, resonators and optical computing. (2) BS
A silenite material having a tetrahedral oxide structure such as O, BGO and BTO. The bandwidth of BTO is narrower than that of BSO and BGO, and is noted from the viewpoint of application to infrared wavelengths. Although the gain of sillenite is small, the speed of photorefractive response is considerably faster than that of BaTiO ₃ or LiNbO ₃ .
(3) II of GaAs, GaSb, InAs, InSb, etc.
IV group, CuCl, CdS, CdSe, CdTe, Z
II-of nS, ZnSe, ZnTe, HgSe, HgS, etc.
Photorefractive material for Group VI semiconductor crystals. GaAs
There is an example where a picosecond photorefractive response was obtained using a crystal. Utilizing high-speed response, optical information processing,
It can be used for optical computing and optical switch. Photorefractive effect of semiconductor crystal is 0.9-1.6μ
Occurs at the wavelength of.

Recently, a photorefractive material obtained by adding a sensitizer to an electro-optical and photoconductive organic material has received a great deal of attention in the technical field of holography. Photorefractive materials are highly likely to be capable of synthesizing a wide variety of photoconductive or electro-optical materials, and their compositions exhibit high photorefractive properties. The first organic photorefractive material was obtained by the combination of tetracyanoquinodimethane (TCNQ) and the organic nonlinear optical material COANP. This is Kei Shutta Jay
Freger Gunter "Solid State Communication" (K.Sutter J.Hulliger Gunter, "Solid St.
ate Communication Magazine, Vol. 74, p. 867 (1990))
There is a description in. Since then, novel photorefractive polymers have become an important element for application to the field of photonics. Doped with 3-fluoro-4-N, N'-diethylamino-β-nitrostyrene, 2,4,7
-PVK sensitized with trinitrofluorenone (TNF)
The organic composition consisting of showed a large photorefractive property. This is MCDonckers et al., Optics Letter.
Magazine, Vol. 18, p. 1044 (1993) and WE Moerner.
Other work, Organic Thin Films for Photonic Applications
(1993) Technical Digest Series Volume 17, AC
S / OSA Joint Meeting (Toronto, Canada, August 6)
-8 days)) See page 220. Poly- (4-n-butoxyphenyl) ethylsilane doped with a non-linear optical dye group such as TNF or C ₆₀ or a sensitizing additive is
Diffraction grating formation was observed in 39 ms. This is the Sm Silence Etoal “Journal of Optical Society of America” (SMSi
lence et al, Journal of Optical Society of America
Journal, Volume B (1993)). Similar PVK
Addition of non-linear optical dyes or sensitizers to them forms new photorefractive polymers. Es de Calm
Etoaru “Physical Review” (S.Ducharme et a
l, Physical Review, 66, 1846 (199)
0) and SMSilence, Optics Letter, 17th
Vol., P. 1107 (1992)). Photorefractive polymers sensitized with doping and additives of non-linear optical dyes are very promising for future holographic applications. B.Kippelen et al, "Electronic Letter"
Electronic Letter, Vol. 29, p. 1873 (1993
, B.Kippelen et al., Organic Thin Films for Photo
nic Applications (1993) Technical Digest Ser
ies, Volume 17, ACS / OSA Joint Meeting (Toronto, Canada, held August 6-8) 228, etc.

[0005]

Various kinds of inorganic crystal photorefractive materials have been developed, but none of them have sufficient moldability and processability and cannot be integrated. Furthermore, it is generally difficult to form a homogeneous single crystal or thin film with an inorganic photorefractive material. In order to manufacture a new device from these photorefractive materials, there is a problem that all structural requirements such as a multilayer structure cannot be satisfied. An object of the present invention is to provide a novel photorefractive polymer formed from the novel photorefractive polymer.

Photorefractive polymers that can be used for the photorefractive effect are a novel invention. In order to realize this hypothesis, various polymers whose synthesis methods are exemplified below were synthesized.

Organic polymers are important and interesting materials in terms of chemistry and peculiar physics related to material science.

An object of the present invention is to develop a single polymer having an electro-optical property and a photo-conductive molecule, which is a photorefractive medium exhibiting a large electro-optical effect and photo-conductivity.

The polymer of the present invention is excellent in mechanical or thermal properties and exhibits excellent environmental resistance and chemical stability. Furthermore, they have good adhesion and can be processed into ultra thin films. The polymer of the present invention is far superior to conventional inorganic or organic compositions in physical properties in that it can be easily processed, molded or chemically modified and is stable for a long period of time. Another object of the present invention is to provide a polymer material for photonics and electronics, which has good processability, mechanical strength, and thermal and environmental stability.

Another object of the present invention is to provide a photorefractive polymer having durability, strength and stability, which is applicable as a nonlinear optical material.

Another object of the present invention is to provide a photorefractive medium exhibiting a high electro-optic constant and photoconductivity.

Another object of the present invention is to provide a photorefractive material which is easy to synthesize, has processability, high mechanical strength and stability.

[0013]

The present invention solves the conventional problems by the means described below. That is, the present invention is a photorefractive polymer having a group exhibiting photoconductivity. The present invention is also a photorefractive device using a polymer having a photoconductive group.

The present invention is a polymer represented by the following chemical formula 1.

[0015]

[Chemical 1]

However, in the formula, A is C and Si, B is O, alkyl, fluoroalkyl, CH ₂ O, CF ₂ O,
CF ₂ , allyl, fluoroallyl, etc., D is hydrogen,
Halogen, CF ₃ , cyano, etc., R is hydrogen, halogen, or optionally substituted benzene, pyridine, stilbene, azobenzene, tolan, triazine,
Benzylidene, azomethine, azine, azulene, fluorene, heterocycle, naphthalene, phenanthrene, anthracene, chrysene, biphenyl, phenylhithrazone,
A group having a non-linear optical characteristic such as thiazole, X
Is hydrogen, halogen or optionally substituted carbazole, phthalocyanine, porphyrin, porphyrazine, metallocene, squalene, azo dye, naphthalene,
Naphthacene, pyrene, perylene dye, styrylanthracene, anthrylethylene, anthracenophene, anthracenocrown ether, triphenylmethane dye,
Rhodamine, perinone, picene, acene, thiapyrylium salt, cyanine dye, phenylhydrazone, dithion,
Fullerene, dihaloanthrendione, epindridione, trihalopyranslenion, quinacridone, tetrahalothioindigo, azurenium dye, anthracene dye, anthraquinone, chlorodiene blue, benzothiazole, oxazole, hydrazone, quinoline, stilbene, azobenzene, benzylidene, It is a group having photoconductivity such as acridine, fluorene, indole, heterocycle, and thynoline. In addition, trinitrofluorenone
Sensitizers such as (TNF), diazonaphthaquinone, azide, allyl ketone, alkanone and allyl aldehyde may be used.

The present invention is a polymer in which both R and X in the chemical formula 1 are photoconductive organic compounds as described above.
Further, a sensitizer may be added.

The present invention is a polymer represented by Chemical formula 2.

[0019]

[Chemical 2]

However, in the formula, A is NH, N (CnH2n +
1), CONH, CON (CnH2n + 1), COO (Cn
H2n + 1) or the like, B is hydrogen, fluorine, allyl or the like, R is a non-linear optical characteristic or photoconductive group as described above, and X is a photoconductive group as described above. Is.

The present invention is a polymer represented by Chemical formula 3.

[0022]

[Chemical 3]

However, in the formula, B is hydrogen or fluorine, R is a non-linear optical property or photoconductive group as described above, and X is a photoconductive group as described above.

The present invention is a polymer represented by Chemical formula 4.

[0025]

[Chemical 4]

However, in the formula, A is O, S, alkyl, fluoroalkyl, CH ₂ O, CF ₂ O, allyl, fluoroallyl, etc., and R is a group having the above-mentioned nonlinear optical characteristics or photoconductive property. And X is a photoconductive group as described above.

The present invention is a polymer represented by Chemical formula 5.

[0028]

[Chemical 5]

However, in the formula, A is hydrogen, alkyl, fluoroalkyl, allyl, fluoroallyl, etc., R is a non-linear optical characteristic or photoconductive group as described above, and X is light as described above. It is a conductive group.

The present invention is a polymer represented by Chemical formula 6.

[0031]

[Chemical 6]

However, in the formula, A is hydrogen, alkyl, fluoroalkyl, allyl, fluoroallyl, etc., R is a non-linear optical characteristic or photoconductive group as described above, and X is light as described above. It is a conductive group.

The present invention is a polymer represented by Chemical formula 7.

[0034]

[Chemical 7]

However, in the formula, A is hydrogen, alkyl such as F, CH _{3 and the} like, fluoroalkyl such as CF _{3 and the} like, allyl, fluoroallyl and the like, B is O or S, and R is the above-mentioned nonlinearity. It is an optical characteristic or photoconductive group, and X is a photoconductive group as described above.

The present invention is a polymer represented by Chemical Formula 8.

[0037]

[Chemical 8]

However, in the formula, R is a non-linear optical characteristic or photoconductive group as described above, and X is a photoconductive group as described above.

The present invention is a polymer represented by Chemical formula 9.

[0040]

[Chemical 9]

However, in the formula, R is a non-linear optical characteristic or photoconductive group as described above, and X is a photoconductive group as described above.

The present invention is a polymer represented by Chemical formula 10.

[0043]

[Chemical 10]

However, in the formula, R is a non-linear optical characteristic or photoconductive group as described above, and X is a photoconductive group as described above.

The present invention is a polymer represented by Chemical formula 11.

[0046]

[Chemical 11]

In the formula, R is a non-linear optical characteristic or photoconductive group as described above, and X is a photoconductive group as described above.

The present invention is a polymer represented by Chemical formula 12.

[0049]

[Chemical 12]

However, in the formula, R is a non-linear optical characteristic or photoconductive group as described above, and X is a photoconductive group as described above.

The present invention is a polymer represented by Chemical formula 13.

[0052]

[Chemical 13]

In the formula, R is a non-linear optical characteristic or photoconductive group as described above, and X is a photoconductive group as described above.

The present invention is a polymer represented by Chemical formula 14.

[0055]

[Chemical 14]

However, in the formula, R is a non-linear optical characteristic or photoconductive group as described above, and X is a photoconductive group as described above.

The present invention is a polymer represented by Chemical formula 15.

[0058]

[Chemical 15]

However, in the formula, R is a nonlinear optical characteristic or photoconductive group as described above, and X is a photoconductive group as described above.

The present invention is a polymer represented by Chemical formula 16.

[0061]

[Chemical 16]

However, in the formula, R is a nonlinear optical characteristic or photoconductive group as described above, and X is a photoconductive group as described above.

The present invention is a polymer represented by Chemical formula 17.

[0064]

[Chemical 17]

However, in the formula, R is a non-linear optical characteristic or photoconductive group as described above, and X is a photoconductive group as described above.

The present invention is a polymer represented by Chemical formula 18.

[0067]

[Chemical 18]

However, in the formula, Mc is a metallocene and R
Is a group having the above-mentioned nonlinear optical characteristics or photoconductivity.

The present invention is a polymer represented by Chemical formula 9.

[0070]

[Chemical 19]

However, in the formula, Pc is a phthalocyanine containing Si, Ge, Al, etc., and R is a group having the above-mentioned nonlinear optical characteristics or photoconductivity.

The present invention is a polymer represented by Chemical Formula 20.

[0073]

[Chemical 20]

However, in the formula, M is an organic metal group, metal-free phthalocyanine, metal phthalocyanine, porphyrin, annulene, metallocene, etc., and R is a group having the above-mentioned nonlinear optical characteristics or photoconductivity.

The present invention is a polymer represented by Chemical formula 21.

[0076]

[Chemical 21]

However, in the formula, R is a non-linear optical characteristic or photoconductive group as described above, and X is a photoconductive group as described above.

The present invention is a polymer having one of the compounds having the above-mentioned nonlinear optical characteristics and the photoconductive compound as a main chain and the other as a side chain.

The present invention comprises carboxylic acid, cholesteryl, phenyl ester, Schiff base, benzylidene, azoxybenzene, biphenyl, chiral alkole, benzoic acid, benzaldehyde, phenol, aniline, acetophenone, cyclohexanebiphenyl, benzonitrile, cyclohexanecarboxylic acid, Ferroelectric liquid crystals made of compounds such as alkylhalobenzene and chalcone, and polymers made of the above photoconductive compounds.

The present invention is characterized by using the above-mentioned non-linear optical property or a biopolymer comprising a photoconductive compound and cellulose, chitosan, amylose, levan, monan, xylan, chicken, peptide, inulin and the like. It is a polymer.

The present invention is a polymer comprising the above non-linear optical property compound and polyvinylcarbazole and poly-4-phenyl-2,6- (p-phenoxy) quinoline.

The present invention is a polymer comprising the above-exemplified nonlinear optical characteristic compound and a photochromic compound such as spiropyran, viologen, hemithioindigo, porphyrin, phthalocyanine, and diarylene.

The present invention is a polymer comprising an organic photoresist, an organic light emitting material, or an organic superconducting material and the above-mentioned nonlinear optical characteristic compound.

The polymer of the present invention has a film thickness of 0.1 to 5
A continuous solid film of 00 μ can be formed by a conventionally known method such as spin coating or molding. The molecular composition structure of the polymer of the present invention can be controlled by the selection and type of dispersion medium. The polymer of the present invention exhibits good heat resistance and chemical stability.

The present invention can be further embodied to provide a polymer of an organic electro-optical material exhibiting a large photorefractive characteristic. The response time can be selected in the range of millisecond to subpicosecond according to the type of polymer.

[0086]

The present invention will be described in more detail with reference to examples.

(Example 1) 0.1 g of chloromethyl-substituted polystyrene was dissolved in DMSO (15 ml). To this solution, 0.02 g of tetraaminocopper phthalocyanine D
MSO (15 ml) solution was added and the mixture was heated to 100-120 ° C for 3
The reaction was carried out for 6 hours. The product was poured into methanol, washed, and filtered. A dark blue polymer of the invention was obtained. Yield 50%.

(Example 2) 3.63 g of 2,2-bis (4-aminophenyl) hexafluoropropane was added to 2.
83 g of 4-fluoronitrobenzene was reacted in DMF with potassium carbonate as a catalyst at 80 ° C. for 6 hours. An 8-hexyl substituted product of dichlorosilicon phthalocyanine in an equimolar amount to the product was reacted in DMF with potassium carbonate as a catalyst at 100 ° C. for 24 hours. The product was vacuum dried to obtain the polymer of the present invention. Yield 55%.

[0089]

According to the present invention, a high-performance photorefractive polymer superior to conventional ones is provided and can be suitably used for various optical applications.

Claims (1)

[Claims] 1. A photorefractive polymer having a group having photoconductivity in its structure.