CN101859879A - White organic electroluminescent device and preparation method thereof - Google Patents
White organic electroluminescent device and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a white organic electroluminescent device and a preparation method thereof. The device consists of an ITO glass substrate, a buffer layer, a cavity transport layer, a single-subject blue light layer, a double-subject red light layer, an electronic transport layer and a composite cathode sequentially. Each structural layer is prepared by a vacuum evaporation method. In the structure of the invention, a luminous layer consists of the single-subject blue light layer and the red light layer with a double-subject structure, and the subject of the blue light layer and one of the subjects of the red light layer are made of the same material, and the other material of the subject of the red light layer is the same as the material of the electronic transport layer. The device with the structure has higher luminous efficiency, can effectively disperse excitons, enhances carrier infusion and transport balance, and inhibits color error and efficiency reduction under a higher drive current. With the structure, the white organic electroluminescent device with the structure can be widely applied on a hi-fi organic full-color display device.
Description
Technical field
The present invention relates to a kind of ruddiness layer and adopt two agent structures, have white color organic electroluminescence device of two luminescent layers and preparation method thereof, especially under the higher drive current, the preparation method of the white color organic electroluminescence device of efficient and chroma stability.
Background technology
White color organic electroluminescence device (White Organic Light Emitting Device, OLED) because have that ultralight is thin, pliability, response are fast, low-power consumption and make characteristics such as simple, have very big application potential in fields such as flat-panel monitor, LCD module backlight and illuminations, and be expected to replace traditional fluorescent lighting.These application requirements white light OLEDs have high brightness, high efficiency, long-life, characteristics such as chroma stability.
OLED device principle of luminosity is the extremely thin organic material of deposition between two electrodes, this luminous organic material is passed to direct current make it make it luminous.The method of normally used realization white light OLED device has: the single-shot photosphere, and promptly adopt the single material that emits white light, or multiple dyestuff is mixed, or utilize incomplete energy delivery principle, the blue light dyestuff that the gold-tinted dyestuff is mixed the broad stopband produces white light; Two luminescent layers promptly prepare the two-layer adjacent emissive layers of gold-tinted and blue light and produce white light; Three luminescent layers promptly adopt three luminescent layers of R, G, B three primary colors to produce white light.Single-shot photosphere device preparation technology is simple, and cost is low, and owing to have only an exciton recombination zone territory, its chromaticity coordinates can not change with driving voltage/electric current, but EL efficient is lower usually.The multi-luminescent layer device is more much higher than single-shot photosphere device efficiency, but the charge carrier recombination region can be moved with the variation of driving voltage/electric current, and along with the rising of driving voltage, blue light strengthens usually, and ruddiness weakens, and causes CIE
X, yCoordinate changes with driving voltage/electric current.And luminescent layer is thicker, causes the operating voltage of device higher, is difficult to avoid the quenching effect of current induced under high current drives.In order to obtain the white light parts of chromaticity coordinates near equal-energy white point and chroma stability, energy delivery is particularly crucial in designs between restriction exciton recombination zone territory and the control Subjective and Objective.
The common method that adopts of problem that solves the colourity variation has: introduce HBL layer and EBL layer and be inhibited, but introduce the HBL layer can be that driving voltage raises, may cause thermal effect damage device, and this complex devices structure is unfavorable for being applied to production field; Adopt the single-shot photosphere that a recombination region is only arranged, the shortcoming front of this structure is mentioned; Adopt the differential big material of energy HOMO or LUMO to form well structure, but can cause charge carrier to assemble like this, driving voltage is raise the exciton confinement, the efficient reduction, and can produce Joule heat, and the quenching effect of current induced takes place easily, influence device lifetime.
Summary of the invention
The objective of the invention is to solve the problem that prior art exists, a kind of organic electroluminescence device that can realize high efficiency, chroma stability and preparation method thereof is provided.
For achieving the above object, the present invention adopts following technical proposals:
A kind of white color organic electroluminescence device comprises ito glass substrate, resilient coating, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode successively, it is characterized in that described luminescent layer is to be made of single main body blu-ray layer and the ruddiness layer with two agent structures, and the relative position relation of two luminescent layers is, blu-ray layer is near anode, and the ruddiness layer is near negative electrode.And one of the main body of blu-ray layer and ruddiness layer main body adopt same material, and the another kind of material of ruddiness layer main body is identical with material that electron transfer layer adopts, and two kinds of material of main parts of ruddiness layer have specific phase Comparative Examples relation.
Above-mentioned resilient coating material therefor is CuPc, and thickness is 15nm.
Above-mentioned hole transmission layer material therefor is NPB, and thickness is 50nm.
The used material of main part of above-mentioned blu-ray layer can be fluorescent material TBADN, AND, MADN or the CBP of broad stopband, and the blue fluorescent dyes of doping can be DSA-ph or DPVBi, and doping content is 3wt%, and thickness is 30nm.
The a kind of of two main body material therefors of above-mentioned ruddiness layer can be TBADN, AND, MADN or CBP, and another kind can be BAlq2 or Alq3, and the doping red fluorescence dyestuff can be DCJTB or rubrene, and doping content is 1wt%～2%, and thickness is 40nm.
Above-mentioned electron transfer layer material therefor is Alq3 or BAlq2, and thickness is 20nm.
Above-mentioned composite cathode material therefor is LiF/Al, and LiF thickness is 0.5nm, and Al thickness is 100nm.Wherein Al can also use Li, Ca, Ba, Mg or Ag instead.
According to purpose of the present invention, the preparation method of above-mentioned white light organic electroluminescent device is evaporation resilient coating, hole transmission layer, blu-ray layer, ruddiness layer, electron transfer layer and a composite cathode successively on ito glass substrate.
The processing step of above-mentioned manufacture method is as follows:
(1) select the to meet the requirements ito glass substrate of size and sheet resistance cleans the back oven dry;
(2) method of employing vacuum evaporation, evaporation CuPc resilient coating on above-mentioned glass substrate;
(3) method of employing vacuum evaporation, evaporation NPB hole transmission layer on above-mentioned resilient coating;
(4) method of employing vacuum evaporation, evaporation blu-ray layer material of main part and dopant dye on above-mentioned hole transmission layer;
(5) adopt the method for vacuum evaporation, two kinds of materials of the two agent structure of evaporation ruddiness layer and dopant dye simultaneously on above-mentioned blu-ray layer;
(6) method of employing vacuum evaporation, evaporation electron transfer layer on above-mentioned ruddiness layer;
(7) method of employing vacuum evaporation, evaporation composite cathode on above-mentioned electron transfer layer.
The present invention compares with the method for existing realization white light organic electroluminescent device has following advantage: adopt fluorescent material to make two luminescent layers, simple than three luminescent layer device preparation technology, cost is lower; TBADN, AND, MADN and CBP are and are bipolar materials, hole and electronics mobility therein is all higher, and the electron mobility height of BAlq2 and Alq3, the transporting holes ability, luminescent layer adopts said structure, helping electronics injects to the ruddiness layer by the Alq3 (or BAlq2) of electron transfer layer and the Alq3 (or BAlq2) of ruddiness layer main body, and help the hole by TBADN (AND, MADN or CBP) inject to the ruddiness layer by blu-ray layer, the electron recombination of capturing with DCJTB (or rubrene), produce excitonic luminescence, otherwise, if only adopt Alq3 (or BAlq2) to make the ruddiness material of main part, because TBADN (AND, MADN or CBP) and HOMO and the lumo energy difference of NPB all very big, as shown in Figure 2, exciton will be mainly at this NPB/TBADN (AND, MADN or CBP) the interface generation, exciton diffusion length is less than blu-ray layer thickness, the energy that passes to DCJTB (or rubrene) is less, causes almost not having ruddiness and sends; Find through experiment, TBADN in two main bodys (AND, MADN or CBP) is big than Alq3 (or BAlq2) ratio, helping superfluous hole is transferred in the ruddiness layer by TBADN (AND, MADN or CBP), effectively exciton is distributed in the ruddiness layer on the one hand, reduce too much exciton and accumulate the Joule heat that produces at NPB/TBADN (AND, MADN or CBP) at the interface, thereby suppress the electric current quenching effect, improve the lifetime stability of device; On the other hand, TBADN (AND, MADN or CBP) composition increases, cavity transmission ability strengthens, under higher drive/electric current, to there be more hole to inject the ruddiness layer, help strengthening charge carrier injection and transmission balance in the ruddiness layer, and red light intensity increase, the situation that the red light intensity that has suppressed can to take place under the common high driving voltage effectively weakens helps device and keeps chroma stability.The white light parts of this chroma stability is for realizing that Hi-Fi display device is highly beneficial.
Description of drawings
Fig. 1 is the structural representation of white color organic electroluminescence device of the present invention.
Fig. 2 is a kind of invention example of the white color organic electroluminescence device of Fig. 1 example, i.e. ITO/CuPc/NPB/TBADN:DSA-ph/ (TBADN+Alq3): the device level structure figure of DCJTB/Alq3/LiF/Al structure.
Fig. 3 is under the different driving electric current, Fig. 2 structure respective devices, and TBADN accounts for different quality mark respective devices luminous efficiency change curve in two kinds of material of main part of ruddiness layer.
Fig. 4 is in Fig. 2 structure respective devices, and when TBADN accounted for the different quality mark in the two main body of ruddiness layer, corresponding device efficiency was with the drive current variations curve chart.
Embodiment
Further specify below in conjunction with accompanying drawing with to this example.
As shown in Figure 1, this white organic electroluminescence device, it comprises an ito glass substrate 1, be positioned at resilient coating 2, hole transmission layer 3 on the aforesaid substrate, be positioned at blu-ray layer 4 on the above-mentioned hole transmission layer 3, be positioned at two main body ruddiness layers 5 on the above-mentioned blu-ray layer 4, be positioned at 7 and 8 of above-mentioned pair of electron transfer layer 6, the composite cathode on the main body ruddiness layer 5.
The preparation method's of this white organic electroluminescence device detailed step and technology are as follows:
(1) size (effective area 5mm * 5mm) and the sheet resistance (ito glass substrate 1 of 10 Ω/) of selecting to meet the requirements, ito glass cleans with cleanser earlier, use acetone, absolute ethyl alcohol, deionized water ultrasonic cleaning 30min more successively, in baking oven, dry, after carrying out the UV-Ozone processing, put into vacuum evaporation apparatus;
(2) in 4 * 10-4 vacuum environment, use the organic substance mask plate, evaporation CuPc resilient coating 2 on above-mentioned glass substrate 1, evaporation rate is controlled at～0.1nm/s, and evaporation thickness is 15nm;
(3) evaporation NPB hole transmission layer 3 on above-mentioned resilient coating 2, evaporation rate is controlled at～0.1nm/s, and evaporation thickness is 50nm;
(4) evaporation blu-ray layer 4 on above-mentioned hole transmission layer 3 is promptly used two evaporation source TBADN (AND, MADN or CBP) and DSA-ph (or DPVBi), evaporates simultaneously, controls the evaporation rate of the two respectively, and doping content is 3wt%, and thickness is 30nm;
(5) evaporation ruddiness layer 5 on above-mentioned blu-ray layer 4 promptly uses three evaporation source TBADN (AND, MADN or CBP), Alq3 (or BAlq2) and DCJTB (or rubrene), evaporates two material of main parts and dopant dye simultaneously, controls three's evaporation rate respectively; The mass fraction ratio of TBADN (AND, MADN or CBP) and Alq3 (or BAlq2) is 75: 25, and the doping content of DCJTB (or rubrene) is 1wt%～2wt%, and thickness is 40nm;
(6) evaporation electron transfer layer 6Alq3 (or BAlq2) on above-mentioned ruddiness layer 5, evaporation rate is controlled at～0.1nm/s, and evaporation thickness is 20nm;
(7) evaporation composite cathode 7 and 8 on above-mentioned electron transfer layer 6, wherein the evaporation rate of LiF layer 7 is controlled at～0.04nm/s, thickness 0.5nm.Change the electrode mask plate, evaporating Al on LiF layer 7 (or Li, Ca, Ba, Mg or Ag) cathode layer 8, evaporation rate is controlled at 0.4～0.6nm/s, and evaporation thickness is 100nm.
The white color organic electroluminescence device that uses this kind method to prepare is compared with three luminescent layer devices, and simple in structure, preparation cost is lower.For a kind of invention example wherein, promptly adopt ITO/CuPc/NPB/TBADN:DSA-ph/ (TBADN+Alq3): the device of DCJTB/Alq3/LiF/Al structure, by the mass fraction ratio of change TBADN with Alq3, the device efficiency of finding 75: 25 is the highest, as shown in Figure 3, and the device of this structure also has following advantage: chromaticity coordinates is (0.344,0.344), near the equal-energy white point; Stabilised efficiency, 20mA/cm
2The time be 6.27cd/A, 200mA/cm
2The time be 6.15cd/A, as shown in Figure 4; Chromaticity stability is good, is 20mA/cm in current density
2The time, the CIE chromaticity coordinates of device is (0.364,0.348), 200mA/cm
2The time, chromaticity coordinate is (0.344,0.344).Drive current density is from 20mA/cm
2Change to 200mA/cm
2The time, the chromaticity coordinates variation delta CIE of device
X, yOnly be ± (0.01,0.002).TBADN also can adopt AND, MADN or CBP to substitute, Alq3 can adopt BAlq2 to substitute, DCJTB can adopt rubrene to substitute, the Al electrode can be changed to Li, Ca, Ba, Mg or Ag, more than substitute and to adopt separately, the employing of also can arranging in pairs or groups is believed according to the influence principle of summary of the invention part described material behavior in front to device performance, can realize colourity and stabilised efficiency white color organic electroluminescence device equally.
Claims (9)
1. white color organic electroluminescence device, comprise ito glass substrate (1), resilient coating (2), hole transmission layer (3), luminescent layer (4,5), electron transfer layer (6) and composite cathode (7,8) successively, it is characterized in that: described luminescent layer (4,5) is to be made of the blu-ray layer (4) of single main body and ruddiness layer (5) with two agent structures, and the relative position relation of two luminescent layers is, blu-ray layer (4) is near anode, and ruddiness layer (5) is near negative electrode.
2. white color organic electroluminescence device according to claim 1 is characterized in that: one of main body of the main body of blu-ray layer (4) and ruddiness layer (5) adopts same material.
3. white color organic electroluminescence device according to claim 1, it is characterized in that: the material of main part of ruddiness layer (5), remove identical with blu-ray layer (4) material of main part a kind of, its another kind of material and electron transfer layer (6) the material that adopts identical, have the good characteristics of electron transport property.
4. white color organic electroluminescence device according to claim 1, it is characterized in that: adopt ambipolar TBADN, AND, MADN or CBP material of main part as blu-ray layer (4), with wherein a kind of identical of two material of main parts of ruddiness layer (5), another material of main part of ruddiness layer (5) adopts good Alq3 or the BAlq2 of electron transport property, in (5) two kinds of material of main part of ruddiness layer, TBADN, AND, MADN or CBP be more than another kind, i.e. Alq3 or BAlq2.
5. white color organic electroluminescence device according to claim 1 is characterized in that: blu-ray layer (4) dopant dye adopts DSA-ph or DPVBi, and doping content is 3wt%, and thickness is 30nm; Ruddiness layer (5) dopant dye adopts DCJTB or rubrene, and doping content is 1wt%～2%, and thickness is 40nm.
6. white color organic electroluminescence device according to claim 1 is characterized in that: it is NPB that hole transmission layer (3) adopts material, and its thickness is 50nm.
7. white color organic electroluminescence device according to claim 1 is characterized in that: it is Alq3 or BAlq2 that electron transfer layer (6) adopts material, and its thickness is 20nm.
8. white color organic electroluminescence device according to claim 1 is characterized in that: composite cathode adopts LiF/Al (Li, Ca, Ba, Mg or Ag) structure, and LiF thickness is 0.5nm, and Al, Li, Ca, Ba, Mg or Ag thickness are 100nm.
9. be used to prepare white color organic electroluminescence device according to claim 1, it is characterized in that the operating procedure for preparing is as follows:
(1) select the to meet the requirements ito glass substrate of size and sheet resistance cleans the back oven dry;
(2) method of employing vacuum evaporation, evaporation CuPc resilient coating on above-mentioned glass substrate;
(3) method of employing vacuum evaporation, evaporation NPB hole transmission layer on above-mentioned resilient coating;
(4) method of employing vacuum evaporation, evaporation blu-ray layer material of main part and dopant dye on above-mentioned hole transmission layer;
(5) method of employing vacuum evaporation, the two material of main part of evaporation ruddiness layer on above-mentioned blu-ray layer, and dopant dye;
(6) method of employing vacuum evaporation, evaporation electron transfer layer on above-mentioned ruddiness layer;
(7) method of employing vacuum evaporation, evaporation composite cathode on above-mentioned electron transfer layer.
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| CN103280535A (en) * | 2013-06-08 | 2013-09-04 | 广州创维平面显示科技有限公司 | White light organic electroluminescence device |
| CN104124345A (en) * | 2013-04-24 | 2014-10-29 | 海洋王照明科技股份有限公司 | Organic electroluminescent device and preparation method thereof |
| CN104253240A (en) * | 2013-06-28 | 2014-12-31 | 乐金显示有限公司 | Organic light emitting device |
| CN104505463A (en) * | 2014-09-28 | 2015-04-08 | 桂林电子科技大学 | White light OLED (organic light emitting diode) device with double-layer light emitting layer structure |
| CN103280535B (en) * | 2013-06-08 | 2016-11-30 | 广州创维平面显示科技有限公司 | A kind of white light organic electroluminescent device |
| CN106459747A (en) * | 2014-06-18 | 2017-02-22 | 默克专利有限公司 | Compositions for electronic devices |
| CN108281557A (en) * | 2017-01-05 | 2018-07-13 | 昆山工研院新型平板显示技术中心有限公司 | Organic luminescent device and preparation method thereof and display device |
| CN108281558A (en) * | 2017-01-05 | 2018-07-13 | 昆山工研院新型平板显示技术中心有限公司 | Organic luminescent device and preparation method thereof and display device |
| CN109309177A (en) * | 2018-10-31 | 2019-02-05 | 苏州大学 | A kind of high performance electroluminescent organic device and preparation method thereof |
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| CN104124345A (en) * | 2013-04-24 | 2014-10-29 | 海洋王照明科技股份有限公司 | Organic electroluminescent device and preparation method thereof |
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| CN104253240A (en) * | 2013-06-28 | 2014-12-31 | 乐金显示有限公司 | Organic light emitting device |
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| CN106459747A (en) * | 2014-06-18 | 2017-02-22 | 默克专利有限公司 | Compositions for electronic devices |
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| CN108281557A (en) * | 2017-01-05 | 2018-07-13 | 昆山工研院新型平板显示技术中心有限公司 | Organic luminescent device and preparation method thereof and display device |
| CN108281558A (en) * | 2017-01-05 | 2018-07-13 | 昆山工研院新型平板显示技术中心有限公司 | Organic luminescent device and preparation method thereof and display device |
| CN108281557B (en) * | 2017-01-05 | 2020-03-17 | 昆山工研院新型平板显示技术中心有限公司 | Organic light emitting device, preparation method thereof and display device |
| CN109309177A (en) * | 2018-10-31 | 2019-02-05 | 苏州大学 | A kind of high performance electroluminescent organic device and preparation method thereof |
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Application publication date: 20101013 |