CN104835923A - Method for changing exciton distribution in organic light-emitting diode - Google Patents
Method for changing exciton distribution in organic light-emitting diode Download PDFInfo
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- H—ELECTRICITY
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- H10K2101/00—Properties of the organic materials covered by group H10K85/00
- H10K2101/40—Interrelation of parameters between multiple constituent active layers or sublayers, e.g. HOMO values in adjacent layers
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- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
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- H10K50/00—Organic light-emitting devices
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- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
- H10K50/125—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers specially adapted for multicolour light emission, e.g. for emitting white light
- H10K50/13—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers specially adapted for multicolour light emission, e.g. for emitting white light comprising stacked EL layers within one EL unit
- H10K50/131—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers specially adapted for multicolour light emission, e.g. for emitting white light comprising stacked EL layers within one EL unit with spacer layers between the electroluminescent layers
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- H10K50/00—Organic light-emitting devices
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- H10K50/14—Carrier transporting layers
- H10K50/15—Hole transporting layers
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Abstract
The invention discloses a method for changing exciton distribution in an organic light-emitting diode, which is characterized by using a material whose highest occupied molecular orbit (HOMO) energy level is higher than the HOMO energy level of a main body material or a material whose lowest unoccupied molecular orbit (LUMO) energy level is lower than the LUMO energy level of the main body material to act as an ultrathin non-doped luminescent layer, and the material is inserted into the main body material so as to play a role of capturing a large number of current carriers, thereby changing exciton distribution in the organic light-emitting diode. The main body material comprises an electron-transporting main body material and a hole-transporting main body material. The ultrathin non-doped luminescent layer mainly comprises the electron-transporting material and the hole-transporting material. The method disclosed by the invention can change exciton distribution in the organic light-emitting diode simply and effectively, and particularly has very ideal effects in the aspect of changing a light-emitting weight of the ultrathin non-doped luminescent layer based organic light-emitting diode.
Description
Technical field
The present invention relates to organic semiconductor field of electronic materials, particularly relate to a kind of method changing exciton distribution in organic electroluminescent LED.
Background technology
Organic electroluminescent LED (Organic Light-Emitting Diodes, OLED) is a kind of just in flourish, promising Display Technique, is regarded as the future of Display Technique.Organic electroluminescent LED is due to its outstanding characteristic, as self-luminous, wide viewing angle, wide colour gamut, fast response time, there are the potentiality making flexible apparatus and low cost, more and more become the center of gravity of display industry research, and through technological innovation for many years, organic electroluminescent LED product realizes scale of mass production, covers the consumer electronics of large, medium and small size.
The operation principle of organic electroluminescent LED is such, electronics and hole are respectively by negative electrode and the anode injection of OLED, then (hole injection layer is comprised through functional layer, hole transmission layer, electron injecting layer, electron transfer layer) transmission arrive luminescent layer and be combined into exciton, these excitons are decayed and are got back to ground state thus luminous on luminescent material molecule; Here luminescent layer is all generally adopt host-guest system system, and doping content has vital impact to device performance; Ultra-thin undoped luminescent layer also can be selected as one in addition, the fluorescence ultra-thin by one deck or phosphorescent light-emitting materials, with the direct evaporation of the mode of undoped in material of main part, forms the luminescent layer that one deck is very thin.
Material of main part is in organic electroluminescent LED, plays and supports that luminescent material is luminous, the material of conduction electron and cavitation, i.e. the electronics of material of main part layer receiving function layer conduction and hole, electronics and hole are conducted wherein and be finally compounded to form exciton.Material of main part layer is generally between hole transmission layer and electron transfer layer, electronics and hole are directly compounded to form exciton relaxation luminescence on luminescent material molecule, or be first combined into exciton on host material molecules, then energy is transformed on luminescent material molecule by host material molecules and forms luminescence.Material of main part is divided into electron-transporting type and hole-transporting type, and electron-transporting type refers to that the electron conductivity of material is higher than hole-conductive rate, and hole-transporting type refers to that the hole-conductive rate of material is higher than electron conductivity.Due to electric transmission or the hole transporting properties of material of main part, add electronics or the hole transporting properties of functional layer, cause exciton in organic electroluminescent LED, have different distribution situations: to adopt the exciton complex centre of the organic electroluminescent LED of electron-transporting type material of main part near hole transmission layer, and adopt the exciton complex centre of the organic electroluminescent LED of hole-transporting type material of main part near electron transfer layer.This uneven distribution can cause some problems, especially can cause luminous uneven in the organic electroluminescent LED utilizing ultra-thin undoped luminescent layer.
Therefore, those skilled in the art is devoted to develop a kind of method that can change exciton distribution in organic electroluminescent LED.
Summary of the invention
Because the above-mentioned defect of prior art, technical problem to be solved by this invention is luminous unbalanced problem in organic electroluminescent LED.
For achieving the above object, the invention provides a kind of method changing exciton distribution in organic electroluminescent LED, described method uses HOMO highest occupied molecular orbital (Highest Occupied Molecular Orbit, HOMO) material that energy level is higher than the HOMO energy level of described material of main part or lowest unoccupied molecular orbital (Lowest Unoccupied MolecularOrbit, LUMO) material that energy level is lower than the lumo energy of described material of main part is as ultra-thin undoped luminescent layer, described ultra-thin undoped luminescent layer catches a large amount of charge carrier, thus the exciton distribution in change organic electroluminescent LED, described ultra-thin undoped luminescent layer to be positioned among described material of main part or adjacent with described material of main part.
Further, in described change organic electroluminescent LED, the method for exciton distribution also comprises:
Described ultra-thin undoped luminescent layer catches a large amount of hole, and the hole concentration of described ultra-thin undoped luminescent layer position is increased, and the exciton concentration that the electron recombination in described hole and described material of main part is formed also increases; Or
Described ultra-thin undoped luminescent layer catches a large amount of electronics, and the electron concentration of described ultra-thin undoped luminescent layer position is increased, and the exciton concentration that the hole-recombination in described electronics and described material of main part is formed also increases.
Further, described material of main part be support in organic electroluminescent LED that luminescent material is luminous, the material of conduction hole and electronics, comprise electron-transporting type material of main part and hole-transporting type material of main part.
Further, described luminescent material comprises fluorescence luminescent material and phosphorescent light-emitting materials; Described luminescent material is entrained in described material of main part.
Further, the thickness of described ultra-thin undoped luminescent layer is between 0.01nm to 5nm.
Further, described electron-transporting type material of main part is the material of electron conductivity higher than hole-conductive rate, and thickness is between 1nm to 200nm; Described electron-transporting type material of main part comprises Alq3, BPhen, Balq, BCP or TPBi.Alq
3refer to three (oxine) aluminium, i.e. Tris (8 – hydroxyquinoline) aluminum; BePhen refers to 4,7-diphenyl-1,10-ferrosin, i.e. 4,7 – diphenyl-1,10-phenanthroline; Balq refers to two (2-methyl-oxine)-4-phenylphenol-aluminium, i.e. aluminum (III) bis (2 – methyl – 8 – quinolinate) – 4 – phenylphenolate; BCP refers to 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene, i.e. 2,9 – dimethyl-4,7 – diphenyl-1,10 – phenanthroline; TPBI refers to 1,3,5-tri-(N-phenyl-2-base) benzene, i.e. 1,3,5 – tris (N – phenylbenzimidazol – 2 – yl) benzene.
Further, described hole-transporting type material of main part is the material of hole-conductive rate higher than electron conductivity, and thickness is between 1nm to 200nm; Described hole-transporting type material of main part comprises mCP, TCTA, TAPC, NPB, TmPyPB or MADN.MCP refers to 1,3-bis-(9-carbazyl) benzene, i.e. 1,3-bis (9-carbazolyl) benzene; TCTA refers to 4,4 ', 4 '-three (N-carbazyl) aniline, namely 4,4 ', 4 " and-tris (N-carbazolyl) triphenylamine; TAPC refers to 1,1-two (two (4tolylamino) phenyl) cyclohexane, i.e. 1,1-bis ((di-4-tolylamino) phenyl) cyclohexane; NPB refers to N, N '-two (naphthalene-1-base)-N, N '-two (phenyl) benzidine, i.e. N, N '-bis (naphthalen-1-yl)-N, N '-bis (phenyl) benzidine; TmPyPB refers to 1,3,5 three (rice-pyridin-3-yl-phenyl) benzene, i.e. 1,3,5-tri (m-pyrid-3-yl-phenyl) benzene; MADN refers to 2-methyl-two-naphthyl anthracene, i.e. 2-methyl-9,10-di-[2-naphthyl] anthracene.
Further, described ultra-thin undoped emitting layer material comprises Bephen, TPBi, NPB, TAPC, TmPyPB or BCP.BePhen refers to 4,7-diphenyl-1,10-ferrosin, i.e. 4,7 – diphenyl-1,10-phenanthroline; TPBI refers to 1,3,5-tri-(N-phenyl-2-base) benzene, i.e. 1,3,5 – tris (N – phenylbenzimidazol – 2 – yl) benzene; NPB refers to N, N '-two (naphthalene-1-base)-N, N '-two (phenyl) benzidine, i.e. N, N '-bis (naphthalen-1-yl)-N, N '-bis (phenyl) benzidine; TAPC refers to 1,1-two (two (4tolylamino) phenyl) cyclohexane, i.e. 1,1-bis ((di-4-tolylamino) phenyl) cyclohexane; TmPyPB refers to 1,3,5 three (rice-pyridin-3-yl-phenyl) benzene, i.e. 1,3,5-tri (m-pyrid-3-yl-phenyl) benzene; BCP refers to 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene, i.e. 2,9 – dimethyl-4,7 – diphenyl-1,10 – phenanthroline.
Further, described doping to refer to described luminescent material by hot evaporation or solution preparation, is mixed with in organic electroluminescent LED with doping ratio with described material of main part.
Further, the percentage of described doping ratio luminescent material evaporation rate and described luminescent material and overall evaporation rate of described material of main part described in described hot evaporation preparation method middle finger; The quality of described luminescent material and the mass ratio of described luminescent material and described material of main part gross mass is referred in described solution manufacturing method; Described doping ratio is from 0.01% to 99.99%.
The method of exciton distribution in change organic electroluminescent LED of the present invention, utilize the character that HOMO highest occupied molecular orbital (HOMO) energy level of ultra-thin insert layer material is lower than the HOMO energy level of material of main part, hole is transmitted on the HOMO energy level of organic material, the trend of under the effect of electric field, oriented higher HOMO energy level moving, the ultra-thin insert layer that HOMO energy level is higher than material of main part is introduced in material of main part, this ultra-thin insert layer plays the effect catching a large amount of hole, this ultra-thin insert layer position hole concentration is increased, the exciton concentration formed with electron recombination also increases, thus reach the effect changing exciton distribution in material of main part.
Be described further below with reference to the technique effect of accompanying drawing to design of the present invention, concrete structure and generation, to understand object of the present invention, characteristic sum effect fully.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of the method for the invention;
Fig. 2 is the structural representation of the organic electroluminescent LED of a preferred embodiments of the method for the invention;
Fig. 3 is the spectrum effects figure with the organic electroluminescent LED of structure in Fig. 2 of the method for the invention.
Embodiment
Elaborate to embodiments of the invention below in conjunction with accompanying drawing, the present embodiment is implemented under with technical solution of the present invention prerequisite, give detailed execution mode and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
In the present embodiment, that the material of main part in organic electroluminescent LED adopts is mCP, and that ultra-thin insert layer material adopts is TAPC, and this organic electroluminescent LED adopts ultra-thin undoped luminous layer structure.
Fig. 1 is schematic diagram of the present invention.Wherein, mCP is as the material of main part of organic electroluminescent LED, and TAPC is as ultra-thin insert layer material; HOMO highest occupied molecular orbital (HOMO) energy level of ultra-thin insert layer material TAPC is higher than the HOMO energy level of mCP, because hole is conducted on HOMO energy level, the trend under the effect of electric field, oriented higher HOMO energy level shifted, therefore hole is caught by the ultra-thin insert layer of TAPC, hole concentration in the position of ultra-thin insert layer increases, and the exciton concentration formed with electron recombination also raises.
Fig. 2 is the structural representation of the organic electroluminescent LED of a preferred embodiments of the present invention.This organic electroluminescent LED adopts ultra-thin undoped luminescent layer, wherein Firpic and red doping (Red Dopant) are respectively as blue and the ultra-thin undoped luminescent layer of redness, material of main part adopts mCP, that ultra-thin insert layer adopts is TAPC, Firpic layer is between mCP layer and TPBi layer, and Red Dopant layer is among mCP layer.
The complete structure of the organic electroluminescent LED in this example is: ITO/PEDOT:PSS (25nm)/TAPC (20nm)/mCP (9) //mCP (9)/TAPC (0 or 1nm)/Red Dopant (0.1)/mCP (6)/FIrpic (0.2)/TPBi (40nm)/LiF (1nm)/Al (100nm), wherein the TPBi of TAPC and 40nm of 20nm is respectively as hole transmission layer and electron transfer layer, ITO/PEDOT:PSS (25nm) is as anode, and LiF/Al is as negative electrode.
Ultra-thin insert layer TAPC in this example is adjacent with red light emitting layer Red Dopant, thickness is 1nm, object catches a large amount of hole herein exciton concentration is raised, this can judge effect by the spectrum observing organic electroluminescent LED, according to the lifting seeing red color light component after the ultra-thin insert layer of TAPC, be the effect of the change exciton distribution of the ultra-thin insert layer of TAPC.
Fig. 3 is the spectrum effects figure of the example of the organic electroluminescent LED with structure in Fig. 2.Wherein, No. 1 device does not have ultra-thin insert layer TAPC, and No. 2 devices insert the TAPC of 1nm at Red Dopant adjacent.Can see from spectrogram, the introducing of the ultra-thin insert layer of TAPC greatly improves red color light component (peak value is at the composition of about 600nm), illustrates that this ultra-thin insert layer serves the effect increasing exciton concentration, achieves the change of exciton concentration distribution.
More than describe preferred embodiment of the present invention in detail.Should be appreciated that the ordinary skill of this area just design according to the present invention can make many modifications and variations without the need to creative work.Therefore, all technical staff in the art, all should by the determined protection range of claims under this invention's idea on the basis of existing technology by the available technical scheme of logical analysis, reasoning, or a limited experiment.
Claims (10)
1. one kind changes the method for exciton distribution in organic electroluminescent LED, it is characterized in that, described method uses HOMO highest occupied molecular orbital (Highest Occupied Molecular Orbit, HOMO) material that energy level is higher than the HOMO energy level of described material of main part or lowest unoccupied molecular orbital (Lowest Unoccupied Molecular Orbit, LUMO) material that energy level is lower than the lumo energy of described material of main part is as ultra-thin undoped luminescent layer, described ultra-thin undoped luminescent layer catches a large amount of charge carrier, thus the exciton distribution in change organic electroluminescent LED, described ultra-thin undoped luminescent layer to be positioned among described material of main part or adjacent with described material of main part.
2. the method changing exciton distribution in organic electroluminescent LED as claimed in claim 1, is characterized in that, in described change organic electroluminescent LED, the method for exciton distribution also comprises:
Described ultra-thin undoped luminescent layer catches a large amount of hole, and the hole concentration of described ultra-thin undoped luminescent layer position is increased, and the exciton concentration that the electron recombination in described hole and described material of main part is formed also increases; Or
Described ultra-thin undoped luminescent layer catches a large amount of electronics, and the electron concentration of described ultra-thin undoped luminescent layer position is increased, and the exciton concentration that the hole-recombination in described electronics and described material of main part is formed also increases.
3. the method changing exciton distribution in organic electroluminescent LED as claimed in claim 1, it is characterized in that, described material of main part be support in organic electroluminescent LED that luminescent material is luminous, the material of conduction hole and electronics, comprise electron-transporting type material of main part and hole-transporting type material of main part.
4. the method changing exciton distribution in organic electroluminescent LED as claimed in claim 3, it is characterized in that, described luminescent material comprises fluorescence luminescent material and phosphorescent light-emitting materials; Described luminescent material is entrained in described material of main part.
5. the method changing exciton distribution in organic electroluminescent LED as claimed in claim 4, it is characterized in that, the thickness of described ultra-thin undoped luminescent layer is between 0.01nm to 5nm.
6. the method changing exciton distribution in organic electroluminescent LED as claimed in claim 3, it is characterized in that, described electron-transporting type material of main part is the material of electron conductivity higher than hole-conductive rate, and thickness is between 1nm to 200nm; Described electron-transporting type material of main part comprises Alq3, BPhen, Balq, BCP or TPBi.
7. the method changing exciton distribution in organic electroluminescent LED as claimed in claim 3, it is characterized in that, described hole-transporting type material of main part is the material of hole-conductive rate higher than electron conductivity, and thickness is between 1nm to 200nm; Described hole-transporting type material of main part comprises mCP, TCTA, TAPC, NPB, TmPyPB or MADN.
8. the method changing exciton distribution in organic electroluminescent LED as claimed in claim 1, it is characterized in that, described ultra-thin undoped emitting layer material comprises Bephen, TPBi, NPB, TAPC, TmPyPB or BCP.
9. the method changing exciton distribution in organic electroluminescent LED as claimed in claim 4, it is characterized in that, described doping to refer to described luminescent material by hot evaporation or solution preparation, is mixed with in organic electroluminescent LED with doping ratio with described material of main part.
10. the method changing exciton distribution in organic electroluminescent LED as claimed in claim 9, it is characterized in that, the percentage of described doping ratio luminescent material evaporation rate and described luminescent material and the overall evaporation rate of described material of main part described in described hot evaporation preparation method middle finger; The quality of described luminescent material and the mass ratio of described luminescent material and described material of main part gross mass is referred in described solution manufacturing method; Described doping ratio is from 0.01% to 99.99%.
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| CN201510260797.3A CN104835923A (en) | 2015-05-20 | 2015-05-20 | Method for changing exciton distribution in organic light-emitting diode |
| CN201510424314.9A CN104993062A (en) | 2015-05-20 | 2015-07-17 | A method for adjusting the white light spectrum of white organic electroluminescent light-emitting diodes |
| CN201510424312.XA CN105070844A (en) | 2015-05-20 | 2015-07-17 | Method for changing exciter distribution in organic light-emitting diode |
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| CN201510424314.9A Pending CN104993062A (en) | 2015-05-20 | 2015-07-17 | A method for adjusting the white light spectrum of white organic electroluminescent light-emitting diodes |
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Cited By (3)
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| CN109830611A (en) * | 2019-01-31 | 2019-05-31 | 瑞声科技（南京）有限公司 | A kind of Organic Light Emitting Diode and production method |
| CN113097402A (en) * | 2021-04-12 | 2021-07-09 | 京东方科技集团股份有限公司 | Organic electroluminescent device, preparation method thereof and display panel |
| CN115000317A (en) * | 2022-06-29 | 2022-09-02 | 太原理工大学 | White organic light emitting diode based on phosphorescent ultrathin layer |
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| CN110416419B (en) * | 2018-04-28 | 2021-03-26 | 江苏三月科技股份有限公司 | Organic electroluminescent device |
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| US6580213B2 (en) * | 2000-01-31 | 2003-06-17 | Semiconductor Energy Laboratory Co., Ltd. | Light-emitting device and method of manufacturing the same |
| CN101079471B (en) * | 2006-05-25 | 2010-06-09 | 清华大学 | An organic EL part |
| CN101394696A (en) * | 2007-09-20 | 2009-03-25 | 清华大学 | Organic EL device |
| CN103219473A (en) * | 2013-04-26 | 2013-07-24 | 上海大学 | White organic light emitting device with single light emitting layer structure |
| CN204257709U (en) * | 2014-11-07 | 2015-04-08 | 京东方科技集团股份有限公司 | Monochromatic OLED and OLED display panel |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109830611A (en) * | 2019-01-31 | 2019-05-31 | 瑞声科技（南京）有限公司 | A kind of Organic Light Emitting Diode and production method |
| CN113097402A (en) * | 2021-04-12 | 2021-07-09 | 京东方科技集团股份有限公司 | Organic electroluminescent device, preparation method thereof and display panel |
| CN113097402B (en) * | 2021-04-12 | 2024-04-16 | 京东方科技集团股份有限公司 | Organic electroluminescent device, preparation method thereof and display panel |
| CN115000317A (en) * | 2022-06-29 | 2022-09-02 | 太原理工大学 | White organic light emitting diode based on phosphorescent ultrathin layer |
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| CN104993062A (en) | 2015-10-21 |
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Application publication date: 20150812 |