CN104638141A - Organic light-emitting device and production method thereof - Google Patents
Organic light-emitting device and production method thereof Download PDFInfo
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Abstract
The invention relates to an organic light-emitting device and a production method thereof. The organic light-emitting device is of a layered structure and comprises an anode conducting substrate, a hole injection layer, a hole transmission layer, a light-emitting layer, an electron transmission layer, an electron injection layer and a cathode layer which are stacked in sequence; the electron injection layer comprises a cesium salt layer, a rubidium compound doping layer and a pathalocyanine metal compound layer. Injection efficiency of electrons can be improved by the aid of the cesium salt layer, transmission speed of the electrons can be increased by the aid of the rubidium compound doping layer, and light-emitting efficiency can be improved by the aid of the pathalocyanine metal compound layer.
Description
Technical field
The present invention relates to field of optoelectronic devices, particularly relate to a kind of organic electroluminescence device.The invention still further relates to the preparation method of this organic electroluminescence device.
Background technology
1987, C.W.Tang and VanSlyke of Eastman Kodak company of the U.S. reported the breakthrough in organic electroluminescent research.Utilize ultrathin film technology to prepare high brightness, high efficiency double-deck organic electroluminescence device (OLED), its brightness under 10V reaches 1000cd/m
2, its luminous efficiency is 1.51lm/W, the life-span is greater than 100 hours.
But in existing organic electroluminescence device, electron injecting layer is one of important functional layer, in the fabrication process, because the exclusion of water oxygen of electron injecting layer selected materials is indifferent, steam can infiltrate via crack and affect the electrical of thin-film transistor.Selected materials is also unfavorable for the injection being conducive to electronics simultaneously, therefore the transmission rate of electronics is lower, two or three orders of magnitude lower than hole transport speed, therefore, very easily cause the low of exciton recombination probability, and easily make the region of its compound not in light-emitting zone, thus luminous efficiency is reduced.
Summary of the invention
The object of the invention is to solve above-mentioned prior art Problems existing and deficiency, provide a kind of organic electroluminescence device and preparation method thereof to improve the light extraction efficiency of organic electroluminescence device.
The present invention is directed to above-mentioned technical problem and the technical scheme proposed is: a kind of organic electroluminescence device, this organic electroluminescence device is layer structure, this layer structure is: the anode conducting substrate, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the cathode layer that stack gradually, and described electron injecting layer comprises cesium salt layer, rubidium compound doped layer and phthalocyanine metal compound layer; Wherein,
The material of described cesium salt layer is cesium fluoride, cesium carbonate, nitrine caesium or cesium chloride;
The material of described rubidium compound doped layer is rubidium compound and rhenium compound, and described rubidium compound is rubidium carbonate, rubidium chloride, rubidium nitrate or rubidium sulfate, and described rhenium compound is rhenium heptoxide, rhenium trioxide, rhenium dioxide or oxidation two rheniums;
The material of described phthalocyanine metal compound layer is CuPc, Phthalocyanine Zinc or magnesium phthalocyanine.
Further, the doping mass ratio of described rubidium compound and described rhenium compound is 1:1 ~ 5:1.
Further, the thickness of described cesium salt layer is 20 ~ 40nm, and the thickness of described rubidium compound doped layer is 20 ~ 80nm, and the thickness of described phthalocyanine metal compound layer is 20 ~ 50nm.
Further,
The material of described hole injection layer is molybdenum trioxide, tungstic acid or vanadic oxide;
The material of described hole transmission layer is 1,1-bis-[4-[N, N '-two (p-tolyl) are amino] phenyl] cyclohexane, 4,4', 4''-tri-(carbazole-9-base) triphenylamine or N, N '-(1-naphthyl)-N, N '-diphenyl-4,4 '-benzidine;
The material of described luminescent layer is 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river pyridine of a specified duration-9-vinyl)-4H-pyrans, 9,10-bis--β-naphthylene anthracene, 4, two (9-ethyl-3-carbazole vinyl)-1, the 1'-biphenyl of 4'-or oxine aluminium;
The material of described electron transfer layer is 4,7-diphenyl-1,10-phenanthroline, 1,2,4-triazole derivative or N-aryl benzimidazole;
The material of described negative electrode is silver, aluminium, platinum or gold.
The present invention also proposes a kind of preparation method of organic electroluminescence device, and it comprises the steps:
A () glass after the cleaning prepares conductive anode film by magnetron sputtering apparatus and obtains anode conducting substrate, then on described anode conducting substrate evaporation hole injection layer, hole transmission layer, luminescent layer, electron transfer layer successively;
B () uses thermal resistance evaporated device thermal resistance evaporation on the electron transfer layer that step (a) is obtained to prepare cesium salt layer, then on described cesium salt layer, thermal resistance evaporation prepares rubidium compound doped layer, finally on described rubidium compound doped layer, thermal resistance evaporation prepares phthalocyanine metal compound layer, thus obtains electron injecting layer; Wherein,
The material of described cesium salt layer is cesium fluoride, cesium carbonate, nitrine caesium or cesium chloride;
Rubidium compound and the rhenium compound of the material of described rubidium compound doped layer to be doping mass ratio be 1:1 ~ 5:1, described rubidium compound is rubidium carbonate, rubidium chloride, rubidium nitrate or rubidium sulfate, and described rhenium compound is rhenium heptoxide, rhenium trioxide, rhenium dioxide or oxidation two rheniums;
The material of described phthalocyanine metal compound layer is CuPc, Phthalocyanine Zinc or magnesium phthalocyanine.
C () evaporation on the electron injecting layer that step (b) is obtained prepares cathode layer, thus obtain described organic electroluminescence device.
Further, in described step (a), the accelerating voltage of described magnetron sputtering apparatus is 300 ~ 800V, and magnetic field is 50 ~ 200G, and power density is 1 ~ 40W/cm
2; The evaporation rate of described hole transmission layer, luminescent layer and electron transfer layer is 0.1 ~ 1nm/s.
Further, in described step (b), the evaporation rate of described thermal resistance evaporated device is 0.1 ~ 1nm/s, and the thickness of described cesium salt layer is 20 ~ 40nm, the thickness of described rubidium compound doped layer is 20 ~ 80nm, and the thickness of described phthalocyanine metal compound layer is 20 ~ 50nm.
Further, in described step (c), the evaporation rate of described cathode layer is 1 ~ 10nm/s.
The performance of each component of described electron injecting layer is as follows:
Described cesium salt layer evaporating temperature is lower, easy processing, good film-forming property, membranous layer stability can be improved, in addition, the lumo energy of its work function and electron transfer layer is more close, electron injection potential barrier can be reduced, improve electron injection efficiency, the thickness of cesium salt layer is 20 ~ 40nm simultaneously, and this thickness is moderate, cesium salt layer can be avoided blocked up and make cesium salt layer form cluster, thus form electronic defects and affect the transmission of electric charge, cesium salt layer also can be avoided too thin and cause electronics to lose transmission path, thus reducing transmission rate;
The material of described rubidium compound doped layer is rubidium compound and rhenium compound, rubidium compound fusing point is lower, easy evaporation, owing to there being the existence of metal ion, work function is lower, be conducive to the injection of electronics, and metal ion can strengthen the transmission rate of electronics, and rhenium compound film forming is better, rete planarization can be improved, reduce the existence of rete defect, in addition, the HOMO energy level of rhenium compound is darker, negative electrode can be traversed to by blocking hole, effectively avoid the generation of hole quenching phenomenon, simultaneously, the doping mass ratio of rubidium compound and rhenium compound is 1:1 ~ 5:1, the performance of rubidium compound can be ensured in this scope, also can prevent rhenium compound from too much making rubidium compound doped layer lose activity, thus be unfavorable for transmitting charge carrier, the thickness of rubidium compound doped layer is 20 ~ 80nm in addition, this thickness is moderate, rubidium compound doped layer can be avoided blocked up and make rubidium compound doped layer form electronic defects, also rubidium compound doped layer can be avoided too thin and rubidium compound doped layer is punctured by electric current, thus organic electroluminescence device is burnt out,
The easy crystallization of phthalocyanine metal compound in described phthalocyanine metal compound layer, after crystallization, the arrangement of its segment is regular, to light generation scattering, light scattering is got back in the middle of bottom, thus improves light extraction efficiency, thus be conducive to the luminous efficiency improving organic electroluminescence device.In addition, phthalocyanine metal compound layer thickness is 20 ~ 50nm, and this thickness is moderate in be conducive to improving scattering.
In general, compared with prior art, organic electroluminescence device of the present invention and preparation method thereof, has following advantage: cesium salt layer can improve electron injection efficiency, and rubidium compound doped layer can strengthen the transmission rate of electronics, phthalocyanine metal compound layer can improve light extraction efficiency.
Accompanying drawing explanation
Fig. 1 is the structural representation of the organic electroluminescence device of the embodiment of the present invention 1.
Fig. 2 is the graph of a relation of the organic electroluminescence device of embodiment 1 and the current density of comparative example and current efficiency.
Embodiment
Below in conjunction with embodiment, elaboration is further given to the present invention.
Organic electroluminescence device of the present invention is layer structure, and every layer is followed successively by: anode conducting substrate, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and cathode layer.
To the preparation method of above-mentioned organic electroluminescence device, specifically comprise the following steps:
1, after glass distilled water, alcohol flushing is clean, be placed in isopropyl alcohol and soak an evening.
Conductive anode film preparing by the glass 2, after above-mentioned steps cleans and obtain anode conducting substrate, then on anode conducting substrate, evaporation prepares hole injection layer, hole transmission layer, luminescent layer, electron transfer layer successively.
3, then on above-mentioned electron transfer layer, prepare electron injecting layer, described electron injecting layer is cesium salt layer, rubidium compound doped layer and phthalocyanine metal compound layer form.Described cesium salt layer, described rubidium compound doped layer and described phthalocyanine metal compound layer are all steamed by thermal resistance and cross preparation, and its evaporation rate is 0.1 ~ 1nm/s.The material of described cesium salt layer is cesium fluoride (CsF), cesium carbonate (Cs
2cO
3), nitrine caesium (CsN
3) or cesium chloride (CsCl), its thickness is 20-40nm.Described rubidium compound doped layer is that rubidium compound and rhenium compound form; The doping mass ratio of described rubidium compound and rhenium compound is 1:1 ~ 5:1; Described rubidium compound is rubidium carbonate (Rb
2cO
3), rubidium chloride (RbCl), rubidium nitrate (RbNO
3), rubidium sulfate (Rb
2sO
4); Described rhenium compound is rhenium heptoxide (Re
2o
7), rhenium trioxide (ReO
3), rhenium dioxide (ReO
2) or oxidation two rhenium (Re
2o); The thickness of described rubidium compound doped layer is 20-80nm.
4, finally metallic cathode is prepared.
In organic electroluminescence device, material and the thickness of other functional layers are as follows:
Described glass is available glass.
Conductive anode film is indium and tin oxide film (ITO), mix the zinc-oxide film (AZO) of aluminium or mix the zinc-oxide film (IZO) of indium, and adopt magnetron sputtering preparation, thickness is 50 ~ 300nm, and be preferably ITO, thickness is 160nm.
Anode conducting substrate comprises conductive anode film and glass, the material of its conductive anode film is conductive oxide, comprise tin indium oxide (ITO), Al-Doped ZnO (AZO), mix indium zinc oxide (IZO) or mix any one of fluorine zinc oxide (FTO), the material of its substrate can be glass, plastics or metal, can make by oneself, also can commercially obtain.In actual applications, the material can other being selected as required suitable is as anode conducting substrate.In actual applications, the anode pattern of required organic electroluminescence device can be prepared on anode conducting substrate.Anode conducting substrate is prior art, does not repeat them here.
Described hole injection layer material adopts molybdenum trioxide (MoO
3), also can adopt tungstic acid (WO
3) or vanadic oxide (V
2o
5), thickness is 20-80nm, is preferably MoO
3, thickness is 25nm.
What described hole mobile material adopted is 1,1-bis-[4-[N, N '-two (p-tolyl) is amino] phenyl] cyclohexane (TAPC), 4,4', 4''-tri-(carbazole-9-base) triphenylamine (TCTA), N, N '-(1-naphthyl)-N, N '-diphenyl-4,4 '-benzidine (NPB).Thickness is 20-60nm, and be preferably TCTA, thickness is 50nm.
Described luminescent layer is 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river pyridine of a specified duration-9-vinyl)-4H-pyrans (DCJTB), 9,10-bis--β-naphthylene anthracene (ADN), 4,4'-two (9-ethyl-3-carbazole vinyl)-1,1'-biphenyl (BCzVBi), oxine aluminium (Alq
3), thickness is 5-40nm, and be preferably BCzVBi, thickness is preferably 26nm.
Described electron transfer layer adopts 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2,4-triazole derivative (as TAZ) or N-aryl benzimidazole (TPBI), and thickness is 40-250nm, and be preferably Bphen, thickness is 130nm.
Described negative electrode is silver (Ag), aluminium (Al), platinum (Pt) or gold (Au), and thickness is 80-250nm, and be preferably Ag, thickness is 150nm.
With embodiment 1 ~ 4, organic electroluminescence device of the present invention and preparation method thereof is illustrated below:
Embodiment 1
As shown in Figure 1, the organic electroluminescence device in the present embodiment is layer structure, and every layer is followed successively by:
The hole transmission layer 103 of the anode conducting substrate 101 of glass/ITO, the hole injection layer 102 of MoO3 material, TCTA material, the luminescent layer 104 of BCzVBi material, the electron transfer layer 105 of Bphen material, the cesium salt layer 106 of CsF material, Rb
2cO
3: ReO
3the cathode layer 109 of the rubidium compound doped layer 107 of material, the phthalocyanine metal compound layer 108 of CuPc material and Ag material.Cesium salt layer 106, rubidium compound doped layer 107 and phthalocyanine metal compound layer 108 form electron injecting layer.(wherein colon ": " represents doping mutually)
Above-mentioned organic electroluminescence device is prepared successively as follows:
1, after glass distilled water, alcohol flushing is clean, be placed in isopropyl alcohol and soak an evening.
2, under the glass after above-mentioned steps 1 being cleaned is placed in magnetron sputtering apparatus, the technological parameter of magnetron sputtering apparatus is set to the accelerating voltage of 700V, the magnetic field of 120G and 250W/cm
2power density, use magnetron sputtering apparatus on glass, to prepare material for ITO and the thickness conductive anode film that is 160nm, thus obtained anode conducting substrate 101.
Technological parameter prepared by thermal resistance evaporation, under the preparation of thermal resistance evaporation, is set to the evaporation rate and 8 × 10 of 0.2nm/s by anode conducting substrate 101 transposition 3, then step 2 be prepared into
-4the operating pressure of Pa, use thermal resistance evaporation be prepared in anode conducting substrate 101 successively deposition material be MoO
3and thickness be the hole injection layer 102 of 25nm, material be TCTA and thickness be the hole transmission layer 103 of 50nm, material be BCzVBi and thickness be the luminescent layer 104 of 26nm, material is Bphen and thickness is the electron transfer layer 105 of 130nm.
4, then on above-mentioned electron transfer layer 105, blunt cesium salt layer 106, rubidium compound doped layer 107 and phthalocyanine metal compound layer 108 is prepared successively, from formation electron injecting layer:
First adopt thermal resistance evaporation to prepare the cesium salt layer 106 of CsF material, evaporation rate is 0.2nm/s, and obtained cesium salt layer 106 thickness is 25nm;
Then on cesium salt layer 106, adopt thermal resistance evaporation to prepare Rb
2cO
3: ReO
3the rubidium compound doped layer 107, Rb of material
2cO
3with ReO
3doping mass ratio be 1.5:1, evaporation rate is 0.2nm/s, and obtained rubidium compound doped layer 107 thickness is 50nm;
Finally, rubidium compound doped layer 107 adopts thermal resistance evaporation prepare the phthalocyanine metal compound layer 108 of CuPc material, evaporation rate is 0.2nm/s, and obtained phthalocyanine metal compound layer 108 thickness is 40nm;
5, last evaporation prepares metal cathode layer 109, and material used is silver, and evaporation rate is 2nm/s, and thickness is 150nm, thus obtains required electroluminescent device.
Fig. 2 is the organic electroluminescence device of the present embodiment 1 and the luminous efficiency of general device and the graph of a relation of current density.
Test and Preparation equipment are high vacuum coating system (scientific instrument development center, Shenyang Co., Ltd), the USB4000 fiber spectrometer testing electroluminescent spectrum of U.S. marine optics Ocean Optics, the Keithley2400 of Keithley company of the U.S. tests electric property, the CS-100A colorimeter test brightness of Japanese Konica Minolta company and colourity.
The structure of described general device is simple glass/ITO/MoO
3/ TCTA/BCzVBi/Bphen/CsF/Rb
2cO
3: ReO
3/ CuPc/Ag.In Fig. 2, abscissa is the size of current density, ordinate is the size of luminous efficiency, and curve 1 is the current density of embodiment 1 organic electroluminescence device and the relation curve of luminous efficiency, and curve 2 is the current density of comparative example device and the relation curve of luminous efficiency.
As seen from Figure 2, under different current density, the current efficiency of embodiment 1 is all larger than comparative example, and the maximum current efficiency efficiency of embodiment 1 is 8.5cd/A, and comparative example be only 7.2cd/A, this illustrates, patent of the present invention, by preparing electron injecting layer, improves membranous layer stability, improve electron injection efficiency, strengthen the transmission rate of electronics, effectively avoid the generation of hole quenching phenomenon that light scattering is got back in the middle of bottom, thus improve light extraction efficiency.This method is conducive to the luminous efficiency improving device.
Embodiment 2
The layer structure of the organic electroluminescence device of following examples 2-4 is substantially identical with the layer structure of embodiment 1, therefore no longer adds at this and illustrate.
Organic electroluminescence device in the present embodiment is layer structure, and every layer is followed successively by:
The anode conducting substrate of glass/IZO, V
2o
5the hole injection layer of material, the hole transmission layer of TCTA material, the luminescent layer of DCJTB material, the electron transfer layer of TPBi material, Cs
2cO
3the cesium salt layer of material, RbCl:Re
2o
7the cathode layer of the rubidium compound doped layer of material, the phthalocyanine metal compound layer of ZnPc material and Pt material.Cesium salt layer, rubidium compound doped layer and phthalocyanine metal compound layer composition electron injecting layer.(wherein colon ": " represents doping mutually)
Above-mentioned organic electroluminescence device is prepared successively as follows:
1, after glass distilled water, alcohol flushing is clean, be placed in isopropyl alcohol and soak an evening.
2, under the glass after above-mentioned steps 1 being cleaned is placed in magnetron sputtering apparatus, the technological parameter of magnetron sputtering apparatus is set to the accelerating voltage of 300V, the magnetic field of 50G and 40W/cm
2power density, use magnetron sputtering apparatus on glass, to prepare material for IZO and the thickness conductive anode film that is 50nm, thus obtained anode conducting substrate.
Technological parameter prepared by thermal resistance evaporation, under the preparation of thermal resistance evaporation, is set to the evaporation rate and 2 × 10 of 0.1nm/s by the anode conducting substrate transposition 3, then step 2 be prepared into
-4the operating pressure of Pa, use thermal resistance evaporation be prepared in anode conducting substrate 101 successively deposition material be V
2o
5and thickness be the hole injection layer of 40nm, material be TCTA and thickness be the hole transmission layer of 45nm, material be DCJTB and thickness be 8nm luminescent layer, material is TPBi and thickness is the electron transfer layer of 65nm.
4, then on above-mentioned electron transfer layer, blunt cesium salt layer, rubidium compound doped layer and phthalocyanine metal compound layer is prepared successively, from formation electron injecting layer:
First thermal resistance evaporation is adopted to prepare Cs
2cO
3the cesium salt layer of material, evaporation rate is 0.1nm/s, and obtained cesium salt layer thickness is 40nm;
Then on cesium salt layer, adopt thermal resistance evaporation to prepare RbCl:Re
2o
7the rubidium compound doped layer of material, RbCl and Re
2o
7doping mass ratio be 1:1, evaporation rate is 0.1nm/s, and obtained rubidium compound doped layer thickness is 20nm;
Finally, rubidium compound doped layer adopts thermal resistance evaporation prepare the phthalocyanine metal compound layer of ZnPc material, evaporation rate is 0.1nm/s, and obtained phthalocyanine metal compound layer thickness is 20nm;
5, last evaporation prepares metal cathode layer, and material used is Pt, and evaporation rate is 10nm/s thickness is 80nm, thus obtains required electroluminescent device.
Embodiment 3
Organic electroluminescence device in the present embodiment is layer structure, and every layer is followed successively by:
The anode conducting substrate of glass/IZO, WO
3the hole injection layer of material, the hole transmission layer of TAPC material, the luminescent layer of ADN material, the electron transfer layer of TPBi material, CsN
3the cesium salt layer of material, RbNO
3: ReO
2the cathode layer of the rubidium compound doped layer of material, the phthalocyanine metal compound layer of MgPc material and Au material.Cesium salt layer, rubidium compound doped layer and phthalocyanine metal compound layer composition electron injecting layer.(wherein colon ": " represents doping mutually)
Above-mentioned organic electroluminescence device is prepared successively as follows:
1, after glass distilled water, alcohol flushing is clean, be placed in isopropyl alcohol and soak an evening.
2, under the glass after above-mentioned steps 1 being cleaned is placed in magnetron sputtering apparatus, the technological parameter of magnetron sputtering apparatus is set to the accelerating voltage of 800V, the magnetic field of 200G and 1W/cm
2power density, use magnetron sputtering apparatus on glass, to prepare material for IZO and the thickness conductive anode film that is 300nm, thus obtained anode conducting substrate.
Technological parameter prepared by thermal resistance evaporation, under the preparation of thermal resistance evaporation, is set to the evaporation rate and 5 × 10 of 0.1nm/s by the anode conducting substrate transposition 3, then step 2 be prepared into
-5the operating pressure of Pa, use thermal resistance evaporation be prepared in anode conducting substrate 101 successively deposition material be WO
3and thickness be the hole injection layer of 20nm, material be TAPC and thickness be the hole transmission layer of 60nm, material be ADN and thickness be 10nm luminescent layer, material is TPBi and thickness is the electron transfer layer of 200nm.
4, then on above-mentioned electron transfer layer, blunt cesium salt layer, rubidium compound doped layer and phthalocyanine metal compound layer is prepared successively, from formation electron injecting layer:
First thermal resistance evaporation is adopted to prepare CsN
3the cesium salt layer of material, evaporation rate is 0.1nm/s, and obtained cesium salt layer thickness is 20nm;
Then on cesium salt layer, adopt thermal resistance evaporation to prepare RbNO
3: ReO
2the rubidium compound doped layer of material, RbNO
3with ReO
2doping mass ratio be 5:1, evaporation rate is 0.1nm/s, and obtained rubidium compound doped layer thickness is 80nm;
Finally, rubidium compound doped layer adopts thermal resistance evaporation prepare the phthalocyanine metal compound layer of MgPc material, evaporation rate is 0.1nm/s, and obtained phthalocyanine metal compound layer thickness is 50nm;
5, last evaporation prepares metal cathode layer, and material used is Au, and evaporation rate is 1nm/s thickness is 100nm, thus obtains required electroluminescent device.
Embodiment 4
Organic electroluminescence device in the present embodiment is layer structure, and every layer is followed successively by:
The anode conducting substrate of glass/AZO, V
2o
5the hole injection layer of material, the hole transmission layer of NPB material, Alq
3the luminescent layer of material, the electron transfer layer of TAZ material, the cesium salt layer of CsCl material, Rb
2sO
4: Re
2the cathode layer of the rubidium compound doped layer of O material, the phthalocyanine metal compound layer of MgPc material and Al material.Cesium salt layer, rubidium compound doped layer and phthalocyanine metal compound layer composition electron injecting layer.(wherein colon ": " represents doping mutually)
Above-mentioned organic electroluminescence device is prepared successively as follows:
1, after glass distilled water, alcohol flushing is clean, be placed in isopropyl alcohol and soak an evening.
2, under the glass after above-mentioned steps 1 being cleaned is placed in magnetron sputtering apparatus, the technological parameter of magnetron sputtering apparatus is set to the accelerating voltage of 600V, the magnetic field of 100G and 30W/cm
2power density, use magnetron sputtering apparatus on glass, to prepare material for AZO and the thickness conductive anode film that is 180nm, thus obtained anode conducting substrate.
Technological parameter prepared by thermal resistance evaporation, under the preparation of thermal resistance evaporation, is set to the evaporation rate and 2 × 10 of 0.5nm/s by the anode conducting substrate transposition 3, then step 2 be prepared into
-4the operating pressure of Pa, use thermal resistance evaporation be prepared in anode conducting substrate 101 successively deposition material be V
2o
5and thickness be the hole injection layer of 80nm, material be NPB and thickness be the hole transmission layer of 60nm, material is Alq
3and thickness be 40nm luminescent layer, material is TAZ and thickness is the electron transfer layer of 35nm.
4, then on above-mentioned electron transfer layer, blunt cesium salt layer, rubidium compound doped layer and phthalocyanine metal compound layer is prepared successively, from formation electron injecting layer:
First adopt thermal resistance evaporation to prepare the cesium salt layer of CsCl material, evaporation rate is 0.5nm/s, and obtained cesium salt layer thickness is 35nm;
Then on cesium salt layer, adopt thermal resistance evaporation to prepare Rb
2sO
4: Re
2the rubidium compound doped layer of O material, Rb
2sO
4with Re
2the doping mass ratio of O is 3:1, and evaporation rate is 0.5nm/s, and obtained rubidium compound doped layer thickness is 40nm;
Finally, rubidium compound doped layer adopts thermal resistance evaporation prepare the phthalocyanine metal compound layer of MgPc material, evaporation rate is 0.5nm/s, and obtained phthalocyanine metal compound layer thickness is 25nm;
5, last evaporation prepares metal cathode layer, and material used is Al, and evaporation rate is 6m/s thickness is 250nm, thus obtains required electroluminescent device.
Compared with prior art, organic electroluminescence devices of the present invention and preparation method thereof, there is following advantage: the cesium salt layer of organic electroluminescence device of the present invention can improve electron injection efficiency, and rubidium compound doped layer can strengthen the transmission rate of electronics, phthalocyanine metal compound layer can improve light extraction efficiency.
Foregoing; be only preferred embodiment of the present invention; not for limiting embodiment of the present invention; those of ordinary skill in the art are according to central scope of the present invention and spirit; can carry out corresponding flexible or amendment very easily, therefore protection scope of the present invention should be as the criterion with the protection range required by claims.
Claims (8)
1. an organic electroluminescence device, this organic electroluminescence device is layer structure, this layer structure is: the anode conducting substrate, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the cathode layer that stack gradually, it is characterized in that, described electron injecting layer comprises cesium salt layer, rubidium compound doped layer and phthalocyanine metal compound layer; Wherein,
The material of described cesium salt layer is cesium fluoride, cesium carbonate, nitrine caesium or cesium chloride;
The material of described rubidium compound doped layer is rubidium compound and rhenium compound, and described rubidium compound is rubidium carbonate, rubidium chloride, rubidium nitrate or rubidium sulfate, and described rhenium compound is rhenium heptoxide, rhenium trioxide, rhenium dioxide or oxidation two rheniums;
The material of described phthalocyanine metal compound layer is CuPc, Phthalocyanine Zinc or magnesium phthalocyanine.
2. organic electroluminescence device according to claim 1, is characterized in that, the doping mass ratio of described rubidium compound and described rhenium compound is 1:1 ~ 5:1.
3. organic electroluminescence device according to claim 1, is characterized in that, the thickness of described cesium salt layer is 20 ~ 40nm, and the thickness of described rubidium compound doped layer is 20 ~ 80nm, and the thickness of described phthalocyanine metal compound layer is 20 ~ 50nm.
4. organic electroluminescence device according to claim 1, is characterized in that,
The material of described hole injection layer is molybdenum trioxide, tungstic acid or vanadic oxide;
The material of described hole transmission layer is 1,1-bis-[4-[N, N '-two (p-tolyl) are amino] phenyl] cyclohexane, 4,4', 4''-tri-(carbazole-9-base) triphenylamine or N, N '-(1-naphthyl)-N, N '-diphenyl-4,4 '-benzidine;
The material of described luminescent layer is 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river pyridine of a specified duration-9-vinyl)-4H-pyrans, 9,10-bis--β-naphthylene anthracene, 4, two (9-ethyl-3-carbazole vinyl)-1, the 1'-biphenyl of 4'-or oxine aluminium;
The material of described electron transfer layer is 4,7-diphenyl-1,10-phenanthroline, 1,2,4-triazole derivative or N-aryl benzimidazole;
The material of described negative electrode is silver, aluminium, platinum or gold.
5. a preparation method for organic electroluminescence device, is characterized in that, comprises the steps:
A () glass after the cleaning prepares conductive anode film by magnetron sputtering apparatus and obtains anode conducting substrate, then on described anode conducting substrate evaporation hole injection layer, hole transmission layer, luminescent layer, electron transfer layer successively;
B () uses thermal resistance evaporated device thermal resistance evaporation on the electron transfer layer that step (a) is obtained to prepare cesium salt layer, then on described cesium salt layer, thermal resistance evaporation prepares rubidium compound doped layer, finally on described rubidium compound doped layer, thermal resistance evaporation prepares phthalocyanine metal compound layer, thus obtains electron injecting layer; Wherein,
The material of described cesium salt layer is cesium fluoride, cesium carbonate, nitrine caesium or cesium chloride;
Rubidium compound and the rhenium compound of the material of described rubidium compound doped layer to be doping mass ratio be 1:1 ~ 5:1, described rubidium compound is rubidium carbonate, rubidium chloride, rubidium nitrate or rubidium sulfate, and described rhenium compound is rhenium heptoxide, rhenium trioxide, rhenium dioxide or oxidation two rheniums;
The material of described phthalocyanine metal compound layer is CuPc, Phthalocyanine Zinc or magnesium phthalocyanine;
C () evaporation on the electron injecting layer that step (b) is obtained prepares cathode layer, thus obtain described organic electroluminescence device.
6. preparation method according to claim 5, is characterized in that, in described step (a), the accelerating voltage of described magnetron sputtering apparatus is 300 ~ 800V, and magnetic field is 50 ~ 200G, and power density is 1 ~ 40 W/cm
2; The evaporation rate of described hole transmission layer, luminescent layer and electron transfer layer is 0.1 ~ 1nm/s.
7. preparation method according to claim 5, it is characterized in that, in described step (b), the evaporation rate of described thermal resistance evaporated device is 0.1 ~ 1nm/s, the thickness of described cesium salt layer is 20 ~ 40nm, the thickness of described rubidium compound doped layer is 20 ~ 80nm, and the thickness of described phthalocyanine metal compound layer is 20 ~ 50nm.
8. preparation method according to claim 5, is characterized in that, in described step (c), the evaporation rate of described cathode layer is 1 ~ 10nm/s.
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