CN101087012B - Organic EL component - Google Patents
Organic EL component Download PDFInfo
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- CN101087012B CN101087012B CN200610083130A CN200610083130A CN101087012B CN 101087012 B CN101087012 B CN 101087012B CN 200610083130 A CN200610083130 A CN 200610083130A CN 200610083130 A CN200610083130 A CN 200610083130A CN 101087012 B CN101087012 B CN 101087012B
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Abstract
The invention relates to a kind of organic electrization irradiance subassembly, it possesses irradiance layer, the irradiance layer includes macromolecule conducting main material which can be solidified by illumination, fits for colored display by spin coating method, and the irradiance layer includes at least one little molecule irradiance material to realize high irradiance efficiency. The subassembly can not be limited by molecular weight distributing of macromolecule conducting main material on color fineness.
Description
Technical field
The present invention is about a kind of organic EL component, especially in regard to a kind of macromolecule organic EL component, its luminescent layer pbz polymer conduction main material, this conductive polymer main material has the photo-crosslinking group in main chain or side chain functionalities, can be subjected to illumination crosslinked and solidify, and this luminescent layer comprise at least one micromolecule luminescent material.
Background technology
The flat display apparatus that the macromolecule organic EL component is constituted has many advantages, long, shatter-proof such as low cost of manufacture, life-span, reply fast, the visual angle is wide, driving voltage is low, thin and can large scaleization.The luminescent layer of this luminescence component and carrier transport layer material are different from the organic EL component based on the micromolecule dyestuff based on the conjugated polymer of conduction.Compared to the micromolecule organic electroluminescence display device,, the relatively poor shortcoming of luminous efficiency is arranged though the macromolecule organic EL component has the advantage of low driving voltage and energy large scaleization on display performance.On display was made, small molecule material must be by expensive vacuum evaporation film forming; Macromolecular material but has solubility, can use the ink jet printing art, accurately luminescent layer material under RGB (RGB) three primary colors is independently sprayed cloth (three looks independently luminous is the luminous efficiency soprano) on predetermined sub-pixel pattern in various full-colorization technology, as for the more simple and easy spin-coating method cheaply that reaches, the shortcoming that then has three looks location to be difficult for; In addition, be that the molecular weight distribution of the macromolecular material of purpose must be in the face of harsh requirement with luminous, in the hope of preferable colorimetric purity, this causes higher processing procedure difficulty.
The sandwich construction that organic EL component is supported by substrate typically.Between first electrode and second electrode, the carrier transport layer is arranged, luminescent layer is then arranged therebetween.Transport layer is injected by electrode in electronics and hole under forward bias, move to luminescent layer, again in conjunction with and form exciton, its energy shifts and makes light emitting molecule become excitation state, deactivates to get back to ground state and luminous.As is known to the person skilled in the art, this typical basic structure can be made any suitable modification.For instance, the Taiwan patent gazette is announced No. 560224 and is disclosed similar structure, wherein still there is an electron injecting layer to be adjacent to negative electrode, yet, this luminescence component must use high-molecular luminous material so that its luminous efficiency not as the person that utilizes the small molecule material, and its spin coating mode is helpless to the lifting of full-colorization Display Technique.That is to say that the improvement of this modular construction of class there is no help for the luminous efficiency of macromolecule organic electroluminescence display device and three looks location processing procedure.
Recently, more existing ways are conceived to the material of organic layer.As preferable luminous source, this way has been exposed in United States Patent (USP) the 6th, 784 in luminescent layer polymeric main material in the small molecule material blending, and 016,6,870,198 and 6,843, No. 937.But the used Display Technique of these patents is not still taken off ink jet printing art category.
In addition, United States Patent (USP) the 6th, 814 discloses a kind of organic EL component and method for making thereof No. 887, uses the photo-crosslinking polymeric composition to form luminescent layer.Macromol.Rapid Commun.20 224 (1999), 21 583 (2000) and 35 2426 (2002) also has illustrated to this.This kind polymeric composition is irradiation crosslinking curing on predetermined sub-pixel pattern optionally, and uncured portion is then dissolved by organic solvent and removed.After this kind polymeric composition irradiation was crosslinked, its carrier transport capability as carrier transport factor, did not change.So, this photo-crosslinking character is convenient to and spin-coating method combination utilization, and effective and cheap full-colorization demonstration can be provided.Describe in detail for instance, can be referring to the report of people such as Becker in SID 03 Digest 1286-1289 page or leaf.Yet the luminous efficiency of obtaining like this does not break through existing macromolecule organic electric-excitation luminescent skill level, and the distribution of luminescent layer material molecule amount still must be faced harsh requirement.
Therefore, the organic EL component that need provide novel is arranged just, be able to spin-coating method and implement full-colorization demonstration, and have high-luminous-efficiency, and its photochromic purity is not subjected to the influence of luminescent layer material molecule amount distribution.
Summary of the invention
An object of the present invention is to provide a kind of macromolecule organic EL component, it is able to spin-coating method and implements full-colorization demonstration.
Another object of the present invention provides a kind of macromolecule organic EL component, and it has higher photoluminescence efficiency.
A further object of the present invention provides a kind of macromolecule organic EL component, the influence that its photochromic purity is not distributed by luminescent layer material molecule amount.
For reaching above-mentioned purpose, the invention provides a kind of macromolecule organic EL component, supported by a substrate, between first electrode and second electrode, dispose organic luminorphor, this organic luminorphor comprises a luminescent layer at least, this luminescent layer comprises the conductive polymer main material, and the main chain of this main material or side chain functionalities have the photo-crosslinking group, can be crosslinked and solidify through irradiation; And this luminescent layer comprises at least one micromolecule luminescent material, and this luminescent material can receive the energy of the main material that is excited and be luminous.In organic EL component of the present invention, the non-staple in fact luminous source of this polymeric main material mainly provides conductive characteristic, does not influence the photochromic purity of this organic EL component so its molecular weight polymeric distributes.In organic EL component of the present invention, the conductivity of this polymeric main material does not change because of irradiation is crosslinked in fact to some extent.
In organic EL component of the present invention, this at least one micromolecule luminescent material can be caught the energy that receives the main material that is excited by energy transfer or carrier, thereby carries out luminescence process.
The present invention is in addition about a kind of method that forms the macromolecule organic EL component, it comprises step: at first, there is the conductive polymer main material of micromolecule luminescent material to be formed on a plurality of sub-pixel patterns blending, wherein the main chain of this main material or side chain functionalities have the photo-crosslinking group, this micromolecule luminescent material can receive the energy of the main material that is excited and luminous, and the corresponding organic EL component of each sub-pixel pattern; Then, the presumptive area of this sub-pixel pattern of irradiation crosslinking curing; Then, remove this uncured part through the main material of blending.
In the method for formation macromolecule organic EL component luminescent layer of the present invention, but this conductive polymer main material and this micromolecule luminescent material blending are in solvent, particularly in the organic solvent.
In the method for formation macromolecule organic EL component luminescent layer of the present invention, this uncured part through the conductive polymer main material of blending can be passed through solvent, particularly organic solvent, comes wash-out and removes.
According to the method for formation macromolecule organic EL component luminescent layer of the present invention, wherein the main material of blending different color light luminescent material is formed at this luminescent layer on the predetermined sub-pixel pattern in regular turn, so can realize full-colorization demonstration.
Method according to formation macromolecule organic EL component luminescent layer of the present invention has the conductive polymer main material of micromolecule luminescent material to be formed on a plurality of sub-pixel patterns blending with spin-coating method.
According to an embodiment of the present invention, this organic EL component comprises substrate; First electrode is formed on this substrate; Hole transport layer is formed on this first electrode; Luminescent layer, be formed on this hole transport layer, wherein this luminescent layer comprises the conductive polymer main material, the main chain of this main material or side chain functionalities have the photo-crosslinking group, but thereby on predetermined sub-pixel pattern irradiation crosslinking curing and on all the other positions, can being removed, and this luminescent layer contains at least one micromolecule luminescent material, and this luminescent material can receive the energy of the main material that is excited, thereby main in fact luminous mechanism is provided; The hole barrier layer is formed on this luminescent layer; Electron transport layer is formed on this hole barrier layer; Electron injecting layer is formed on this electron transport layer; And second electrode, be formed on this electron injecting layer.
According to this embodiment of organic EL component of the present invention, this micromolecule luminescent material accounts for about 0.001% to about 50% of luminescent layer material by weight.
According to this embodiment of organic EL component of the present invention, this luminescent layer is other material of blending further, in order to mate the energy rank or preferable thermal stability and film forming is provided.
According to this embodiment of organic EL component of the present invention, the material of this electron transport layer can or provide preferable thermal stability and film forming in order to coupling energy rank.
These and other feature of the present invention, aspect and advantage, claims and accompanying drawing by following examples illustrate, enclose will obtain better understanding.
Description of drawings
Fig. 1 is the generalized section according to the organic EL component structure of an embodiment of the present invention;
The embodiment of Fig. 2 A-2I displayed map 1 is applied to display base plate 10, each colour light emitting layer processing procedure of each organic EL component corresponding with a plurality of sub-pixels.
Description of reference numerals
10 substrates, 12 first electrodes
13 pixel openings, 13 ' insulation wall
14 hole transport layers, 15 green light materials
15 ' red light material, 15 " blue light materials
The red luminescent layer of the green luminescent layer 15b of 15a
Blue luminescent layer 16 luminescent layers of 15c
18 hole barrier layers, 20 electron transport layer
22 electron injecting layers, 24 second electrodes
Embodiment
Please refer to Fig. 1, the structure of its expression embodiment of the invention, wherein first electrode 12 is formed on the substrate 10, hole transport layer 14 is formed on first electrode 12, luminescent layer 16 is formed on the hole transport layer 14, and hole barrier layer 18 is formed on the luminescent layer 16, and electron transport layer 20 is formed on the hole barrier layer 18, electron injecting layer 22 is formed on the electron transport layer 20, and second electrode 24 is formed on the electron injecting layer 22.
According to the present invention, substrate 10 is with suitable glass, and such as quartz glass or soda-lime glass, or the deflection material is made.First electrode, 12 material therefors such as indium tin oxide (ITO), indium-zinc oxide (IZO), aluminium zinc oxide (AZO), and analog, thickness about 50 nanometers to about 600 in meter scope.14 of hole transport layers are selected the proper polymer electric conducting material for use, as polyaniline, Bayer (BayerAG) product P EDOT/PSS (that is, gathering 3, the water-borne dispersions of 4-ethylene dioxythiophene/polystyrene-based sulfonic acid), and analog, thickness in about 0.5 nanometer to about 250 nanometer range.
The main material of luminescent layer 16 can adopt poly-to phenylethylene (PPV), polyvinylcarbazole (PVK), poly-2, and 7-(9.9-dialkyl group) fluorenes, or the derivative of poly-alkylthrophene are all the individual layer conducting polymer and the photo-crosslinking group is arranged in main chain or side chain functionalities.The luminescent material of luminescent layer 16 can adopt a kind of or more than a kind of micromolecule luminescent dye, such as blue light material DPAVBi (that is, 4,4 '-two { 2-[4-(N, N-two diphenylamines) phenyl] vinyl biphenyl), the IDE 102 that produces of Idemitsu (Japan), and analog; Green light material C545T (that is, 10-(2-[4-morpholinodithio)-2,3,6,7-tetrahydrochysene-1,1,7,7 ,-tetramethyl 1-1H, 5H, 11H-[1] chromene [6,7,8-ij] quinolizine-11-ketone), and analog; And red light material DCJTB (promptly, the 4-cyanogen methylene-2-tert-butyl group-6-(1,1,7,7-tetramethyl julolidine groups-9-Ene alkynyl base-4H-pyrans)), and analog. but this main material and this luminescent material blending are in solvent, particularly in the organic solvent. the red light material colorimetric purity under the skill level is all undesirable at present, for example, DCJTB is inclined to one side orange, can be aided with the gold-tinted material rubrene to this, make photochromic bathochromic effect. luminescent layer further blending other such as three (oxine) aluminium (Alq3), 1,2,4-triazole (TAZ), two (2-methyl-oxines-N1, O8)-(1,1 '-hydroxy Al (BAlq) of diphenyl-4-), 2-(4-diphenyl)-5-(4-t-butyl-phenyl)-1,3,4-oxadiazoles (PBD), in order to mate the energy rank or preferable thermal stability and film forming be provided. in the method for formation macromolecule organic EL component luminescent layer of the present invention, this uncured part through the main material of blending can be passed through solvent, organic solvent particularly comes wash-out and removes. the thickness of luminescent layer 16 in about 0.5 nanometer to about 250 nanometer range. this luminescent material accounts for about 0.001% to about 50%. of luminescent layer material by weight
The material that hole barrier layer 18 can be used such as small molecule material BCP (that is, and 2,9-dimethyl-4,7-diphenyl-1, the 10-phenanthroline), TPBI (that is, and 2,2 ', 2 " (1; 3,5 benzene) three (1-phenyl-1H-benzimidazole)), and analog; or macromolecular material such as F8/TFB (that is, poly-(2,7-9; the hot fluorenes of 9-two-n-)/poly-(2,7-9, the hot fluorenes of 9-two-n-)-(1; 4-benzene-((4-secondary butyl phenenyl) imido)-1,4-benzene)), and analog.Thickness in about 0.5 nanometer to about 100 nanometer range.
The material that electron transport layer 20 can be used is such as three (oxine) aluminium, 1,2,4-triazole, two (2-methyl-oxine-N1, O8)-(1,1 '-diphenyl-4-) hydroxy Al, 2-(4-diphenyl)-5-(4-t-butyl-phenyl)-1,3, the 4-oxadiazoles, and analog, in order to mate the energy rank or preferable thermal stability and film forming be provided.Thickness in about 0.5 nanometer to about 200 nanometer range.
Electron injecting layer 22 used materials can be lithium fluoride, strontium fluoride, strontium, lithium, and analog.Thickness in about 0.01 nanometer to about 200 nanometer range.
Second electrode, 24 material therefors can be single layer structure and comprise such as aluminium, silver etc., or sandwich construction comprises such as calcium/aluminium, barium/aluminium, calcium/magnesium: aluminium, barium/magnesium: aluminium etc.
Embodiment
According to the structure of above-mentioned embodiment, full-colorization display unit can be made (please refer to Fig. 2 A-2I) by following steps:
Form pattern of pixels: coating photosensitive high molecular insulating material on the substrate 10 and first electrode 12 forms required pixel openings 13 and insulation wall 13 ' pattern at interval, the corresponding organic EL component of each sub-pixel pattern through the photoresistance pattern.
Form hole transport layer 14:, in inert gas environment, toast with spin-coating method coating PEDOT/PSS.
Form luminescent layer 16: be dissolved in the green light material 15 of an amount of dimethylbenzene on hole transport layer 14 with the spin-coating method coating, it is composed as follows: polyvinylcarbazole; C545T as luminescent material, accounts for about 2% of luminescent layer material by weight; And three (oxine) aluminium, in order to mate the energy rank and preferable thermal stability and film forming be provided, account for about 20% (please refer to Fig. 2 A) of luminescent layer material by weight. then, see through light shield, with this coating of UV-irradiation, make green light material 15 crosslinking curing (please refer to Fig. 2 B) on predetermined sub-pixel pattern. then, with dimethylbenzene the uncured portion eccysis is formed green luminescence layer 15a (please refer to Fig. 2 C). with the same manner, can on the structure that existing green luminescent layer 15a forms, form red luminescent layer 15b (please refer to Fig. 2 D-2F), inferior and form blue luminescent layer 15c (please refer to Fig. 2 G-2I). red light material 15 ' composed as follows: polyvinylcarbazole; DCJTB and rubrene as luminescent material, account for luminescent layer material about respectively 3.5% and 15% by weight; And three (oxine) aluminium, can rank and preferable thermal stability and film forming is provided in order to coupling, account for about 15%. blue light materials 15 of luminescent layer material by weight " composed as follows: polyvinylcarbazole; IDE 102, as luminescent material, account for about 5% of luminescent layer material by weight; And the TC1552 that produced of brilliant suitable chemistry (Taiwan Miaoshu), in order to coupling energy rank, account for luminescent layer material about 15% by weight.Intact back becomes, and toasts in inert gas environment.
Formation each layer that continue: with vapour deposition method, form hole barrier layer 18, electron transport layer 20, electron injecting layer 22 in regular turn, and second electrode 24.Barrier layer 18 materials in hole are TBPI.Electron transport layer 20 materials are three (oxine) aluminium.Electron injecting layer 22 materials are lithium fluoride.Second electrode, 24 materials are aluminium.
Encapsulation: the film of evaporation water proof and oxygen above second electrode 24.The side disposes glass cover-plate thereon again, and the side that cover plate and substrate constituted solidifies through heating coated with frame glue.
Test and test result: the result of this specific embodiment is with brightness photometer (PhotoResearchPR650) reading of data, and classic again exciting light diode (OLED) the photoelectric characteristic Survey Software that has is come computational analysis.
Test result is as follows: the green light component briliancy reach 8,000 candelas/square metre; Under 50 milliamperes/square centimeter of current densities, its luminous efficiency with produced luminous flux to about 6.5 lumens/watt of the ratio meter of institute's consumption of electric power (lm/W); And the cie color coordinate is (0.30,0.63).Ruddiness assembly briliancy reach 2,500 candelas/square metre; Under 50 milliamperes/square centimeter of current densities, its luminous efficiency with produced luminous flux to about 1.9 lumens/watt of the ratio meter of institute's consumption of electric power (lm/W); And the cie color coordinate is (0.65,0.35).The blue light component briliancy reach 4,000 candelas/square metre; Under 50 milliamperes/square centimeter of current densities, its luminous efficiency with produced luminous flux to about 3.1 lumens/watt of the ratio meter of institute's consumption of electric power (lm/W); And the cie color coordinate is (0.15,0.27).
Following table 1 compares people such as this result and Becker in the report of SID 03 Digest 1286-1289 page or leaf.
Table 1
| G | R | B | |
| This specific embodiment | 6.5 | 1.9 | 3.1 |
| People such as Becker | 4.88 | 0.69 | 2.08 |
Unit: lm/W
Under 50 milliamperes/square centimeter of current densities
By last explanation, organic EL component of the present invention, the non-staple in fact luminous source of the main material of its luminescent layer is not so its molecular weight distribution influences the photochromic purity of this organic EL component, in addition, the conductivity of this main material does not change because of irradiation is crosslinked in fact to some extent; Moreover this at least one luminescent material can be caught the energy that receives the main material that is excited by energy transfer or carrier, thereby carries out luminescence process, and luminous efficiency then exceeds known macromolecule conducting material.
Though the present invention has done detailed explanation with regard to its certain embodiment, other execution mode also belongs to feasible.The present invention is not limited to this execution mode through explanation, and any those skilled in the art under the spirit and scope that do not break away from patent claim of the present invention, can do various changes and modification to the present invention.
Claims (17)
1. organic EL component, comprise substrate, first electrode, organic luminorphor and second electrode, this first electrode is formed on this substrate, this organic luminorphor is formed on this first electrode and comprises a luminescent layer at least, this second electrode then is formed on this organic luminorphor, it is characterized in that described luminescent layer comprises: the conductive polymer main material, its main chain or side chain functionalities have the photo-crosslinking group; And at least one micromolecule luminescent material, this micromolecule luminescent material is blended into this main material.
2. organic EL component according to claim 1 is characterized in that described organic luminorphor comprises: hole transport layer is configured between described first electrode and the described luminescent layer; The hole barrier layer is configured on the described luminescent layer; Electron transport layer is configured on the barrier layer of described hole; And electron injecting layer, be configured on the described electron transport layer.
3. organic EL component according to claim 1, it is poly-to phenylethylene, polyvinylcarbazole, poly-2,7-(9.9-dialkyl group) fluorenes, or the derivative of poly-alkylthrophene to it is characterized in that described main material comprises.
4. organic EL component according to claim 1 is characterized in that described luminescent material is a green light material.
5. organic EL component according to claim 4 is characterized in that described green light material comprises 10-(2-[4-morpholinodithio)-2,3,6,7-tetrahydrochysene-1,1,7,7 ,-tetramethyl 1-1H, 5H, 11H-[1] chromene [6,7,8-ij] quinolizine-11-ketone.
6. organic EL component according to claim 1 is characterized in that described luminescent material is a red light material.
7. organic EL component according to claim 6 is characterized in that described red light material comprises the 4-cyanogen methene-2-tert-butyl group-6-(1,1,7,7-tetramethyl julolidine groups-9-Ene alkynyl base-4H-pyrans).
8. organic EL component according to claim 6 is characterized in that described red light material comprises rubrene.
9. organic EL component according to claim 1 is characterized in that described luminescent material is a blue light material.
10. organic EL component according to claim 9, it is characterized in that described blue light material comprise 4,4 '-two { 2-[4-(N, N-two diphenylamines) phenyl] vinyl } biphenyl.
11. organic EL component according to claim 1 is characterized in that described luminescent material accounts for 0.001% to 50% of luminescent layer material by weight.
12. a method that forms organic EL component is characterized in that this method comprises the following step:
With blending the conductive polymer main material of micromolecule luminescent material be disposed on a plurality of sub-pixel patterns, the main chain of this main material or side chain functionalities have the photo-crosslinking group, wherein the corresponding organic EL component of each sub-pixel pattern;
Irradiation crosslinking curing this main material on predetermined sub-pixel pattern; And
Remove this uncured part through the main material of blending.
13. the method for formation organic EL component according to claim 12 is characterized in that described main material and described luminescent material blending are in solvent.
14. the method for formation organic EL component according to claim 12 is characterized in that the uncured part of described main material through blending removes by solvent elution.
15. the method for formation organic EL component according to claim 12 is characterized in that in regular turn described luminescent layer being formed at the main material of the variant coloured light luminescent material of this method blending on the predetermined sub-pixel pattern.
16. the method for formation organic EL component according to claim 12 is characterized in that described main material through blending coats with spin-coating method on a plurality of sub-pixel patterns.
17., it is characterized in that described solvent is an organic solvent according to the method for claim 13 or 14 described formation organic EL components.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1459483A (en) * | 2002-05-17 | 2003-12-03 | 中国科学院化学研究所 | Blue coloured electroluminous organic film and its preparation method |
| CN1568103A (en) * | 2003-06-11 | 2005-01-19 | 胜华科技股份有限公司 | Method and apparatus for fabricating macromolecule organic luminescent element with cross linking luminescent layer |
| CN1585578A (en) * | 2004-05-21 | 2005-02-23 | 复旦大学 | Producing method for organic electroluminescent device |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1459483A (en) * | 2002-05-17 | 2003-12-03 | 中国科学院化学研究所 | Blue coloured electroluminous organic film and its preparation method |
| CN1568103A (en) * | 2003-06-11 | 2005-01-19 | 胜华科技股份有限公司 | Method and apparatus for fabricating macromolecule organic luminescent element with cross linking luminescent layer |
| CN1585578A (en) * | 2004-05-21 | 2005-02-23 | 复旦大学 | Producing method for organic electroluminescent device |
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