CN104124361A - Organic light-emitting device and preparation method thereof - Google Patents
Organic light-emitting device and preparation method thereof Download PDFInfo
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- CN104124361A CN104124361A CN201310143932.7A CN201310143932A CN104124361A CN 104124361 A CN104124361 A CN 104124361A CN 201310143932 A CN201310143932 A CN 201310143932A CN 104124361 A CN104124361 A CN 104124361A
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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
- H10K50/805—Electrodes
- H10K50/82—Cathodes
- H10K50/826—Multilayers, e.g. opaque multilayers
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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
Abstract
The invention provides an organic light-emitting device and a preparation method thereof. A conductive anode substrate, a fullerene derivative layer, and a bipolar metallic oxide layer are successively laminated and are used as the cathode. Therefore, the light emitting efficiency of the device can be improved and the stability of the device can be enhanced, so that the light can reach the conductive anode glass substrate effectively and thus the luminous efficiency of the device is improved. According to the invention, the preparation method is simple and is easy to control and operate; and the raw material is easy to access.
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 conductive oxide layer, fullerene derivate layer and the bipolarity metal oxide layer stacking gradually; The material of described conductive oxide layer is a kind of in indium tin oxide, aluminium zinc oxide and indium-zinc oxide, the material of described fullerene derivate layer is football alkene (C60), carbon 70(C70), [6,6]-phenyl-C61-methyl butyrate (P61BM) and [6,6] a kind of in-phenyl-C71-methyl butyrate (P71BM), the material of described bipolarity metal oxide layer is a kind of in molybdenum trioxide, tungstic acid and vanadic oxide.
Preferably, conductive anode substrate of glass is a kind of in indium tin oxide glass, aluminium zinc oxide glass and indium-zinc oxide glass.
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 NPB.
Preferably, the thickness of hole transmission layer is 20～60nm.More preferably, the thickness of hole transmission layer is 50nm.
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 20nm.
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 50nm.
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 1nm.
Negative electrode is arranged on electron injecting layer.Negative electrode comprises conductive oxide layer, fullerene derivate layer and the bipolarity metal oxide layer stacking gradually.
The material of conductive oxide layer is a kind of in indium tin oxide (ITO), aluminium zinc oxide (AZO) and indium-zinc oxide (IZO).
Preferably, the thickness of conductive oxide layer is 50～150nm.
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.
On electron injecting layer, prepare the conductive oxide layer that one deck consists of conductive oxide, can improve conductivity and the electron concentration of device, thereby improve exciton recombination probability.Segment marshalling after fullerene derivate crystallization, film surface forms wave structure, change direction of light, make the light scattering of Vertical Launch, thereby can not be coupled with the free electron of metal level, the loss of avoiding parallel free electron to produce with vertical photon coupling, improves photon utilance.Meanwhile, fullerene is electron rich material, can further improve electron concentration.
Preferably, the thickness of fullerene derivate layer is 20～100nm.
The material of bipolarity metal oxide layer is a kind of in molybdenum trioxide, tungstic acid and vanadic oxide.
Bipolarity metal oxide layer is arranged on fullerene derivate layer, bipolarity metal oxide reflects light, make light get back to device bottom outgoing, effectively improved the luminous efficiency of device, simultaneously, bipolarity metal oxide has good stability, can further improve the stability of device.
Preferably, the thickness of bipolarity metal oxide layer is 50～200nm.
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, prepare negative electrode, described negative electrode comprises conductive oxide layer, fullerene derivate layer and the bipolarity metal oxide layer stacking gradually, wherein:
Described conductive oxide layer is prepared by magnetically controlled sputter method, the material of described conductive oxide layer is a kind of in indium tin oxide, aluminium zinc oxide and indium-zinc oxide, the condition of described magnetron sputtering is accelerating voltage 300～800V, magnetic field 50～200G, power density 1～40W/cm
2;
Described fullerene derivate layer is prepared by spin coating, concrete operations are by football alkene, carbon 70, [6,6]-phenyl-C61-methyl butyrate and [6,6] a kind of in-phenyl-C71-methyl butyrate is dissolved in and in organic solvent, obtains the first solution, described the first solution is spin-coated in described conductive oxide layer, and condition is rotating speed 2000～8000rpm, time 10～30s, after spin coating, under 50～300 ° of C, toast 10～30min, obtain described fullerene derivate layer;
Described bipolarity metal oxide layer is prepared by spin coating, concrete operations are by a kind of being dissolved in ammoniacal liquor in molybdenum trioxide, tungstic acid and vanadic oxide, obtain the second solution, described the second solution is spin-coated on described fullerene derivate layer, condition is rotating speed 4000～8000rpm, time 10～30s toasts 10～30min after spin coating under 100～200 ° of C, obtains described bipolarity metal oxide layer;
After above step completes, obtain described organic electroluminescence device.
Preferably, conductive anode substrate of glass is a kind of in indium tin oxide glass, aluminium zinc oxide glass and indium-zinc oxide glass.
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 described 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 NPB.
Preferably, the thickness of hole transmission layer is 20～60nm.More preferably, the thickness of hole transmission layer is 50nm.
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 20nm.
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 50nm.
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 1nm.
Negative electrode is arranged on electron injecting layer.Negative electrode comprises conductive oxide layer, fullerene derivate layer and the bipolarity metal oxide layer stacking gradually.
Conductive oxide layer is arranged on electron injecting layer by magnetically controlled sputter method.
The material of conductive oxide layer is a kind of in indium tin oxide (ITO), aluminium zinc oxide (AZO) and indium-zinc oxide (IZO).
The condition of magnetron sputtering is accelerating voltage 300～800V, magnetic field 50～200G, power density 1～40W/cm
2.
Preferably, the thickness of conductive oxide layer is 50～150nm.
Fullerene derivate layer is prepared and is arranged in conductive oxide layer by spin coating, concrete operations are by football alkene, carbon 70, [6,6]-phenyl-C61-methyl butyrate and [6,6] a kind of in-phenyl-C71-methyl butyrate is dissolved in and in organic solvent, obtains the first solution, the first solution is spin-coated in described conductive oxide layer, and condition is rotating speed 2000～8000rpm, time 10～30s, after spin coating, under 50～300 ° of C, toast 10～30min, obtain fullerene derivate layer.
Preferably, organic solvent is a kind of in chlorobenzene, toluene, paraxylene and chloroform.
Preferably, the mass concentration of the first solution is 8～20mg/mL.
On electron injecting layer, prepare the conductive oxide layer that one deck consists of conductive oxide, can improve conductivity and the electron concentration of device, thereby improve exciton recombination probability.Fullerene derivate is dissolved in organic solvent, slowly crystallization after spin coating, spin coating method is simply controlled, can control preferably thickness, and wait reprocessing can control crystallization degree by baking, segment marshalling after fullerene derivate crystallization, film surface forms wave structure, change direction of light, make the light scattering of Vertical Launch, thereby can not be coupled with the free electron of metal level, the loss of avoiding parallel free electron to produce with vertical photon coupling, improves photon utilance.Meanwhile, fullerene is electron rich material, can further improve electron concentration.
Preferably, the thickness of fullerene derivate layer is 20～100nm.
Bipolarity metal oxide layer is arranged on fullerene derivate layer by the method for thermal resistance evaporation.
Bipolarity metal oxide layer is prepared by spin coating, concrete operations are by a kind of being dissolved in ammoniacal liquor in molybdenum trioxide, tungstic acid and vanadic oxide, obtain the second solution, the second solution is spin-coated on fullerene derivate layer, condition is rotating speed 4000～8000rpm, time 10～30s toasts 10～30min after spin coating under 100～200 ° of C, obtains described bipolarity metal oxide layer.
Preferably, the mass concentration of the second solution is 5～30mg/mL.
Method by bipolarity metal oxide by spin coating is arranged on fullerene derivate layer, can be connected with fullerene derivate layer closely, bipolarity metal oxide reflects light, make light get back to device bottom outgoing, effectively improved the luminous efficiency of device, meanwhile, bipolarity metal oxide has good stability, can further improve the stability of device.
Preferably, the thickness of bipolarity metal oxide layer is 50～200nm.
The present invention has following beneficial effect:
(1) organic electroluminescence device that prepared by the present invention adopts the conductive oxide layer, fullerene derivate layer and the bipolarity metal oxide layer that stack gradually as negative electrode, improved the stability of device, and make luminous energy more effectively arrive at conductive anode substrate of glass, thereby improve the luminous efficiency of device.
(2) conductive oxide layer improves conductivity and the electron concentration of device, thereby improves exciton recombination probability; Segment marshalling after fullerene derivate crystallization, film surface forms wave structure, changes direction of light, makes the light scattering of Vertical Launch, improves photon utilance; Bipolarity metal oxide reflects light, makes light get back to device bottom outgoing, has effectively improved the luminous efficiency of device.
(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 luminous 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.
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 NPB, and thickness is 50nm; The material of luminescent layer is Alq3, and thickness is 20nm; The material of electron transfer layer is TAZ, and thickness is 50nm; The material of electron injecting layer is LiF, and thickness is 1nm;
Wherein, MoO
3with the evaporation speed of LiF be 3nm/s, the evaporation speed of NPB, 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:
First magnetron sputtering is prepared conductive oxide layer, and the material of conductive oxide layer is ITO, and thickness is 100nm, and magnetron sputtering condition is accelerating voltage 500V, magnetic field 150G, power density 10W/cm
2;
Fullerene derivate layer is prepared in spin coating again, concrete operations are for to be dissolved in P71BM in chlorobenzene, obtaining mass concentration is the first solution of 16mg/mL, this first solution is spin-coated in conductive oxide layer, condition is rotating speed 4000rpm, and time 15s toasts 20min after spin coating under 250 ° of C, obtain fullerene derivate layer, thickness is 60nm;
Finally, bipolarity metal oxide layer is prepared in spin coating, and concrete operations are by MoO
3be dissolved in ammoniacal liquor, obtaining mass concentration is the second solution of 20mg/mL, and this second solution is spin-coated on fullerene derivate layer, condition is rotating speed 6000rpm, and time 15s toasts 20min after spin coating under 150 ° of C, obtain bipolarity metal oxide layer, thickness is 180nm;
After above step completes, obtain a kind of organic electroluminescence device, structure is specifically expressed as: ITO/MoO
3/ NPB/Alq3/TAZ/LiF/ITO/P71BM/MoO
3.
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 conductive oxide layer 701, fullerene derivate layer 702, bipolarity metal oxide layer 703).
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 MoO
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 CsF, and thickness is 10nm;
Wherein, MoO
3with the evaporation speed of CsF be 10nm/s, the evaporation speed of TCTA, ADN and TAZ is 0.1nm/s;
(3) at pressure, be 2 * 10
-3under the condition of Pa, on electron injecting layer, prepare negative electrode:
First magnetron sputtering is prepared conductive oxide layer, and the material of conductive oxide layer is IZO, and thickness is 150nm, and magnetron sputtering condition is accelerating voltage 800V, magnetic field 50G, power density 40W/cm
2;
Fullerene derivate layer is prepared in spin coating again, concrete operations are for to be dissolved in C60 in toluene, obtaining mass concentration is the first solution of 20mg/mL, this first solution is spin-coated in conductive oxide layer, condition is rotating speed 2000rpm, and time 10s toasts 10min after spin coating under 300 ° of C, obtain fullerene derivate layer, thickness is 100nm;
Finally, bipolarity metal oxide layer is prepared in spin coating, and concrete operations are by WO
3be dissolved in ammoniacal liquor, obtaining mass concentration is the second solution of 5mg/mL, and this second solution is spin-coated on fullerene derivate layer, condition is rotating speed 8000rpm, and time 30s toasts 30min after spin coating under 100 ° of C, obtain bipolarity metal oxide layer, thickness is 50nm;
After above step completes, obtain a kind of organic electroluminescence device, structure is specifically expressed as: AZO/MoO
3/ TCTA/ADN/TAZ/CsF/IZO/C60/WO
3.
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 TCTA, and thickness is 30nm; The material of luminescent layer is BCzVBi, and thickness is 40nm; The material of electron transfer layer is TPBi, 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 TCTA, BCzVBi and TPBi is 1nm/s;
(3) at pressure, be 5 * 10
-5under the condition of Pa, on electron injecting layer, prepare negative electrode:
First magnetron sputtering is prepared conductive oxide layer, and the material of conductive oxide layer is AZO, and thickness is 50nm, and magnetron sputtering condition is accelerating voltage 300V, magnetic field 200G, power density 1W/cm
2;
Fullerene derivate layer is prepared in spin coating again, concrete operations are for to be dissolved in C70 in paraxylene, obtaining mass concentration is the first solution of 8mg/mL, this first solution is spin-coated in conductive oxide layer, condition is rotating speed 8000rpm, and time 30s toasts 30min after spin coating under 50 ° of C, obtain fullerene derivate layer, thickness is 20nm;
Finally, bipolarity metal oxide layer is prepared in spin coating, and concrete operations are by V
2o
5be dissolved in ammoniacal liquor, obtaining mass concentration is the second solution of 30mg/mL, and this second solution is spin-coated on fullerene derivate layer, condition is rotating speed 4000rpm, and time 10s toasts 10min after spin coating under 200 ° of C, obtain bipolarity metal oxide layer, thickness is 200nm;
After above step completes, obtain a kind of organic electroluminescence device, structure is specifically expressed as: IZO/V
2o
5/ TCTA/BCzVBi/TPBi/Cs
2cO
3/ AZO/C70/V
2o
5.
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 WO
3, thickness is 30nm; The material of hole transmission layer is TAPC, and thickness is 20nm; The material of luminescent layer is DCJTB, and thickness is 5nm; The material of electron transfer layer is Bphen, and thickness is 40nm; The material of electron injecting layer is CsN
3, thickness is 1nm;
Wherein, WO
3and CsN
3evaporation speed be 5nm/s, the evaporation speed of TAPC, DCJTB and Bphen is 0.2nm/s;
(3) at pressure, be 5 * 10
-4under the condition of Pa, on electron injecting layer, prepare negative electrode:
First magnetron sputtering is prepared conductive oxide layer, and the material of conductive oxide layer is AZO, and thickness is 120nm, and magnetron sputtering condition is accelerating voltage 600V, magnetic field 70G, power density 15W/cm
2;
Fullerene derivate layer is prepared in spin coating again, concrete operations are for to be dissolved in PC61BM in chloroform, obtaining mass concentration is the first solution of 15mg/mL, this first solution is spin-coated in conductive oxide layer, condition is rotating speed 3000rpm, and time 25s toasts 15min after spin coating under 150 ° of C, obtain fullerene derivate layer, thickness is 70nm;
Finally, bipolarity metal oxide layer is prepared in spin coating, and concrete operations are by MoO
3be dissolved in ammoniacal liquor, obtaining mass concentration is the second solution of 10mg/mL, and this second solution is spin-coated on fullerene derivate layer, condition is rotating speed 5000rpm, and time 20s toasts 20min after spin coating under 120 ° of C, obtain bipolarity metal oxide layer, thickness is 80nm;
After above step completes, obtain a kind of organic electroluminescence device, structure is specifically expressed as: IZO/WO
3/ TAPC/DCJTB/Bphen/CsN
3/ AZO/PC61BM/MoO
3.
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, electron injecting layer and negative electrode successively in clean conductive anode substrate of glass;
Particularly, in the present embodiment, the material of hole injection layer is MoO
3, thickness is 40nm; The material of hole transmission layer is TCTA, and thickness is 50nm; The material of luminescent layer is Alq3, and thickness is 20nm; The material of electron transfer layer is TAZ, and thickness is 200nm; The material of electron injecting layer is LiF, and thickness is 0.7nm; The material of negative electrode is Ag, and thickness is 150;
Wherein, MoO
3, LiF and Ag evaporation speed be 3nm/s, the evaporation speed of NPB, 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 luminous efficiency.Wherein, curve 1 is the current density of organic electroluminescence device and the graph of a relation of luminous efficiency of embodiment 1; The current density of organic electroluminescence device and the graph of a relation of luminous efficiency that curve 2 provides for comparative example.
As can see from Figure 2, under different current densities, the luminous efficiency of embodiment 1 is large than comparative example all, the maximum luminous efficiency of embodiment 1 is 9.14lm/W, and that comparative example is only 7.31lm/W, meanwhile, along with the raising of current density, the luminous efficiency decay of embodiment 1 is slower, this explanation, negative electrode prepared by the present invention has improved electron concentration and the photon utilance of device, and light is reflected, make light get back to device bottom outgoing, effectively improved the luminous efficiency of device.
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 (9)
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 conductive oxide layer, fullerene derivate layer and the bipolarity metal oxide layer stacking gradually; The material of described conductive oxide layer is a kind of in indium tin oxide, aluminium zinc oxide and indium-zinc oxide, 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 bipolarity metal oxide layer is a kind of in molybdenum trioxide, tungstic acid and vanadic oxide.
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, prepare negative electrode, described negative electrode comprises conductive oxide layer, fullerene derivate layer and the bipolarity metal oxide layer stacking gradually, wherein:
Described conductive oxide layer is prepared by magnetically controlled sputter method, the material of described conductive oxide layer is a kind of in indium tin oxide, aluminium zinc oxide and indium-zinc oxide, the condition of described magnetron sputtering is accelerating voltage 300～800V, magnetic field 50～200G, power density 1～40W/cm
2;
Described fullerene derivate layer is prepared by spin coating, concrete operations are by football alkene, carbon 70, [6,6]-phenyl-C61-methyl butyrate and [6,6] a kind of in-phenyl-C71-methyl butyrate is dissolved in and in organic solvent, obtains the first solution, described the first solution is spin-coated in described conductive oxide layer, and condition is rotating speed 2000～8000rpm, time 10～30s, after spin coating, under 50～300 ° of C, toast 10～30min, obtain described fullerene derivate layer;
Described bipolarity metal oxide layer is prepared by spin coating, concrete operations are by a kind of being dissolved in ammoniacal liquor in molybdenum trioxide, tungstic acid and vanadic oxide, obtain the second solution, described the second solution is spin-coated on described fullerene derivate layer, condition is rotating speed 4000～8000rpm, time 10～30s toasts 10～30min after spin coating under 100～200 ° of C, obtains described bipolarity metal oxide layer;
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, described organic solvent is a kind of in chlorobenzene, toluene, paraxylene and chloroform.
7. the preparation method of organic electroluminescence device as claimed in claim 4, is characterized in that, the mass concentration of described the first solution is 8～20mg/mL.
8. the preparation method of organic electroluminescence device as claimed in claim 4, is characterized in that, the mass concentration of described the second solution is 5～30mg/mL.
9. 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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