CN104993062A - A method for adjusting the white light spectrum of white organic electroluminescent light-emitting diodes - Google Patents
A method for adjusting the white light spectrum of white organic electroluminescent light-emitting diodes Download PDFInfo
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- 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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Abstract
The invention provides a method for adjusting the white light spectrum of white organic electroluminescent light-emitting diodes (OLED). The method is characterized in that a material with a HOMO (highest occupied molecular orbit) energy level and an LUMO (lowest unoccupied molecular orbit) energy level different from those of a main body material serves as an ultrathin functional layer which is inserted in a light-emitting layer of a white OLED to change the light-emitting weight of a certain color, and thus the white light spectrum of the white OLED can be adjusted. The degree of the adjustment of the white light spectrum of the white OLED varies with the thickness of the ultrathin functional layer. The main body material contains an electronic transmission type main body material and a hole transmission type main body material. The ultrathin functional layer material mainly contains an electronic transmission material and a hole transmission material. The method can simply and effectively adjust the white light spectrum of the white OLED by using the thickness of the ultrathin functional layer, and in particular achieves an ideal effect in adjustment of the white light spectrum of the white OLED based on an ultrathin non-doped light-emitting layer.
Description
Technical field
The present invention relates to organic semiconductor field of electronic materials, particularly relate to a kind of method adjusting the white-light spectrum of white organic electroluminescent diode.
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.
White organic electroluminescent diode (WOLED) is the Main way that present stage OLED studies, and this is because WOLED has huge potentiality to be used on the display screen of following full gamut and the lighting source of large size panel.On the whole, the white light of WOLED or can mix Red Green Blue and obtains by the complementary color of mixing two kinds (as red and blue, red and orange, orange and blue).
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, this have impact on the luminous weight of shades of colour in the white-light spectrum of white organic electroluminescent diode.Usually adopt CIE index to weigh white light quality in the world, CIE index is whiter the closer to the white light better quality of (0.33,0.33).In white-light spectrum, the luminous weight of each color is directly connected to the CIE index of white light.
Therefore, those skilled in the art is devoted to develop a kind of method that can adjust the white-light spectrum of white organic electroluminescent diode.
Summary of the invention
Because the above-mentioned defect of prior art, technical problem to be solved by this invention is the problem that in the white-light spectrum of white organic electroluminescent diode, each colour light emitting weight is undesirable.
For achieving the above object, the invention provides a kind of method adjusting the white-light spectrum of white organic electroluminescent diode, described method uses HOMO highest occupied molecular orbital (Highest Occupied Molecular Orbit, HOMO) energy level or lowest unoccupied molecular orbital (Lowest Unoccupied Molecular Orbit, LUMO) HUMO of energy level and described material of main part or the differentiated material of lumo energy are as ultrathin functional layer, described ultrathin functional layer is inserted in the luminescent layer of white organic electroluminescent diode, described ultrathin functional layer catches a large amount of charge carrier, play the effect changing certain colour light emitting weight, thus the white-light spectrum of adjustment white organic electroluminescent diode, described ultrathin functional layer to be positioned among described material of main part or adjacent with described material of main part.
Further, described white organic electroluminescent diode comprises:
The white organic electroluminescent diode of R-G-B (RGB) three-colour light-emitting, and the white organic electroluminescent diode of red-blue (RB) or red-orange (RO) or orange-blue (BO) dichromatism luminescence.
Further, the method for the white-light spectrum of described adjustment white organic electroluminescent diode comprises:
Described ultrathin functional layer catches a large amount of hole, and the hole concentration of described ultrathin functional layer position is increased, and the luminous weight of certain color of described white organic electroluminescent diode is changed; Or
Described ultrathin functional layer catches a large amount of electronics, and the electron concentration of described ultrathin functional layer position is increased, and the luminous weight of certain color of described white organic electroluminescent diode is changed.
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.
Further, described luminescent layer is entrained in described material of main part by described luminescent material to be prepared from, or exist with the form of ultra-thin undoped luminescent layer.
Further, described ultra-thin undoped luminescent layer is that thickness is between 0.01nm to 5nm using luminescent material as independently luminescent layer, be prepared from undoped form.
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 HOMO highest occupied molecular orbital (Highest Occupied Molecular Orbit, HOMO) energy level or lowest unoccupied molecular orbital (Lowest Unoccupied Molecular Orbit, LUMO) HUMO of energy level and described material of main part or lumo energy have difference to refer to the HUMO energy level of HUMO energy level higher than material of main part of ultrathin functional layer material, or the lumo energy of ultrathin functional layer material is lower than the lumo energy of material of main part.
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, the thickness of described ultrathin functional layer is between 0.01nm to 10nm.
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 the white-light spectrum of adjustment white organic electroluminescent diode of the present invention, utilize the character that the HOMO highest occupied molecular orbital of ultrathin functional layer material (HOMO) energy level is higher 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, this ultrathin functional layer plays the effect catching a large amount of hole, this ultra-thin insert layer position hole concentration is increased, play the effect changing certain colour light emitting weight, thus the white-light spectrum of adjustment white organic electroluminescent diode.
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 principle schematic of the method for the invention;
Fig. 2 is the structural representation of the red green blue tricolor white organic electroluminescent diode of a preferred embodiments of the method for the invention;
Fig. 3 is the spectrum effects figure with the white organic electroluminescent diode of structure in Fig. 2 of the method for the invention;
Fig. 4 is the structural representation of the double-colored white organic electroluminescent diode of red indigo plant of another preferred embodiments of the method for the invention;
Fig. 5 is the spectrum effects figure with the white organic electroluminescent diode of structure in Fig. 4 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 ultrathin functional layer material adopts is TAPC, and white organic electroluminescent diode 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 ultrathin functional layer material; HOMO highest occupied molecular orbital (HOMO) energy level of ultrathin functional 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 TAPC ultrathin functional layer, cause the light emitting layer luminesces weight be positioned near TAPC ultrathin functional layer to increase, thus have adjusted the white-light spectrum of white organic electroluminescent diode.
Fig. 2 is the structural representation of the red green blue tricolor white organic electroluminescent diode of a preferred embodiments of the present invention.This organic electroluminescent LED adopts ultra-thin undoped luminescent layer, wherein red doping (Red Dopant), Ir (ppy)
3with Firpic respectively as red, green and blue ultra-thin undoped luminescent layer, material of main part adopts mCP, blue light-emitting layer is positioned at the interface place of material of main part mCP and electron transfer layer TPBi, red light emitting layer is positioned among material of main part mCP, and green light emitting layer is arranged in electron transfer layer TPBi; That ultrathin functional layer adopts is TAPC, is inserted near blue light-emitting layer.
The complete structure of the red green blue tricolor white organic electroluminescent diode in this example is: ITO/PEDOT:PSS (25nm)/TAPC (20nm)/mCP (11)/Red Dopant (0.2)/mCP (4)/Firpic (0.2)/TAPC (0 or 0.4 or 0.8 or 1nm)/TPBi (8nm)/Ir (ppy)
3/ TPBi (38nm)/LiF (1nm)/Al (100nm), wherein TAPC and TPBi is respectively as hole transmission layer and electron transfer layer, and ITO/PEDOT:PSS (25nm) is as anode, and LiF/Al is as negative electrode.
Ultrathin functional layer TAPC in this example is adjacent with blue light-emitting layer, object catches a large amount of hole herein thus regulates blue-light-emitting weight, this can judge effect by the spectrum observing organic electroluminescent LED, according to seeing after TAPC ultrathin functional layer that blue-light-emitting weight strengthens, be the effect of the change exciton distribution of TAPC ultrathin functional layer.
Fig. 3 is the spectrum effects figure of the example of the red green blue tricolor white organic electroluminescent diode with structure in Fig. 2.Wherein, D1 device does not have ultrathin functional layer TAPC, No. D2, No. D3, D4 device Firpic adjacent insert respectively thickness be 0.4,0.8, the TAPC ultrathin functional layer of 1nm.Can see from spectrogram, the introducing of TAPC ultrathin functional layer changes the luminous weight of each color in white-light spectrum, the luminous weight of blueness (peak value is at the composition of about 470nm) and green (peak value is at the composition of about 510nm) is increased, and the luminous weight of ruddiness (peak value is at the composition of about 600nm) is reduced, have adjusted white-light spectrum.The more important thing is: TAPC ultrathin functional layer is thicker, this regulating action is stronger, namely TAPC is thicker, blue and green emitting weight is higher, and emitting red light weight is lower, illustrate that this ultrathin functional layer serves the effect of adjustment white-light spectrum, and TAPC functional layer is thicker, stronger to the regulating action of white-light spectrum.
Fig. 4 is the structural representation of the double-colored white organic electroluminescent diode of red indigo plant of another preferred embodiments of the present invention.This red indigo plant double-colored white organic electroluminescent diode also 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 ultrathin functional 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)/TAPC (0 or 1nm)/Red Dopant (0.2)/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 thus regulates emitting red light weight, this can judge effect by the spectrum observing organic electroluminescent LED, according to seeing after TAPC ultrathin functional layer that red light-emitting weight strengthens, be the effect of the change exciton distribution of TAPC ultrathin functional layer.
Fig. 5 is the spectrum effects figure of the example with the double-colored white organic electroluminescent diode of the red indigo plant of structure in Fig. 4.Wherein, No. 1 device does not have ultrathin functional layer TAPC, and No. 2 devices insert the TAPC of 1nm at Red Dopant adjacent.Can see from spectrogram, the introducing of TAPC ultrathin functional layer greatly improves red color light component (peak value is at the composition of about 600nm), illustrates that this ultrathin functional layer serves the effect of adjustment white-light spectrum.
More than describe two 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 (14)
1. one kind adjusts the method for the white-light spectrum of white organic electroluminescent diode, it is characterized in that, described method uses HOMO highest occupied molecular orbital (Highest Occupied Molecular Orbit, HOMO) energy level or lowest unoccupied molecular orbital (Lowest Unoccupied Molecular Orbit, LUMO) HUMO of energy level and described material of main part or the differentiated material of lumo energy are as ultrathin functional layer, described ultrathin functional layer is inserted in the luminescent layer of white organic electroluminescent diode, described ultrathin functional layer catches a large amount of charge carrier, play the effect changing certain colour light emitting weight, thus the white-light spectrum of adjustment white organic electroluminescent diode, different along with the thickness difference of described ultrathin functional layer to the adjustment dynamics of the white-light spectrum of described white organic electroluminescent diode, described ultrathin functional layer to be positioned among described material of main part or adjacent with described material of main part.
2. the method for the white-light spectrum of adjustment white organic electroluminescent diode as claimed in claim 1, it is characterized in that, described white organic electroluminescent diode comprises:
The white organic electroluminescent diode of R-G-B (RGB) three-colour light-emitting, and the white organic electroluminescent diode of red-blue (RB) or red-orange (RO) or orange-blue (BO) dichromatism luminescence.
3. the method for the white-light spectrum of adjustment white organic electroluminescent diode as claimed in claim 1, is characterized in that,
Described ultrathin functional layer catches a large amount of hole, and the hole concentration of described ultrathin functional layer position is increased, and the luminous weight of certain color of described white organic electroluminescent diode is changed; Or
Described ultrathin functional layer catches a large amount of electronics, and the electron concentration of described ultrathin functional layer position is increased, and the luminous weight of certain color of described white organic electroluminescent diode is changed.
4. the method for the white-light spectrum of adjustment white organic electroluminescent diode 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.
5. the method for the white-light spectrum of adjustment white organic electroluminescent diode as claimed in claim 4, it is characterized in that, described luminescent material comprises fluorescence luminescent material and phosphorescent light-emitting materials.
6. the method for the white-light spectrum of adjustment white organic electroluminescent diode as claimed in claim 1, it is characterized in that, described luminescent layer is entrained in described material of main part by described luminescent material to be prepared from, or exist with the form of ultra-thin undoped luminescent layer.
7. the method for the white-light spectrum of adjustment white organic electroluminescent diode as claimed in claim 6, it is characterized in that, described ultra-thin undoped luminescent layer is that thickness is between 0.01nm to 5nm using luminescent material as independently luminescent layer, be prepared from undoped form.
8. the method for the white-light spectrum of adjustment white organic electroluminescent diode as claimed in claim 4, 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.
9. the method for the white-light spectrum of adjustment white organic electroluminescent diode as claimed in claim 4, 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.
10. the method for the white-light spectrum of adjustment white organic electroluminescent diode as claimed in claim 1, it is characterized in that, described HOMO highest occupied molecular orbital (Highest Occupied Molecular Orbit, HOMO) energy level or lowest unoccupied molecular orbital (Lowest Unoccupied Molecular Orbit, LUMO) HUMO of energy level and described material of main part or lumo energy have difference to refer to the HUMO energy level of HUMO energy level higher than material of main part of ultrathin functional layer material, or the lumo energy of ultrathin functional layer material is lower than the lumo energy of material of main part.
The method of the white-light spectrum of 11. adjustment white organic electroluminescent diodes as claimed in claim 10, it is characterized in that, described ultrathin functional layer material comprises Bephen, TPBi, NPB, TAPC, TmPyPB or BCP.
The method of the white-light spectrum of 12. adjustment white organic electroluminescent diodes as claimed in claim 1, it is characterized in that, the thickness of described ultrathin functional layer is between 0.01nm to 10nm.
The method of the white-light spectrum of 13. adjustment white organic electroluminescent diodes as claimed in claim 6, 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.
The method of the white-light spectrum of 14. adjustment white organic electroluminescent diodes as claimed in claim 13, 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 |
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| 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 |
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| CN109361788A (en) * | 2018-10-31 | 2019-02-19 | 上海理工大学 | A kind of mobile terminal device of 100% screen accounting |
| WO2019206290A1 (en) * | 2018-04-28 | 2019-10-31 | 江苏三月光电科技有限公司 | Organic electroluminescent device |
| CN113036047A (en) * | 2021-03-08 | 2021-06-25 | 上海大学 | OLED plant growth light source and preparation method thereof |
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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 |
| 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 |
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| CN105070844A (en) | 2015-11-18 |
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