CN1571601A - Preparation method of white organic electroluminescent device - Google Patents
Preparation method of white organic electroluminescent device Download PDFInfo
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- CN1571601A CN1571601A CN 200410010818 CN200410010818A CN1571601A CN 1571601 A CN1571601 A CN 1571601A CN 200410010818 CN200410010818 CN 200410010818 CN 200410010818 A CN200410010818 A CN 200410010818A CN 1571601 A CN1571601 A CN 1571601A
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Abstract
The invention discloses a producing method of organic white light device, mixing red light dye and/or green dye or blue dye into cavity transporting material by 1% chroma at the same time, to mixing into cavity transporting material and electric transporting material, producing structure of indium stannum oxide/NPB/DCJTB:C545T:NPB(or DCJTB: NPB)/NPB( or TPB:NPB)/DNA/BCP/Alq3(or C545T:Alq3)/LiF/mental electrode EL device, the device is drived by direct current, and getting white light with color coordinate 0.329, 0.332, the biggest electroluminescence efficiency is 12.4 cd/A, the biggest luminescence brightness is 13550cd/ sq m.
Description
Technical field
The present invention relates to a kind of preparation method of white color organic electroluminescence device.
Background technology
In recent years, ORGANIC ELECTROLUMINESCENCE DISPLAYS has been regarded as emerging Display Technique the most popular in the Flat Panel Display Industry and has obtained extensive studies.Use for organic light emitting display, the colored demonstration is the final goal that people pursue, and variegating filter formation red-green-blue pixel with the simple white light of technology is to realize organic colored a kind of important method that shows at present.Except being used for doing colored the demonstration, this ultra-thin white organic light emitting device also is the perfect light source of liquid crystal background and following illumination.Yet the efficient of organic light emitting display and brightness and spectrum stability thereof also are far from satisfying the requirement of using.Therefore, how start with and solve the emphasis that the problems referred to above are these area researches from material and device architecture design.
At present, diverse ways has been used to prepare the white-light organic light-emitting display device, and as three primary colors mixing and doping, sandwich construction, exciplex (excimer), spin coating individual layer etc., material divides systems such as organic molecule, polymer and electrophosphorescent organic molecule.Delivered the multilayer white organic light emitting device made from the fluorescence organic small molecule material as people such as nineteen ninety-five J.Kido at Science, high-high brightness has surpassed 2000cd/m
2, power efficiency 0.5Lm/W, operating voltage is at 15 volts to 16 volts, and this is the result of the multilayer white organic light emitting device of early stage report.
1999, R.S.Forrest seminar developed high brightness multilayer white organic light emitting device with the fluorescence organic small molecule material, and the doping content by control interfacial layer thickness and dyestuff has obtained good white luminous, and high-high brightness has reached 13500cd/m
2This device emission spectrum does not have significant change with drive current, still launches good white light in wide drive current range, and chromaticity coordinate is 0.33,0.33, near desirable white light, yet, the maximum electroluminescence quantum efficiency of this device has only 0.5%, and power efficiency has only 0.3Lm/W.
J.Shinar seminar in 2002 white organic light emitting device of fluorescence organic molecule preparation, high-high brightness has surpassed 50000cd/m
2, maximum power efficiency 4.1Lm/W, maximum quantum efficiency has reached 3%, yet finds that the spectrum of this device is with the voltage significant change.People such as Y.Wang in 2002 have further improved the efficient of the white organic light emitting device made from the fluorescence organic molecule, adopt bi-layer devices simple in structure, maximum electroluminescent efficiency has reached 6.5cd/A (3.6Lm/W), this device is realized white light emission by the excite state ground level compound that forms between the organic layer, but this white light parts does not have good spectrum stability usually.The electroluminescent efficiency of white organic light emitting device can further be improved with the electrophosphorescent organic molecule material, as 2002, R.S.Forrest seminar iridium electrophosphorescent material, adopt sandwich construction, high efficiency, high-brightness white-light device, this device high-high brightness 31000cd/m have been realized by controlling the exciton diffusion effectively
2, maximal efficiency 11cd/A (6.4Lm/W).But the problem that has the spectrum stability difference equally.
Summary of the invention
The purpose of this invention is to provide a kind of white color organic electroluminescence device;
Another object of the present invention provides a kind of preparation method of white color organic electroluminescence device.
The present invention adopts dye adulterated method, by sandwich construction the injection of charge carrier and the regulation and control of transmission and exciton recombination zone is realized white color organic electroluminescence device.
The hole mobile material that the present invention uses is N, N '-two (1-naphthyl)-N, and N '-diphenyl-1,1 '-diphenyl-4,4 '-diamines (NPB), its molecular structure is as follows:
The electron transport material that the present invention uses is oxine aluminium (Alq
3), its molecular structure is as follows:
Hole barrier/electron transport material that the present invention uses is 2,9-dimethyl-4, and 7-diphenyl-1,10-o-phenanthroline (BCP), its molecular structure is as follows:
Fluorescence organic molecule material that the present invention uses and structure thereof are as follows respectively:
The 2-{2-tert-butyl group-6-[2-(1,1,7, the 7-tetramethyl)-2,3,6,7-tetrahydrochysene-1H, 5H-pyrido [3,2,1-ij] quinoline-9-yl]-vinyl }-pyrans-4-inner salt alkene }-malononitrile (DCJTB)
10-(2-[4-morpholinodithio base)-2,3,6,7-tetrahydrochysene-1,1,7,7-tetramethyl-1H, 5H, 11H-(1)-benzo give a tongue-lashing the ketone group of muttering-(6,7,8-ij) quinolizine-11-ketone (C545T)
9,10-dinaphthyl-anthracene (DAN)
1,1,4,4-tetraphenylbutadiene (TPB)
Preparation process:
On through the indium tin oxide glass substrate that fully cleans, 10
-4Carry out evaporation under the pressure of handkerchief.Ground floor is the N of 20～30nm with the speed evaporation thickness of 2～3 /s, N '-two (1-naphthyl)-N, N '-diphenyl-1,1 '-diphenyl-4,4 '-diamines; The second layer is the N of 5～10nm with the speed evaporation thickness of 2～3 /s, N '-two (1-naphthyl)-N, N '-diphenyl-1,1 '-diphenyl-4,4 '-diamines doping mass ratio is the 2-{2-tert-butyl group-6-[2-(1 of 0.8～1.5%, 1,7, the 7-tetramethyl)-2,3,6,7-tetrahydrochysene-1H, 5H-pyrido [3,2,1-ij] quinoline-9-yl]-vinyl }-pyrans-4-inner salt alkene }-malononitrile is or/and mass ratio is 0.8～1.5% 10-(2-[4-morpholinodithio base)-2,3,6,7-tetrahydrochysene-1,1,7,7-tetramethyl-1H, 5H, 11H-(1)-benzo is given a tongue-lashing the ketone group of muttering-(6,7,8-ij) quinolizine-11-ketone; The 3rd layer is the N of 4～10nm with the speed evaporation thickness of 2～3 /s, N '-two (1-naphthyl)-N, N '-diphenyl-1,1 '-diphenyl-4,4 '-diamines or doping mass ratio be 0.8～1.5% 1,1,4, the 4-tetraphenylbutadiene; The 4th layer is 9 of 0～10nm with the speed evaporation thickness of 2～3 /s, 10-dinaphthyl-anthracene; Layer 5 is 2 of 1～10nm with the speed evaporation thickness of 2～3 /s, 9-dimethyl-4,7-diphenyl-1, the adjacent Fei Luolin of 10-; Layer 6 is that the oxine aluminium of 20～30nm or doping mass ratio are 0.8～1.5% 10-(2-[4-morpholinodithio base)-2,3,6 with the speed evaporation thickness of 2～3 /s, 7-tetrahydrochysene-1,1,7,7-tetramethyl-1H, 5H, 11H-(1)-benzo give a tongue-lashing the ketone group of muttering-(6,7,8-ij) quinolizine-11-ketone; Layer 7 is the lithium fluoride of 0.5～1.5nm with the speed evaporation thickness of 0.5～1 /s; The 8th layer is the aluminium of 80～100nm with the speed evaporation thickness of 5～10 /s.Being prepared into structure is indium tin oxide/N, N '-two (1-naphthyl)-N, N '-diphenyl-1,1 '-diphenyl-4,4 '-diamines/fluorescent dye: N, N '-two (1-naphthyl)-N, N '-diphenyl-1,1 '-diphenyl-4,4 '-diamines/N, N '-two (1-naphthyl)-N, N '-diphenyl-1,1 '-diphenyl-4,4 '-diamines/9,10-dinaphthyl-anthracene/2,9-dimethyl-4,7-diphenyl-1, the electroluminescent device of 10-o-phenanthroline/oxine aluminium/lithium fluoride boundary layer/aluminum metal electrode.The obtained device direct voltage drive can obtain colorimetric purity white light preferably.
Description of drawings
1) is coated in indium tin oxide conductive anode on the glass substrate;
2) hole transmission layer: N, N '-two (1-naphthyl)-N, N '-diphenyl-1,1 '-diphenyl-4,4 '-diamines;
3) fluorescent dye: main body organic material doped layer;
4) blue light-emitting: 9,10-dinaphthyl-anthracene is or/and N, N '-two (1-naphthyl)-N, N '-diphenyl-1,1 '-diphenyl-4,4 '-diamines;
5) hole blocking layer: 2,9-dimethyl-4,7-diphenyl-1, the adjacent Fei Luolin of 10-;
6) electron transfer layer: oxine aluminium or electron transfer layer doped with fluorescent dyes;
7) boundary layer: lithium fluoride;
8) metallic cathode: aluminium;
Fluorescent dye among the present invention is the 2-{2-tert-butyl group-6-[2-(1,1,7, the 7-tetramethyl)-2,3,6,7-tetrahydrochysene-1H, 5H-pyrido [3,2,1-ij] quinoline-9-yl]-vinyl }-pyrans-4-inner salt alkene }-malononitrile, 10-(2-[4-morpholinodithio base)-2,3,6,7-tetrahydrochysene-1,1,7,7-tetramethyl-1H, 5H, 11H-(1)-benzo give a tongue-lashing the ketone group of muttering-(6,7,8-ij) quinolizine-11-ketone, 9,10-dinaphthyl-anthracene, 1,1,4, the 4-tetraphenylbutadiene.
Fig. 2 is the electric current-brightness-voltage response of electroluminescent device, as can be seen from the figure, luminosity raises along with the rising of voltage, and the bright voltage that opens of device is 5.9 volts, at voltage is 25.5 volts, and electric current is that 0.043 ampere-hour device obtains high-high brightness 13500cd/m
2
Fig. 3 is the luminous efficiency-current characteristics curve of electroluminescent device, and the luminous efficiency of device reduces with the increase of electric current, and maximum current efficient is 12.3cd/A.
Fig. 4 is the electroluminescent spectrum of device, and the chromaticity coordinates that calculates of spectrum is thus: 0.329,0.332, and very near desirable white light 0.33,0.33.
Fig. 5 is the electroluminescent spectrum of device under different voltages, and as seen from the figure, in a bigger voltage range, luminescent spectrum has stability preferably.
Advantage of the present invention is that the White Organic Light-emitting Devices of preparation has high efficiency, high brightness, characteristics that color stability is good.
Prepared electroluminescent device, according to different material systems, best chromaticity coordinate is 0.329,0.332, very near desirable white light 0.33,0.33 best chromaticity coordinate is 0.355,0.380, all well be positioned at white light area, current efficiency reaches 3.15～12.3cd/A, and power efficiency reaches 2.3～6.8lm/w, and luminosity reaches 3669～13500cd/m
2, electroluminescent efficiency and luminosity obtain authentication from accompanying drawing 2,3.Color stability obtains authentication from accompanying drawing 5.
Embodiment
Embodiment 1:
Be doped to DCJTB that to be prepared into structure as luminescent layer among the NPB be ITO/NPB/DCJTB:NPB/NPB/BCP/Alq
3The electroluminescent device of/LiF/Al is in vacuum degree 10
-4Organic and the metal electrode layer of evaporation under the pressure of handkerchief, the evaporation rate controlled of organic layer is at 2 /s, the evaporation rate of LiF is controlled 0.5 /s, and the evaporation rate controlled of metal is at 5 /s, and doping content is controlled at 1%, wherein, the NPB layer thickness is 30～35nm, and the DCJTB:NPB layer is 3～5nm, and the NPB layer is 8～10nm, the BCP layer is 9～10nm, Alq
3Layer is 25～30nm, and the LiF layer is 0.8～1.5nm, and the Al layer is 80～100nm, and the obtained device direct voltage drive can obtain white luminously, and maximum current efficient is 3.15cd/A, high-high brightness 3669cd/m
2
Embodiment 2:
Be doped to respectively with DCJTB and TPB that to be prepared into structure as luminescent layer among the NPB be ITO/NPB/DCJTB:NPB/TPB:NPB/BCP/Alq
3The electroluminescent device of/LiF/Al is in vacuum degree 10
-4Organic and the metal electrode layer of evaporation under the pressure of handkerchief, the evaporation rate controlled of organic layer is at 2 /s, evaporation rate controlled 0.5 /s of LiF, the evaporation rate controlled of metal is at 5 /s, and doping content all is controlled at 1%, wherein, the NPB layer thickness is 25～30nm, and the DCJTB:NPB layer is 8～10nm, and the TPB:NPB layer is 9～10nm, the BCP layer is 8～10nm, Alq
3Layer is 25～30nm, and the LiF layer is 0.8～1.5nm, and the Al layer is 80～100nm, and the obtained device direct voltage drive can obtain white luminously, and maximum current efficient is 4.33cd/A, high-high brightness 6183cd/m
2
Embodiment 3:
Be doped to DCJTB that to be prepared into structure as luminescent layer among the NPB be ITO/NPB/DCJTB:NPB/NPB/DNA/BCP/Alq
3The electroluminescent device of/LiF/Al is in vacuum degree 10
-4Organic and the metal electrode layer of evaporation under the pressure of handkerchief, the evaporation rate controlled of organic layer is at 2 /s, and the evaporation rate of LiF is controlled 0.5 /s, and the evaporation rate controlled of metal is at 5 /s, doping content is controlled at 1%, wherein, the NPB layer thickness is 25～30nm, and the DCJTB:NPB layer is 8～10nm, the NPB layer is 4～6nm, the DNA layer is 4～5nm, and the BCP layer is 9～10nm, Alq
3Layer is 25～30nm, and the LiF layer is 0.8～1.5nm, and the Al layer is 80～100nm, and the obtained device direct voltage drive can obtain white luminously, and maximal efficiency is 10.3cd/A, high-high brightness 10800cd/m
2
Embodiment 4:
Be doped to NPB and Alq respectively with DCJTB and C545T
3In to be prepared into structure as luminescent layer be ITO/NPB/DCJTB:NPB/NPB/DNA/BCP/C545T:Alq
3/ Alq
3The electroluminescent device of/LiF/Al is in vacuum degree 10
-4Organic and the metal electrode layer of evaporation under the pressure of handkerchief, the evaporation rate controlled of organic layer is at 1～3 /s, and the evaporation rate of LiF is controlled 0.5～1 /s, and the evaporation rate controlled of metal is at 5～10 /s, doping content is controlled at 0.8～1.5%, wherein, the NPB layer thickness is 20～25nm, and the DCJTB:NPB layer is 5～9nm, the NPB layer is 4～6nm, the DNA layer is 8～12nm, and the BCP layer is 0.5～2nm, C545T:Alq
3Layer is 8～12nm, Alq
3Layer is 25～35nm, and the LiF layer is 0.8～1.5nm, and the Al layer is 80～100nm, and the obtained device direct voltage drive can obtain white luminously, and maximal efficiency is 12.4cd/A, and high-high brightness is 12200cd/m
2
Embodiment 5:
Be doped to simultaneously with DCJTB and C545T that to be prepared into structure as luminescent layer among the NPB be ITO/NPB/DCJTB:C545T:NPB/NPB/DNA/BCP/Alq
3The electroluminescent device of/LiF/Al is in vacuum degree 10
-4Organic and the metal electrode layer of evaporation under the pressure of handkerchief, the evaporation rate controlled of organic layer is at 2 /s, and the evaporation rate of LiF is controlled 0.5 /s, and the evaporation rate controlled of metallic aluminium is at 5 /s, doping content was controlled at 1%: 1%: 1, wherein, the NPB layer thickness is 25～30nm, and the DCJTB:C545T:NPB layer is 8～10nm, the NPB layer is 3～4nm, the DNA layer is 6～8nm, and the BCP layer is 7～9nm, Alq
3Layer is 25～30nm, and the LiF layer is 0.8～1.5nm, and the Al layer is 80～100nm, and the obtained device direct voltage drive can obtain white luminously, and maximum current efficient is 12.3cd/A, high-high brightness 13550cd/m
2
Claims (3)
1. white color organic electroluminescence device has following structure:
1) is coated in indium tin oxide conductive anode on the glass substrate;
2) hole transmission layer: N, N '-two (1-naphthyl)-N, N '-diphenyl-1,1 '-diphenyl-4,4 '-diamines;
3) fluorescent dye: main body organic material doped layer;
4) blue light-emitting: 9,10-dinaphthyl-anthracene is or/and N, N '-two (1-naphthyl)-N, N '-diphenyl-1,1 '-diphenyl-4,4 '-diamines;
5) hole blocking layer: 2,9-dimethyl-4,7-diphenyl-1, the adjacent Fei Luolin of 10-;
6) electron transfer layer: oxine aluminium or electron transfer layer doped with fluorescent dyes;
7) boundary layer: lithium fluoride;
8) metallic cathode: aluminium.
2. a white color organic electroluminescence device preparation method is characterized in that the hole mobile material of selecting is N, N '-two (1-naphthyl)-N, and N '-diphenyl-1,1 '-diphenyl-4,4 '-diamines, its molecular structure is as follows:
Electron transport material is an oxine aluminium, and its molecular structure is as follows:
Hole barrier/electron transport material is 2,9-dimethyl-4, and 7-diphenyl-1, the 10-o-phenanthroline, its molecular structure is as follows:
Fluorescence organic molecule material and structure thereof are as follows respectively:
The 2-{2-tert-butyl group-6-[2-(1,1,7, the 7-tetramethyl)-2,3,6,7-tetrahydrochysene-1H, 5H-pyrido [3,2,1-ij] quinoline-9-yl]-vinyl }-pyrans-4-inner salt alkene }-malononitrile
10-(2-[4-morpholinodithio base)-2,3,6,7-tetrahydrochysene-1,1,7,7-tetramethyl-1H, 5H, 11H-(1)-benzo give a tongue-lashing the ketone group of muttering-(6,7,8-ij) quinolizine-11-ketone
9,10-dinaphthyl-anthracene
1,1,4, the 4-tetraphenylbutadiene
Preparation process:
On through the indium tin oxide glass substrate that fully cleans, 10
-4Carry out evaporation under the pressure of handkerchief:
Ground floor is the N of 20～30nm with the speed evaporation thickness of 2～3 /s, N '-two (1-naphthyl)-N, N '-diphenyl-1,1 '-diphenyl 4,4 '-diamines;
The second layer is the N of 5～10nm with the speed evaporation thickness of 2～3 /s, N '-two (1-naphthyl)-N, N '-diphenyl-1,1 '-diphenyl-4,4 '-diamines doping mass ratio is the 2-{2-tert-butyl group-6-[2-(1 of 0.8～1.5%, 1,7, the 7-tetramethyl)-2,3,6,7-tetrahydrochysene-1H, 5H-pyrido [3,2,1-ij] quinoline-9-yl]-vinyl }-pyrans-4-inner salt alkene }-malononitrile is or/and mass ratio is 0.8～1.5% 10-(2-[4-morpholinodithio base)-2,3,6,7-tetrahydrochysene-1,1,7,7-tetramethyl-1H, 5H, 11H-(1)-benzo is given a tongue-lashing the ketone group of muttering-(6,7,8-ij) quinolizine-11-ketone;
The 3rd layer is the N of 4～10nm with the speed evaporation thickness of 2～3 /s, N '-two (1-naphthyl)-N, N '-diphenyl-1,1 '-diphenyl-4,4 '-diamines or doping mass ratio be 0.8～1.5% 1,1,4, the 4-tetraphenylbutadiene;
The 4th layer is 9 of 0～10nm with the speed evaporation thickness of 2～3 /s, 10-dinaphthyl-anthracene;
Layer 5 is 2 of 1～10nm with the speed evaporation thickness of 2～3 /s, 9-dimethyl-4,7-diphenyl-1, the adjacent Fei Luolin of 10-;
Layer 6 is that the oxine aluminium of 20～30nm or doping mass ratio are 0.8～1.5% 10-(2-[4-morpholinodithio base)-2,3,6 with the speed evaporation thickness of 2～3 /s, 7-tetrahydrochysene-1,1,7,7-tetramethyl-1H, 5H, 11H-(1)-benzo give a tongue-lashing the ketone group of muttering-(6,7,8-ij) quinolizine-11-ketone;
Layer 7 is the lithium fluoride of 0.5～1.5nm with the speed evaporation thickness of 0.5～1 /s;
The 8th layer is the aluminium of 80～100nm with the speed evaporation thickness of 5～10 /s;
The white color organic electroluminescence device that makes, the poorest chromaticity coordinate are 0.355,0.380, best chromaticity coordinate is 0.329,0.332, and current efficiency reaches 3.15～12.3cd/A, power efficiency reaches 2.3～6.8lm/w, and luminosity reaches 3669～13500cd/m
2
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| CN101916830B (en) * | 2010-07-14 | 2012-05-02 | 中国科学院长春应用化学研究所 | White organic electroluminescent device and preparation method thereof |
| CN102130301A (en) * | 2011-01-04 | 2011-07-20 | 上海大学 | White organic electroluminescence device based on color conversion and manufacturing method thereof |
| CN102130301B (en) * | 2011-01-04 | 2012-08-29 | 上海大学 | White organic electroluminescence device based on color conversion and manufacturing method thereof |
| CN102738399A (en) * | 2011-03-31 | 2012-10-17 | 海洋王照明科技股份有限公司 | White light electroluminescent device |
| CN111146258A (en) * | 2019-12-30 | 2020-05-12 | 维沃移动通信有限公司 | Display screen and electronic equipment |
| WO2022247266A1 (en) * | 2021-05-24 | 2022-12-01 | Tcl科技集团股份有限公司 | Quantum dot device and preparation method therefor |
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| CN100386903C (en) | 2008-05-07 |
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