CN1887937A - Prepn process of double dot bond connected organic-inorganic hybridized non-linear optical material - Google Patents
Prepn process of double dot bond connected organic-inorganic hybridized non-linear optical material Download PDFInfo
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- CN1887937A CN1887937A CN 200610052047 CN200610052047A CN1887937A CN 1887937 A CN1887937 A CN 1887937A CN 200610052047 CN200610052047 CN 200610052047 CN 200610052047 A CN200610052047 A CN 200610052047A CN 1887937 A CN1887937 A CN 1887937A
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- double dot
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- nonlinear optical
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- 239000000463 material Substances 0.000 title claims abstract description 44
- 230000003287 optical effect Effects 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title description 6
- 238000002360 preparation method Methods 0.000 claims abstract description 19
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 claims abstract description 10
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002243 precursor Substances 0.000 claims abstract description 8
- 230000007062 hydrolysis Effects 0.000 claims abstract description 7
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 238000007259 addition reaction Methods 0.000 claims abstract description 3
- 239000000758 substrate Substances 0.000 claims abstract description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 24
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 12
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 125000001261 isocyanato group Chemical group *N=C=O 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- -1 silicon alkoxide Chemical class 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 4
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 238000002386 leaching Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 abstract description 4
- 238000004528 spin coating Methods 0.000 abstract description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 abstract 1
- 239000007788 liquid Substances 0.000 abstract 1
- 230000005693 optoelectronics Effects 0.000 abstract 1
- 229910000077 silane Inorganic materials 0.000 abstract 1
- 230000010287 polarization Effects 0.000 description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000013019 agitation Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 230000005684 electric field Effects 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000009396 hybridization Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000012982 microporous membrane Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000010365 information processing Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
Landscapes
- Silicon Polymers (AREA)
- Optical Modulation, Optical Deflection, Nonlinear Optics, Optical Demodulation, Optical Logic Elements (AREA)
Abstract
The present invention is preparation process of double dot bond connected or-inorganic hybridized non-linear optical material. Siloxane precursor is first prepared through the addition reaction between hydroxyl group-containing azobenzene dye and isocyazopropyltriethoxy silane, and then dissolved in organic solvent together with silanolate for full hydrolysis of the precursor and the silanolate. After stilling to age, filtering to obtain the clear liquid and spin coating on clean substrate, double dot bond connected or-inorganic hybridized non-linear optical material may be prepared. The preparation process is simple, and the prepared material has excellent non-linear optical performance and excellent polarizing orientation stability, and is expected to find practical application in optoelectronic modulating device.
Description
Technical field
The present invention relates to the preparation method of the double dot bond connected organic-inorganic hybridized nonlinear optical material of a class.
Background technology
Nonlinear optics plays a part very crucial to the development of photoelectron, photon technology, the material that utilization has different non-linear optical effects can produce such as various important components and parts that carry out optical information processing such as modulation, switch, storage and amplitude limits, thereby nonlinear optical material has become one of critical material indispensable in the photoelectron technology development.
The organic-inorganic hybridized non-linear optical material of sol-gel method preparation then is a kind of novel nonlinear optical material that occurs in recent years, it forms the unorganic glass network by metal alkoxide hydrolysis at ambient temperature, polycondensation, and organic constituent then combines with inorganic matrix by the mode of mixing or key connects.Broken through the boundary of traditional inorganic, organic non linear optical material by the organic-inorganic hybridized non-linear optical material of this method preparation, organic non-linear molecule and inorganic matrix are combined together on molecular level, not only have inorganic, both performance advantages of organic materials concurrently, and can realize the compound and cooperate optimization of function, be considered to one of the novel non-linearity optical material that obtains practical application that most possibly takes the lead in, thereby attracted various countries scientists' research interest and research enthusiasm.
Make the inorganic-organic hybridization material have second order nonlinear optical effect, must utilize external electric field that the organic chromophore molecular polarization in the film is orientated, detailed process is: when film is heated to certain temperature, add the external electric field processing that polarizes, chromophore molecule is orientated by direction of an electric field, for some time postcooling is to room temperature and remove external electric field, makes chromophore's orientation freeze.From thermodynamics, this polarization orientation of chromophore's dipole is a kind of " metasable state ", exists the trend to the state of disarray relaxation all the time, and along with this unstable trend of the rising of temperature just is serious more.Thereby, the key issue that the thermostability of improving the nonlinear material polarization orientation is it in electro-optical device is used must overcome.
In order to improve the stability of chromophore molecule polarization orientation, design and synthetic material system with multiple spot key company are considered to improve an effective way of chromophore's orientation stability.Because form crosslinked network structure, the free volume of material system will reduce, so the motion of chromophore molecule will be subjected to more constraint, and its polarization orientation is also just more stable.
Summary of the invention
The object of the present invention is to provide the preparation method of double dot bond connected organic-inorganic hybridized nonlinear optical material.This material not only has good non-linear optical property, and has excellent polarization orientation stability, is expected to obtain in electro-optical modulation device practical application.
The preparation method of double dot bond connected organic-inorganic hybridized nonlinear optical material provided by the invention, step is as follows:
Obtain the siloxane precursor body by the azobenzene dye and the addition reaction of isocyanato propyl-triethoxysilicane that contain two hydroxyls, containing the azobenzene dye of two hydroxyls and the mol ratio of isocyanato propyl-triethoxysilicane is 1: 1-2, again silicon alkoxide and siloxane precursor body are dissolved in organic solvent jointly, stirring and splashing into the pH value down is 1～4 acidic aqueous solution, continue to stir and make silicon alkoxide and the abundant hydrolysis of siloxane precursor body, mixed solution is after under the room temperature airtight still aging 1～15 day, cross the leaching clear liquor, be spin-coated on the clean substrate, get double dot bond connected organic-inorganic hybridized nonlinear optical material.
Among the above-mentioned preparation method the said azobenzene dye that contains two hydroxyls can adopt 4 '-(N, N-dihydroxy ethyl)-amido-4-nitroazobenzene or 4 '-(N, N-dihydroxy ethyl)-amido-2-chloro-4-nitroazobenzene; Said silicon alkoxide can be tetraethoxy, Union carbide A-162 or vinyltriethoxysilane; Said organic solvent can be tetrahydrofuran (THF), ethanol or acetone; Said acidic aqueous solution is aqueous hydrochloric acid, aqueous nitric acid or aqueous formic acid.
Beneficial effect of the present invention is:
Double dot bond connected organic-inorganic hybridized nonlinear optical material preparation method of the present invention is simple, this material not only has good non-linear optical property, and has excellent polarization orientation stability, be expected in electro-optical modulation device, obtain practical application, enriched the research contents of nonlinear optical material.
Embodiment
Embodiment 1:
Azobenzene dye is 4 '-(N, N-dihydroxy ethyl)-amido-4-nitroazobenzene, the preparation route of double dot bond connected organic-inorganic hybridized nonlinear optical material is:
The preparation method is:
Add 4 of 10mmol '-(N in the three-necked bottle of anhydrous and oxygen-free device toward reflux condensing tube being housed and connecting under the room temperature, the N-dihydroxy ethyl)-amido-4-nitroazobenzene, open anhydrous and oxygen-free device and logical nitrogen after 30 minutes, tetrahydrofuran (THF) and 8-10 that the firm drying treatment of adding 30ml is crossed drip triethylamine, magnetic agitation, the isocyanato propyl-triethoxysilicane that adds 5.92g (24mmol) again dropwises post-heating to 90 ℃, refluxes 60 hours.Pour reaction solution into normal hexane after reaction finishes and produce precipitation, obtain scarlet thickness oily product, use oil pump to remove solvent residual in the product, add the tetraethoxy of 50mmol and the tetrahydrofuran (THF) of 500mmol, after the magnetic agitation 30 minutes, dropwise add 240mmol pH and be 1 aqueous hydrochloric acid, continue to stir 6 hours, make the abundant hydrolysis of siloxane dye and tetraethoxy.The at room temperature airtight ageing of mixed solution is after 7 days, become colloidal sol with certain viscosity, after its via hole diameter is the filtering with microporous membrane of 0.22 μ m, use spin-coating method, promptly get required double dot bond connected organic-inorganic hybridized nonlinear optical material at the ito glass surface filming.
Inorganic-organic hybridization material in the present embodiment has bigger non-linear optical property, its second harmonic coefficient d
33Value is for 32.5pm/V, the material after the polarization under 160 ℃ through 10 minutes after, its d
33The value wave system is counted d
33Value is for 32.5pm/V, the material after the polarization under 160 ℃ through 10 minutes after, its d
33Value also remains 83% of initial value, after 30 minutes, also remains 74%.And at 100 ℃ of following constant temperature after 30 minutes, its d
33Value does not almost change.
Embodiment 2:
Azobenzene dye is 4 '-(N, N-dihydroxy ethyl)-amido-4-nitroazobenzene, the preparation method of double dot bond connected organic-inorganic hybridized nonlinear optical material is:
Add 4 of 10mmol '-(N in the three-necked bottle of anhydrous and oxygen-free device toward reflux condensing tube being housed and connecting under the room temperature, the N-dihydroxy ethyl)-amido-4-nitroazobenzene, open anhydrous and oxygen-free device and logical nitrogen after 30 minutes, tetrahydrofuran (THF) and 8-10 that the firm drying treatment of adding 30ml is crossed drip triethylamine, magnetic agitation, the isocyanato propyl-triethoxysilicane that adds 5.92g (24mmol) again dropwises post-heating to 90 ℃, refluxes 60 hours.Pour reaction solution into normal hexane after reaction finishes and produce precipitation, obtain scarlet thickness oily product, use oil pump to remove solvent residual in the product, add the vinyltriethoxysilane of 100mmol and the ethanol of 2mol, after the magnetic agitation 3 hours, dropwise add 400mmol pH and be 2 aqueous nitric acid, continue to stir 50 hours, make the abundant hydrolysis of siloxane dye and vinyltriethoxysilane.The at room temperature airtight ageing of mixed solution is after 15 days, become colloidal sol with certain viscosity, after its via hole diameter is the filtering with microporous membrane of 0.22 μ m, use spin-coating method, promptly get required double dot bond connected organic-inorganic hybridized nonlinear optical material at the ito glass surface filming.
Inorganic-organic hybridization material in the present embodiment has bigger non-linear optical property, its second harmonic coefficient d
33Value is for 41.3pm/V, and the material after the polarization is at 100 ℃ of following constant temperature after 30 minutes, its d
33Value does not almost change.
Embodiment 3:
Azobenzene dye is 4 '-(N, N-dihydroxy ethyl)-amido-2-chloro-4-nitroazobenzene, the synthetic route of double dot bond connected organic-inorganic hybridized nonlinear optical material is:
The preparation method is:
Add 4 of 10mmol '-(N in the three-necked bottle of anhydrous and oxygen-free device toward reflux condensing tube being housed and connecting under the room temperature, the N-dihydroxy ethyl)-amido-2-chloro-4-nitroazobenzene, open anhydrous and oxygen-free device and logical nitrogen after 30 minutes, tetrahydrofuran (THF) and 8-10 that the firm drying treatment of adding 30ml is crossed drip triethylamine, magnetic agitation, the isocyanato propyl-triethoxysilicane that adds 5.92g (24mmol) again dropwises post-heating to 90 ℃, refluxes 60 hours.Pour reaction solution into normal hexane after reaction finishes and produce precipitation, obtain thickness oily product, use oil pump to remove solvent residual in the product, add the Union carbide A-162 of 10mmol and the acetone of 200mmol, after the magnetic agitation 5 minutes, dropwise add 40mmol pH and be 4 aqueous formic acid, continue to stir 0.5 hour, make the abundant hydrolysis of siloxane dye and Union carbide A-162.The at room temperature airtight ageing of mixed solution is after 1 day, become colloidal sol with certain viscosity, after its via hole diameter is the filtering with microporous membrane of 0.22 μ m, use spin-coating method, promptly get required double dot bond connected organic-inorganic hybridized nonlinear optical material at the ito glass surface filming.
Inorganic-organic hybridization material in the present embodiment has bigger non-linear optical property, its second harmonic coefficient d
33Value is for 53.4pm/V, and the material after the polarization is at 100 ℃ of following constant temperature after 30 minutes, its d
33Value does not almost change.
The experimental result of above embodiment shows that all this double dot bond connected organic-inorganic hybridized nonlinear optical material not only has good non-linear optical property, and has excellent polarization orientation stability, is expected to obtain in electro-optical modulation device practical application.
Claims (5)
1. double dot bond connected type is inorganic-preparation method of organic hybrid nonlinear optical material, it is characterized in that may further comprise the steps:
Obtain the siloxane precursor body by the azobenzene dye and the addition reaction of isocyanato propyl-triethoxysilicane that contain two hydroxyls, containing the azobenzene dye of two hydroxyls and the mol ratio of isocyanato propyl-triethoxysilicane is 1: 1-2, again silicon alkoxide and siloxane precursor body are dissolved in organic solvent jointly, stirring and splashing into the pH value down is 1～4 acidic aqueous solution, continue to stir and make silicon alkoxide and the abundant hydrolysis of siloxane precursor body, mixed solution is after under the room temperature airtight still aging 1～15 day, cross the leaching clear liquor, be spin-coated on the clean substrate, double dot bond connected type inorganic-the organic hybrid nonlinear optical material.
2. double dot bond connected type according to claim 1 is inorganic-preparation method of organic hybrid nonlinear optical material, it is characterized in that the said azobenzene dye that contains two hydroxyls be 4 '-(N, the N-dihydroxy ethyl)-amido-4-nitroazobenzene or 4 '-(N, N-dihydroxy ethyl)-amido-2-chloro-4-nitroazobenzene.
3. double dot bond connected type according to claim 1 is inorganic-preparation method of organic hybrid nonlinear optical material, it is characterized in that said silicon alkoxide is tetraethoxy, Union carbide A-162 or vinyltriethoxysilane.
4. double dot bond connected type according to claim 1 is inorganic-preparation method of organic hybrid nonlinear optical material, it is characterized in that said organic solvent is tetrahydrofuran (THF), ethanol or acetone.
5. double dot bond connected type according to claim 1 is inorganic-preparation method of organic hybrid nonlinear optical material, it is characterized in that said acidic aqueous solution is aqueous hydrochloric acid, aqueous nitric acid or aqueous formic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200610052047 CN1887937A (en) | 2006-06-19 | 2006-06-19 | Prepn process of double dot bond connected organic-inorganic hybridized non-linear optical material |
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|---|---|---|---|
| CN 200610052047 CN1887937A (en) | 2006-06-19 | 2006-06-19 | Prepn process of double dot bond connected organic-inorganic hybridized non-linear optical material |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008138726A2 (en) * | 2007-05-11 | 2008-11-20 | Basf Se | Polymeric dyes |
| CN101921196B (en) * | 2009-06-10 | 2013-05-22 | 宁波大学 | Organic amine phosphate nonlinear optical crystal [C6H9N3O2][HPO4] |
| CN101266378B (en) * | 2007-12-28 | 2014-04-02 | 中国科学院上海硅酸盐研究所 | Organic-inorganic composite non-linear optical film and method for making same |
-
2006
- 2006-06-19 CN CN 200610052047 patent/CN1887937A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008138726A2 (en) * | 2007-05-11 | 2008-11-20 | Basf Se | Polymeric dyes |
| WO2008138726A3 (en) * | 2007-05-11 | 2009-04-02 | Ciba Holding Inc | Polymeric dyes |
| US7976585B2 (en) | 2007-05-11 | 2011-07-12 | BASF SE Ludwigshafen | Polymeric dyes |
| CN101266378B (en) * | 2007-12-28 | 2014-04-02 | 中国科学院上海硅酸盐研究所 | Organic-inorganic composite non-linear optical film and method for making same |
| CN101921196B (en) * | 2009-06-10 | 2013-05-22 | 宁波大学 | Organic amine phosphate nonlinear optical crystal [C6H9N3O2][HPO4] |
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