CN104124340A - Organic light-emitting device and preparation method thereof - Google Patents
Organic light-emitting device and preparation method thereof Download PDFInfo
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- CN104124340A CN104124340A CN201310143873.3A CN201310143873A CN104124340A CN 104124340 A CN104124340 A CN 104124340A CN 201310143873 A CN201310143873 A CN 201310143873A CN 104124340 A CN104124340 A CN 104124340A
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- H10K50/00—Organic light-emitting devices
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- H—ELECTRICITY
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- H10K50/00—Organic light-emitting devices
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- H10K50/854—Arrangements for extracting light from the devices comprising scattering means
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- H—ELECTRICITY
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- H10K50/00—Organic light-emitting devices
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- 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 comprising a conductive anode substrate, a hole injection layer, a hole transport layer, a luminescent layer, an electron transport layer, an electron injection layer and a composite cathode layer. The above-mentioned layers are successively laminated. The composite electrode includes a first doping layer, a metal layer, and a second doping layer, wherein the layers are successively laminated. The first doping layer is made of a mixing material formed by a metallic oxide and a metal material with the work function of -2.0eV to -3.5eV, wherein the metallic oxide can be titanium dioxide, zinc oxide, magnesium oxide or zirconium oxide; the metal layer is made of silver, aluminum, platinum or gold; and the second doping material is made of a mixing material formed by metal sulfide and the metal material, wherein the metal sulfide can be zinc sulfide, cadmium sulfide, magnesium sulfide or copper sulphide. Because of the composite cathode layer, the light can be scattered and then be emitted to the bottom of the device, thereby improving the luminous efficiency of the device. In addition, the invention also provides a preparation method of 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 Eastman Kodak company of the U.S. 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 in 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 entirety 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, improve 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, metal level and the second doped layer that lamination arranges successively
The material of described the first doped layer is that metal oxide and work function are-composite material that the metal material of 2.0eV～-3.5eV is mixed to form, and described metal oxide is titanium dioxide (TiO
2), zinc oxide (ZnO), magnesium oxide (MgO) or zirconia (ZrO
2); The material of described metal level is silver (Ag), aluminium (Al), platinum (Pt) or gold (Au); The material of described the second doped layer is that metal sulfide and work function are-composite material that the metal material of 2.0eV～-3.5eV is mixed to form, and described metal sulfide is zinc sulphide (ZnS), cadmium sulfide (CdS), magnesium sulfide (MgS) or copper sulfide (CuS).
Preferably, described work function be-metal material of 2.0eV～-3.5eV is magnesium (Mg), calcium (Ca), ytterbium (Yb) or strontium (Sr).
Preferably, in described the first doped layer, the mass ratio of described metal oxide and metal material is 1:0.2～1.
Preferably, in described the second doped layer, the mass ratio of described metal sulfide and metal material is 1:1～10.
Preferably, the thickness of described the first doped layer is 20～60nm, and the thickness of described metal level is 5～20nm, and the thickness of described the second doped layer is 100～300nm.
Composite cathode layer comprises the first doped layer, metal level and the second doped layer that lamination arranges successively.On electron injecting layer, prepare the first doped layer, be made up of low workfunction metal material and metal oxide, low workfunction metal work function is lower, be conducive to improve the injection of electronics, reduce the injection barrier of electronics, avoid energy loss, metal oxide refractive index is 2.0～2.4, be white or canescence material, specific area is larger, and aperture is larger, can play the effect of scattering, make to get back to Road to the light scattering of both sides transmitting, improve light extraction efficiency; Then prepare metal level, metal can improve the conductivity of device, and meanwhile, metal exists a large amount of free electrons, can improve electron concentration, is conducive to improve exciton recombination probability; Prepare again the second doped layer, formed by low workfunction metal material and metal sulfide, low workfunction metal is conducive to the injection of electronics, metal sulfide reflects light, improve the reflection efficiency of negative electrode, avoid light from top outgoing, this composite cathode layer finally can effectively improve the luminous efficiency of device.
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 tungstic acid, and 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 20nm.
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 1,2,4-triazole derivative, and thickness is 120nm.
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 on described electron injecting layer, prepare the first doped layer by the mode of electron beam evaporation plating, on described the first doped layer, prepare successively metal level and the second doped layer by the mode of vacuum evaporation again, obtain organic electroluminescence device;
The material of described the first doped layer is that metal oxide and work function are-composite material that the metal material of 2.0eV～-3.5eV is mixed to form, and described metal oxide is titanium dioxide, zinc oxide, magnesium oxide or zirconia; The material of described metal level is silver, aluminium, platinum or gold; The material of described the second doped layer is that metal sulfide and work function are-composite material that the metal material of 2.0eV～-3.5eV is mixed to form, and described metal sulfide is zinc sulphide, cadmium sulfide, magnesium sulfide or copper sulfide;
The energy density of described electron beam evaporation plating is 10～l00W/cm
2, in described vacuum evaporation process, vacuum degree is 2 × 10
-3～5 × 10
-5pa, the material evaporation speed of described the first doped layer, metal level and the second doped layer is 1～10nm/s.
Preferably, described work function be-metal material of 2.0eV～-3.5eV is magnesium, calcium, ytterbium or strontium.
Preferably, in described the first doped layer, the mass ratio of described metal oxide and metal material is 1:0.2～1.
Preferably, in described the second doped layer, the mass ratio of described metal sulfide and metal material is 1:1～10.
Preferably, the thickness of described the first doped layer is 20～60nm, and the thickness of described metal level is 5～20nm, and the thickness of described the second doped layer is 100～300nm.
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, the 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 DEG C, 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 molybdenum trioxide, and thickness 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) 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 oxine aluminium (Alq
3), thickness is 10nm.
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 1,2,4-triazole derivative, and thickness is 120nm.
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, metal level and the second doped layer that lamination arranges successively, the first doped layer is made up of low workfunction metal material and metal oxide, low workfunction metal is conducive to improve the injection of electronics, reduce the injection barrier of electronics, avoid energy loss, metal oxide specific area is larger, aperture is larger, can play the effect of scattering, make to get back to Road to the light scattering of both sides transmitting, improve light extraction efficiency; Metal level can improve the conductivity of device, improves exciton recombination probability; The second doped layer is made up of low workfunction metal material and metal sulfide, and low workfunction metal is conducive to the injection of electronics, and metal sulfide reflects light, can improve the reflection efficiency of negative electrode, avoids light from top outgoing;
(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.
Brief description of the drawings
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 embodiment 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, instead of whole embodiment.Based on the embodiment in the present invention, those of ordinary skill in the art, 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 DEG C, 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 NPB, and thickness is 50nm; The material of luminescent layer is Alq
3, light emitting layer thickness is 10nm; The material of electron transfer layer is TAZ, and thickness is 120nm; 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, metal level and the second doped layer that stack 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 35nm on electron injecting layer, material is Mg and TiO
2the composite material being mixed to form, is expressed as (Mg:TiO
2), Mg and TiO
2mass ratio be 0.5:1, the energy density of electron beam evaporation plating is 50W/cm
2, evaporation speed is 3nm/s; Adopt the mode of vacuum evaporation on the first doped layer, to prepare the metal level that a layer thickness is 15nm, material is Ag again, and evaporation speed is 3nm/s; Finally on metal level, the second doped layer that a layer thickness is 150nm is prepared in vacuum evaporation, material is the composite material that Mg and ZnS are mixed to form, and is expressed as (Mg:ZnS), and the mass ratio of Mg and ZnS is 5:1, evaporation speed is 3nm/s, and 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 second doped layer 73 that the first doped layer 71 of 35nm, metal level 72 that a layer thickness is 15nm and a layer thickness are 150nm successively.The structure of this organic electroluminescence device is: ito glass/MoO
3/ NPB/Alq
3/ TAZ/LiF/Mg:TiO
2(0.5:1)/Ag/Mg:ZnS(5:1).Wherein, slash "/" represents layer structure, Mg:TiO
2in colon ": " represent to mix, 0.5:1 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 DEG C, and vacuum degree is 1 × 10
-5pa.Wherein, 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 CsN
3, thickness is 10nm.
(3) on electron injecting layer, prepare composite cathode layer, obtain organic electroluminescence device; Composite cathode layer comprises the metal oxide layer, metal phthalocyanine compound layer and the metal level that stack 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 the composite material that Sr and ZnO are mixed to form, be expressed as (Sr:ZnO), the mass ratio of Sr and ZnO is 0.2:1, and the energy density of electron beam evaporation plating is 10W/cm
2, evaporation speed is 10nm/s; Adopt the mode of vacuum evaporation on the first doped layer, to prepare the metal level that a layer thickness is 5nm, material is Al again, and evaporation speed is 10nm/s; Finally on metal level, the second doped layer that a layer thickness is 100nm is prepared in vacuum evaporation, material is the composite material that Ca and CdS are mixed to form, and is expressed as (Ca:CdS), and the mass ratio of Ca and CdS is 10:1, evaporation speed is 10nm/s, and 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/MoO
3/ TCTA/ADN/TAZ/CsN
3/ Sr:ZnO(0.2:1)/Al/Ca:CdS(10:1).
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 DEG C, 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 TPBi, 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 metal oxide layer, metal phthalocyanine compound layer and the metal level that stack 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 60nm on electron injecting layer, material is the composite material that Ca and MgO are mixed to form, be expressed as (Ca:MgO), the mass ratio of Ca and MgO is 1:1, and the energy density of electron beam evaporation plating is 100W/cm
2, evaporation speed is 1nm/s; Adopt the mode of vacuum evaporation on the first doped layer, to prepare the metal level that a layer thickness is 20nm, material is Pt again, and evaporation speed is 1nm/s; Finally on metal level, the second doped layer that a layer thickness is 300nm is prepared in vacuum evaporation, material is the composite material that Yb and MgS are mixed to form, and is expressed as (Yb:MgS), and the mass ratio of Yb and MgS is 1:1, evaporation speed is 1nm/s, and 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/ TPBi/CsF/Ca:MgO(1:1)/Pt/Yb:MgS(1:1).
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 DEG C, 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 Bphen, 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 metal oxide layer, metal phthalocyanine compound layer and the metal level that stack 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 40nm on electron injecting layer, material is Yb and ZrO
2the composite material being mixed to form, is expressed as (Yb:ZrO
2), Yb and ZrO
2mass ratio be 0.8:1, the energy density of electron beam evaporation plating is 100W/cm
2, evaporation speed is 5nm/s; Adopt the mode of vacuum evaporation on the first doped layer, to prepare the metal level that a layer thickness is 10nm, material is Au again, and evaporation speed is 5nm/s; Finally on metal level, the second doped layer that a layer thickness is 300nm is prepared in vacuum evaporation, material is the composite material that Sr and CuS are mixed to form, and is expressed as (Sr:CuS), and the mass ratio of Sr and CuS is 2:1, evaporation speed is 5nm/s, and 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/Bphen/Cs
2cO
3/ Yb:ZrO
2(0.8:1)/Au/Sr:CuS(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/MoO
3/ NPB/Alq
3/ TAZ/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 Keithley company of the U.S., CS-100A colorimeter test brightness and the colourity of Konica Minolta company of Japan, obtain the luminous efficiency of organic electroluminescence device 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 organic electroluminescence device and the current density of comparative example luminescent device and the graph of a relation of luminous efficiency of the present embodiment.Wherein, curve 1 is the graph of a relation of current density and the luminous efficiency of the present embodiment organic electroluminescence device; Curve 2 is the graph of a relation of current density and the luminous efficiency of comparative example organic electroluminescence device.As can see from Figure 2, under different current densities, all large than comparative example organic electroluminescence device of the luminous efficiency of the present embodiment organic electroluminescence device, the maximum luminous efficiency of the present embodiment is 6.60lm/W, and that comparative example is only 4.73lm/W, meanwhile, along with the increase of current density, the luminous efficiency of comparative example decays sooner.This explanation, the composite cathode layer structure of the present embodiment, form the first doped layer by first preparing by low workfunction metal material and metal oxide, low workfunction metal has improved the injection of electronics, metal oxide plays the effect of scattering, make to get back to Road to the light scattering of both sides transmitting, improved light extraction efficiency; Prepare again the conductivity that metal level has improved device, improved exciton recombination probability; Finally prepare the second doped layer being formed by low workfunction metal material and metal sulfide, low workfunction metal is conducive to the injection of electronics, metal sulfide reflects light, improve the reflection efficiency of negative electrode, avoid light from top outgoing, thereby this composite cathode layer finally improve the luminous efficiency of device.
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, metal level and the second doped layer that lamination arranges successively
The material of described the first doped layer is that metal oxide and work function are-composite material that the metal material of 2.0eV～-3.5eV is mixed to form, and described metal oxide is titanium dioxide, zinc oxide, magnesium oxide or zirconia; The material of described metal level is silver, aluminium, platinum or gold; The material of described the second doped layer is that metal sulfide and work function are-composite material that the metal material of 2.0eV～-3.5eV is mixed to form, and described metal sulfide is zinc sulphide, cadmium sulfide, magnesium sulfide or copper sulfide.
2. organic electroluminescence device as claimed in claim 1, is characterized in that, and described work function is-and the metal material of 2.0eV～-3.5eV is magnesium, calcium, ytterbium or strontium.
3. organic electroluminescence device as claimed in claim 1, it is characterized in that, in described the first doped layer, the mass ratio of described metal oxide and metal material is 1:0.2～1, in described the second doped layer, the mass ratio of described metal sulfide and metal material is 1:1～10.
4. organic electroluminescence device as claimed in claim 1, is characterized in that, the thickness of described the first doped layer is 20～60nm, and the thickness of described metal level is 5～20nm, and the thickness of described the second doped layer is 100～300nm.
5. organic electroluminescence device as claimed in claim 1, is characterized in that, the material of described hole injection layer is molybdenum trioxide, tungstic acid or vanadic oxide; The material of described hole transmission layer is 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane, 4,4', 4''-tri-(carbazole-9-yl) triphenylamine or N, N '-(1-naphthyl)-N, N '-diphenyl-4,4 '-benzidine; The luminescent material of described 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--β-naphthylene anthracene, 4, two (the 9-ethyl-3-carbazole vinyl)-1 of 4'-, 1'-biphenyl or oxine aluminium; The material of described electron transfer layer is 4,7-diphenyl-1,10-phenanthroline, 1,2,4-triazole derivative or N-aryl benzimidazole; The material of described electron injecting layer is cesium carbonate, cesium fluoride, nitrine caesium or lithium fluoride.
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 on described electron injecting layer, prepare the first doped layer by the mode of electron beam evaporation plating, on described the first doped layer, prepare successively metal level and the second doped layer by the mode of vacuum evaporation again, obtain organic electroluminescence device;
The material of described the first doped layer is that metal oxide and work function are-composite material that the metal material of 2.0eV～-3.5eV is mixed to form, and described metal oxide is titanium dioxide, zinc oxide, magnesium oxide or zirconia; The material of described metal level is silver, aluminium, platinum or gold; The material of described the second doped layer is that metal sulfide and work function are-composite material that the metal material of 2.0eV～-3.5eV is mixed to form, and described metal sulfide is zinc sulphide, cadmium sulfide, magnesium sulfide or copper sulfide;
The energy density of described electron beam evaporation plating is 10～l00W/cm
2, in described vacuum evaporation process, vacuum degree is 2 × 10
-3～5 × 10
-5pa, the material evaporation speed of described the first doped layer, metal level and the second doped layer is 1～10nm/s.
7. the preparation method of organic electroluminescence device as claimed in claim 6, is characterized in that, and described work function is-and the metal material of 2.0eV～-3.5eV is magnesium, calcium, ytterbium or strontium.
8. the preparation method of organic electroluminescence device as claimed in claim 6, it is characterized in that, in described the first doped layer, the mass ratio of described metal oxide and metal material is 1:0.2～1, in described the second doped layer, the mass ratio of described metal sulfide and metal material is 1:1～10.
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 20～60nm, and the thickness of described metal level is 5～20nm, and the thickness of described the second doped layer is 100～300nm.
10. the preparation method of organic electroluminescence device as claimed in claim 6, it is characterized in that, described hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer adopt the mode of vacuum evaporation to prepare, and the material of described hole injection layer is molybdenum trioxide, tungstic acid or vanadic oxide; The material of described hole transmission layer is 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane, 4,4', 4''-tri-(carbazole-9-yl) triphenylamine or N, N '-(1-naphthyl)-N, N '-diphenyl-4,4 '-benzidine; The luminescent material of described 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--β-naphthylene anthracene, 4, two (the 9-ethyl-3-carbazole vinyl)-1 of 4'-, 1'-biphenyl or oxine aluminium; The material of described electron transfer layer is 4,7-diphenyl-1,10-phenanthroline, 1,2,4-triazole derivative or N-aryl benzimidazole; The material of described electron injecting layer is cesium carbonate, cesium fluoride, nitrine caesium or lithium fluoride.
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| CN110112325A (en) * | 2019-06-19 | 2019-08-09 | 京东方科技集团股份有限公司 | Transparent cathode structure, Organic Light Emitting Diode, array substrate and display device |
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