CN104845051A - Neutral conjugated polymer-layered double hydroxides composite film and preparation method thereof - Google Patents
Neutral conjugated polymer-layered double hydroxides composite film and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the field of organic-inorganic composite material and preparation technology thereof, and discloses a neutral conjugated polymer-layered double hydroxides composite film and a preparation method thereof. According to the preparation method, a neutral conjugated polymer with opto-electronic functions and layered double hydroxides (LDHs) nanosheets obtained via separation from an organic solvent are subjected to layer-by-layer assembling so as to obtain the neutral conjugated polymer-layered double hydroxides composite film material. The preparation method is simple; opto-electronic functions and thickness of the neutral conjugated polymer-layered double hydroxides composite film are accurate and controllable in nanoscale; the neutral conjugated polymer-layered double hydroxides composite film is obtained based on non-electrostatic force, Van der Waals' force and hydrogen bonds; a limit that LDHs subject can only be assembled with anion object is broken through; layer by layer self-assembly of the neutral conjugated polymer with the layered double hydroxides nanosheets is realized with creativity; opto-electronic function optimization and regulation of the conjugated polymer are realized; assembling range and application range of inorganic supramolecular materials are widened; and fundamental research is provided for application of LDHs in the field of conjugated polymer molecular photovoltaic device preparation.
Description
Technical field
The invention belongs to composite organic-inorganic material and preparing technical field thereof, in particular, provide a kind of neutral conjugated polymers and hydrotalcite composite film and preparation method thereof.
Background technology
Conjugated polymers typically refers to molecule and has included linear π-π
*one class conjugated polyolef iotans of electron-conjugated system, the polymkeric substance of poly-aromatic ring and fragrant heterocycle etc.Normally non-water-soluble, there is very strong light absorptive and fluorescence emitting characteristics, and molecular chain has molecular wire function, energy and electric charge can conduct fast along the large π-electron conjugated system in backbone structure, make conjugated polymers have the character of semi-conductor.Organic semiconductor material and the conducting polymer materials of application prospect is had so class conjugated polymers is also a kind of pole.Conjugated polymers photoelectron material had both had the electrical and optical properties of metal and inorganic semiconductor, had again the pliable and tough mechanical property of organic polymer and workability, electrochemical redox activity.Its most important feature is that the photoelectric characteristics such as its absorption, transmitting and conduction are easily undertaken improving and regulating by simple chemically modified (namely introducing specific functional group), thus by realizing the control of the performance such as photoelectricity, sensing to device to the chemically modified of material.These features determine conjugated polymers photoelectron material and will play a significant role in the exploitation of the organic optoelectronic device in future and electrochemical device and development above.In nearest time more than ten years, the photoelectric characteristic of its uniqueness, makes to grip polymkeric substance altogether and obtains investigation and application very widely in the fields such as polymer photoelectron device and chemical switch, fluorescence sense, biochemical sensor, photovaristor, polymer laser such as photodiode (LED), solar cell, field-effect transistors.
The kind of conjugated polymers is more, mainly contains: polyphenylene ethylene (PPV), polyaniline (PANI), polyvinyl carbazole (PVK), Polythiophene (PTh), polypyrrole (PPy), polyacetylene (PA), polydiacetylene, poly-to benzene (PPP), polyparaphenylene's acetylene (PPE), polyfluorene (PFO), polyvinylpyridine (P2VP) etc. and derivative thereof.
Poly-(3-hexyl thiophene) (P3HT) is the electron donor material that organic solar batteries is dominated.[6,6]-phenyl-C61-methyl-butyrate (PCBM) is the derivative of soccerballene, as electron acceptor(EA), is widely used in polymer device.From 2002, based on poly-(3-hexyl thiophene-2,5-bis-base) the bulk-heterojunction organic solar batteries of (P3HT) and [6,6]-phenyl C61 methyl-butyrate (PCBM) become at present popular research field in the world.But its efficiency of conversion is also lower.Therefore, how improving effciency of energy transfer is problem in the urgent need to address at present.Polyfluorene and derivative thereof are representative, the current extensively research of a class most and the blue emitting material having development potentiality most.Polyparaphenylene's acetylene and derivative thereof are the conjugated polymerss of another kind of blue light-emitting.Also be famous organic photoconductor containing carbazole type polymkeric substance.
Layered double hydroxide (Layered Double Hydroxides), be abbreviated as LDHs, also known as hydrotalcite, being the anionic type laminated material of a quasi-representative, is the three-dimensional crystalline structure that the two-dimentional oxyhydroxide laminate of positively charged and interlayer anion are piled up in order by electrostatic interaction and formed.The mutual high dispersing of oxyhydroxide of divalence and trivalent metal ion is also formed main body laminate with ionic linkage, interlayer anion ordered arrangement, and with electrostatic force balance main body laminate electric charge, entirety presents electric neutrality.Its laminate metallic element kind, ratio is adjustable, and interlayer ion is commutative, and the individual layer nanometer sheet of peelable one-tenth high dispersing, therefore can design and synthesis several functions matrix material.
In theory, the LDHs based on electrostatic force is easier to realize with negatively charged ion object LBL self-assembly ratio, and neutral molecule cannot realize the LBL self-assembly with LDHs due to neutral.Polymer anion, title complex negatively charged ion etc. with negative charge are carried out alternately assembling forming composite superthin film with hydrotalcite nano piece, of common occurrence, but, the research that hydrotalcite nano piece and neutral molecule are assembled also is rarely had report so far.Organic photoelectric function neutral conjugated polymers is due to the π-π * electron-conjugated system of its uniqueness, its molecule has larger deformability and polarizability, based on the Van der Waals force (London force, inductive capacity and dipole-dipole force) between itself and LDHs or hydrogen bond, the invention achieves the LBL self-assembly of water-insoluble not ionizable organic photoelectric function neutral conjugated polymers and LDHs.
Summary of the invention
The object of this invention is to provide a kind of neutral conjugated polymers and hydrotalcite composite film and preparation method thereof.Its preparation process is simple, and film photoelectric performance and thickness can at Nano grade controllable precise.
Technical scheme of the present invention is: by the hydrotalcite nano piece peeled off in photoelectric functional neutral conjugated polymers and organic solvent through layer assembly method, form structurally ordered neutral conjugated polymers and hydrotalcite composite film material.This composite functional material takes full advantage of the rigid structure of hydrotalcite and the confinement effect of two-dimensional space and host-guest interaction, and the pre-support of neutral conjugated polymers and carry the micromolecular effect of organic photoelectric functional, make polymkeric substance and organic molecule dispersed in hydrotalcite layers, achieve photoelectric functional optimization and the regulation and control of conjugated polymers, for the further functionalization of molecular self-assembly and conjugated conductive polymer and device have paved road.
Neutral conjugated polymers of the present invention and hydrotalcite composite film, described film is photoelectric function thin films, it is by organic constituent neutral conjugated polymers or add the neutral conjugated polymers of neutral organic molecule and inorganic component hydrotalcite nano piece and alternately to assemble layer by layer at three-dimensional space and formed, there is obvious laminate structure feature, simultaneously according to the assembling difference of the number of plies and the difference of neutral conjugated polymers concentration, film thickness evenly can regulate and control between 8-600 nanometer.
The preparation process of neutral conjugated polymers of the present invention and hydrotalcite composite film is as follows:
1. preparing interlayer anion is NO
3 -, laminate divalence, trivalent metal cation mol ratio are the hydrotalcite precursor of 2.0-4.0; Then add in formamide solvent and peel off, add-on is 0.05-2g/L, and stirring velocity is 3000-5000 rev/min, to react after 12-48 hour 1000-3000 rev/min centrifugal, discard throw out, obtain clear nitrate radical intercalated houghite colloidal solution B;
2. prepare the neutral conjugated polymers solution C of 0.01g/L-1g/L, solvent is chlorobenzene or toluene;
3. prepare the mixing solutions D of neutral conjugated polymers and neutral organic molecule, wherein the mass ratio of neutral conjugated polymers and organic molecule is (10:1)-(1:10), the concentration of neutral conjugated polymers is 0.01g/L-1g/L, and solvent is chlorobenzene or toluene;
4. by the quartz plate after hydrophilicity-imparting treatment, silicon chip or ITO sheet are put into solution B and are soaked 10-20 minute, take out, after fully cleaning with deionized water, place in solution C or solution D again, soak after 10-20 minute and take out, fully clean with dehydrated alcohol, the neutral conjugated polymers once circulated and hydrotalcite composite film;
5. repeating step 4 in solution B, and alternate immersion operation 1-100 time in solution C or solution D, obtains multilayer neutral conjugated polymers and hydrotalcite composite film.
The laminate divalent metal of described hydrotalcite precursor is Mg
2+, Co
2+, Ni
2+, Zn
2+, Cd
2+, Ca
2+, Cu
2+, Fe
2+or Mn
2+, trivalent metal cation is Al
3+, Cr
3+, Ga
3+, In
3+, Co
3+, Fe
3+or V
3+.
Described neutral conjugated polymers is poly-3-hexyl thiophene, polyparaphenylene's acetylene, poly-(9,9-dihexyl fluorenes), conjugated polymers containing fluorenes and carbazole structure.
Described neutral conjugated polymers is poly-(3-hexyl thiophene-2,5-bis-base), poly-(2,5-bis-(2 '-ethylhexyl)-Isosorbide-5-Nitrae-ethynylene), poly-(9,9-di-n-hexyl fluorenyl-2,7-bis-base), poly-(9,9-n-dihexyl-2,7-fluorenes-alt-9-phenyl-3,6-carbazole), poly-[(9,9-dihexyl fluorenes-2,7-bis-base)-co-(9-ethyl carbazole-2,7-bis-base)].
Described organic molecule is fullerene derivate.
Described organic molecule is [6,6]-phenyl C61 methyl-butyrate.
Described method of hydrophilizing is: by quartz plate, and silicon chip or ITO sheet volume ratio are the dense H of (9:1)-(1:1)
2sO
4soak 30-60 minute with hydrogen peroxide mixed solution, then fully clean with deionized water.
The invention has the beneficial effects as follows: based on non-electrostatic force, i.e. intermolecular weak Van der Waals force and hydrogen bond, and unconventional stronger electrostatic force, the present invention takes the lead in achieving with Polythiophene, polyfluorene, polyparaphenylene's acetylene photoelectric functional molecule is the serial neutral conjugated polymers of representative and the layer assembly of organic photoelectric function small molecules and LDH nanometer sheet, breach in the past LDHs main body only can with negatively charged ion, the boundary of cation guests assembling, creativeness achieves the LBL self-assembly of neutral conjugated polymers and inorganic hydrotalcite nano piece, achieve conjugated polymers photoelectric functional to optimize and regulation and control, assembling category and the range of application of inorganic supramolecular materials are expanded, and provide fundamental research in the application of conjugated polymers molecular optoelectronic device preparation field for hydrotalcite.
Accompanying drawing explanation
The uv absorption spectra of Fig. 1 to be the assembling number of plies that embodiment 1 obtains be poly-3-alkylthrophene/hydrotalcite composite luminescent ultrathin film of 4 to 20 layers, for carrying out a UV spectrum test every 4 layers in figure.Illustration is the changing conditions that 515 and 554 nanometers absorbancys increase with the assembling number of plies.
Fig. 2 to be the assembling number of plies of poly-(9,9-dihexyl fluorenes)/hydrotalcite composite film that the embodiment of the present invention 2 obtains be fluorescence emission spectrogram of 4 to 16 layers.Excitation wavelength 386 nanometer.
Fig. 3 to be the assembling number of plies of polyhenylene acetylene/hydrotalcite composite film that the embodiment of the present invention 3 obtains be fluorescence emission spectrogram of 4 to 16 layers.Excitation wavelength 365 nanometer.
Fig. 4 to be the assembling number of plies that embodiment 4 obtains be 5 to 20 layers poly-(9,9-n-dihexyl-2,7-fluorenes-alt-9-phenyl-3,6-carbazole) uv absorption spectra of/hydrotalcite composite luminescent ultrathin film, for carrying out a UV spectrum test every 5 layers in figure.Illustration is the changing conditions that 237 and 341 nanometers absorbancys increase with the assembling number of plies.
Fig. 5 to be the assembling number of plies of poly-(9,9-n-dihexyl-2,7-fluorenes-alt-9-phenyl-3,6-carbazole)/hydrotalcite composite film that the embodiment of the present invention 4 obtains be fluorescence emission spectrogram of 5 to 20 layers.Excitation wavelength 353 nanometer.
Fig. 6 to be the assembling number of plies that embodiment 5 obtains be 5 to 20 layers poly-[(9,9-dihexyl fluorenes-2,7-bis-base)-co-(9-ethyl carbazole-2,7-bis-base)] uv absorption spectra of/hydrotalcite composite luminescent ultrathin film, for carrying out a UV spectrum test every 5 layers in figure.Illustration is 215,237, and the changing conditions that 379 nanometers absorbancys increase with the assembling number of plies.
Fig. 7 to be the assembling number of plies of poly-[(9,9-dihexyl fluorenes-2,7-bis-base)-co-(9-ethyl carbazole-2,7-bis-base)]/hydrotalcite composite film that the embodiment of the present invention 5 obtains be fluorescence emission spectrogram of 5 to 20 layers.Excitation wavelength 380 nanometer.
Fig. 8 is the assembling number of plies that embodiment 6 obtains is the poly-3-hexyl thiophene of 5 to 40 layers, the uv absorption spectra of [6,6]-phenyl C61 methyl-butyrate (PCBM)/hydrotalcite composite film, for carrying out a UV spectrum test every 5 layers in figure.Illustration is the changing conditions that 267,336 and 455 nanometers absorbancys increase with the assembling number of plies.
The little angle XRD figure that Fig. 9 is poly-3-hexyl thiophene, [6,6]-phenyl C61 methyl-butyrate (PCBM)/hydrotalcite composite film assembling number of plies that the embodiment of the present invention 6 obtains when being 50 layers.
Embodiment
[embodiment 1]
1. coprecipitation method prepares nitrate radical hydrotalcite precursor:
A. nitrate mixed solution A is prepared, by the solid Mg (NO of 0.02mol
3)
26H
2solid Al (the NO of O and 0.01mol
3)
39H
2o is dissolved in 50mL except CO
2deionized water in;
B. 0.06mol NaOH is dissolved in 50mL except CO
2deionized water in;
C. the alkaline solution that step b prepares is placed in four-hole bottle, at N
2under the condition of gas shielded, vigorous stirring, while the solution A that step a prepares slowly dripped in four-hole bottle, about 0.5h drips off, and after being added dropwise to complete, by the NaOH solution of 5mol/L, its pH value is adjusted to 8,60 DEG C of water-bath 24h, with removing CO
2deionization hot water centrifuge washing be about 7 to pH, 70 DEG C of dry 24h, obtain magnalium type nitrate radical intercalated houghite;
2. get the above-mentioned nitrate radical intercalated houghite of 0.1g to stir 24 hours in 100 milliliters of formamide solvent, stirring velocity is 3000 revs/min, by the hydrotalcite solution centrifugal after stripping, and rotating speed 1500 revs/min, discard throw out, obtain clear magnalium type nitrate radical intercalated houghite colloidal solution B;
3. prepare the chlorobenzene solution C of the poly-3-hexyl thiophene of 0.1g/L;
4. by dense for quartz plate volume ratio 7:3 H
2sO
4soak 30 minutes, after deionized water fully cleans with hydrogen peroxide mixed solution, put into solution B and soak 10 minutes.Take out, after fully cleaning with deionized water, then place in solution C, soak 10 minutes and fully clean with ethanolic soln, the poly-3-hexyl thiophene once circulated and hydrotalcite composite film;
5. repeating step 4, obtains multilayer and gathers 3-hexyl thiophene and hydrotalcite composite film.
The film that the assembling number of plies is 20 layers is characterized: as shown in Figure 1, poly-3-hexyl thiophene and hydrotalcite composite film are along with the increase of assembling the number of plies, the maximum absorption band of its ultra-violet absorption spectrum presents continuous rising tendency, and absorbancy and the assembling number of plies are close to linear relationship, show that the poly-3-hexyl thiophene of each assembling is fixed value.
[embodiment 2]
1. nucleation/crystallization isolation method prepares nitrate radical hydrotalcite precursor:
A. nitrate mixed solution A is prepared, by the solid Mg (NO of 0.02mol
3)
26H
2solid Al (the NO of O and 0.01mol
3)
39H
2o is dissolved in 50mL except CO
2deionized water in;
B. 0.06mol NaOH is dissolved in 50mL except CO
2deionized water in;
C. the nitrate mixed solution A prepared by step a and the alkaline solution of step b add colloidal mill simultaneously, control rotating speed 4000 revs/min, react 1 minute, proceed in the water heating kettle of polytetrafluoroethylsubstrate substrate, and 110 DEG C are reacted 24 hours, adopt except CO
2deionization hot water centrifuge washing to neutral, 70 DEG C of dryings 24 hours, obtain magnalium type nitrate radical intercalated houghite;
2. get the above-mentioned nitrate radical intercalated houghite of 0.1g to stir 24 hours in 100 milliliters of formamide solvent, stirring velocity is 3000 revs/min, by the hydrotalcite solution centrifugal after stripping, and rotating speed 1500 revs/min, discard throw out, obtain clear magnalium type nitrate radical intercalated houghite colloidal solution B;
3. prepare the toluene solution C of poly-(9, the 9-dihexyl fluorenes) of 0.01g/L;
4. by the dense H of volume ratio 7:3 quartz plate
2sO
4soak 30 minutes, after deionized water fully cleans with hydrogen peroxide mixed solution, put into solution B and soak 10 minutes.Take out, after fully cleaning with deionized water, then place in solution C, soak 10 minutes and fully clean with ethanolic soln, poly-(9, the 9-dihexyl fluorenes) and the hydrotalcite composite superthin film that are once circulated;
5. repeating step 4, obtains multilayer poly-(9,9-dihexyl fluorenes) and hydrotalcite composite film.
Characterize the film that the assembling number of plies is 16 layers: characterized from the fluorescence emission spectrum of Fig. 2, poly-(9,9-dihexyl fluorenes) is 422,446 nanometers with the emission wavelength of hydrotalcite laminate ordered fabrication film, is blue light emitting region.
[embodiment 3]
By the method in embodiment 2, the toluene solution of poly-(9, the 9-dihexyl fluorenes) of 0.01g/L in step 3 is changed into the toluene solution of polyparaphenylene's acetylene of 0.01g/L.Obtain multilayer polyparaphenylene acetylene and hydrotalcite composite film.
Be that polyparaphenylene's acetylene of 16 layers and hydrotalcite composite film characterize to the gained assembling number of plies: characterized from the fluorescence emission spectrum of Fig. 3, the emission wavelength of polyparaphenylene's acetylene and hydrotalcite laminate ordered fabrication film is 417,442 nanometers are blue light emitting region.
[embodiment 4]
By the method in embodiment 2, the toluene solution of poly-(9, the 9-dihexyl fluorenes) of 0.01g/L in step 3 is changed into the toluene solution of poly-(9,9-n-dihexyl-2,7-fluorenes-alt-9-phenyl-3, the 6-carbazole) of 0.01g/L.Obtain multilayer poly-(9,9-n-dihexyl-2,7-fluorenes-alt-9-phenyl-3,6-carbazole) and hydrotalcite composite film.
Be 20 layers poly-(9 to the gained assembling number of plies, 9-n-dihexyl-2,7-fluorenes-alt-9-phenyl-3,6-carbazole) characterize with hydrotalcite composite film: as shown in Figure 4, this laminated film is along with the increase of the assembling number of plies, the maximum absorption band of its ultra-violet absorption spectrum presents continuous rising tendency, and absorbancy and the assembling number of plies are close to linear relationship, show poly-(9, the 9-n-dihexyl-2 of each assembling, 7-fluorenes-alt-9-phenyl-3,6-carbazole) be fixed value.Characterized from the fluorescence emission spectrum of Fig. 5, the emission wavelength of this ordered fabrication film is 403 nanometers, is blue light emitting region.
[embodiment 5]
By the method in embodiment 2, the toluene solution of poly-(9, the 9-dihexyl fluorenes) of 0.01g/L in step 3 is changed into poly-[(9, the 9-dihexyl fluorenes-2 of 0.01g/L, 7-bis-base)-co-(9-ethyl carbazole-2,7-bis-base)] toluene solution.Obtain multilayer poly-[(9,9-dihexyl fluorenes-2,7-bis-base)-co-(9-ethyl carbazole-2,7-bis-base)] and hydrotalcite composite film.
Be 20 layers poly-[(9 to the gained assembling number of plies, 9-dihexyl fluorenes-2,7-bis-base)-co-(9-ethyl carbazole-2,7-bis-base)] characterize with hydrotalcite composite film: as shown in Figure 6, this laminated film is along with the increase of the assembling number of plies, the maximum absorption band of its ultra-violet absorption spectrum presents continuous rising tendency, and absorbancy and the assembling number of plies are close to linear relationship, show poly-[(9 of each assembling, 9-dihexyl fluorenes-2,7-bis-base)-co-(9-ethyl carbazole-2,7-bis-base)] be fixed value.Characterized from the fluorescence emission spectrum of Fig. 7, the emission wavelength of this ordered fabrication film is 420,444 nanometers, is blue light emitting region.
[embodiment 6]
1. ion exchange method prepares nitrate radical hydrotalcite precursor:
A. by the solid Mg (NO of 0.015mol
3)
26H
2solid Al (the NO of O and 0.0075mol
3)
39H
2o and 0.075mol urea is dissolved in the deionized water of 75mL, and in the tetrafluoroethylene pressure reacting container of 100 milliliters, under 100 DEG C of conditions, crystallization 12 hours, is about 7 with deionized water centrifuge washing to pH, and 70 DEG C of dry 12h, obtain carbonate hydrotalcite;
B. above-mentioned carbonate hydrotalcite 0.3g and solid NaNO is got
363.75g is dissolved in 300mL except CO
2deionized water in, after dispersed, after adding 0.1mL concentrated nitric acid, stir under nitrogen atmosphere condition, normal temperature carries out ion exchange reaction after 12 hours with except CO
2deionization hot water centrifuge washing be about 7 to pH, 70 DEG C of dry 18h, obtain magnalium type nitrate radical intercalated houghite;
2. get the above-mentioned nitrate radical intercalated houghite of 0.1g to stir 24 hours in 100 milliliters of formamide solvent, stirring velocity is 4000 revs/min, by the hydrotalcite solution centrifugal after stripping, and rotating speed 1500 revs/min, discard throw out, obtain clear magnalium type nitrate radical intercalated houghite colloidal solution B;
3. the poly-3-hexyl thiophene and [6 of preparation, the mixing chlorobenzene solution D of 6]-phenyl C61 methyl-butyrate (PCBM), wherein the concentration of poly-3-hexyl thiophene is 0.5g/L, and it is 1:5 with the mass ratio of [6,6]-phenyl C61 methyl-butyrate (PCBM);
4. by dense for quartz plate volume ratio 7:3 H
2sO
4soak 30 minutes, after deionized water fully cleans with hydrogen peroxide mixed solution, put into solution B and soak 10 minutes.Take out, after fully cleaning with deionized water, then place in solution D, soak 10 minutes and fully clean with ethanolic soln, the poly-3-hexyl thiophene, [6,6]-phenyl C61 methyl-butyrate (PCBM) and the hydrotalcite composite film that are once circulated;
5. repeating step 4, obtains that multilayer gathers 3-hexyl thiophene, [6,6]-phenyl C61 methyl-butyrate (PCBM) and hydrotalcite assemble laminated film altogether.
The film that the assembling number of plies is 40 layers is characterized: as shown in Figure 8, poly-3-hexyl thiophene, [6,6]-phenyl C61 methyl-butyrate (PCBM) and hydrotalcite composite film are along with the increase of assembling the number of plies, the maximum absorption band of its ultra-violet absorption spectrum presents continuous rising tendency, and absorbancy and the assembling number of plies are close to linear relationship, show that poly-3-hexyl thiophene and [6,6]-phenyl C61 methyl-butyrate (PCBM) of each assembling are fixed value.
The little angle XRD of Fig. 9 characterizes known, poly-3-hexyl thiophene and [6,6]-phenyl C61 methyl-butyrate (PCBM) and the success of hydrotalcite ordered fabrication, in its XRD spectra, 003 diffraction peak appears at 1.15 °, calculate interlamellar spacing and be about 7.68nm, illustrate that poly-3-hexyl thiophene and [6,6]-phenyl C61 methyl-butyrate (PCBM) are at hydrotalcite layers ordered arrangement.
[embodiment 7]
1. ion exchange method prepares nitrate radical hydrotalcite precursor:
A. by the solid Mg (NO of 0.015mol
3)
26H
2solid Al (the NO of O and 0.0075mol
3)
39H
2o and 0.075mol urea is dissolved in the deionized water of 75mL, and in the tetrafluoroethylene pressure reacting container of 100 milliliters, under 100 DEG C of conditions, crystallization 12 hours, is about 7 with deionized water centrifuge washing to pH, and 70 DEG C of dry 12h, obtain carbonate hydrotalcite;
B. above-mentioned carbonate hydrotalcite 0.3g and solid NaNO is got
363.75g is dissolved in 300mL except CO
2deionized water in, after dispersed, after adding 0.1mL concentrated nitric acid, stir under nitrogen atmosphere condition, normal temperature carries out ion exchange reaction after 12 hours with except CO
2deionization hot water centrifuge washing be about 7 to pH, 70 DEG C of dry 18h, obtain magnalium type nitrate radical intercalated houghite;
2. get the above-mentioned nitrate radical intercalated houghite of 0.1g to stir 24 hours in 100 milliliters of formamide solvent, stirring velocity is 4000 revs/min, by the hydrotalcite solution centrifugal after stripping, and rotating speed 1500 revs/min, discard throw out, obtain clear magnalium type nitrate radical intercalated houghite colloidal solution B;
3. prepare the toluene solution C of polyparaphenylene's acetylene of 0.01g/L;
4. the poly-3-hexyl thiophene and [6 of preparation, the mixing chlorobenzene solution D of 6]-phenyl C61 methyl-butyrate (PCBM), wherein the concentration of poly-3-hexyl thiophene is 0.5g/L, and it is 1:5 with the mass ratio of [6,6]-phenyl C61 methyl-butyrate (PCBM);
5. by dense for quartz plate volume ratio 7:3 H
2sO
4soak 30 minutes, after deionized water fully cleans with hydrogen peroxide mixed solution, put into solution B and soak 10 minutes, take out, after fully cleaning with deionized water, then place in solution C, soak 10 minutes and fully clean with ethanolic soln, then putting into solution B immersion 10 minutes.Take out, after fully cleaning with deionized water, then place in solution D, soak 10 minutes and fully clean with ethanolic soln;
6. repeating step 4,20 times, obtains multilayer polyparaphenylene acetylene, poly-3-hexyl thiophene, [6,6]-phenyl C61 methyl-butyrate (PCBM) and hydrotalcite and assembles laminated film altogether.
Claims (8)
1. a neutral conjugated polymers and hydrotalcite composite film, it is characterized in that, described film is photoelectric function thin films, it is by organic constituent neutral conjugated polymers or add the neutral conjugated polymers of neutral organic molecule and inorganic component hydrotalcite nano piece and alternately to assemble layer by layer at three-dimensional space and formed, there is obvious laminate structure feature, simultaneously according to the assembling difference of the number of plies and the difference of neutral conjugated polymers concentration, film thickness evenly can regulate and control between 8-600 nanometer.
2. a preparation method for neutral conjugated polymers and hydrotalcite composite film, is characterized in that, its concrete operation step is as follows:
1). preparation interlayer anion is NO
3 -, laminate divalence, trivalent metal cation mol ratio are the hydrotalcite precursor of 2.0-4.0; Then add in formamide solvent and peel off, add-on is 0.05-2g/L, and stirring velocity is 3000-5000 rev/min, to react after 12-48 hour 1000-3000 rev/min centrifugal, discard throw out, obtain clear nitrate radical intercalated houghite colloidal solution B;
2). the neutral conjugated polymers solution C of preparation 0.01g/L-1g/L, solvent is chlorobenzene or toluene;
3). the mixing solutions D of preparation neutral conjugated polymers and neutral organic molecule, wherein the mass ratio of neutral conjugated polymers and organic molecule is (10:1)-(1:10), the concentration of neutral conjugated polymers is 0.01g/L-1g/L, and solvent is chlorobenzene or toluene;
4). by the quartz plate after hydrophilicity-imparting treatment, silicon chip or ITO sheet are put into solution B and are soaked 10-20 minute, take out, after fully cleaning with deionized water, place in solution C or solution D again, soak after 10-20 minute and take out, fully clean with dehydrated alcohol, the neutral conjugated polymers once circulated and hydrotalcite composite film;
5). repeating step 4) in solution B, and alternate immersion operation 1-100 time in solution C or solution D, obtains multilayer neutral conjugated polymers and hydrotalcite composite film.
3. preparation method according to claim 2, is characterized in that, the laminate divalent metal of described hydrotalcite precursor is Mg
2+, Co
2+, Ni
2+, Zn
2+, Cd
2+, Ca
2+, Cu
2+, Fe
2+or Mn
2+, trivalent metal cation is Al
3+, Cr
3+, Ga
3+, In
3+, Co
3+, Fe
3+or V
3+.
4. preparation method according to claim 2, is characterized in that, described neutral conjugated polymers is poly-3-hexyl thiophene, polyparaphenylene's acetylene, poly-(9,9-dihexyl fluorenes), conjugated polymers containing fluorenes and carbazole structure.
5. preparation method according to claim 2, it is characterized in that, described neutral conjugated polymers is poly-(3-hexyl thiophene-2,5-bis-base), poly-(2,5-bis-(2 '-ethylhexyl)-1,4-ethynylene), poly-(9,9-di-n-hexyl fluorenyl-2,7-bis-base), poly-(9,9-n-dihexyl-2,7-fluorenes-alt-9-phenyl-3,6-carbazole), poly-[(9,9-dihexyl fluorenes-2,7-bis-base)-co-(9-ethyl carbazole-2,7-bis-base)].
6. preparation method according to claim 2, is characterized in that, described organic molecule is fullerene derivate.
7. preparation method according to claim 2, is characterized in that, described organic molecule is [6,6]-phenyl C61 methyl-butyrate.
8. preparation method according to claim 2, is characterized in that, described method of hydrophilizing is: by quartz plate, and silicon chip or ITO sheet volume ratio are the dense H of (9:1)-(1:1)
2sO
4soak 30-60 minute with hydrogen peroxide mixed solution, then fully clean with deionized water.
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