CN104124350A - Organic light-emitting device and preparation method thereof - Google Patents
Organic light-emitting device and preparation method thereof Download PDFInfo
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- CN104124350A CN104124350A CN201310143690.1A CN201310143690A CN104124350A CN 104124350 A CN104124350 A CN 104124350A CN 201310143690 A CN201310143690 A CN 201310143690A CN 104124350 A CN104124350 A CN 104124350A
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- H—ELECTRICITY
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- H10K50/00—Organic light-emitting devices
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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
- H10K50/80—Constructional details
- H10K50/85—Arrangements for extracting light from the devices
- H10K50/854—Arrangements for extracting light from the devices comprising scattering means
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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
- H10K50/80—Constructional details
- H10K50/85—Arrangements for extracting light from the devices
- H10K50/856—Arrangements for extracting light from the devices comprising reflective means
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Abstract
The invention discloses an organic light-emitting device which includes a conductive anode glass substrate, a hole injection layer, a hole transmission layer, a light-emitting layer, an electronic transmission layer, an electronic injection layer and a composite cathode, which are sequentially laminated. The composite cathode layer includes a first doping layer and a second doping layer, which are arranged to be laminated sequentially. The material of the first doping layer is a mixed material formed by a metal phthalocyanine compound and a cesium salt. The metal phthalocyanine compound is copper phthalocyanine, zinc phthalocyanine, vanadium phthalocyanine or magnesium phthalocyanine. The cesium salt is cesium carbonate, cesium fluoride, cesium azide or cesium chloride. The material of the second doping layer is a mixed material of a metal oxide and a metal. The metal oxide is molybdenum trioxide, tungsten trioxide or vanadium pentoxide. The metal is silver, aluminum, platinum or gold. The composite cathode layer of the organic light-emitting device is capable of enabling light to be scattered so that the light-emitting efficiency of the device is improved. The invention also provides a preparation method for the organic light-emitting device.
Description
Technical field
The present invention relates to organic electroluminescence device, be specifically related to a kind of organic electroluminescence device and preparation method thereof.
Background technology
1987, the C.W.Tang of U.S. Eastman Kodak company and VanSlyke reported the breakthrough in organic electroluminescent research.Utilize ultrathin film technology to prepare high brightness, high efficiency double-deck organic electroluminescence device (OLED).In this double-deck device, under 10V, brightness reaches 1000cd/m
2, its luminous efficiency is 1.51lm/W, life-span to be greater than 100 hours.
In traditional luminescent device, it is to be transmitted into device outside that the light of device inside only has 18% left and right, and other part can consume at device outside with other forms, this be due between interface, there is refractive index poor (as the specific refractivity between glass and ITO, glass refraction is that 1.5, ITO is 1.8, light arrives glass from ITO, will there is total reflection), caused the loss of total reflection, thereby it is lower to cause the integral body of luminescent device to go out optical property.
Summary of the invention
For overcoming the defect of above-mentioned prior art, the invention provides a kind of organic electroluminescence device and preparation method thereof.By prepare composite cathode layer on electron injecting layer, improved the luminous efficiency of organic electroluminescence device.
On the one hand, the invention provides a kind of organic electroluminescence device, comprise the conductive anode substrate, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the composite cathode layer that stack gradually, described composite cathode layer comprises the first doped layer and the second doped layer that lamination arranges successively
The material of described the first doped layer is the composite material that metal phthalocyanine compound and cesium salt form, and described metal phthalocyanine compound is CuPc (CuPc), Phthalocyanine Zinc (ZnPc), phthalocyanine vanadium (VPc) or magnesium phthalocyanine (MgPc); Described cesium salt is cesium carbonate (Cs
2cO
3), cesium fluoride (CsF), nitrine caesium (CsN
3) or cesium chloride (CsCl);
The material of described the second doped layer is the composite material that metal oxide and metal form, and described metal oxide is molybdenum trioxide (MoO
3), tungstic acid (WO
3) or vanadic oxide (V
2o
5), described metal is silver (Ag), aluminium (Al), platinum (Pt) or gold (Au).
Preferably, in described the first doped layer, the mass ratio of described metal phthalocyanine compound and cesium salt is 1:0.2～0.8.
Preferably, in described the second doped layer, the mass ratio of described metal oxide and metal is 0.1～0.5:1.
Preferably, the thickness of described the first doped layer is 20～100nm.
Preferably, the thickness of described the second doped layer is 200～500nm.
Composite cathode layer comprises the first doped layer and the second doped layer that lamination arranges successively.The first doped layer of preparing metal phthalocyanine compound and cesium salt on electron injecting layer, due to the easy crystallization of metal phthalocyanine compound, by crystallization, can make the surface forming is no longer even curface, but be with effigurate wave structure, this structure can change the refraction angle of light, make light carry out scattering, minimizing is to the light of device both sides transmitting, can make the functional layer that rear preparation is got on can keep wave structure simultaneously, be conducive to light scattering, and the metal cesium salt material of doping, can improve the transmitance of light, be conducive to light and see through crystallizing layer through scattering, under high temperature, easily decompose, and with electron injecting layer be material of the same type, eliminated the interface potential barrier between two-layer, be there is not to obstruction in electronic injection, the second doped layer that preparation is formed by metal oxide and metal on the first doped layer again, if the conductivity of master metal enhance device, reduce contact resistance, light to scattering reflects, and make it get back to bottom outgoing, and doping object metal oxide is conventional hole injection metal oxide materials, this material filming temperature is low, easily film forming, can reduce the roughness of metal-doped layer, and this composite cathode layer can effectively improve luminous efficiency.
Conductive anode substrate can be conducting glass substrate or organic PETG substrate that conducts electricity.Preferably, conductive anode substrate is indium tin oxide glass (ITO), aluminium zinc oxide glass (AZO) or indium-zinc oxide glass (IZO).More preferably, conductive anode substrate is indium tin oxide glass.
The material of hole injection layer, hole transmission layer, electron transfer layer, electron injecting layer and luminescent layer is not done concrete restriction, and this area current material is all applicable to the present invention.
Preferably, the material of hole injection layer is molybdenum trioxide (MoO
3), tungstic acid (WO
3) or vanadic oxide (V
2o
5), the thickness of hole injection layer is 20～80nm.
More preferably, the material of hole injection layer is molybdenum trioxide (MoO
3), thickness is 40nm.
Preferably, the material of hole transmission layer is 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane (TAPC), 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA) or N, N '-(1-naphthyl)-N, N '-diphenyl-4,4 '-benzidine (NPB), thickness is 20～60nm.
More preferably, the material of hole transmission layer is N, N '-(1-naphthyl)-N, and N '-diphenyl-4,4 '-benzidine (NPB), thickness is 50nm.
Preferably, the luminescent material of luminescent layer is 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans (DCJTB), 9,10-bis--β-naphthylene anthracene (ADN), 4, two (the 9-ethyl-3-carbazole vinyl)-1 of 4'-, 1'-biphenyl (BCzVBi) or oxine aluminium (Alq
3), thickness is 5～40nm.
More preferably, the luminescent material of luminescent layer is two (the 9-ethyl-3-carbazole vinyl)-1 of 4,4'-, 1'-biphenyl (BCzVBi), and thickness is 30nm.
Preferably, the material of electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2, and 4-triazole derivative (as TAZ) or N-aryl benzimidazole (TPBI), thickness is 40～300nm.
More preferably, the material of electron transfer layer is N-aryl benzimidazole (TPBI), and thickness is 200nm.
Preferably, the material of electron injecting layer is cesium carbonate (Cs
2cO
3), cesium fluoride (CsF), nitrine caesium (CsN
3) or lithium fluoride (LiF); Thickness is 0.5～10nm.
More preferably, the material of electron injecting layer is lithium fluoride (LiF), and thickness is 1nm.
On the other hand, the invention provides a kind of preparation method of organic electroluminescence device, comprise the following steps:
On conductive anode substrate, prepare successively hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer;
On described electron injecting layer, prepare composite cathode layer: first by the mode of electron beam evaporation plating, on described electron injecting layer, prepare successively the first doped layer, by the mode of vacuum evaporation, on described the first doped layer, prepare the second doped layer again, obtain organic electroluminescence device;
The material of described the first doped layer is the composite material that metal phthalocyanine compound and cesium salt form, and described metal phthalocyanine compound is CuPc, Phthalocyanine Zinc, phthalocyanine vanadium or magnesium phthalocyanine; Described cesium salt is cesium carbonate (Cs
2cO
3), cesium fluoride (CsF), nitrine caesium (CsN
3) or cesium chloride (CsCl);
The material of described the second doped layer is the composite material that metal oxide and metal form, and described metal oxide is molybdenum trioxide (MoO
3), tungstic acid (WO
3) or vanadic oxide (V
2o
5), described metal is silver, aluminium, platinum or gold.
The energy density of described electron beam evaporation plating is 10～l00W/cm
2, the material evaporation speed of described the first doped layer is 1～10nm/s; In described vacuum evaporation process, vacuum degree is 2 * 10
-3～5 * 10
-5pa, described the second doped layer material evaporation speed is 1～10nm/s.
Preferably, in described the first doped layer, the mass ratio of described metal phthalocyanine compound and cesium salt is 1:0.2～0.8.
Preferably, in described the second doped layer, the mass ratio of described metal oxide and metal is 0.1～0.5:1.
Preferably, the thickness of described the first doped layer is 20～100nm.
Preferably, the thickness of described the second doped layer is 200～500nm.
Conductive anode substrate can be conducting glass substrate or organic PETG substrate that conducts electricity.Preferably, conductive anode substrate is indium tin oxide glass (ITO), aluminium zinc oxide glass (AZO) or indium-zinc oxide glass (IZO).More preferably, conductive anode substrate is indium tin oxide glass.
Preferably, anode substrate is carried out to following clean: adopt successively liquid detergent, each ultrasonic cleaning of deionized water 15 minutes, and then stand-by by oven for drying.
The material of hole injection layer, hole transmission layer, electron transfer layer, electron injecting layer and luminescent layer is not done concrete restriction, and this area current material is all applicable to the present invention.Hole injection layer, hole transmission layer, electron transfer layer, electron injecting layer and luminescent layer all can adopt the mode of vacuum evaporation to prepare, and its concrete operations condition is not made particular determination.
Preferably, the temperature of vacuum evaporation is 100～500 ℃, and vacuum degree is 1 * 10
-3～1 * 10
-5pa.
Preferably, the material of hole injection layer is molybdenum trioxide (MoO
3), tungstic acid (WO
3) or vanadic oxide (V
2o
5), the thickness of hole injection layer is 20～80nm.
More preferably, the material of hole injection layer is vanadic oxide (V
2o
5), thickness is 60nm.
Preferably, the material of hole transmission layer is 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane (TAPC), 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA) or N, N '-(1-naphthyl)-N, N '-diphenyl-4,4 '-benzidine (NPB), thickness is 20～60nm.
More preferably, the material of hole transmission layer is N, N '-(1-naphthyl)-N, and N '-diphenyl-4,4 '-benzidine (NPB), thickness is 50nm.
Preferably, the luminescent material of luminescent layer is 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans (DCJTB), 9,10-bis--β-naphthylene anthracene (ADN), 4, two (the 9-ethyl-3-carbazole vinyl)-1 of 4'-, 1'-biphenyl (BCzVBi) or oxine aluminium (Alq
3), thickness is 5～40nm.
More preferably, the luminescent material of luminescent layer is two (the 9-ethyl-3-carbazole vinyl)-1 of 4,4'-, 1'-biphenyl (BCzVBi), and thickness is 30nm.
Preferably, the material of electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2, and 4-triazole derivative (as TAZ) or N-aryl benzimidazole (TPBI), thickness is 40～300nm.
More preferably, the material of electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (Bphen), and thickness is 250nm.
Preferably, the material of electron injecting layer is cesium carbonate (Cs
2cO
3), cesium fluoride (CsF), nitrine caesium (CsN
3) or lithium fluoride (LiF); Thickness is 0.5～10nm.
More preferably, the material of electron injecting layer is lithium fluoride (LiF), and thickness is 1nm.
The invention provides a kind of organic electroluminescence device and preparation method thereof and there is following beneficial effect:
(1) organic electroluminescence device provided by the invention, there is composite cathode layer structure, composite cathode layer comprises the first doped layer and the second doped layer that lamination arranges successively, the easy crystallization of metal phthalocyanine compound of the first doped layer, can make surface form and be with effigurate wave structure, thereby change the refraction angle of light, make light carry out scattering, can make the functional layer that rear preparation is got on also can keep nutty structure, be conducive to light scattering simultaneously; Metal cesium salt can improve the transmitance of light, eliminated and electron injecting layer between interface potential barrier; The metal of the second doped layer can enhance device conductivity, reduce contact resistance, the light of scattering is reflected, make it get back to bottom outgoing, metal oxide film-forming temperature is low, easily film forming, can reduce the roughness of the second doped layer, this composite cathode layer finally can effectively improve luminous efficiency;
(2) preparation technology of organic electroluminescence device of the present invention is simple, and easily large area preparation is suitable for large-scale industrialization and uses.
Accompanying drawing explanation
Fig. 1 is the structural representation of the organic electroluminescence device that makes of the embodiment of the present invention 1;
Fig. 2 is the current density of organic electroluminescence device and the graph of a relation of luminous efficiency prepared by the embodiment of the present invention 1 and comparative example.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely described, obviously, described embodiment is only the present invention's part embodiment, rather than whole embodiment.Embodiment based in the present invention, those of ordinary skills, not making the every other embodiment obtaining under creative work prerequisite, belong to the scope of protection of the invention.
Embodiment 1
A preparation method for organic electroluminescence device, comprises the following steps:
(1) substrate of glass is used to liquid detergent successively, deionized water, ultrasonic 15min, the organic pollution of removal glass surface;
(2) adopt the method for vacuum evaporation on ito glass substrate, to prepare successively hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer;
The evaporation of hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer is vacuum evaporation, and evaporation temperature is 400 ℃, and vacuum degree is 1 * 10
-5pa.Wherein, the material of hole injection layer is V
2o
5, thickness is 60nm; The material of hole transmission layer is NPB, and thickness is 50nm; The material of luminescent layer is BCzVBi, and light emitting layer thickness is 30nm; The material of electron transfer layer is Bphen, and thickness is 250nm; The material of electron injecting layer is LiF, and thickness is 1nm.
(3) on electron injecting layer, prepare composite cathode layer, obtain organic electroluminescence device; Composite cathode layer comprises the first doped layer and the second doped layer stacking gradually;
The preparation of composite cathode layer: first adopt the mode of electron beam evaporation plating to prepare the first doped layer that a layer thickness is 50nm on electron injecting layer, material is CuPc and Cs
2cO
3the composite material forming (is expressed as CuPc:Cs
2cO
3), CuPc and Cs
2cO
3mass ratio be 1:0.5, evaporation speed is 3nm/s, the energy density of electron beam evaporation plating is 30W/cm
2; Adopt the mode of vacuum evaporation on the first doped layer, to prepare the second doped layer that a layer thickness is 250nm, material is MoO again
3the composite material forming with Ag (is expressed as MoO
3: Ag), MoO
3with the mass ratio of Ag be 0.1:1, evaporation speed is 3nm/s, the vacuum degree of vacuum evaporation process is 8 * 10
-5pa.
Fig. 1 is the structural representation of the organic electroluminescence device that makes of the embodiment of the present invention 1.As shown in Figure 1, the present embodiment organic electroluminescence device, comprises ito glass substrate 1, hole injection layer 2, hole transmission layer 3, luminescent layer 4, electron transfer layer 5, electron injecting layer 6 and composite cathode layer 7 successively.Described composite cathode layer 7 comprises that a layer thickness is the first doped layer 71 of 50nm and the second doped layer 72 that a layer thickness is 250nm successively.The structure of this organic electroluminescence device is: ito glass/V
2o
5/ TCTA/BCzVBi/Bphen/LiF/CuPc:Cs
2cO
3(1:0.5)/MoO
3: Ag (0.1:1), wherein, slash "/" represents layer structure, MoO
3: colon ": " in Ag represents to mix, and 0.1:1 represents the former and the latter's mass ratio, after in embodiment each meaning that meets expression identical.
Embodiment 2
A preparation method for organic electroluminescence device, comprises the following steps:
(1) substrate of glass is used to liquid detergent successively, deionized water, ultrasonic 15min, the organic pollution of removal glass surface;
(2) adopt the method for vacuum evaporation on AZO glass substrate, to prepare successively hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer;
The evaporation of hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer is vacuum evaporation, and evaporation temperature is 400 ℃, and vacuum degree is 1 * 10
-5pa.Wherein, the material of hole injection layer is WO
3, thickness is 80nm; The material of hole transmission layer is TCTA, and thickness is 60nm; The material of luminescent layer is ADN, and thickness is 5nm; The material of electron transfer layer is TAZ, and thickness is 200nm; The material of electron injecting layer is CsN
3, thickness is 10nm.
(3) on electron injecting layer, prepare composite cathode layer, obtain organic electroluminescence device; Composite cathode layer comprises the first doped layer and the second doped layer stacking gradually;
The preparation of composite cathode layer: first adopt the mode of electron beam evaporation plating to prepare the first doped layer that a layer thickness is 100nm on electron injecting layer, material is the composite material (being expressed as MgPc:CsF) that MgPc and CsF form, the mass ratio of MgPc and CsF is 1:0.8, evaporation speed is 10nm/s, and the energy density of electron beam evaporation plating is 10W/cm
2; Adopt the mode of vacuum evaporation on the first doped layer, to prepare the second doped layer that a layer thickness is 500nm, material is WO again
3the composite material forming with Al (is expressed as WO
3: Al), WO
3with the mass ratio of Al be 0.1:1, evaporation speed is 10nm/s, the vacuum degree of vacuum evaporation process is 2 * 10
-3pa.
The structure of the organic electroluminescence device that the present embodiment provides is: AZO glass/WO
3/ TCTA/ADN/TAZ/CsN
3/ MgPc:CsF (1:0.8)/WO
3: Al (0.1:1).
Embodiment 3
A preparation method for organic electroluminescence device, comprises the following steps:
(1) substrate of glass is used to liquid detergent successively, deionized water, ultrasonic 15min, the organic pollution of removal glass surface;
(2) adopt the method for vacuum evaporation on IZO glass substrate, to prepare successively hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer;
The evaporation of hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer is vacuum evaporation, and evaporation temperature is 400 ℃, and vacuum degree is 1 * 10
-5pa.Wherein, the material of hole injection layer is V
2o
5, thickness is 20nm; The material of hole transmission layer is TCTA, and thickness is 30nm; The material of luminescent layer is Alq
3, thickness is 40nm; The material of electron transfer layer is Bphen, and thickness is 60nm; The material of electron injecting layer is CsF, and thickness is 0.5nm.
(3) on electron injecting layer, prepare composite cathode layer, obtain organic electroluminescence device; Composite cathode layer comprises the first doped layer and the second doped layer stacking gradually;
The preparation of composite cathode layer: first adopt the mode of electron beam evaporation plating to prepare the first doped layer that a layer thickness is 20nm on electron injecting layer, material is ZnPc and CsN
3the composite material forming (is expressed as ZnPc:CsN
3), ZnPc and CsN
3mass ratio be 1:0.2, evaporation speed is 1nm/s, the energy density of electron beam evaporation plating is 100W/cm
2; Adopt the mode of vacuum evaporation on the first doped layer, to prepare the second doped layer that a layer thickness is 200nm, material is V again
2o
5the composite material forming with Pt (is expressed as V
2o
5: Pt), V
2o
5with the mass ratio of Pt be 0.5:1, evaporation speed is 1nm/s, the vacuum degree of vacuum evaporation process is 5 * 10
-5pa.
The structure of the organic electroluminescence device that the present embodiment provides is: IZO glass/V
2o
5/ TCTA/Alq
3/ Bphen/CsF/ZnPc:CsN
3(1:0.2)/V
2o
5: Pt (0.5:1).
Embodiment 4
A preparation method for organic electroluminescence device, comprises the following steps:
(1) substrate of glass is used to liquid detergent successively, deionized water, ultrasonic 15min, the organic pollution of removal glass surface;
(2) adopt the method for vacuum evaporation on IZO glass substrate, to prepare successively hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer;
The evaporation of hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer is vacuum evaporation, and evaporation temperature is 400 ℃, and vacuum degree is 1 * 10
-5pa.Wherein, the material of hole injection layer is MoO
3, thickness is 30nm; The material of hole transmission layer is TAPC, and thickness is 50nm; The material of luminescent layer is DCJTB, and thickness is 5nm; The material of electron transfer layer is TPBi, and thickness is 40nm; The material of electron injecting layer is Cs
2cO
3, thickness is 1nm.
(3) on electron injecting layer, prepare composite cathode layer, obtain organic electroluminescence device; Composite cathode layer comprises the first doped layer and the second doped layer stacking gradually;
The preparation of composite cathode layer: first adopt the mode of electron beam evaporation plating to prepare the first doped layer that a layer thickness is 80nm on electron injecting layer, material is the composite material (being expressed as VPc:CsCl) that VPc and CsCl form, the mass ratio of VPc and CsCl is 1:0.3, evaporation speed is 5nm/s, and the energy density of electron beam evaporation plating is 80W/cm
2; Adopt the mode of vacuum evaporation on the first doped layer, to prepare the second doped layer that a layer thickness is 350nm, material is WO again
3the composite material forming with Au (is expressed as WO
3: Au), WO
3with the mass ratio of Au be 0.2:1, evaporation speed is 5nm/s, the vacuum degree of vacuum evaporation process is 5 * 10
-4pa.
The structure of the organic electroluminescence device that the present embodiment provides is: IZO glass/MoO
3/ TAPC/DCJTB/TPBi/Cs
2cO
3/ VPc:CsCl (1:0.3)/WO
3: Au (0.2:1).
Comparative example
For embodying creativeness of the present invention, the present invention is also provided with comparative example, the difference of comparative example and embodiment 1 is that the negative electrode in comparative example is metal simple-substance silver (Ag), and thickness is 150nm, and the concrete structure of comparative example's organic electroluminescence device is ito glass/V
2o
5/ TCTA/BCzVBi/Bphen/LiF/Ag, respectively corresponding conductive anode substrate of glass, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode.
Adopt the USB4000 fiber spectrometer testing electroluminescent spectrum of U.S. marine optics Ocean Optics, the current-voltage tester Keithley2400 test electric property of U.S. Keithley company, CS-100A colorimeter test brightness and the colourity of Japan Konica Minolta company, obtain organic electroluminescence device luminous efficiency with current density change curve, to investigate the luminous efficiency of device, tested object is organic electroluminescence device prepared by embodiment 1 and comparative example.Test result as shown in Figure 2.
Fig. 2 is the current density of organic electroluminescence device and the graph of a relation of luminous efficiency prepared with comparative example of embodiment 1.Wherein, curve 1 is the current density of organic electroluminescence device and the graph of a relation of luminous efficiency of embodiment 1 preparation; The current density of organic electroluminescence device and the graph of a relation of luminous efficiency that curve 2 is prepared for comparative example.As can see from Figure 2, under different current densities, the luminous efficiency of the organic electroluminescence device of embodiment 1 preparation is large than comparative example all, and the maximum luminous efficiency of the organic electroluminescence device of embodiment 1 preparation is 10.86lm/W, and that comparative example is only 6.15lm/W.This explanation, the composite cathode layer structure of the organic electroluminescence device of embodiment 1 preparation, the easy crystallization of metal phthalocyanine compound of the first doped layer, can make surface form and be with effigurate wave structure, thereby change the refraction angle of light, make light carry out scattering, can make the functional layer that rear preparation is got on also can keep nutty structure, be conducive to light scattering simultaneously; Metal cesium salt can improve the transmitance of light, eliminated and electron injecting layer between interface potential barrier; The metal of the second doped layer can enhance device conductivity, reduce contact resistance, the light of scattering is reflected, make it get back to bottom outgoing, metal oxide film-forming temperature is low, easily film forming, can reduce the roughness of the second doped layer, this composite cathode layer finally can effectively improve luminous efficiency.
The above is the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications are also considered as protection scope of the present invention.
Claims (10)
1. an organic electroluminescence device, comprise the conductive anode substrate, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the composite cathode layer that stack gradually, it is characterized in that, described composite cathode layer comprises the first doped layer and the second doped layer that lamination arranges successively
The material of described the first doped layer is the composite material that metal phthalocyanine compound and cesium salt form, and described metal phthalocyanine compound is CuPc, Phthalocyanine Zinc, phthalocyanine vanadium or magnesium phthalocyanine; Described cesium salt is cesium carbonate, cesium fluoride, nitrine caesium or cesium chloride;
The material of described the second doped layer is the composite material that metal oxide and metal form, and described metal oxide is molybdenum trioxide, tungstic acid or vanadic oxide, and described metal is silver, aluminium, platinum or gold.
2. organic electroluminescence device as claimed in claim 1, is characterized in that, in described the first doped layer, the mass ratio of described metal phthalocyanine compound and cesium salt is 1:0.2～0.8.
3. organic electroluminescence device as claimed in claim 1, is characterized in that, in described the second doped layer, the mass ratio of described metal oxide and metal is 0.1～0.5:1.
4. organic electroluminescence device as claimed in claim 1, is characterized in that, the thickness of described the first doped layer is 20～100nm.
5. organic electroluminescence device as claimed in claim 1, is characterized in that, the thickness of described the second doped layer is 200～500nm.
6. a preparation method for organic electroluminescence device, is characterized in that, comprises the following steps:
On conductive anode substrate, prepare successively hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer;
On described electron injecting layer, prepare composite cathode layer: first by the mode of electron beam evaporation plating, on described electron injecting layer, prepare successively the first doped layer, by the mode of vacuum evaporation, on described the first doped layer, prepare the second doped layer again, obtain organic electroluminescence device;
The material of described the first doped layer is the composite material that metal phthalocyanine compound and cesium salt form, and described metal phthalocyanine compound is CuPc, Phthalocyanine Zinc, phthalocyanine vanadium or magnesium phthalocyanine; Described cesium salt is cesium carbonate, cesium fluoride, nitrine caesium or cesium chloride;
The material of described the second doped layer is the composite material that metal oxide and metal form, and described metal oxide is molybdenum trioxide, tungstic acid or vanadic oxide, and described metal is silver, aluminium, platinum or gold.
The energy density of described electron beam evaporation plating is 10～l00W/cm
2, the material evaporation speed of described the first doped layer is 1～10nm/s; In described vacuum evaporation process, vacuum degree is 2 * 10
-3～5 * 10
-5pa, described the second doped layer material evaporation speed is 1～10nm/s.
7. the preparation method of organic electroluminescence device as claimed in claim 6, is characterized in that, in described the first doped layer, the mass ratio of described metal phthalocyanine compound and cesium salt is 1:0.2～0.8.
8. the preparation method of organic electroluminescence device as claimed in claim 6, is characterized in that, in described the second doped layer, the mass ratio of described metal oxide and metal is 0.1～0.5:1.
9. the preparation method of organic electroluminescence device as claimed in claim 6, is characterized in that, the thickness of described the first doped layer is 20～100nm.
10. the preparation method of organic electroluminescence device as claimed in claim 6, is characterized in that, the thickness of described the second doped layer is 200～500nm.
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| CN202067838U (en) * | 2011-04-14 | 2011-12-07 | 陕西科技大学 | OLED device with composite cathode structure |
| CN202076330U (en) * | 2011-04-22 | 2011-12-14 | 陕西科技大学 | Cathode structure of organic electroluminescent device |
| CN102714902A (en) * | 2010-01-15 | 2012-10-03 | 住友化学株式会社 | Polymer light emitting element |
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| CN101853877A (en) * | 2009-02-09 | 2010-10-06 | 三星移动显示器株式会社 | Organic light emitting diode display |
| CN102714902A (en) * | 2010-01-15 | 2012-10-03 | 住友化学株式会社 | Polymer light emitting element |
| CN202067838U (en) * | 2011-04-14 | 2011-12-07 | 陕西科技大学 | OLED device with composite cathode structure |
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