CN1302049C - Hyperbranched high-molecular electroluminescent materials - Google Patents
Hyperbranched high-molecular electroluminescent materials Download PDFInfo
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- CN1302049C CN1302049C CNB2005100262236A CN200510026223A CN1302049C CN 1302049 C CN1302049 C CN 1302049C CN B2005100262236 A CNB2005100262236 A CN B2005100262236A CN 200510026223 A CN200510026223 A CN 200510026223A CN 1302049 C CN1302049 C CN 1302049C
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Abstract
The present invention relates to a high molecular electroluminescent material in a hyperbranched structure, which is favorable for the improvement of the balance between electron injection and hole injection, the prevention of molecular chain aggregation and the formation of an excimer. The material belongs to the technical field of electroluminescent materials. The material is prepared by polymerizing n-type molecules as hyperbranched cores performing favorable transmission action on electrons and p-type molecules performing favorable transmission action on holes or prepared by polymerizing the p-type molecules as the cores and the n-type molecules. The molecules obtained by copolymerizing the p-type molecules and the n-type molecules are favorable for the balance between the electron injection and the hole injection. In addition, the aggregation among the molecules can be prevented through the structural design, and fluorescent quenching can be avoided so that the luminescence efficiency of the material and that of an electroluminescent device are improved.
Description
Technical field
The invention belongs to the electroluminescent material technical field, be specifically related to a kind of electronics and hole to be had poising action, and can prevent intermolecular gathering effectively, the organic polymer electroluminescent material of avoiding base complex to produce.
Background technology
(Organic/Polymer Light-Emitting Device OLED/PLED) is one of the focus forward position in current scientific research field to the organic/polymer electroluminescent device.Advantages such as the indicating meter made from it has high image quality, and screen size can arbitrarily be adjusted, and energy consumption is low, and light weight and approaching adopts the flexible macromolecule substrate collapsible, and tooling cost is low, thus represented the development trend of following technique of display.
C.W.Tang in 1987 etc. successfully develop a kind of Organic Light Emitting Diode (OLED), do hole transmission layer (HTL) with aniline-TPD, and aluminium and 8-hydroxy-quinoline complex compound-ALQ are as luminescent layer (EML).Its operating voltage is less than 10V, and brightness is up to 1000cd/m
2Nineteen ninety, people's reported first such as the breadboard J.H.Burroughes of the Cavendish of univ cambridge uk with PPV (poly (p-phenylene vinylene), the polymeric film electroluminescent device of p-phenylene vinylene's preparation, obtained the blue green light output of direct-current biasing driving less than 14V, its quantum yield is 0.05%.Subsequently, the D.Braum of California, USA university and A.J.Heerge have reported that in 1992 its trigger voltage is 3V, has obtained the luminous of effective green and orange-yellow two kinds of colors with the photodiode of PPV and derivative preparation thereof.These breakthrough progress make this field become a research focus in recent years.
From 1987 till now, OLED technical development very rapid, especially the stability of device is greatly improved, and reaches practical requirement basically.Wherein the transformation period of green light material has reached 2～50,000 hours, and the transformation period of blue light material is also above 30,000 hours.And aspect luminous efficiency, OLED then is higher than the level of PDP and TFT-LCD far away.Aspect the colorize of device, proposed to comprise that three primary colours method, white light add multiple schemes such as colour filter embrane method, blue light energy transformation method, and had many companies to release the OLED sample that full color shows.
Organic electroluminescence device belongs to the two injection type luminescent devices of current carrier, is that injected electrons and hole are compound and luminous by radiation deexcitation generation in organism.Therefore, the injection balance in electronics and hole realizes that to device higher luminous efficiency is very important.Now, in order to solve electronics, this problem of hole transport balance, people have introduced electron transfer layer (ETL) or hole transmission layer (HTL) in organic electroluminescence device, formed the multilayer device structure, and use the material of low work content to make negative electrode.Though these methods can improve quantum yield to a certain extent, also have many problems.For example, the multilayer device structure has very big difficulty on technology of preparing, and low work function materials is extremely responsive for the variation of atmospheric gas pressure, extremely difficult compression.So producing the intrinsic structure for the PLEDs that develops efficient stable just has the polymkeric substance of equilibrated electron hole transmission performance just to seem highly significant.
In order to solve the existing unbalanced problem of electroluminescent macromolecule material carrier transmission performance, people utilize so-called p-n ampholyte copolymer design concept, the monomer that is about to have better electric transmission effect (n-type) and hole transport effect (p-type) carries out copolymerization, to obtain electronics, comparatively the equilibrated material is by this method for the hole transport performance, successfully developed a series of with the p-n junction monomer form the high-molecular optical electric material, and find by changing p-type and the monomeric ratio of n-type in the molecule, really can improve electronics and cavity transmission ability balance, can obtain electronics, the hole transport performance comparatively the equilibrated material (as J.Appl.Phys.1994,75:1659; J.Am.Chem.Soc.2001,123,946; Chem.Mater.1997,9,1077; J.Appl.Phys.2001,89:1866 etc.).
In recent years, a kind of polymkeric substance-dendriform of novel texture and hyperbranched polymer have received increasing concern.Because its specific molecule structure and chemico-physical properties, can be applied to many fields, and develop into gradually luminous, show and the exploitation of other photoelectric material in.Be divided into three parts on this quasi-molecule structure: (1) centronucleus, the branch that (2) are highly branched, (3) and outermost layer group, improve processing performance to material, electrical properties etc. and regulate and control independently modification that like this can be by different piece.This just this class material obviously be better than common line polymer part.In addition, some electroluminescent polymer materials of having developed at present mainly are rectilinear, there are some problems in it, assemble as being easy between molecular chain, in the fabricate devices process, under comparatively high temps, have base complex and produce, also have the partial crystallization phenomenon, the purity of color that this all will influence material and device causes luminous efficiency to reduce.But these can improve by the improvement of material self structure.Consider the highly branched and topological framework of dendriform and hyperbranched polymer, should improve the stability and the efficient of material, and can be than being easier to form uniform film.Therefore, synthetic dendroid of design or hyperbranched polymers are to improve one of existing issue perfect method.
Summary of the invention
The objective of the invention is to propose a kind of electronics and hole to be had the organic high molecular polymer of poising action, and can prevent that the molecule interchain from assembling, avoid forming base complex, improve the luminous efficiency of this class material.
The organic high molecular polymer that the present invention proposes is a kind of p-n junction polymkeric substance of dissaving structure.Particularly, by the nuclear of the n-type molecule that electronics is had the good transmission effect, the hole had the branch of the p-type molecule of good transmission effect as polymkeric substance as hyperbranched polymer; Perhaps with the nuclear of described p-type molecule as hyperbranched polymer, described n-type molecule is as the branch of hyperbranched polymer.By regulating the ratio of p-type and n-type, control the balance in electronics and hole and inject.And prevent intermolecular gathering by this structure Design, avoid the generation of base complex.
Electronics is had the n-type molecule of good transmission effect, can form by n-type monomer that electronics is had the good transmission effect and the p-type monomer that the hole is had the good transmission effect, but its general effect is beneficial to electric transmission; Also can be that different n-type monomers replace, random or orderly composition; Preferably can also be all by forming with a kind of n-type monomer that electronics is had a good transmission effect.
Above-mentioned n-type monomer can be 1,3, one or more compositions in the monomers such as 4-oxadiazole class, substituted benzene amine, substituted phenylethylene class, pyridines, benzimidazoles, naphthalene class, perylene imide class, triazole species, thiazoles, quinoline, thiadiazole class, phenazinyl, quinoxaline, 8-hydroxy-quinoline metal species.The most frequently used is 1,3, monomers such as 4-oxadiazole class, thiazoles, substituted benzene amine.
The hole is had the p-type molecule of good transmission effect, can form by p-type monomer that the hole is had the good transmission effect and the n-type monomer that electronics is had the good transmission effect, but its general effect is beneficial to hole transport; Also can be that different p-type monomers replace, random or orderly composition; Preferably can also be all by forming with a kind of p-type monomer that electronics is had a good transmission effect.
Above-mentioned p-type monomer can be made up of in the monomers such as fluorenes class, thiophene-based, PPV class, carbazoles, pyroles, triphen amine, luxuriant and rich with fragrance class, pyrene class one or more.The most frequently used mainly is monomers such as fluorenes class, thiophene-based, PPV class, carbazoles.
The synthetic method of the organic high molecular polymer of dissaving structure of the present invention adopts Suzuki, Yamamoto and Stille reaction, perhaps various condensation reactions such as hydroxyl-amine, hydroxyl-aldehyde.
Macromolecule polymer material of the present invention can obtain in fields such as electroluminescent device, organic field effect tube, solar cell, organic laser, information recording device, biosensors to use.
Description of drawings
Fig. 1 is that film is at N
2In the atmosphere respectively at 25,100,150 and 200 ℃ of following fluorescence spectrums behind the annealing 1h.
Fig. 2 be film in air respectively at 25,100,150 and 200 ℃ of following fluorescence spectrums behind the annealing 1h.
Embodiment
By the following examples the present invention is further specified, rather than limits the scope of the invention:
Embodiment 1
Prepare intermediate (1), (2) and (3) by the following method, and make (4) and (5) with similar method.(1), (2) feed intake by different mol ratios with (3), as by 0: 3: 2,10: 11.5: 1 equal proportions, utilizes the Suzuki reaction with three's coupling then, react after 5 days, drop into a certain proportion of (4) and (5) and trimethylammonium phosphorus palladium, reacted again 2 days, promptly obtain hyperbranched polymer I.
Fig. 1 and 2 be hyperbranched polymer I (mol ratio by 10: 11.5: 1 feeds intake) after spin-coating film on the quartz plate, under nitrogen and air atmosphere, respectively 100,150 and 200 ℃ down behind the annealing 1h with room temperature under the comparison of film fluorogram.As can be seen from the figure, under nitrogen and air atmosphere, behind differing temps annealing 1h, spectrogram does not have to change substantially.It should be noted that the peak that does not occur the common green glow that turns blue in the poly-fluorenes annealing of linear back on its fluorogram, this illustrates that promptly the polymkeric substance of dissaving structure can prevent intermolecular gathering really, improves the purity of color of material.
Embodiment 2
With embodiment 1, preparation intermediate (1), (2), (4) and (5) are with the synthetic intermediate (6) that obtains of following method.(1), (2) feed intake by different mol ratios with (6), as by 0: 3: 2,10: 11.5: 1 equal proportions, utilizes the Suzuki reaction with three's coupling then, react after 5 days, drop into a certain proportion of (4) and (5) and trimethylammonium phosphorus palladium, reacted again 2 days, promptly obtain hyperbranched polymer II.
Embodiment 3
With embodiment 1, preparation intermediate (1), (2), (4) and (5) are with the synthetic intermediate (7) that obtains of following method.(1), (2) feed intake by different mol ratios with (7), as by 0: 3: 2,10: 11.5: 1 equal proportions, utilizes the Suzuki reaction with three's coupling then, react after 5 days, drop into a certain proportion of (4) and (5) and trimethylammonium phosphorus palladium, reacted again 2 days, promptly obtain hyperbranched polymer III.
Embodiment 4
With embodiment 1, preparation intermediate (1), (2), (4) and (5) are with the synthetic intermediate (8) that obtains of following method.(1), (2) feed intake by different mol ratios with (8), as by 0: 3: 2,10: 11.5: 1 equal proportions, utilizes the Suzuki reaction with three's coupling then, react after 5 days, drop into a certain proportion of (4) and (5) and trimethylammonium phosphorus palladium, reacted again 2 days, promptly obtain hyperbranched polymer IV.
Embodiment 5
Prepare intermediate (9) and (10) by the following method, and the single bromine body (11) and the single boric acid body (12) that make carbazole with similar method.Other synthesis steps are with embodiment 1, (9), (10) and (3) feed intake by different mol ratio, as pressing 0: 3: 2,10: 11.5: 1 equal proportions, utilize the Suzuki reaction with three's coupling then, react after 5 days, drop into a certain proportion of (11) and (12) and trimethylammonium phosphorus palladium, reacted again 2 days, promptly obtain hyperbranched polymer V.
Embodiment 6
With embodiment 2, (9), (10) feed intake by different mol ratios with (6), utilize the Suzuki reaction with three's coupling then, react after 5 days, drop into a certain proportion of (11) and (12) and trimethylammonium phosphorus palladium, reacted again 2 days, promptly obtain hyperbranched polymer VI.
Embodiment 7
With embodiment 3, (9), (10) feed intake by different mol ratios with (7), utilize the Suzuki reaction with three's coupling then, react after 5 days, drop into a certain proportion of (11) and (12) and trimethylammonium phosphorus palladium, reacted again 2 days, promptly obtain hyperbranched polymer VII.
Embodiment 8
With embodiment 4, (9), (10) feed intake by different mol ratios with (8), utilize the Suzuki reaction with three's coupling then, react after 5 days, drop into a certain proportion of (11) and (12) and trimethylammonium phosphorus palladium, reacted again 2 days, promptly obtain hyperbranched polymer VIII.
Embodiment 9
Prepare intermediate (13) by the following method.(13) and (14) by preparation hyperbranched polymer A commonly used
2+ B
3Method, utilize Suzuki reaction with both couplings, react after 5 days, drop into a certain proportion of (4) and trimethylammonium phosphorus palladium, reacted again 2 days, promptly obtain hyperbranched polymer IX.
Embodiment 10
Prepare intermediate (15) by the following method.(15) and (16) by preparation hyperbranched polymer A commonly used
2+ B
3Method, utilize Witting reaction with both couplings, react after 2 days, drop into a certain proportion of (17), react half a day again, promptly obtain hyperbranched polymer X.
Claims (3)
1, a kind of organic high molecular polymer of dissaving structure is characterized in that by the nuclear of the n-type molecule that electronics is had the good transmission effect as hyperbranched polymer, the hole is had the branch of the p-type molecule of good transmission effect as hyperbranched polymer; Perhaps by the nuclear of described p-type molecule as hyperbranched polymer, described n-type molecule is as the branch of hyperbranched polymer;
The said hyperbranched nuclear of n-type that electronics is had a good transmission effect is 1,3,4-oxadiazole class, phenyl amines, styrenic, benzimidazoles, naphthalene class, perylene imide class, triazole species, thiazoles, quinoline, thiadiazole class, quinoxaline, 8-hydroxy-quinoline monomer a kind of;
The said hyperbranched nuclear of p-type that the hole is had a good transmission effect is a kind of of fluorenes class, thiophene-based, p-phenylene vinylene's class, carbazoles, pyroles, phenyl amines, luxuriant and rich with fragrance class, pyrene class;
The said branch that electronics is had the n-type hyperbranched polymer of good transmission effect is by 1,3, one or more compositions in 4-oxadiazole class, phenyl amines, styrenic, pyridines, benzimidazoles, naphthalene class, perylene imide class, triazole species, thiazoles, quinoline, thiadiazole class, quinoxaline, the 8-hydroxy-quinoline monomer;
The branch of the said p-type hyperbranched polymer that the hole is had a good transmission effect is made up of in fluorenes class, thiophene-based, p-phenylene vinylene's class, carbazoles, pyroles, phenyl amines, luxuriant and rich with fragrance class, the pyrene class monomer one or more.
2, a kind of synthetic method of organic high molecular polymer of dissaving structure as claimed in claim 1 is characterized in that adopting Suzuki, Yamamoto and Stille reaction, perhaps hydroxyl-amine, hydroxyl-aldehyde condensation reaction.
3, the application of organic high molecular polymer material in electroluminescent device, organic field effect tube, solar cell, organic laser, information recording device or biosensor of dissaving structure according to claim 1.
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| CN1302049C true CN1302049C (en) | 2007-02-28 |
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| JP5664200B2 (en) * | 2009-12-16 | 2015-02-04 | 東レ株式会社 | Conjugated polymer, electron donating organic material, photovoltaic device material and photovoltaic device using the same |
| CN106784404B (en) * | 2016-12-23 | 2018-03-23 | 江苏聚龙显示科技有限公司 | It is a kind of can coating and printing OLED long-chains photoelectric material and preparation method |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5837865A (en) * | 1993-10-15 | 1998-11-17 | Trustees Of The University Of Pennsylvania | Phosphorescent dendritic macromolecular compounds for imaging tissue oxygen |
| CN1533406A (en) * | 2001-07-17 | 2004-09-29 | Photoactive materials | |
| CN1583946A (en) * | 2004-05-21 | 2005-02-23 | 复旦大学 | Star-structure p-n polymer electroluminescent materials |
| CN1587344A (en) * | 2004-07-15 | 2005-03-02 | 复旦大学 | Star shape double block conjugate polymer and its preparing method |
| CN1613961A (en) * | 2004-09-01 | 2005-05-11 | 复旦大学 | Organic electroluminescent materials containing difluorene segments and its synthesis |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5837865A (en) * | 1993-10-15 | 1998-11-17 | Trustees Of The University Of Pennsylvania | Phosphorescent dendritic macromolecular compounds for imaging tissue oxygen |
| CN1533406A (en) * | 2001-07-17 | 2004-09-29 | Photoactive materials | |
| CN1583946A (en) * | 2004-05-21 | 2005-02-23 | 复旦大学 | Star-structure p-n polymer electroluminescent materials |
| CN1587344A (en) * | 2004-07-15 | 2005-03-02 | 复旦大学 | Star shape double block conjugate polymer and its preparing method |
| CN1613961A (en) * | 2004-09-01 | 2005-05-11 | 复旦大学 | Organic electroluminescent materials containing difluorene segments and its synthesis |
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