CN104124394A - Organic light-emitting device and preparation method thereof - Google Patents
Organic light-emitting device and preparation method thereof Download PDFInfo
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- CN104124394A CN104124394A CN201310143751.4A CN201310143751A CN104124394A CN 104124394 A CN104124394 A CN 104124394A CN 201310143751 A CN201310143751 A CN 201310143751A CN 104124394 A CN104124394 A CN 104124394A
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- 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 provides an organic light-emitting device and a preparation method thereof. The organic light-emitting device adopts a metal doping layer, a phthalocyanine metal compound layer, a fullerene derivative layer and a metal layer, which are laminated sequentially, as a cathode so that electron injection capability and stability of the device are improved and light is enabled to reach a conductive anode glass substrate more effectively and thus the light-emitting efficiency of the device is improved. The preparation method is simple and easy in control and operation and raw materials are easy to obtain.
Description
Technical field
The invention belongs to organic electroluminescent field, be specifically related to a kind of organic electroluminescence device and preparation method thereof.
Background technology
Organic electroluminescence device (OLED) is a kind ofly to take organic material as luminescent material, the energy conversion device that can be luminous energy the electric energy conversion applying.It has the outstanding properties such as ultra-thin, self-luminous, response are fast, low-power consumption, in fields such as demonstration, illuminations, has application prospect very widely.
The structure of organic electroluminescence device is sandwich structure, accompanies one or more layers organic film between negative electrode and conductive anode.In containing the device of sandwich construction, inner side, the two poles of the earth mainly comprises luminescent layer, implanted layer and transport layer.Organic electroluminescence device is carrier injection type luminescent device, at anode and negative electrode, add after operating voltage, hole is from anode, electronics is injected into respectively the organic material layer of device work from negative electrode, it is luminous that two kinds of charge carriers form hole-duplet in luminous organic material, and then light sends from electrode.
In traditional luminescent device, general is all to using the metal of low work function or alloy as negative electrode, in this structure, the metallochemistry character of low work function is active, in air, be easy to oxidation, make the less stable of device, and the electronic injection ability of negative electrode is not good, cause device luminous efficiency, to go out optical property lower.
Summary of the invention
In order to address the above problem, the present invention aims to provide a kind of organic electroluminescence device compared with high light-emitting efficiency and preparation method thereof that has.
First aspect, the invention provides a kind of organic electroluminescence device, comprise the conductive anode substrate of glass, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the negative electrode that stack gradually, described negative electrode comprises metal-doped layer, phthalocyanine metal compound layer, fullerene derivate layer and the metal level stacking gradually; The material of described metal-doped layer is the composite material that ratio that a kind of in cesium salt and magnesium, strontium, calcium and ytterbium is 0.05:1～0.2:1 according to mass ratio forms, and described cesium salt is a kind of in cesium oxide, cesium carbonate, nitrine caesium and cesium chloride; The material of described phthalocyanine metal compound layer is phthalocyanine metal compound, and described phthalocyanine metal compound is a kind of in CuPc, Phthalocyanine Zinc, phthalocyanine vanadium and magnesium phthalocyanine; The material of described fullerene derivate layer is a kind of in football alkene, carbon 70, [6,6]-phenyl-C61-methyl butyrate and [6,6]-phenyl-C71-methyl butyrate, and the material of described metal level is a kind of in silver, aluminium, platinum and gold.
Preferably, conductive anode substrate of glass is a kind of in indium tin oxide glass (ITO), aluminium zinc oxide glass (AZO) and indium-zinc oxide glass (IZO).
Preferably, the material of hole injection layer is molybdenum trioxide (MoO
3), tungstic acid (WO
3) and vanadic oxide (V
2o
5) in a kind of.More preferably, the material of hole injection layer is MoO
3.
Preferably, the thickness of hole injection layer is 20～80nm.More preferably, the thickness of hole injection layer is 30nm.
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) and N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4, a kind of in 4'-diamines (NPB).More preferably, the material of hole transmission layer is TCTA.
Preferably, the thickness of hole transmission layer is 20～60nm.More preferably, the thickness of hole transmission layer is 40nm.
Preferably, the 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-(betanaphthyl) anthracene (ADN), 4,4 '-bis-(9-ethyl-3-carbazole vinyl)-1,1 '-biphenyl (BCzVBi) and oxine aluminium (Alq
3) in a kind of.More preferably, the material of luminescent layer is Alq
3.
Preferably, the thickness of luminescent layer is 5～40nm.More preferably, the thickness of luminescent layer is 30nm.
The material of electron transfer layer is to have higher electron mobility, effectively the organic molecule material of conduction electron.
Preferably, the material of electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2, a kind of in 4-triazole derivative and 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi).
More preferably, 1,2,4-triazole derivative is 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole (TAZ).More preferably, the material of electron transfer layer is TAZ.
Preferably, the thickness of electron transfer layer is 40～200nm.More preferably, the thickness of electron transfer layer is 180nm.
Preferably, the material of electron injecting layer is cesium carbonate (Cs
2cO
3), cesium fluoride (CsF), nitrine caesium (CsN
3) and lithium fluoride (LiF) in a kind of.More preferably, the material of the second electron injecting layer is LiF.
Preferably, the thickness of electron injecting layer is 0.5～10nm.More preferably, the thickness of electron injecting layer is 0.7nm.
Negative electrode is arranged on electron injecting layer.Negative electrode comprises metal-doped layer, phthalocyanine metal compound layer, fullerene derivate layer and the metal level stacking gradually.
The material of metal-doped layer is the composite material of a kind of ratio formation that is 0.05:1～0.2:1 according to mass ratio in cesium salt and magnesium (Mg), strontium (Sr), calcium (Ca) and ytterbium (Yb).
Magnesium, strontium, calcium or ytterbium belong to low workfunction metal, work function is-2.0eV～-3.5eV, the work function of cesium salt and low workfunction metal differs the left and right into 0.3eV, the work function of cesium salt is lower, electronics can inject cesium salt by electron injecting layer, and then injects low workfunction metal, and cesium salt has good coupling with low workfunction metal, reduced and overcome the energy that potential barrier is wanted loss, made electronic injection more effective.
Cesium salt is cesium oxide (Cs
2o), cesium carbonate (Cs
2cO
3), nitrine caesium (CsN
3) and cesium chloride (CsCl) in a kind of.
Preferably, the thickness of metal-doped layer is 10～30nm.
The material of phthalocyanine metal compound layer is phthalocyanine metal compound.
The easy crystallization of phthalocyanine metal compound layer, forms orderly crystal structure after crystallization, and makes film surface form wave structure, makes light carry out scattering, avoids, to the transmitting of device both sides, improving light extraction efficiency.
Phthalocyanine metal compound is a kind of in CuPc (CuPc), Phthalocyanine Zinc (ZnPc), phthalocyanine vanadium (VPc) and magnesium phthalocyanine (MgPc).
Preferably, the thickness of phthalocyanine metal compound layer is 100～200nm.
The material of fullerene derivate layer is a kind of in football alkene, carbon 70, [6,6]-phenyl-C61-methyl butyrate and [6,6]-phenyl-C71-methyl butyrate.
The easy film forming of fullerene derivate, can make rete roughness reduce after film forming, reduce the existence of boundary defect, prevents the generation of electron trap, and meanwhile, fullerene has good electron transport ability, can improve the transmission rate of electronics.
Preferably, the thickness of fullerene derivate layer is 1～5nm.
The material of metal level is a kind of in silver, aluminium, platinum and gold.
Use the high-work-function metals such as silver, aluminium, platinum or gold as metal level material, can improve the resistance to overturning of negative electrode, the while can effectively be improved light in the reflection of cathode terminal, makes light reflex to the bottom outgoing of device, finally improves the luminous efficiency of device.
Preferably, the thickness of metal level is 200～500nm.
Preferably, the thickness of negative electrode is 311～735nm.
Second aspect, the invention provides a kind of preparation method of organic electroluminescence device, comprises the following steps:
Clean conductive anode substrate of glass is provided;
In described conductive anode substrate of glass, thermal resistance evaporation is prepared hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer successively, and the condition of described thermal resistance evaporation is pressure 5 * 10
-5～2 * 10
-3pa, the evaporation speed of described hole injection layer and electron injecting layer is 1～10nm/s, the evaporation speed of described hole transmission layer, luminescent layer and electron transfer layer is 0.1～1nm/s;
On described electron injecting layer, thermal resistance evaporation is prepared metal-doped layer, phthalocyanine metal compound layer, fullerene derivate layer and metal level successively, obtains negative electrode; Wherein, the material of described metal-doped layer is the composite material that ratio that a kind of in cesium salt and magnesium, strontium, calcium and ytterbium is 0.05:1～0.2:1 according to mass ratio forms, and described cesium salt is a kind of in cesium oxide, cesium carbonate, nitrine caesium and cesium chloride; The material of described phthalocyanine metal compound layer is phthalocyanine metal compound, and described phthalocyanine metal compound is a kind of in CuPc, Phthalocyanine Zinc, phthalocyanine vanadium and magnesium phthalocyanine; The material of described fullerene derivate layer is football alkene, carbon 70, [6,6]-phenyl-C61-methyl butyrate and [6,6] a kind of in-phenyl-C71-methyl butyrate, the material of described metal level is a kind of in silver, aluminium, platinum and gold, described thermal resistance evaporation condition is pressure 5 * 10
-5～2 * 10
-3pa, speed 1～10nm/s;
After above step completes, obtain described organic electroluminescence device.
Preferably, conductive anode substrate of glass is a kind of in indium tin oxide glass (ITO), aluminium zinc oxide glass (AZO) and indium-zinc oxide glass (IZO).
Preferably, conductive anode substrate of glass is carried out to photoetching treatment, be then cut into needed size.
By the cleaning to conductive anode substrate of glass, remove surperficial organic pollution.
Particularly, the clean operation of conductive anode substrate of glass is: conductive anode substrate of glass is used to liquid detergent, each ultrasonic cleaning of deionized water 15min successively, remove surperficial organic pollution, obtain clean conductive anode substrate of glass.
By the method for thermal resistance evaporation, in clean conductive anode substrate of glass, evaporation arranges hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer successively.Wherein, the condition of thermal resistance evaporation is pressure 5 * 10
-5～2 * 10
-3pa, the evaporation speed of hole injection layer and electron injecting layer is 1～10nm/s, the evaporation speed of hole transmission layer, luminescent layer and electron transfer layer is 0.1～1nm/s.
Preferably, the material of hole injection layer is molybdenum trioxide (MoO
3), tungstic acid (WO
3) and vanadic oxide (V
2o
5) in a kind of.More preferably, the material of hole injection layer is MoO
3.
Preferably, the thickness of hole injection layer is 20～80nm.More preferably, the thickness of hole injection layer is 30nm.
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) and N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4, a kind of in 4'-diamines (NPB).More preferably, the material of hole transmission layer is TCTA.
Preferably, the thickness of hole transmission layer is 20～60nm.More preferably, the thickness of hole transmission layer is 40nm.
Preferably, the 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-(betanaphthyl) anthracene (ADN), 4,4 '-bis-(9-ethyl-3-carbazole vinyl)-1,1 '-biphenyl (BCzVBi) and oxine aluminium (Alq
3) in a kind of.More preferably, the material of luminescent layer is Alq
3.
Preferably, the thickness of luminescent layer is 5～40nm.More preferably, the thickness of luminescent layer is 30nm.
The material of electron transfer layer is to have higher electron mobility, effectively the organic molecule material of conduction electron.
Preferably, the material of electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2, a kind of in 4-triazole derivative and 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi).
More preferably, 1,2,4-triazole derivative is 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole (TAZ).More preferably, the material of electron transfer layer is TAZ.
Preferably, the thickness of electron transfer layer is 40～200nm.More preferably, the thickness of electron transfer layer is 180nm.
Preferably, the material of electron injecting layer is cesium carbonate (Cs
2cO
3), cesium fluoride (CsF), nitrine caesium (CsN
3) and lithium fluoride (LiF) in a kind of.More preferably, the material of the second electron injecting layer is LiF.
Preferably, the thickness of electron injecting layer is 0.5～10nm.More preferably, the thickness of electron injecting layer is 0.7nm.
Negative electrode is arranged on electron injecting layer by thermal resistance evaporation.Negative electrode comprises metal-doped layer, phthalocyanine metal compound layer, fullerene derivate layer and the metal level stacking gradually.
Metal-doped layer is arranged on electron injecting layer by the method for thermal resistance evaporation.
The material of metal-doped layer is the composite material of a kind of ratio formation that is 0.05:1～0.2:1 according to mass ratio in cesium salt and magnesium, strontium, calcium and ytterbium.
Magnesium, strontium, calcium or ytterbium belong to low workfunction metal, work function is-2.0eV～-3.5eV, the work function of cesium salt and low workfunction metal differs the left and right into 0.3eV, the work function of cesium salt is lower, electronics can inject cesium salt by electron injecting layer, and then injects low workfunction metal, and cesium salt has good coupling with low workfunction metal, reduced and overcome the energy that potential barrier is wanted loss, made electronic injection more effective.
Cesium salt is cesium oxide (Cs
2o), cesium carbonate (Cs
2cO
3), nitrine caesium (CsN
3) and cesium chloride (CsCl) in a kind of.
Preferably, the thickness of metal-doped layer is 10～30nm.
Phthalocyanine metal compound layer is arranged on metal-doped layer by the method for thermal resistance evaporation.
The easy crystallization of phthalocyanine metal compound layer, forms orderly crystal structure after crystallization, and makes film surface form wave structure, makes light carry out scattering, avoids, to the transmitting of device both sides, improving light extraction efficiency.
Phthalocyanine metal compound is a kind of in CuPc (CuPc), Phthalocyanine Zinc (ZnPc), phthalocyanine vanadium (VPc) and magnesium phthalocyanine (MgPc).
Preferably, the thickness of phthalocyanine metal compound layer is 100～200nm.
Fullerene derivate layer is arranged on phthalocyanine metal compound layer by the method for thermal resistance evaporation.
The material of fullerene derivate layer is a kind of in football alkene, carbon 70, [6,6]-phenyl-C61-methyl butyrate and [6,6]-phenyl-C71-methyl butyrate.
The easy film forming of fullerene derivate, can make rete roughness reduce after film forming, reduce the existence of boundary defect, prevents the generation of electron trap, and meanwhile, fullerene has good electron transport ability, can improve the transmission rate of electronics.
Preferably, the thickness of fullerene derivate layer is 1～5nm.
Metal level is arranged on fullerene derivate layer by the method for thermal resistance evaporation.
The material of metal level is a kind of in silver, aluminium, platinum and gold.
Use the high-work-function metals such as silver, aluminium, platinum or gold as metal level material, can improve the resistance to overturning of negative electrode, the while can effectively be improved light in the reflection of cathode terminal, makes light reflex to the bottom outgoing of device, finally improves the luminous efficiency of device.
Preferably, the thickness of metal level is 200～500nm.
Preferably, the thickness of negative electrode is 311～735nm.
The present invention has following beneficial effect:
(1) organic electroluminescence device that prepared by the present invention adopts the metal-doped layer, phthalocyanine metal compound layer, fullerene derivate layer and the metal level that stack gradually as negative electrode, electronic injection ability, the stability of device have been improved, and make luminous energy more effectively arrive at conductive anode substrate of glass, thereby improve the luminous efficiency of device;
(2) metal-doped layer formation work function is successively decreased, and has reduced and has overcome the energy that potential barrier is wanted loss, makes electronic injection more effective; Phthalocyanine crystallizing layer makes film surface form wave structure, makes light carry out scattering, avoids launching to device both sides; Fullerene derivate layer reduces rete roughness, improves the transmission rate of electronics; Metal level improves light in the reflection of cathode terminal.
(3) preparation method of the present invention is simple, be easy to control and operation, and raw material easily obtains.
Accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, to the accompanying drawing of required use in embodiment or description of the Prior Art be briefly described below, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skills, do not paying under the prerequisite of creative work, can also obtain according to these accompanying drawings other accompanying drawing.
Fig. 1 is the structure chart of the organic electroluminescence device that provides 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 current efficiency that the organic electroluminescence device that provides of the embodiment of the present invention 1 and comparative example provide.
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.
Be below specific embodiment and comparative example part, wherein, "/" represents stacked, and ": " represents the mass ratio of the former with the latter.
Embodiment 1
A preparation method for organic electroluminescence device, comprises the following steps:
(1) by ito glass liquid detergent, each ultrasonic cleaning of deionized water 15min for substrate, obtain clean conductive anode substrate of glass;
(2) in high vacuum coating system (scientific instrument development center, Shenyang Co., Ltd), pressure is 8 * 10
-5under the condition of Pa, thermal resistance evaporation hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer successively in clean conductive anode substrate of glass;
Particularly, in the present embodiment, the material of hole injection layer is MoO
3, thickness is 30nm; The material of hole transmission layer is TCTA, and thickness is 40nm; The material of luminescent layer is Alq3, and thickness is 30nm; The material of electron transfer layer is TAZ, and thickness is 180nm; The material of electron injecting layer is LiF, and thickness is 0.7nm.
Wherein, MoO
3with the evaporation speed of LiF be 3nm/s, the evaporation speed of TCTA, Alq3 and TAZ is 0.2nm/s;
(3) at pressure, be 8 * 10
-5under the condition of Pa, on electron injecting layer, prepare negative electrode, with the speed of 3nm/s successively thermal resistance evaporation, prepare metal-doped layer, phthalocyanine metal compound layer, fullerene derivate layer and metal level, finally obtain negative electrode.
Particularly, in the present embodiment, the material of metal-doped layer is Cs
2o and Mg are the composite material that 0.1:1 forms according to mass ratio, and thickness is 15nm; The material of phthalocyanine metal compound layer is CuPc, and thickness is 120nm; The material of fullerene derivate layer is PC61BM, and thickness is 2nm; The material of metal level is Ag, and thickness is 300nm.
After above step completes, obtain a kind of organic electroluminescence device, structure is specifically expressed as: ITO/MoO
3/ TCTA/Alq3/TAZ/LiF/Cs
2o:Mg(0.1:1)/CuPc/PC61BM/Ag.
Fig. 1 is the structural representation of the organic electroluminescence device of the present embodiment.As shown in Figure 1, the structure of this organic electroluminescence device comprises that the conductive anode substrate of glass 10, hole injection layer 20, hole transmission layer 30, luminescent layer 40, electron transfer layer 50, electron injecting layer 60 and the negative electrode 70(that stack gradually comprise metal-doped layer 701, phthalocyanine metal compound layer 702, fullerene derivate layer 703 and metal level 704).
Embodiment 2
A preparation method for organic electroluminescence device, comprises the following steps:
(1) by AZO liquid detergent, each ultrasonic cleaning of deionized water 15min for substrate of glass, obtain clean conductive anode substrate of glass;
(2) in high vacuum coating system (scientific instrument development center, Shenyang Co., Ltd), pressure is 2 * 10
-3under the condition of Pa, thermal resistance evaporation hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer successively in clean conductive anode substrate of glass;
Particularly, in the present embodiment, 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 Bphen, and thickness is 200nm; The material of electron injecting layer is CsF, and thickness is 10nm.
Wherein, WO
3with the evaporation speed of CsF be 10nm/s, the evaporation speed of TCTA, ADN and Bphen is 0.1nm/s;
(3) at pressure, be 2 * 10
-3under the condition of Pa, on electron injecting layer, prepare negative electrode, with the speed of 10nm/s successively thermal resistance evaporation, prepare metal-doped layer, phthalocyanine metal compound layer, fullerene derivate layer and metal level, finally obtain negative electrode.
Particularly, in the present embodiment, the material of metal-doped layer is Cs
2cO
3according to mass ratio, be the composite material of 0.05:1 formation with Sr, thickness is 10nm; The material of phthalocyanine metal compound layer is ZnPc, and thickness is 100nm; The material of fullerene derivate layer is C60, and thickness is 1nm; The material of metal level is Al, and thickness is 200nm.
After above step completes, obtain a kind of organic electroluminescence device, structure is specifically expressed as: AZO/WO
3/ TCTA/ADN/Bphen/CsF/Cs
2cO
3: Sr(0.05:1)/ZnPc/C60/Al.
Embodiment 3
A preparation method for organic electroluminescence device, comprises the following steps:
(1) by IZO liquid detergent, each ultrasonic cleaning of deionized water 15min for substrate of glass, obtain clean conductive anode substrate of glass;
(2) in high vacuum coating system (scientific instrument development center, Shenyang Co., Ltd), pressure is 5 * 10
-5under the condition of Pa, thermal resistance evaporation hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer successively in clean conductive anode substrate of glass;
Particularly, in the present embodiment, the material of hole injection layer is V
2o
5, thickness is 20nm; The material of hole transmission layer is TAPC, and thickness is 30nm; The material of luminescent layer is BCzVBi, and thickness is 40nm; The material of electron transfer layer is TAZ, and thickness is 60nm; The material of electron injecting layer is Cs
2cO
3, thickness is 0.5nm.
Wherein, V
2o
5and Cs
2cO
3evaporation speed be 1nm/s, the evaporation speed of TAPC, BCzVBi and TAZ is 1nm/s;
(3) at pressure, be 5 * 10
-5under the condition of Pa, on electron injecting layer, prepare negative electrode, with the speed of 1nm/s successively thermal resistance evaporation, prepare metal-doped layer, phthalocyanine metal compound layer, fullerene derivate layer and metal level, finally obtain negative electrode.
Particularly, in the present embodiment, the material of metal-doped layer is CsN
3according to mass ratio, be the composite material of 0.2:1 formation with Ca, thickness is 30nm; The material of phthalocyanine metal compound layer is VPc, and thickness is 200nm; The material of fullerene derivate layer is C70, and thickness is 5nm; The material of metal level is Pt, and thickness is 500nm.
After above step completes, obtain a kind of organic electroluminescence device, structure is specifically expressed as: IZO/V
2o
5/ TAPC/BCzVBi/TAZ/Cs
2cO
3/ CsN
3: Ca(0.2:1)/VPc/C70/Pt.
Embodiment 4
A preparation method for organic electroluminescence device, comprises the following steps:
(1) by IZO liquid detergent, each ultrasonic cleaning of deionized water 15min for substrate of glass, obtain clean conductive anode substrate of glass;
(2) in high vacuum coating system (scientific instrument development center, Shenyang Co., Ltd), pressure is 5 * 10
-4under the condition of Pa, thermal resistance evaporation hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer successively in clean conductive anode substrate of glass;
Particularly, in the present embodiment, the material of hole injection layer is MoO
3, thickness is 30nm; The material of hole transmission layer is NPB, and thickness is 20nm; 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 CsN
3, thickness is 1nm.
Wherein, MoO
3and CsN
3evaporation speed be 5nm/s, the evaporation speed of NPB, DCJTB and TPBi is 0.2nm/s;
(3) at pressure, be 5 * 10
-4under the condition of Pa, on electron injecting layer, prepare negative electrode, with the speed of 5nm/s successively thermal resistance evaporation, prepare metal-doped layer, phthalocyanine metal compound layer, fullerene derivate layer and metal level, finally obtain negative electrode.
Particularly, in the present embodiment, the material of metal-doped layer is that CsCl and Yb are the composite material that 0.1:1 forms according to mass ratio, and thickness is 25nm; The material of phthalocyanine metal compound layer is MgPc, and thickness is 180nm; The material of fullerene derivate layer is PC71BM, and thickness is 3nm; The material of metal level is Au, and thickness is 350nm.
After above step completes, obtain a kind of organic electroluminescence device, structure is specifically expressed as: IZO/MoO
3/ NPB/DCJTB/TPBi/CsN
3/ CsCl:Yb(0.1:1)/MgPc/PC71BM/Au.
Comparative example
A preparation method for organic electroluminescence device, comprises the following steps:
(1) by ito glass liquid detergent, each ultrasonic cleaning of deionized water 15min for substrate, obtain clean conductive anode substrate of glass;
(2) in high vacuum coating system (scientific instrument development center, Shenyang Co., Ltd), pressure is 8 * 10
-5under the condition of Pa, thermal resistance evaporation hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer successively in clean conductive anode substrate of glass; Thermal resistance evaporation negative electrode on electron injecting layer;
Particularly, in the present embodiment, the material of hole injection layer is MoO
3, thickness is 30nm; The material of hole transmission layer is TCTA, and thickness is 40nm; The material of luminescent layer is Alq3, and thickness is 30nm; The material of electron transfer layer is TAZ, and thickness is 180nm; The material of electron injecting layer is LiF, and thickness is 0.7nm; The material of negative electrode is Ag, and thickness is 300nm.
Wherein, MoO
3, LiF and Ag evaporation speed be 3nm/s, the evaporation speed of TCTA, Alq3 and TAZ is 0.2nm/s;
After above step completes, obtain a kind of organic electroluminescence device, structure is specifically expressed as: ITO/MoO
3/ TCTA/Alq3/TAZ/LiF/Ag.
Utilize the Keithley2400 test electric property of U.S. Keithley company, colorimeter (Japanese Konica Minolta company, model: CS-100A) test brightness and colourity, fiber spectrometer (U.S. marine optics company, model: USB4000) testing electroluminescent spectrum.
Fig. 2 is the organic electroluminescence device of embodiment 1 and the current density of the organic electroluminescence device of comparative example and the graph of a relation of current efficiency.Wherein, curve 1 is the current density of organic electroluminescence device and the graph of a relation of current efficiency of embodiment 1; The current density of organic electroluminescence device and the graph of a relation of current efficiency that curve 2 provides for comparative example.
As can see from Figure 2, under different current densities, the current efficiency of embodiment 1 is large than comparative example all, the maximum current efficiency of embodiment 1 is 8.76cd/A, and that comparative example is only 5.75cd/A, this explanation, negative electrode has reduced and has overcome the energy that potential barrier is wanted loss, makes electronic injection more effective, makes film surface form wave structure, make light carry out scattering, avoid, to the transmitting of device both sides, reducing the existence of boundary defect, improve the transmission rate of electronics, improve light in the reflection of cathode terminal, effectively improve luminous efficiency.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any modifications of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.
Claims (6)
1. an organic electroluminescence device, it is characterized in that, comprise the conductive anode substrate of glass, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the negative electrode that stack gradually, described negative electrode comprises metal-doped layer, phthalocyanine metal compound layer, fullerene derivate layer and the metal level stacking gradually; The material of described metal-doped layer is the composite material that ratio that a kind of in cesium salt and magnesium, strontium, calcium and ytterbium is 0.05:1～0.2:1 according to mass ratio forms, and described cesium salt is a kind of in cesium oxide, cesium carbonate, nitrine caesium and cesium chloride; The material of described phthalocyanine metal compound layer is phthalocyanine metal compound, and described phthalocyanine metal compound is a kind of in CuPc, Phthalocyanine Zinc, phthalocyanine vanadium and magnesium phthalocyanine; The material of described fullerene derivate layer is a kind of in football alkene, carbon 70, [6,6]-phenyl-C61-methyl butyrate and [6,6]-phenyl-C71-methyl butyrate, and the material of described metal level is a kind of in silver, aluminium, platinum and gold.
2. organic electroluminescence device as claimed in claim 1, is characterized in that, described conductive anode substrate of glass is a kind of in indium tin oxide glass, aluminium zinc oxide glass and indium-zinc oxide glass.
3. organic electroluminescence device as claimed in claim 1, is characterized in that, the material of described hole injection layer is a kind of in molybdenum trioxide, tungstic acid and vanadic oxide; The material of hole transmission layer is 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane, 4,4', 4''-tri-(carbazole-9-yl) triphenylamine and N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4, a kind of in 4'-diamines; The 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, 9,10-bis-(betanaphthyl) anthracene, 4,4 '-bis-(9-ethyl-3-carbazole vinyl)-1, a kind of in 1 '-biphenyl and oxine aluminium; The material of electron transfer layer is 4,7-diphenyl-1,10-phenanthroline, 1,2, a kind of in 4-triazole derivative and 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene; The material of electron injecting layer is a kind of in cesium carbonate, cesium fluoride, nitrine caesium and lithium fluoride.
4. a preparation method for organic electroluminescence device, is characterized in that, comprises the following steps:
Clean conductive anode substrate of glass is provided;
In described conductive anode substrate of glass, thermal resistance evaporation is prepared hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer successively, and the condition of described thermal resistance evaporation is pressure 5 * 10
-5～2 * 10
-3pa, the evaporation speed of described hole injection layer and electron injecting layer is 1～10nm/s, the evaporation speed of described hole transmission layer, luminescent layer and electron transfer layer is 0.1～1nm/s;
On described electron injecting layer, thermal resistance evaporation is prepared metal-doped layer, phthalocyanine metal compound layer, fullerene derivate layer and metal level successively, obtains negative electrode; Wherein, the material of described metal-doped layer is the composite material that ratio that a kind of in cesium salt and magnesium, strontium, calcium and ytterbium is 0.05:1～0.2:1 according to mass ratio forms, and described cesium salt is a kind of in cesium oxide, cesium carbonate, nitrine caesium and cesium chloride; The material of described phthalocyanine metal compound layer is phthalocyanine metal compound, and described phthalocyanine metal compound is a kind of in CuPc, Phthalocyanine Zinc, phthalocyanine vanadium and magnesium phthalocyanine; The material of described fullerene derivate layer is football alkene, carbon 70, [6,6]-phenyl-C61-methyl butyrate and [6,6] a kind of in-phenyl-C71-methyl butyrate, the material of described metal level is a kind of in silver, aluminium, platinum and gold, described thermal resistance evaporation condition is pressure 5 * 10
-5～2 * 10
-3pa, speed 1～10nm/s;
After above step completes, obtain described organic electroluminescence device.
5. the preparation method of organic electroluminescence device as claimed in claim 4, is characterized in that, described conductive anode substrate of glass is a kind of in indium tin oxide glass, aluminium zinc oxide glass and indium-zinc oxide glass.
6. the preparation method of organic electroluminescence device as claimed in claim 4, is characterized in that, the material of described hole injection layer is a kind of in molybdenum trioxide, tungstic acid and vanadic oxide; The material of hole transmission layer is 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane, 4,4', 4''-tri-(carbazole-9-yl) triphenylamine and N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4, a kind of in 4'-diamines; The 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, 9,10-bis-(betanaphthyl) anthracene, 4,4 '-bis-(9-ethyl-3-carbazole vinyl)-1, a kind of in 1 '-biphenyl and oxine aluminium; The material of electron transfer layer is 4,7-diphenyl-1,10-phenanthroline, 1,2, a kind of in 4-triazole derivative and 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene; The material of electron injecting layer is a kind of in cesium carbonate, cesium fluoride, nitrine caesium and lithium fluoride.
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| US20070159080A1 (en) * | 2002-11-22 | 2007-07-12 | Luxell Technologies, Inc. | Transparent-cathode for top-emission organic light-emitting diodes |
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