CN104638197A - Organic light-emitting device and production method thereof - Google Patents

Organic light-emitting device and production method thereof Download PDF

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Publication number
CN104638197A
CN104638197A CN201310574096.8A CN201310574096A CN104638197A CN 104638197 A CN104638197 A CN 104638197A CN 201310574096 A CN201310574096 A CN 201310574096A CN 104638197 A CN104638197 A CN 104638197A
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layer
rubidium
compound
rhenium
thickness
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周明杰
黄辉
张振华
王平
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/17—Carrier injection layers
    • H10K50/171—Electron injection layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/84—Passivation; Containers; Encapsulations
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass

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; electron injection layer comprises a passivating layer, a rubidium compound doping layer and a rhenium compound layer; the passivating layer is made of materials of silicon dioxide, aluminum oxide and nickel oxide or copper oxide. Metal ions in the electron injection layer and a cathode can be prevented from penetrating to an organic layer by the passivating layer in the electron injection layer, an electron trap is formed, and electrons are captured and cannot reach the light-emitting layer.

Description

Organic electroluminescence device and preparation method thereof
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 passivation layer, rubidium compound doped layer and rhenium compound layer; Wherein, the material of described passivation layer is silicon dioxide, aluminium oxide, nickel oxide or cupric oxide;
The material of described rubidium compound doped layer is rubidium compound and passivating material; The material of described rubidium compound is rubidium carbonate, rubidium chloride, rubidium nitrate or rubidium sulfate; Described passivating material is silicon dioxide, aluminium oxide, nickel oxide or cupric oxide;
The material of described rhenium compound layer is rhenium heptoxide, rhenium trioxide, rhenium dioxide or oxidation two rheniums.
The doping mass ratio of described rubidium compound and described passivating material is 10:1 ~ 30:1.
The thickness of described passivation layer is 1-10nm, and the thickness of described rubidium compound doped layer is 30-80nm, and the thickness of described rhenium compound layer is 30-60nm.
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, 4,4'-two (9-ethyl-3-carbazole vinyl)-1,1'-biphenyl 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, 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 to adopt electron beam to prepare passivation layer on the electron transfer layer that step (a) is obtained, then on described passivation layer, electron beam prepares rubidium compound doped layer, on described rubidium compound doped layer, thermal resistance evaporation prepares rhenium compound layer again, thus obtains electron injecting layer; Wherein,
The material of described passivation layer is silicon dioxide, aluminium oxide, nickel oxide or cupric oxide;
The material of described rubidium compound doped layer is rubidium compound and passivating material; The material of described rubidium compound is rubidium carbonate, rubidium chloride, rubidium nitrate or rubidium sulfate; Described passivating material is silicon dioxide, aluminium oxide, nickel oxide or cupric oxide;
The material of described rhenium compound layer is rhenium heptoxide, rhenium trioxide, rhenium dioxide or oxidation two rheniums.
C () evaporation on the electron injecting layer that step (b) is obtained prepares cathode layer, thus obtain described organic electroluminescence device.
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.
In described step (b), the energy density of described electron beam evaporation plating is 10-l00W/cm 2; The thickness of described passivation layer is 1-10nm, and the thickness of described passivation layer is 30-80nm, and the thickness of described rhenium compound layer is 30-60nm.
In described step (c), the evaporation rate of described cathode layer is 1 ~ 10nm/s.
Compared with prior art, there is following advantage in organic electroluminescence devices of the present invention and preparation method thereof:
Passivation layer can penetrate in organic layer by the metal ion in block electrons implanted layer and negative electrode, and form electron trap, trapped electrons, makes electronics not arrive luminescent layer; The thickness of passivation layer is 1 ~ 10nm simultaneously, this thickness is moderate, passivation layer can be avoided blocked up and make passivation layer form cluster, thus forms electronic defects and affect the transmission of electric charge, also passivation layer can be avoided too thin and cause electronics to lose transmission path, thus reducing transmission rate;
Rubidium compound layer is that rubidium compound and passivating material form, rubidium compound due to its fusing point lower, easy evaporation, owing to there being the existence of metal ion, work function is lower, the electron injection potential barrier between electron transfer layer and implanted layer can be reduced, be conducive to the injection of electronics, and metal ion can strengthen the transmission rate of electronics further, and rubidium compound less stable, passivating material can improve the stability of doped layer, simultaneously, the doping mass ratio of rubidium compound and passivating material is 10:1 ~ 30:1, the performance of rubidium compound can be ensured in this scope, also can prevent passivating material from too much making material lose activity, thus be unfavorable for transmitting charge carrier, the thickness of rubidium compound doped layer is 30 ~ 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,
And rhenium compound film forming is better, rete planarization can be improved, reduce the existence of rete defect.Meanwhile, the HOMO energy level of rhenium compound is comparatively dark, can traverse to negative electrode by blocking hole, effectively avoid the generation of hole quenching phenomenon.This method is conducive to the luminous efficiency improving device.
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, electron injecting layer is passivation layer, rubidium compound doped layer and rhenium compound layer form.First adopt electron beam to prepare passivation layer, thickness is 1-10nm, and the energy density of electron beam evaporation plating is 10-100W/cm 2.
Adopt electron beam to prepare rubidium compound doped layer again, it is that rubidium compound and passivating material form, and thickness is 30-60nm.The doping mass ratio of described rubidium compound and passivating material is 10:1 ~ 30:1, and the energy density of electron beam evaporation plating is 10-l00W/cm 2.
Finally adopt thermal resistance evaporation to prepare described rhenium compound layer, thickness is 10-30nm.
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.
Described anode conducting substrate 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 100nm.
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 (Alq3), thickness is 5-40nm, and be preferably BCzVBi, thickness is preferably 24nm.
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 150nm.
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 anode conducting substrate 101 of glass/IZO, MoO 3the hole injection layer 102 of material, the hole transmission layer 103 of TAPC material, the luminescent layer 104 of ADN material, the electron transfer layer 105 of TPBI material, Al 2o 3the passivation layer 106 of material, Rb 2cO 3: SiO 2the rubidium compound doped layer 107 of material, ReO 2the rhenium compound layer 108 of material and the cathode layer 109 of Ag material.Passivation layer 106, rubidium compound doped layer 107 and rhenium compound layer 108 form electron injecting layer.(wherein brace "/" represents layer structure, and 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 IZO and the thickness conductive anode film that is 50nm, 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 for tungstic acid and the thickness hole injection layer 102 that is 25nm, material are 1,1-bis-[4-[N, N '-two (p-tolyl) is amino] phenyl] cyclohexane and thickness are the hole transmission layer 103 of 50nm, material is 9,10-bis--β-naphthylene anthracene and thickness is the luminescent layer 104 of 24nm, material is N-aryl benzimidazole and thickness is the electron transfer layer 105 of 150nm.
4, then on above-mentioned electron transfer layer 105, passivation layer 106, rubidium compound doped layer 107 and rhenium compound layer 108 is prepared successively:
First adopt electron beam to prepare passivation layer 106, material is Al 2o 3, obtained thickness is 4nm;
Then on passivation layer 106, electron beam is adopted to prepare Rb 2cO 3: SiO 2the rubidium compound doped layer 107, Rb of material 2cO 3with SiO 2doping mass ratio be 18:1, obtained thickness is 45nm;
Then on rubidium compound doped layer 107, adopt thermal resistance evaporation rhenium compound layer 108, thickness is 16nm, and material is ReO 2.
5, last evaporation prepares metal cathode layer 109, and evaporation rate is 2nm/s, and material used is silver, and thickness is 80nm, thus obtains required electroluminescent device.
Fig. 2 is the organic electroluminescence device of the present embodiment 1 and the current density of general device and the graph of a relation of current efficiency.
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/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 luminous efficiency of embodiment 1 is all larger than comparative example, luminous efficiency is 5.82lm/W, and comparative example be only 4.78lm/W, and the luminous efficiency of comparative example declines fast along with the increase of current density, this explanation, electron injecting layer of the present invention can penetrate in organic layer by the metal ion in block electrons implanted layer and negative electrode, reduce the electron injection potential barrier between electron transfer layer and implanted layer, be conducive to the injection of electronics, and the transmission rate of electronics can be strengthened, improve the stability of doped layer, negative electrode can be traversed to by blocking hole, effectively avoid the generation of hole quenching phenomenon.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, MoO 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, SiO 2the passivation layer of material, the rubidium compound doped layer of RbCl:NiO material, ReO 3the rhenium compound layer of material and the cathode layer of Ag material.Passivation layer, rubidium compound doped layer and rhenium compound layer composition electron injecting layer.(wherein brace "/" represents layer structure, and 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 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 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 for tungstic acid and the thickness hole injection layer that is 25nm, material are 1,1-bis-[4-[N, N '-two (p-tolyl) is amino] phenyl] cyclohexane and thickness are the hole transmission layer 103 of 50nm, material is 9,10-bis--β-naphthylene anthracene and thickness be 24nm luminescent layer, material is N-aryl benzimidazole and thickness is the electron transfer layer of 150nm.
4, then on above-mentioned electron transfer layer, passivation layer, rubidium compound doped layer and rhenium compound layer is prepared successively:
First adopt electron beam to prepare passivation layer, material is SiO 2, obtained thickness is 10nm;
Then adopt electron beam to prepare the rubidium compound doped layer of RbCl:NiO material over the passivation layer, the doping mass ratio of RbCl and NiO is 30:1, and obtained thickness is 30nm;
Then on rubidium compound doped layer, adopt thermal resistance evaporation rhenium compound layer, thickness is 30nm, and material is ReO 3.
5, last evaporation prepares metal cathode layer, and evaporation rate is 2nm/s, and material used is Pt, and 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/ITO, WO 3the luminescent layer of the hole injection layer of material, the hole transmission layer of TAPC material, ADN material, the electron transfer layer of TPBI material, the passivation layer of NiO material, RbNO 3: Al 2o 3the rubidium compound doped layer of material, Re 2o 7the rhenium compound layer of material and the cathode layer of Ag material.Passivation layer, rubidium compound doped layer and rhenium compound layer composition electron injecting layer.(wherein brace "/" represents layer structure, and 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 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 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 successively deposition material be WO 3, thickness is the hole injection layer of 20nm, material is TAPC, and thickness is the hole transmission layer of 60nm, material is ADN, and thickness is the luminescent layer of 10nm, material is TPBi, and thickness is the electron transfer layer of 200nm.
4, then on above-mentioned electron transfer layer, passivation layer, rubidium compound doped layer and rhenium compound layer is prepared successively:
First adopt electron beam to prepare passivation layer, material is NiO, and obtained thickness is 1nm;
Then electron beam is adopted to prepare RbNO over the passivation layer 3: Al 2o 3the rubidium compound doped layer of material, RbNO 3: Al 2o 3doping mass ratio be 30:1, obtained thickness is 60nm;
Then on rubidium compound doped layer, adopt thermal resistance evaporation rhenium compound layer, thickness is 10nm, and material is Re 2o 7.
5, last evaporation prepares metal cathode layer, and evaporation rate is 2nm/s, and material used is Ag, and 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/IZO, V 2o 5the hole injection layer of material, the hole transmission layer of TCTA material, Alq 3the luminescent layer of material, the electron transfer layer of TAZ material, the passivation layer of CuO material, Rb 2sO 4: the rubidium compound doped layer of CuO material, ReO 3the rhenium compound layer of material and the cathode layer of Ag material.Passivation layer, rubidium compound doped layer and rhenium compound layer composition electron injecting layer.(wherein brace "/" represents layer structure, and 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 IZO 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 successively deposition material be V 2o 5, thickness is the hole injection layer of 80nm, material is TCTA, and thickness is the hole transmission layer of 60nm, material is Alq 3, thickness is the luminescent layer of 40nm, material is TAZ, and thickness is the electron transfer layer of 35nm.
4, then on above-mentioned electron transfer layer, passivation layer, rubidium compound doped layer and rhenium compound layer is prepared successively:
First adopt electron beam to prepare passivation layer, material is CuO, and obtained thickness is 6nm;
Then electron beam is adopted to prepare Rb over the passivation layer 2sO 4: the rubidium compound doped layer of CuO material, Rb 2sO 4: the doping mass ratio of CuO is 11:1, and obtained thickness is 35nm;
Then on rubidium compound doped layer, adopt thermal resistance evaporation rhenium compound layer, thickness is 25nm, and material is Re 2o.
5, last evaporation prepares metal cathode layer, and evaporation rate is 2nm/s, and material used is Al, and thickness is 250nm, thus obtains required electroluminescent device.
Compared with prior art,, there is following advantage in organic electroluminescence devices of the present invention and preparation method thereof: passivation layer can penetrate in organic layer by the metal ion in block electrons implanted layer and negative electrode, forms electron trap, trapped electrons, makes electronics not arrive luminescent layer; Rubidium compound layer is that rubidium compound and passivating material form, rubidium compound due to its fusing point lower, easy evaporation, owing to there being the existence of metal ion, work function is lower, the electron injection potential barrier between electron transfer layer and implanted layer can be reduced, be conducive to the injection of electronics, and metal ion can strengthen the transmission rate of electronics further, and rubidium compound less stable, passivating material can improve the stability of doped layer, and rhenium compound film forming is better, rete planarization can be improved, reduce the existence of rete defect.Meanwhile, the HOMO energy level of rhenium compound is comparatively dark, can traverse to negative electrode by blocking hole, effectively avoid the generation of hole quenching phenomenon.This method is conducive to the luminous efficiency improving device.
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, it is characterized in that, 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 passivation layer, rubidium compound doped layer and rhenium compound layer; Wherein, the material of described passivation layer is silicon dioxide, aluminium oxide, nickel oxide or cupric oxide;
The material of described rubidium compound doped layer is rubidium compound and passivating material; The material of described rubidium compound is rubidium carbonate, rubidium chloride, rubidium nitrate or rubidium sulfate; Described passivating material is silicon dioxide, aluminium oxide, nickel oxide or cupric oxide;
The material of described rhenium compound layer is rhenium heptoxide, rhenium trioxide, rhenium dioxide or oxidation two rheniums.
2. organic electroluminescence device according to claim 1, is characterized in that, the doping mass ratio of described rubidium compound and described passivating material is 10:1 ~ 30:1.
3. organic electroluminescence device according to claim 1, is characterized in that, the thickness of described passivation layer is 1-10nm, and the thickness of described rubidium compound doped layer is 30-80nm, and the thickness of described rhenium compound layer is 30-60nm.
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, 4,4'-two (9-ethyl-3-carbazole vinyl)-1,1'-biphenyl 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 to adopt electron beam to prepare passivation layer on the electron transfer layer that step (a) is obtained, then on described passivation layer, electron beam prepares rubidium compound doped layer, on described rubidium compound doped layer, thermal resistance evaporation prepares rhenium compound layer again, thus obtains electron injecting layer; Wherein,
The material of described passivation layer is silicon dioxide, aluminium oxide, nickel oxide or cupric oxide;
The material of described rubidium compound doped layer is rubidium compound and passivating material; The material of described rubidium compound is rubidium carbonate, rubidium chloride, rubidium nitrate or rubidium sulfate; Described passivating material is silicon dioxide, aluminium oxide, nickel oxide or cupric oxide;
The material of described rhenium compound layer is rhenium heptoxide, rhenium trioxide, rhenium dioxide or oxidation two rheniums;
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, is characterized in that, in described step (b), the energy density of described electron beam evaporation plating is 10-100W/cm 2; The thickness of described passivation layer is 1-10nm, and the thickness of described passivation layer is 30-80nm, and the thickness of described rhenium compound layer is 30-60nm.
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.
CN201310574096.8A 2013-11-14 2013-11-14 Organic light-emitting device and production method thereof Pending CN104638197A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105244446A (en) * 2015-08-28 2016-01-13 京东方科技集团股份有限公司 Organic electroluminescent device, preparation method thereof and display device
CN105280821A (en) * 2015-09-05 2016-01-27 苏州瑞晟纳米科技有限公司 Method for preparing copper-doped nickel oxide film under low temperature

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105244446A (en) * 2015-08-28 2016-01-13 京东方科技集团股份有限公司 Organic electroluminescent device, preparation method thereof and display device
CN105244446B (en) * 2015-08-28 2018-06-29 京东方科技集团股份有限公司 Organic electroluminescence device and preparation method thereof, display device
US10566565B2 (en) 2015-08-28 2020-02-18 Boe Technology Group Co., Ltd. Organic light emitting device and method of fabricating the same, and display device
CN105280821A (en) * 2015-09-05 2016-01-27 苏州瑞晟纳米科技有限公司 Method for preparing copper-doped nickel oxide film under low temperature

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