CN101289759B - Method for preparing inorganic-organic hybridized non-linear optical film of second order by electric field induction - Google Patents
Method for preparing inorganic-organic hybridized non-linear optical film of second order by electric field induction Download PDFInfo
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- CN101289759B CN101289759B CN2008100507561A CN200810050756A CN101289759B CN 101289759 B CN101289759 B CN 101289759B CN 2008100507561 A CN2008100507561 A CN 2008100507561A CN 200810050756 A CN200810050756 A CN 200810050756A CN 101289759 B CN101289759 B CN 101289759B
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Abstract
The invention relates to a method for preparing inorganic-organic hybrid second order nonlinear optical assembled monolayers by directionally multi-layer assembling dianion chromophores and siloxane oligomer the end-based bond of which is coupled with aromatic heavy azonia under electric field induction, which comprises the steps of: designing and synthesizing the dianion chromophores and the siloxane oligomer the end-based bond of which is coupled with the aromatic heavy azonia, enabling the chromophores to be directionally assembled with the heavy azonia under the electric field, original mutual static electricity action between diazo groups and carboxyl groups through exposing to ultraviolet light being changed into more stable through ester-based covalent bond connection through diazonium decomposition reaction, fixing the orientation and the molecularity of dipole molecules, and obtaining inorganic-organic hybrid second order nonlinear optical film materials with big second harmonic signals, high thermal stability and good chemical stability. The chromophore of the method has high deposition concentration, the process of high temperature polarization of polarized polymer can be avoided, and the method provides good materials for preparing electro-optic polymer waveguide and second order nonlinear optical devices.
Description
Technical field
The invention belongs to polymeric material field, particularly a kind of electric field induces down oriented multilayer assembling dianion chromophore molecule and end group binding to have the cationic siloxane oligomer of aromatic diazo to prepare the method for inorganic-organic hybridization second nonlinear optic assembling film.
Background technology
Along with the develop rapidly in practical fields such as optical communication, photoelectronics and optical information processing, the high non-linearity optically active material is more and more paid attention in the application prospect in these fields.As the important research direction of organic non linear optical material, polar polymer makes the dipole chromophore molecule in the material obtain high nonlinear optical property along the direction of an electric field orientations by the effect of electric field polarization.But organic materials must satisfy easily electric field polarization simultaneously and have the requirement that higher glass transition temperature is the aspect of these two mutual restriction of high thermal stability, and this is to the requirement of structure Design of macromolecule polymer material own and character harshness.Since nineteen nineties, along with the fast development of small molecules and polyelectrolyte layer-by-layer self-assembling technique, people focus on attention on the high molecular polymer and small molecules assembling film material of each auto-orientation of the self-assembling technique system of utilization.The after-polarization problem that these methods have avoided utilizing electric field to force dipole molecule to be orientated, but utilize molecule or supramolecule technology aligning at microscopic dimensions control chromophore molecule, and then utilize the orientation relaxation of the technology constraint dipole molecule such as crosslinked of polymer segment again, obtained the individual layer and the multilayer self-assembled film system of high SHG effect, this has opened up more wide development space for the development of second-order non-linear optical materials.
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, organic-inorganic hybridized non-linear optical material by this method preparation combines organic non-linear molecule and inorganic matrix 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.
Utilize the layer-by-layer technology to construct to have high molecular dipole auto-orientation degree, high molecule deposition concentration, high layer stability and the organic and inorganic-organic hybridization film layer structure of outstanding optical property just to be pursued by scientists.
Summary of the invention
The purpose of this invention is to provide and a kind ofly induce construction from part to prepare the method for high stability inorganic-organic hybridization Second-order non-linear optical thin film material with electric field.Various raw material of the present invention all is conventional materials, all can obtain from the commercial channel.
Inorganic-organic hybridization second nonlinear optic of the present invention induces assembling film to prepare by following process:
(1) substrate is handled, made its surface be rich in the carbonium group;
(2) under the lucifuge condition, dipole chromophore molecule and the sodium hydroxide that is its twice molar equivalent are made into the aqueous solution of 0.5～2.0mg/ml, the above-mentioned electrode basement that is rich in the carbonium group is put into the assembling pond make anode, with another electrode (as ito glass) relatively its parallel placement make negative electrode, carry out electric field and induce deposit, two interelectrode distances, 2～5mm, assembling volts DS 0.5～3.0V, take out after 15～30 minutes,, dry up with the high purity water flushing;
(3) under the lucifuge condition, the substrate after step (2) handled has in the cationic siloxane oligomer of aromatic diazo at the end group binding soaks 10～30min, takes out post-flush, dries up; Repeat electric field deposit step (2), (3), then assembling obtains non-linear multilayer film in substrate;
(4) non-linear multilayer film is exposed under 15～30W, 365nm wavelength ultraviolet lamp, then obtain the stable inorganic-organic hybridization second nonlinear optic assembling film of covalent cross-linking.
Substrate described in the aforesaid method is an ito glass, the quartz crystal of single face metallizing, the substrates such as silicon chip of single face metallizing.
For ito glass, be that the substrate that is cut into 1～2 * 2～5cm size is ultrasonic 5～20min in 1: 1～2 sodium hydroxide saturated solutions in water/ethanol volume ratio, make the substrate surface hydroxylation; Again substrate is soaked 24～36h in mass percent is 1%～5% mercaptopropyltriethoxysilane benzole soln, make its surface be rich in sulfydryl; Be that 1: 2～10 hydrogen peroxide and acetic acid soak 20～50min and handles with volume ratio again, make surperficial sulfhydryl oxidase become ionogenic sulfonate radical negative ion; At last under the lucifuge condition, the substrate of finishing sulfonate radical negative ion had in the cationic siloxane oligomer of aromatic diazo at the end group binding soak 10～30min, then use distilled water flushing, nitrogen dries up, thereby obtains being rich in the electrode basement of carbonium group;
For the quartz crystal of single face metallizing or the silicon chip of single face metallizing, be with its non-electrode one side carboxylic polymers soln of spin coating (as the poly-propylhomoserin solution among the embodiment 11), make the surface be rich in a large amount of carboxyl negative ions, then it is had in the cationic siloxane oligomer of aromatic diazo at the end group binding and soak, distilled water flushing, nitrogen dries up, thereby obtains the substrate that one side is rich in the carbonium group;
Dipole chromophore molecule described in the aforesaid method has higher order hyperpolarizability (β), and it has following structural formula:
Wherein, R
1It is the alkyl of 1～5 carbon atom; R
2It is the alkyl of 1～4 carbon atom; R
3Be phenyl, thienyl or azobenzene.
Above-mentioned dipole chromophore molecule with higher order hyperpolarizability (β), its preparation method may further comprise the steps:
(1) with mol ratio be 1: 2～5 to the nitro ring for formaldehyde and aqueous sodium polysulfide at ethanol and N, reflux in dinethylformamide (DMF) mixing solutions and stir, wet distillation, extracted with diethyl ether is purified, and obtains after the reduction the amino ring for formaldehyde;
(2) with mol ratio be 1: 1～1.5 to the amino ring for formaldehyde and cyanoacetic acid back flow reaction in dioxane, water washing and precipitating, precipitation obtains ring amino substituting group acetic ester of generation with sodium hydrogen carbonate solution dissolving, salt Acid precipitation;
(3) be the acid of 2～1: 1 haloalkyl with mol ratio with the N-alkyl benzene amine Anhydrous potassium carbonate (haloalkyl acid: Anhydrous potassium carbonate mol ratio=1: 1～2) in water solvent back flow reaction, filter, the salt Acid precipitation obtains (N-alkyl-N-phenyl) amido lipid acid;
(4) with mol ratio be 1: 1～2 to the ring mix cooling for the cyanamide yl acetate with (N-alkyl-N-phenyl) amido lipid acid, with with ring is obtained the atropurpureus powder for the aqueous solution azoization of the equimolar Sodium Nitrite of cyanamide yl acetate, through repeatedly recrystallization purification, obtain product at last.
What described step (1) was used is phenyl, thienyl or azobenzene for the ring of formaldehyde for group to the nitro ring.
Alkyl in (N-alkyl-N-phenyl) amido lipid acid that described step (3) is used is the alkyl of 1～5 carbon atom, and lipid acid is the lipid acid that contains 1～4 carbon atom alkyl.
Have three utmost point subcharacters on this novel chromophore molecule structure, especially the carboxyl functional group at two ends all can form the rigidity dipole molecule of two negative charges in ionization under the alkaline condition, because there is bigger asymmetry in the whole electronic cloud of this dipole molecule, under the effect of certain electrical forces the orientation behavior can take place, this point is utilized electrostatic interaction to assemble down important basis is provided for our inducing at electric field of carrying out in the later stage.
End group binding of the present invention has the cationic siloxane oligomer of aromatic diazo, and it is prepared by following method:
With mol ratio is that (mol ratio of Ursol D and salt of wormwood is 3～1: 1) at Anhydrous potassium carbonate for 1: 1～2 Ursol D and chloropropyl triethoxysilane, at exsiccant N, stirring reaction is 4～12 hours in dinethylformamide (DMF) solvent, filter, the hydrochloric acid and the water mixed solution that add mass concentration 1%～10% in the filtrate, stirring makes system become the silicon sol structure of pH=1～4, and 0～5 ℃ of following dropping makes the end group binding with the equimolar sodium nitrite in aqueous solution of Ursol D the cationic siloxane oligomer of aromatic diazo.
End group binding of the present invention has preparation method's the reaction equation of the cationic siloxane oligomer of aromatic diazo as follows:
The diazonium positively charged ion all contains the ionic structure of aromatic diazo salt, the cationic structural of aromatic diazo salt can with the negatively charged ion chromophore molecule electrostatic attraction of the two negative charges of band after the ionization, behind the uv-exposure, ionic linkage can be converted into the rock steady structure of ester group covalent linkage, the cationic siloxane oligomer of aromatic diazo is arranged the end group binding because the introducing of silica network provides the foundation for preparing the inorganic-organic hybridization assembling film.
Exposure process to the nonlinear optics multilayer film:
Under the uv-vis spectra tracking condition, UV-light with the 365nm wavelength is exposed to the multilayer film of assembling, the photolysis of seeing along with diazonium groups, interionic electrostatic interaction between original chromophore molecule and diazonium positively charged ion changes covalent linkage into, and generation along with crosslinking condition, polymer segment in the rete is cross-linked with each other and the silica network structure all makes the orientation of dipole chromophore molecule be fixed up, thereby can obtain having the inorganic-organic hybridization second nonlinear optic assembling film of high SHG effect and high heat resistance energy and ambient stable performance.
With the template mask exposure that the waveguide ribbon structure is arranged, unexposed part is washed off with the mixing solutions immersion of dimethyl formamide and water, the waveguide ribbon structure that Here it is constructs with direct ultraviolet light wrting method, and then the covering that applies then finally constructs waveguide device.
This assembling rete is tested through actual performance, with nine bilayers of 1.0V volts DS assembling is example, the about 400nm of thicknesses of layers, uniform surface, remove and possess higher second nonlinear optic response, also show outstanding thermostability and environmental stability: be warmed up to more than 200 degrees centigrade by original position after, the SHG response value can remain on more than 95% (Fig. 5) of initial value, (this point can be compared with the thermostability of current best polarized polymer thin film material); By H
2After O/DMF binary mixing solutions soaked 30min, its uv-vis spectra showed that maximum absorption peak only is declined by less than 7% (Fig. 3).In addition, measure by original position angle second harmonic generating technique, under this condition in the assembling rete chromophore molecule and base plane horizontal base line angle be 55 spend about, chromophoric arrangement has higher orientation degree (Fig. 4) in the rete.
The present invention compared with prior art has following advantage and beneficial effect:
(1) among the present invention, chromophore molecule has been orientated and settled density is largely increased in the film that directed assembling forms under electric field, has saved the after-polarization step;
(2) film that forms of assembling can form waveguide and omitted complex steps such as photoresist material mask and plasma etching by directly carrying out method that UV-light writes, for the making of modulation device is provided convenience;
(3) optoelectronic film of assembling formation is behind uv-exposure, dianion chromophoric group and end group binding have and change covalent linkage into by original ionic bonding between the cationic siloxane oligomer of aromatic diazo and link to each other, thereby the diazonium positively charged ion couples together by chromophoric group and forms crosslinking structure, stablized chromophoric orientation, for the thermostability and the permanent stability of the electro-optical characteristic of material provide guarantee;
(4) employing contains the cationic silica network of aromatic diazo oligopolymer, prepares inorganic-organic hybridization second nonlinear optic assembling film.Method of the present invention is fit to produce in enormous quantities in the practical application second nonlinear optic modulation device.
Description of drawings
Fig. 1: electric field induces the assembling process synoptic diagram (to deposit on a. conductive substrates; B. deposit on the insulating substrate);
Among Fig. 2: the embodiment 10, successively assemble the ultraviolet-visible spectrogram that 9 double-deck inorganic-organic hybridized non-linear blooming assembling process follow the tracks of (in the spectrogram curve number of plies increase gradually) from top to bottom under the 1V volts DS;
The inorganic-organic hybridized non-linear optics assembling film of Fig. 3: embodiment 10 methods preparation is at DMF/H
2(b) uv-absorbing spectrogram after (a) and the etching before the etching in the O mixed solvent;
The second harmonic signal intensity of the inorganic-organic hybridized non-linear optics assembling film of Fig. 4: embodiment 10 methods preparation is with the incident angle of light variation diagram;
The second harmonic signal intensity of the inorganic-organic hybridized non-linear optics assembling film of Fig. 5: embodiment 10 methods preparation varies with temperature figure.
As shown in Figure 1, be dipole chromophore molecule electric field induction and deposition device, wherein
(a) be apparatus for assembling on conductive substrates. Comprise: 1V DC voltage 1; Chromophore molecule solution 2; Ito glass conductive layer 3; Ito glass 4;
(b) be apparatus for assembling on dielectric base. Comprise: conducting metal 5 (such as the indium tin oxide among the embodiment 12); Insulating substrate 6 (such as the quartz crystal among the embodiment 12); Carboxylic polymer 7 (such as the polyamic acid of embodiment 11); 2V DC voltage 8.
As shown in Figure 2, the UV absorption intensity at 378nm and the 435nm place assembling number of plies is good linear relationship to be increased, and illustrates that electric field induces and have good order and continuity in the assembling process.
As shown in Figure 3, assembling film by solvent etched after absorption intensity reduce less than 7%, illustrate that covalent cross-linking structure in the film and silica network structure are so that the nonlinear optics assembling film has good environmental stability.
As shown in Figure 4, when incident laser became 55 ° of angles with the rete plane, maximum appearred in the second harmonic signal of assembling film, and this is the expression that shows the dipole directionality on the rete macroscopic view.
As shown in Figure 5, in the time of 200 ℃, the second harmonic signal of assembling film still can keep more than 95% of initial value, illustrates that covalent cross-linking structure in the film and silica network structure are so that the nonlinear optics assembling film has very high heat endurance.
Embodiment:
In order to be illustrated more clearly in the present invention, the embodiment that is listed below, but it does not have any restriction to scope of the present invention.
Embodiment 1:
Synthesizing of p-Aminobenzaldehyde
In the Erlenmeyer flask of 150ml, add Na
2S9H
2O 9.7428g, NaOH 9.0933g, sublimed sulphur 5.1962g, 100ml deionized water are stirred to xanchromatic sulphur and all dissolve on magnetic stirring apparatus, be a bolarious transparent Na this moment
2S
5Solution.
In the three-necked bottle of the 250ml capacity that reflux condensing tube, agitator and dropping funnel are housed, add paranitrobenzaldehyde 18.0798g, 92% ethanol 100ml and account for 1% dimethyl formamide 0.3572g, in water-bath, be heated to little boiling (81 ℃) and make it become homogeneous milk sap, with the fresh Na that makes above
2S
5Solution splashed in 1.5 to 2.0 hours, kept stirring 1 to 1.5 hour, took out reaction solution, carried out wet distillation, and till the pH=7.0 of effluent liquid, raffinate extracts 5 times with anhydrous diethyl ether, uses anhydrous Na
2SO
4Drying reclaims ether with Rotary Evaporators, and underpressure distillation products obtained therefrom low-temperature vacuum drying gets p-Aminobenzaldehyde yellow solid 4.6958g, productive rate 32.56% again.
To synthesizing of phenylamino cyan-acetic ester
In three-necked bottle, add p-Aminobenzaldehyde and the 3.2972g cyanoacetic acid that 4.6958g example 1 obtains, add the 110ml dioxane again, splash into 0.15ml pyridine and 0.45ml acetate, refluxed underpressure distillation 10 hours, remove and desolvate, residuum washes with water, filters, and gets product and places small beaker dry, purified product is the CH of the orange-yellow powder suspension that obtains at 150ml
2CL
2In, adding 220ml, 10% sodium hydrogen carbonate solution again, the stirring system is until residual solids disappeared, use the separating funnel separatory, water layer is transferred pH=4 with 10% hydrochloric acid, filters and obtains yellow mashed prod, azeotropic benzene distillation, underpressure distillation obtain clean product 3.2450g, productive rate 44.53%.
Synthesizing of (N-methyl-N-phenyl) glycine
The chloracetic acid of 7g is dissolved in the 30ml water.To wherein dripping K
2CO
3The aqueous solution to pH=8, be made into the chloracetic acid sodium solution.With 7.9g methylphenylamine and 5.1g K
2CO
3Be dissolved in 30ml water after be added in the above-mentioned chloracetic acid sodium solution for preparing, add ethanol as the solvent of holding concurrently, not stratified up to solution, the back is at N
2Protection refluxed 72 hours down, and 35 ℃ of underpressure distillation boil off ethanol.After add 10% salt acid for adjusting pH value to 1, left standstill 8 hours, obtain white needle-like crystals.Wash solid with a large amount of dehydrated alcohols behind the filtration drying, obtain white powder 6.4g, productive rate 59%.
Chromophore molecule 2-({ 4-[4-(2-carboxyl-2-cyano group-vinyl)-azobenzene]-phenyl }-methyl-amino)-acetate (DRCB) synthetic
To 1g embodiment 2 obtain to cyanamide guanidine-acetic acid fat in splash into the hydrochloric acid of 4ml 10%, ultrasonicly make moltenly, back ice bath cools to below 5 ℃, with 0.039g NaNO
2Be dissolved in the 20ml water, slowly be added drop-wise to above-mentioned solution, continue to keep temperature, 5 ℃ are stirred 30min, solution by pale yellow become orange, (N-methyl-N-phenyl) glycine 0.88g that embodiment 3 obtains is dissolved in 20ml water, slowly be added in the above-mentioned solution, solution colour reddens rapidly and becomes purple more again, keeps low temperature to continue to stir 2h, after rise to normal temperature, add ammoniacal liquor up to pH=8, at this moment produce a large amount of bubbles, stir 2h, salt acid for adjusting pH value to 2 with 10%, separate out a large amount of atropurpureus solids, filter, with a large amount of washings, dry back obtains atropurpureus powder 0.8g, yield 41% with ethyl alcohol recrystallization.FT-IR(KBr)：3385(s，OH)，2217(s，CN)，1716(s，C＝O)，1596(s，benz?ring)，1373(s，N＝N)cm
-1，
1H?NMR(DMSO-d
6，ppm)：δ＝8.39(s，1H，CH＝C)，8.20(d，2H，ArH)，7.92(d，2H，ArH)，7.84(d，2H，ArH)，6.85(d，2H，ArH)，4.29(s，2H，CH
2)，3.12(s，3H，CH
3).UV-vis(C
2H
5OH)：478.5nm。
Synthesizing of 2-({ 4-(4-aldehyde radical-azothiazole base)-phenyl }-methyl-amino)-acetate
(2.5g 10mmol) stirs disposable adding 5-nitro-2-carboxaldehyde radicals thiophene (1.0g with 3.0ml concentrated hydrochloric acid (37%) to the inferior tin of two hydration dichloride, 3.3mmol) tetrahydrofuran (THF) (3.0ml) in, exothermic heat of reaction, temperature rise to 50 ℃, naturally cool to room temperature then.Add glacial acetic acid (10.0ml) and propionic acid (5.0ml), be cooled to-10 ℃, (0.25g, aqueous solution 3.6mmol) dropwise-10 ℃ of reactions 0.5 hour, obtain the diazonium salt solution of clear to add Sodium Nitrite.(N-methyl-N-phenyl) glycine (0.7g that embodiment 3 is obtained, 4.0mmol) be dissolved in 36% acetic acid solution (20ml), add sodium acetate, be cooled to-10 ℃ and splash into above-mentioned diazonium salt solution, dropwise at-5 ℃ and continue reaction 1 hour, suction filtration is collected solid, and wash with water colourless till.Use the acetone solution solid, solution is spin-dried for, collect and obtain solid, separate obtaining red solid, yield 62% through column chromatography (ethyl acetate/petroleum ether=1/3～1/4).
Chromophore molecule 2-({ 4-[4-(2-carboxyl-2-cyano group-vinyl)-azothiazole base]-phenyl }-methyl-amino)-acetate (DRSB) synthetic
In three-necked bottle, add 2-({ 4-(4-aldehyde radical-azothiazole base)-phenyl }-methyl-amino)-acetate and 3.2972g cyanoacetic acid that 11.7584g embodiment 5 obtains, add the 110ml dioxane again, splash into 0.15ml pyridine and 0.45ml acetate, refluxed underpressure distillation 10 hours, remove and desolvate, residuum washes with water, filters, and gets product and places small beaker dry, purified product is the CH of the orange-yellow powder suspension that obtains at 150ml
2CL
2In, at the sodium hydrogen carbonate solution that adds 220ml10%, the stirring system until residual solids disappeared, is used the separating funnel separatory, and water layer is transferred pH=4 with 10% hydrochloric acid, and filter and obtain yellow mashed prod, the azeotropic benzene distillation, underpressure distillation obtains clean product.Yield 55%.
Synthesizing of [4-(2-carboxyl-2-cyano group-vinyl)-azobenzene]-aniline
To 1g embodiment 2 obtain to cyanamide guanidine-acetic acid fat in splash into the hydrochloric acid of 4ml 10%, ultrasonicly make moltenly, back ice bath cools to below 5 ℃, with 0.039g NaNO
2Be dissolved in the 20ml water, slowly be added drop-wise to above-mentioned solution, continue to keep temperature, 5 ℃ are stirred 30min, and solution becomes orangely by pale yellow, and 0.053 gram aniline is dissolved in the 5ml10% hydrochloric acid and slowly is added in the above-mentioned solution again, solution colour reddens rapidly, keeps low temperature to continue to stir 2h, after rise to normal temperature, add ammoniacal liquor up to pH=8, stir 2h, salt acid for adjusting pH value to 2 with 10%, separate out a large amount of atropurpureus solids, filter, with a large amount of washings, dry back obtains the atropurpureus powder with ethyl alcohol recrystallization.Yield 85%.
Chromophore molecule 2-({ 4-[4-(2-carboxyl-2-cyano group-vinyl)-azobenzene]-phenyl }-methyl-amino)-acetate (DRNB) synthetic
Splash into the hydrochloric acid of 4ml 10% in [4-(2-carboxyl-2-cyano group-vinyl)-azobenzene]-aniline that 1.55g example 7 obtains, ultrasonicly make moltenly, back ice bath cools to below 5 ℃, with 0.039g NaNO
2Be dissolved in the 20ml water, slowly be added drop-wise to above-mentioned solution, continue to keep temperature, 5 ℃ are stirred 30min, (N-methyl-N-phenyl) glycine 0.88g that example 3 obtains is dissolved in 20ml water, slowly is added in the above-mentioned solution again, and solution colour becomes purple rapidly, keep low temperature to continue to stir 2h, after rise to normal temperature, add ammoniacal liquor up to pH=8, at this moment produce a large amount of bubbles, stir 2h, salt acid for adjusting pH value to 2 with 10% is separated out a large amount of atropurpureus solids, filters, with a large amount of washings, dry back obtains the atropurpureus powder with ethyl alcohol recrystallization.Yield 77%.
Embodiment 9
The end group key connects the synthetic of aromatic diazo cationic silicone oligopolymer
With 2.617g (20mmol) Ursol D, 4.841g (20mmol) chloropropyl triethoxysilane, 1.380g (10mmol) Anhydrous potassium carbonate is dissolved in 50ml exsiccant N, 95 ℃ of stirring reactions are 8 hours in the dinethylformamide, filter, get and add 30ml water and 60ml N in the filtrate, dinethylformamide (DMF) stirs, and adds concentrated hydrochloric acid 10ml, stirring at room 6 hours, ice bath is cooled to 0-5 ℃, lucifuge drips and contains the 1.38g Sodium Nitrite, and the solution of 5ml water stirs half an hour, filter, it is standby to get the filtrate lucifuge.FT-IR(KBr)：3444(s，-Ar-NH-)，2615(s，Ar-N
2 +)，1097(s，Si-O-Si)cm
-1；Uv-vis：332.6nm(DMF)。
Embodiment 10
The preparation electric field is induced inorganic-organic hybridization second nonlinear optic assembling film in the ITO substrate
The ito glass that will be cut into 2 * 3cm size is that ultrasonic 20min makes the substrate surface hydroxylation in 1: 1 sodium hydroxide saturated solution in water/ethanol volume ratio.The substrate of surface hydroxylation is soaked 24h in mass percent is the benzole soln of 1% mercaptopropyltriethoxysilane, make its surface be rich in sulfydryl, be 1: 2 hydrogen peroxide and acetic acid mixing solutions immersion 30min processing again with volume ratio, make surperficial sulfhydryl oxidase become ionogenic sulfonate radical negative ion, at last under the lucifuge condition, the substrate of finishing sulfonate radical negative ion had in the cationic siloxane oligomer of aromatic diazo at the end group binding soak 10min, distilled water flushing, nitrogen dries up, thereby on the indium tin oxide of ito glass, modify the last layer positive charge, obtain being rich in the electrode basement of carbonium group;
Under the lucifuge condition, embodiment 4 dipole chromophore molecule DRCB that obtains and the sodium hydroxide that is its twice molar equivalent are made into the aqueous solution of 0.5mg/ml, the above-mentioned electrode basement that is rich in the carbonium group is put into the assembling pond make anode, it makes negative electrode relatively with an other ito glass, device carries out electric field and induces deposit as shown in Figure 1a, two interelectrode distance 2.5mm, assembling volts DS 1V, take out after 20 minutes, then on the carbonium group, assemble last layer dipole chromophore molecule in order, with the high purity water flushing, dry up;
Under the lucifuge condition, again the substrate after the top processing is had in the cationic siloxane oligomer of aromatic diazo at the end group binding of embodiment 9 preparation and soak 10min, then deposition last layer end group binding has the cationic siloxane oligomer of aromatic diazo on the dipole chromophore molecule, take out post-flush, dry up.
Repeat the electric field deposit and be soaked in the end group key to connect aromatic diazo cationic silicone oligopolymer step 9 time, then assembling obtains 9 layers non-linear multilayer film; At 25W, 365nm wavelength ultraviolet lamp is exposure down, then obtains the stable inorganic-organic hybridization second nonlinear optic assembling film of covalent cross-linking with non-linear multilayer film.
Synthesizing of polyamic acid
0.184g (1mmol) 4,4 '-diamines yl diphenyl ether is dissolved in 5ml exsiccant N, among the N '-dimethyl formamide (DMF), and 0.294g (1mmol) 3,3 '-4,4 '-BPDA is added gradually and was stirred 24 hours, obtains being rich in the polyamic acid solution of carboxyl.
Embodiment 12
The preparation electric field is induced inorganic-organic hybridized non-linear optics assembling film on quartz substrate
With the poly-propylhomoserin solution of quartz crystal to obtain among 1000 rpms of spin coating last layer embodiment 11, make the surface be rich in a large amount of carboxyl negative ions, at last, in the one side that is not coated with polyamic acid at the indium tin oxide that plates about 0.5 micron of one deck on the vacuum evaporation instrument.
Under the lucifuge condition, the substrate of handling above had in the cationic siloxane oligomer of aromatic diazo at the end group binding soak 10min, distilled water flushing, nitrogen dries up, thereby obtains the substrate that one side is rich in the carbonium group;
Under the lucifuge condition, dipole chromophore molecule DRCB for preparing among the embodiment 4 and the sodium hydroxide that is its twice molar equivalent are made into the aqueous solution of 0.5mg/ml, above-mentioned substrate of being rich in carbonium group and evaporation indium tin chloride electrode put into as Fig. 1 b assembling pond make anode, it makes negative electrode relatively with an other ito glass, carries out electric field and induces deposit, two interelectrode distance 2.5mm, assembling volts DS 2V, take out after 20 minutes,, dry up with the high purity water flushing;
Under the lucifuge condition, the substrate after the top processing is had in the cationic siloxane oligomer of aromatic diazo at the end group binding soak 10min again, take out post-flush, dry up; Repeating the electric field deposit and being soaked in the end group binding has the cationic siloxane oligomer step of aromatic diazo, and then assembling obtains non-linear multilayer film; At 25W, 365nm wavelength ultraviolet lamp is exposure down, then obtains the stable inorganic-organic hybridization second nonlinear optic assembling film of covalent cross-linking with non-linear multilayer film.
Claims (6)
1. the electric field inducement preparation method of inorganic-organic hybridized non-linear optical film of second order, it comprises the steps:
A) substrate is handled, made its surface be rich in the carbonium group;
B) under the lucifuge condition, dipole chromophore molecule and the sodium hydroxide that is its twice molar equivalent are made into the aqueous solution of 0.5～2.0mg/ml, the above-mentioned electrode basement that is rich in the carbonium group is put into the assembling pond make anode, negative electrode is made in relative its parallel placement of another electrode, carried out electric field and induce deposit, two interelectrode distances, 2～5mm, assembling volts DS 0.5～3.0V, take out after 15～30 minutes,, dry up with the high purity water flushing;
C) under the lucifuge condition, the substrate after step b) handled has in the cationic siloxane oligomer of aromatic diazo at the end group binding soaks 10～30min, takes out post-flush, dries up; Repeat electric field deposit step b), c), then assembling obtains non-linear multilayer film in substrate;
D) non-linear multilayer film is exposed under 15～30W, 365nm wavelength ultraviolet lamp, then obtain the stable inorganic-organic hybridization second nonlinear optic assembling film of covalent cross-linking.
2. the electric field inducement preparation method of inorganic-organic hybridized non-linear optical film of second order as claimed in claim 1, it is characterized in that: substrate is the quartz crystal of ito glass, single face metallizing or the silicon chip of single face metallizing.
3. the electric field inducement preparation method of inorganic-organic hybridized non-linear optical film of second order as claimed in claim 1, it is characterized in that: the end group binding has the structural formula of the cationic siloxane oligomer of aromatic diazo as follows,
4. the electric field inducement preparation method of inorganic-organic hybridized non-linear optical film of second order as claimed in claim 1, it is characterized in that: the structural formula of dipole chromophore molecule is as follows,
Wherein, R
1It is the alkyl of 1～5 carbon atom; R
2It is the alkyl of 1～4 carbon atom; R
3Be phenyl, thienyl or azobenzene.
5. the electric field inducement preparation method of inorganic-organic hybridized non-linear optical film of second order as claimed in claim 4 is characterized in that: the dipole chromophore molecule is 2-({ 4-[4-(2-carboxyl-2-cyano group-vinyl)-azobenzene]-phenyl }-methyl-amino)-acetate.
6. the electric field inducement preparation method of inorganic-organic hybridized non-linear optical film of second order as claimed in claim 4 is characterized in that: the dipole chromophore molecule is 2-({ 4-[4-(2-carboxyl-2-cyano group-vinyl)-azothiazole base]-phenyl }-methyl-amino)-acetate.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1456585A (en) * | 2003-05-28 | 2003-11-19 | 武汉大学 | Second order nonlinear optical polyorganosiloxane linked with azoindolol chromogen pendant group and preparation and use thereof |
| CN1866119A (en) * | 2006-06-19 | 2006-11-22 | 浙江大学 | Inorganic-organic hybridized non-linear optical film and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1456585A (en) * | 2003-05-28 | 2003-11-19 | 武汉大学 | Second order nonlinear optical polyorganosiloxane linked with azoindolol chromogen pendant group and preparation and use thereof |
| CN1866119A (en) * | 2006-06-19 | 2006-11-22 | 浙江大学 | Inorganic-organic hybridized non-linear optical film and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| Yao Wang 等.Electric-Field-Induced Layer-by-Layer Fabrication of Second-Order Nonlinear Optical Films with High Thermal Stability.Langmuir20 21.2004,20(21),8952-8954. |
| Yao Wang 等.Electric-Field-Induced Layer-by-Layer Fabrication of Second-Order Nonlinear Optical Films with High Thermal Stability.Langmuir20 21.2004,20(21),8952-8954. * |
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