CN104045827B - A kind of organic electroluminescent nano composite material and its preparation method and application - Google Patents
A kind of organic electroluminescent nano composite material and its preparation method and application Download PDFInfo
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- CN104045827B CN104045827B CN201410252919.XA CN201410252919A CN104045827B CN 104045827 B CN104045827 B CN 104045827B CN 201410252919 A CN201410252919 A CN 201410252919A CN 104045827 B CN104045827 B CN 104045827B
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Abstract
The invention discloses a kind of organic electroluminescent nano composite material, it is with small molecule electroluminescent material for core, and electrically conductive polyaniline is the nucleocapsid structure that shell builds the solution processable made; Described small molecule electroluminescent material is selected from aromatic compound (as benzene, naphthalene, fluorenes etc.) and derivative thereof.The preparation method of this organic electroluminescent nano composite material is as follows: be first mixed with surfactant soln; Then selected part surfactant soln, is dissolved in ammonium persulphate wherein, is denoted as solution A; By aniline monomer and small molecule electroluminescent material dissolves in the surfactant soln of remainder, be denoted as solution B, solution B is stirred in water bath with thermostatic control; Solution B is dropwise joined in solution A, after dropwising, continues to be uniformly mixed liquid; Emulsion splitter breakdown of emulsion is added, then suction filtration, vacuum-drying, obtained organic electroluminescent nano composite material in mixed solution.Above-mentioned organic electroluminescent nano composite material can be applied in organic electroluminescence device.
Description
Technical field
The present invention relates to the organic compound functional materials in Materials science and the application in organic electroluminescent technology thereof, particularly relate to a kind of organic electroluminescent nano composite material and its preparation method and application.
Background technology
Luminescent material in organic electroluminescence device can be divided into Small molecule organic materials and polymer organic materials.Small molecule organic materials is mainly through vacuum vapour deposition film forming, and the method needs vacuum apparatus costly, and waste of material is serious; Polymer organic materials carrys out film forming mainly through spin-coating, silk screen printing and spray ink Printing mode.Wherein spray ink Printing is a kind of non-impact type digital printing technologies, because of its have with low cost, print speed fast, can be applicable to the advantages such as different substrates and be widely used in the processing of organic electroluminescence device, obtain the thin-film device of excellent property.Compare polymer luminescent material, small molecule material have structure determine, synthesize controlled, reproducible, can the advantage such as conventional organic chemistry procedures purifying, need not adulterate, can process and obtain high-level efficiency electroluminescent device.But the equipment cost of the vacuum vapour deposition that organic molecule adopts is higher, technics comparing is complicated, and waste of material is serious, is difficult to realize big area film forming, therefore seriously hinders the industrialization process of organic electroluminescence device (OLED).Say in a sense, the small molecule electroluminescent material of synthesis of soluble liquid processing is the key of dealing with problems.At present, micromolecular solution processable, mainly by carrying out structural modification to small molecule monomer in synthesis, regulates the particular functional group of monomer and structural unit to realize.But this kind of method requires harsher to reaction conditions, and production cost is still higher.Therefore, the commercial applications of efficient OLED be realized, must develop be applicable to low cost, can the material synthesis technology of electroluminous organic small molecular material of big area film forming.
Summary of the invention
Based on above-mentioned technical problem, the object of the present invention is to provide a kind of organic electroluminescent nano composite material and its preparation method and application.
The technology used in the present invention solution is:
A kind of organic electroluminescent nano composite material, it is with small molecule electroluminescent material for core, and electrically conductive polyaniline is the composite material of core-shell structure that shell builds the solution processable made.
Preferably, described small molecule electroluminescent material is selected from aromatic compound and derivative thereof.
More preferred, described small molecule electroluminescent material is selected from following structural compound:
A preparation method for organic electroluminescent nano composite material, comprises the following steps:
A chooses tensio-active agent, is mixed with surfactant soln;
The surfactant soln that b selected part step a is mixed with, is dissolved in ammonium persulphate wherein, is denoted as solution A; By aniline monomer and small molecule electroluminescent material dissolves in the surfactant soln of remainder, be denoted as solution B, solution B is stirred in water bath with thermostatic control;
Solution B dropwise joins in solution A by c, after dropwising, continues to be uniformly mixed liquid;
D adds emulsion splitter breakdown of emulsion, then suction filtration, vacuum-drying, obtained organic electroluminescent nano composite material in the obtained mixed solution of step c.
In step a: described tensio-active agent is preferably Sodium dodecylbenzene sulfonate.
In step b: described small molecule electroluminescent material is preferably selected from following structural compound:
The temperature of described water bath with thermostatic control is preferably 20 DEG C, and churning time is preferably 30min.
In step c: dripping the process used time is preferably 30min, and after dropwising, being uniformly mixed the liquid used time is preferably 2.5h.
In steps d: described emulsion splitter is preferably ethanol, described vacuum-drying temperature is preferably 20 DEG C, and time of drying is preferably 24h.
Above-mentioned organic electroluminescent nano composite material can be used for spray ink Printing, to prepare organic photoelectric core-shell nano composite material film.
Above-mentioned organic electroluminescent nano composite material can be used as electron transport material for the preparation of organic electroluminescence device.
Advantageous Effects of the present invention is:
(1) initiative of the present invention by small molecule electroluminescent material and can the electrically conductive polyaniline of spray ink Printing combine, make it form the matrix material of nano-core-shell structure, this matrix material has solution processable, has good electroconductibility and thermostability simultaneously.
(2) under the impregnable condition of photoelectric properties ensureing material, adopt inkjet technology to realize the preparation of thickness and the homogeneous composite material film of performance, film forming is more even.
(3) present invention process aspect adopts in-situ emulsion polymerization, by regulating shape and the size of micella, and then regulates and controls matrix material pattern; Utilize the quantum size effect of nano material to regulate size and the component concentration of matrix material, achieve the adjustment to material photoelectric properties, easy operation and control.
Accompanying drawing explanation
The preparation process schematic diagram of to be shell organic molecule the be organic electroluminescent nano composite material of core that Fig. 1 is polyaniline;
Fig. 2 a illustrates the infrared spectrogram of matrix material, spectrogram when be the molar content of fluorenes from top to bottom respectively in figure being 0.5%, 1%, 1.5%, 2%, 2.5%;
Fig. 2 b illustrates the x-ray diffraction pattern of matrix material, spectrogram when be the molar content of fluorenes from top to bottom respectively in figure being 0.5%, 1%, 1.5%, 2%, 2.5%;
Fig. 3 illustrates polyaniline, fluorenes and matrix material scanning electron microscope (SEM) photograph; From left to right, from top to bottom respectively polyaniline is shown in Fig. 3 a, fluorenes, fluorenes/polyaniline (molar content of fluorenes is 0.5%), fluorenes/polyaniline (molar content of fluorenes is 1%), the scanning electron microscope (SEM) photograph of fluorenes/polyaniline (molar content of fluorenes is 1.5%); Fluorenes/polyaniline (molar content of fluorenes is 2%) is from left to right shown respectively, the scanning electron microscope (SEM) photograph of fluorenes/polyaniline (molar content of fluorenes is 2.5%) in Fig. 3 b;
Fig. 4 illustrates polyaniline to be shell fluorenes is the specific conductivity of core matrix material.
Embodiment
Embodiment 1
A preparation method for organic electroluminescent nano composite material, comprises the following steps:
A. Sodium dodecylbenzene sulfonate (DBSA) the solution 40ml of 0.21mol/L is prepared.
B. the ammonium persulphate (APS) of 1.14g is dissolved in 20mlDBSA solution, is denoted as solution A; The aniline monomer of 0.47g and 0.12g fluorenes are dissolved in remaining 20mlDBSA solution, be denoted as solution B, this solution stirs 30min in the water bath with thermostatic control of 20 DEG C.
C. B solution dropwise joined in solution A, this process lasts is about 30min.After dropwising, continue to be uniformly mixed liquid 2.5h.
D. in above-mentioned mixed solution, add excess ethyl alcohol breakdown of emulsion, filter, 60 DEG C of vacuum-drying 24h, obtained organic electroluminescent nano composite material.
The matrix material of above-mentioned preparation take fluorenes as core, and electrically conductive polyaniline is that shell builds the nucleocapsid structure made, and has solution processable, has good electroconductibility and thermostability simultaneously.
The luminescent properties of above-mentioned matrix material, electronic transmission performance and solution processability can all realize by the ratio of adjustment nucleocapsid component and size; And the preparation of thickness and the homogeneous composite material film of performance is realized by inkjet technology.
About the preparation process of composite material film, be summarized as follows:
A. dissolving the matrix material of 0.5g at 30mL is in NMP (N-Methyl pyrrolidone) solution of 13mg/mL, magnetic agitation 24h, then ultrasonic agitation 1h.
B. in above-mentioned solution, be slowly added dropwise to ethylene glycol, ethanol and deionized water in proportion can be made into printable ink, the interpolation volume of ethylene glycol, ethanol and deionized water account for respectively liquor capacity 2%, 2%, 70-75%.Regulate the physical parameters such as the viscosity of ink, surface tension and pH value, the printable ink of different ingredients can be made.
Above-mentioned printable ink prints on flexible substrates with ink-jetting style by c respectively, with obtained organic photoelectric core-shell nano composite material film.
Carry out Performance Detection to organic electroluminescent nano composite material, result as in Figure 2-4.
As shown in Figure 2 a, there is the characteristic peak of polyaniline that Witco 1298 Soft Acid adulterate in (phenyl ring faces in and out-of-plane vibration peaks), 1293 (aromatic amine C-Ns), 1504 and 1556 (phenyl group and quinonyl group absorption peaks), 3561 and 3648 (N-H vibration absorption peaks) in 803 and 1127 to polyaniline.The extension vibration mode of 1326 and 1383 place correspondence-C-N-keys, 1467,1499 and 1580 places are the eigen vibration absorption mode of aromatic nucleus skeleton, 1604 places correspond to the skeleton extension vibration mode of-C=C-key in aromatic nucleus, the c h bond in the corresponding aromatic nucleus in 2965 places.
As shown in Figure 2 b, the XRD figure of mixture and PANI contrasts the characteristic diffraction peak all about 20 ° and 25 ° with polyaniline, has all occurred the characteristic diffraction peak of polyaniline at about 22 ° and 24 ° of places.New characteristic diffraction peak has all been there is at 32 ° and 34 ° of places, these two characteristic diffraction peaks are that independent PANI and fluorenes do not have, which illustrate in nucleocapsid structure forming process and may create transition interface between fluorenes and PANI, the result of this phenomenon and FTIR is consistent, indicates polyaniline further and creates coating function to fluorenes.
As shown in Figure 3, the pattern mainly square structure of fluorenes is found by scanning electron microscopic observation, again fluorenes to be compared with the sample of matrix material discovery: the particle diameter of the particle of mixture significantly increases compared to fluorenes, and present lumphy structure, describe the surface that aniline monomer has been adsorbed on fluorenes particulate and carried out in-stiu coating polymerization.This is because polyaniline is a kind of polymkeric substance of indissoluble, aniline monomer can not only be adsorbed on surface by fluorenes particulate, and the effect serving nucleus facilitates the growth of polyaniline on its surface, thus forms the granular substance of dispersion instead of reunite together.In the present invention, n (fluorenes): n (PANI) is up to 2.5%, all the aniline added can be adsorbed on completely surface aggregate form fluorenes/PANI nucleocapsid structure particulate by Fig. 3 b when the molar content that can be observed fluorenes is 2% and 2.5%.Can be observed n (fluorenes): n (PANI) by Fig. 3 a is again 0.5%, 1%, all there is the phenomenon being agglomerated into block in the mixture of 1.5%, this mainly because can not adsorb the aniline monomer in the system of being dispersed in completely when fluorenes content is less, causes it directly to aggregate into the lumphy structure of reunion in the solution.
The specific conductivity of mixture raises along with the increase of fluorenes content as can be seen from Figure 4, and be up to 6.5S/m, minimum is 1.32S/m.Fluorenes is as electron transport material, and its electroconductibility is much stronger than PANI, fluorenes is used as core and is coated in PANI the effect serving and improve matrix material electron transport ability.The conductivity of matrix material and the formation of nucleocapsid structure are also closely-related, when n (fluorenes): n (PANI) is 0.5%, 1%, 1.5%, the spherical micelle formed in the solution due to excessive aniline monomer is assembled agglomerating, has occurred that the aggregated particles of PANI makes specific conductivity promote uneven in mixture.Time n (fluorenes): n (PANI)=2%, specific conductivity presents maximum.This may be because suitable core-shell material mol ratio and good dispersion state effectively prevent the reunion of polyaniline, fluorenes is evenly distributed in polyaniline shell, improves specific conductivity largely.Time n (fluorenes): n (PANI)=2.5%, specific conductivity reduces on the contrary.May be because fluorenes is excessive, in the process preparing dispersion liquid, occur fluorenes coacervate, define fluorenes aggregate/PANI nucleocapsid structure.Fluorenes as electron transport material defines aggregate, although the effect improving electric transmission effect can be played in local, but as can be seen from the shape appearance figure of matrix material: the spacing between macrobead is larger, define larger gap compared with small-sized composite material microparticles, need to apply larger potential difference when carrying out electronic transmission process and just can complete.
Embodiment 2
A preparation method for organic electroluminescent nano composite material, comprises the following steps:
A. Sodium dodecylbenzene sulfonate (DBSA) the solution 40ml of 0.21mol/L is prepared.
B. the ammonium persulphate (APS) of a certain amount of 1.14g is dissolved in 20mlDBSA solution, is denoted as solution A; The aniline monomer of 0.47g and 0.3g anthracene are dissolved in remaining 20mlDBSA solution, be denoted as solution B, this solution stirs 30min in the water bath with thermostatic control of 20 DEG C.
C. B solution dropwise joined in solution A, this process lasts is about 30min.After dropwising, continue to be uniformly mixed liquid 2.5h.
D. in above-mentioned mixed solution, add excess ethyl alcohol breakdown of emulsion, filter, 60 DEG C of vacuum-drying 24h, obtained organic electroluminescent nano composite material.
Embodiment 3
A preparation method for organic electroluminescent nano composite material, comprises the following steps:
A. Sodium dodecylbenzene sulfonate (DBSA) the solution 40ml of 0.21mol/L is prepared.
B. the ammonium persulphate (APS) of a certain amount of 1.14g is dissolved in 20mlDBSA solution, is denoted as solution A; The aniline monomer of 0.47g and 0.21g naphthalene are dissolved in remaining 20mlDBSA solution, be denoted as solution B, this solution stirs 30min in the water bath with thermostatic control of 20 DEG C.
C. B solution dropwise joined in solution A, this process lasts is about 30min.After dropwising, continue to be uniformly mixed liquid 2.5h.
D. in above-mentioned mixed solution, add excess ethyl alcohol breakdown of emulsion, filter, 60 DEG C of vacuum-drying 24h, obtained organic electroluminescent nano composite material.
Claims (8)
1. an organic electroluminescent nano composite material, is characterized in that: this matrix material is with small molecule electroluminescent material for core, and electrically conductive polyaniline is the composite material of core-shell structure that shell builds the solution processable made; Described small molecule electroluminescent material is selected from aromatic compound and derivative thereof.
2. a kind of organic electroluminescent nano composite material according to claim 1, is characterized in that, described small molecule electroluminescent material is selected from following structural compound:
3. a preparation method for organic electroluminescent nano composite material, is characterized in that comprising the following steps:
A chooses tensio-active agent, is mixed with surfactant soln;
The surfactant soln that b selected part step a is mixed with, is dissolved in ammonium persulphate wherein, is denoted as solution A; By aniline monomer and small molecule electroluminescent material dissolves in the surfactant soln of remainder, be denoted as solution B, solution B is stirred in water bath with thermostatic control;
Solution B dropwise joins in solution A by c, after dropwising, continues to be uniformly mixed liquid;
D adds emulsion splitter breakdown of emulsion, then suction filtration, vacuum-drying, obtained organic electroluminescent nano composite material in the obtained mixed solution of step c;
In step b: described small molecule electroluminescent material is selected from following structural compound:
The temperature of described water bath with thermostatic control is 20 DEG C, and churning time is 30min.
4. the preparation method of a kind of organic electroluminescent nano composite material according to claim 3, is characterized in that, in step a: described tensio-active agent is Sodium dodecylbenzene sulfonate.
5. the preparation method of a kind of organic electroluminescent nano composite material according to claim 3, is characterized in that, in step c: dripping the process used time is 30min, and after dropwising, being uniformly mixed the liquid used time is 2.5h.
6. the preparation method of a kind of organic electroluminescent nano composite material according to claim 3, it is characterized in that, in steps d: described emulsion splitter is ethanol, described vacuum-drying temperature is 20 DEG C, and time of drying is 24h.
7. organic electroluminescent nano composite material as claimed in claim 1 is used for spray ink Printing, to prepare organic photoelectric core-shell nano composite material film.
8. organic electroluminescent nano composite material as claimed in claim 1 as electron transport material for the preparation of organic electroluminescence device.
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