CN104124377A - Organic light-emitting device and preparation method thereof - Google Patents
Organic light-emitting device and preparation method thereof Download PDFInfo
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- CN104124377A CN104124377A CN201310144028.8A CN201310144028A CN104124377A CN 104124377 A CN104124377 A CN 104124377A CN 201310144028 A CN201310144028 A CN 201310144028A CN 104124377 A CN104124377 A CN 104124377A
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- H—ELECTRICITY
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- 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
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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 cathode layer includes a first metallic oxide layer, a metal layer, and a second metallic oxide layer, wherein the layers are successively laminated. The first metallic oxide layer is made from titanium dioxide; the metal layer is made of silver, aluminum, platinum, or gold; and the second metallic oxide layer is made from titanium dioxide. Because of the composite cathode layer, the light can be scattered, 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 metal oxide layer, metal level and the second metal oxide layer that lamination arranges successively
The material of described the first metal oxide layer is titanium dioxide, and the material of described metal level is silver (Ag), aluminium (Al), platinum (Pt) or gold (Au), and the material of described the second metal oxide layer is titanium dioxide.
Preferably, the thickness of described the first metal oxide layer is 10～40nm.
Preferably, the thickness of described metal level is 5～30nm.
Preferably, the thickness of described the second metal oxide layer is 200～1000nm.
Composite cathode layer comprises the first metal oxide layer, metal level and the second metal oxide layer that lamination arranges successively.On electron injecting layer, prepare layer of metal oxide skin(coating), material is titanium dioxide, because titanium dioxide granule is larger, after preparation, can make film surface form microspheric structure, no longer smooth, thereby can change the refraction angle of light, make light carry out scattering, reducing to the light of device both sides transmitting, and then prepare metal level, is mainly the effect of playing conduction and printing opacity, finally prepare layer of metal oxide skin(coating), material is titanium dioxide, is mainly the effect of playing reflection, and this composite cathode 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 MoO
3, thickness is 35nm.
Preferably, the material of hole transmission layer is 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane (TAPC), 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA) or N, N '-(1-naphthyl)-N, N '-diphenyl-4,4 '-benzidine (NPB), thickness is 20～60nm.
More preferably, the material of hole transmission layer is N, N '-(1-naphthyl)-N, and N '-diphenyl-4,4 '-benzidine (NPB), thickness is 50nm.
Preferably, the luminescent material of luminescent layer is 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans (DCJTB), 9,10-bis--β-naphthylene anthracene (ADN), 4, two (the 9-ethyl-3-carbazole vinyl)-1 of 4'-, 1'-biphenyl (BCzVBi) or oxine aluminium (Alq
3), thickness is 5～40nm.
More preferably, the luminescent material of luminescent layer is two (the 9-ethyl-3-carbazole vinyl)-1 of 4,4'-, 1'-biphenyl (BCzVBi), and thickness is 30nm.
Preferably, the material of electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2, and 4-triazole derivative (as TAZ) or N-aryl benzimidazole (TPBI), thickness is 40～300nm.
More preferably, the material of electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (Bphen), and thickness is 250nm.
Preferably, the material of electron injecting layer is cesium carbonate (Cs
2cO
3), cesium fluoride (CsF), nitrine caesium (CsN
3) or lithium fluoride (LiF); Thickness is 0.5～10nm.
More preferably, the material of electron injecting layer is lithium fluoride (LiF), and thickness is 1nm.
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 metal oxide layer by the mode of electron beam evaporation plating, on described the first metal oxide layer, prepare metal level by the mode of vacuum evaporation again, finally on metal level, prepare the second metal oxide layer by the mode of electron beam evaporation plating, obtain organic electroluminescence device;
The material of described the first metal oxide layer is titanium dioxide, and the material of described metal level is silver, aluminium, platinum or gold, and the material of described the second metal oxide layer is titanium dioxide;
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 metal oxide layer, metal level and the second metal oxide layer is 1～10nm/s.
Preferably, the thickness of described the first metal oxide layer is 10～40nm.
Preferably, the thickness of described metal level is 5～30nm.
Preferably, the thickness of described the second metal oxide layer is 200～1000nm.
Preferably, the particle diameter of described titanium dioxide is 20～200nm.
For increasing specific surface area, can carry out titanium tetrachloride preliminary treatment to the titanic oxide material of the first metal oxide layer.Preferably, before the first metal oxide layer described in evaporation, further comprise following operating procedure: the titanium tetrachloride (TiCl that the material titanium dioxide of described the first metal oxide layer is joined to 20～60mmol/L
4) in solution, the mass fraction that makes titanium dioxide is 5～30%, fully stirs, and in 50～100 DEG C of insulation 20～60min, filters, and then at 400～600 DEG C, calcines 20～40min.
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 MoO
3, thickness is 35nm.
Preferably, the material of hole transmission layer is 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane (TAPC), 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA) or N, N '-(1-naphthyl)-N, N '-diphenyl-4,4 '-benzidine (NPB), thickness is 20～60nm.
More preferably, the material of hole transmission layer is N, N '-(1-naphthyl)-N, and N '-diphenyl-4,4 '-benzidine (NPB), thickness is 50nm.
Preferably, the luminescent material of luminescent layer is 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans (DCJTB), 9,10-bis--β-naphthylene anthracene (ADN), 4, two (the 9-ethyl-3-carbazole vinyl)-1 of 4'-, 1'-biphenyl (BCzVBi) or oxine aluminium (Alq
3), thickness is 5～40nm.
More preferably, the luminescent material of luminescent layer is two (the 9-ethyl-3-carbazole vinyl)-1 of 4,4'-, 1'-biphenyl (BCzVBi), and thickness is 30nm.
Preferably, the material of electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2, and 4-triazole derivative (as TAZ) or N-aryl benzimidazole (TPBI), thickness is 40～300nm.
More preferably, the material of electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (Bphen), and thickness is 250nm.
Preferably, the material of electron injecting layer is cesium carbonate (Cs
2cO
3), cesium fluoride (CsF), nitrine caesium (CsN
3) or lithium fluoride (LiF); Thickness is 0.5～10nm.
More preferably, the material of electron injecting layer is lithium fluoride (LiF), and thickness is 1nm.
The invention provides a kind of organic electroluminescence device and preparation method thereof and there is following beneficial effect:
(1) organic electroluminescence device provided by the invention, has composite cathode layer structure, and composite cathode layer comprises the first metal oxide layer, metal level and the second metal oxide layer that lamination arranges successively.On electron injecting layer, prepare layer of metal oxide skin(coating), material is titanium dioxide, because titanium dioxide granule is larger, after preparation, can make film surface form microspheric structure, no longer smooth, thereby can change the refraction angle of light, make light carry out scattering, reducing to the light of device both sides transmitting, and then prepare metal level, is mainly the effect of playing conduction and printing opacity, finally prepare layer of metal oxide skin(coating), material is titanium dioxide, is mainly the effect of playing reflection, and this composite cathode finally can effectively improve the luminous efficiency of device;
(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 brightness of organic electroluminescence device and the graph of a relation of current efficiency prepared by the embodiment of the present invention 1 and comparative example.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely described, obviously, described embodiment is only the present invention's part embodiment, 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 WO
3, thickness is 35nm; The material of hole transmission layer is TAPC, and thickness is 50nm; The material of luminescent layer is BCzVBi, and light emitting layer thickness is 30nm; The material of electron transfer layer is Bphen, and thickness is 250nm; The material of electron injecting layer is LiF, and thickness is 1nm.
(3) on electron injecting layer, prepare composite cathode layer, obtain organic electroluminescence device; Composite cathode layer comprises the first metal oxide layer, metal level and the second metal oxide layer that stack gradually;
The preparation of composite cathode layer: first prepare by the mode of electron beam evaporation plating the first metal oxide layer that a layer thickness is 25nm on described electron injecting layer, material is TiO
2, particle diameter is 100nm, evaporation speed is 3nm/s, described TiO before evaporation
2be handled as follows: the titanium tetrachloride (TiCl that titanium dioxide is joined to 40mmol/L
4) in solution, the mass fraction that makes titanium dioxide is 25%, fully stirs, and in 70 DEG C of insulation 30min, filters, and then at 450 DEG C, calcines 30min; On described the first metal oxide layer, prepare by the mode of vacuum evaporation the metal level that a layer thickness is 15nm again, material is Ag, and evaporation speed is 3nm/s, and the vacuum degree of vacuum evaporation process is 8 × 10
-5pa; Finally on metal level, prepare by the mode of electron beam evaporation plating the second metal oxide layer that a layer thickness is 800nm, material is TiO
2, particle diameter is 100nm, and evaporation speed is 3nm/s, and the energy density of electron beam evaporation plating is 30W/cm
2.
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 metal oxide layer 73 that the first metal oxide layer 71 of 25nm, metal level 72 that a layer thickness is 15nm and a layer thickness are 800nm successively.The structure of this organic electroluminescence device is: ito glass/WO
3/ TAPC/BCzVBi/Bphen/LiF/TiO
2/ Ag/TiO
2, wherein, slash "/" represents layer structure, lower same.
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 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 CsN
3, thickness is 10nm.
(3) on electron injecting layer, prepare composite cathode layer, obtain organic electroluminescence device; Composite cathode layer comprises the first metal oxide layer, metal level and the second metal oxide layer that stack gradually;
The preparation of composite cathode layer: first prepare by the mode of electron beam evaporation plating the first metal oxide layer that a layer thickness is 40nm on described electron injecting layer, material is TiO
2, particle diameter is 20nm, evaporation speed is 10nm/s, described TiO before evaporation
2be handled as follows: the titanium tetrachloride (TiCl that titanium dioxide is joined to 20mmol/L
4) in solution, the mass fraction that makes titanium dioxide is 5%, fully stirs, and in 100 DEG C of insulation 20min, filters, and then at 600 DEG C, calcines 20min; On described the first metal oxide layer, prepare by the mode of vacuum evaporation the metal level that a layer thickness is 30nm again, material is Al, and evaporation speed is 10nm/s, and the vacuum degree of vacuum evaporation process is 2 × 10
-3pa; Finally on metal level, prepare by the mode of electron beam evaporation plating the second metal oxide layer that a layer thickness is 1000nm, material is TiO
2, particle diameter is 200nm, and evaporation speed is 10nm/s, and the energy density of electron beam evaporation plating is 10W/cm
2.
The structure of the organic electroluminescence device that the present embodiment provides is: AZO glass/WO
3/ TCTA/ADN/Bphen/CsN
3/ TiO
2/ Al/TiO
2.
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 first metal oxide layer, metal level and the second metal oxide layer that stack gradually;
The preparation of composite cathode layer: first prepare by the mode of electron beam evaporation plating the first metal oxide layer that a layer thickness is 10nm on described electron injecting layer, material is TiO
2, particle diameter is 200nm, evaporation speed is 1nm/s, described TiO before evaporation
2be handled as follows: the titanium tetrachloride (TiCl that titanium dioxide is joined to 60mmol/L
4) in solution, the mass fraction that makes titanium dioxide is 30%, fully stirs, and in 50 DEG C of insulation 60min, filters, and then at 400 DEG C, calcines 40min; On described the first metal oxide layer, prepare by the mode of vacuum evaporation the metal level that a layer thickness is 5nm again, material is Pt, and evaporation speed is 1nm/s, and the vacuum degree of vacuum evaporation process is 5 × 10
-5pa; Finally on metal level, prepare by the mode of electron beam evaporation plating the second metal oxide layer that a layer thickness is 200nm, material is TiO
2, particle diameter is 20nm, and evaporation speed is 1nm/s, and the energy density of electron beam evaporation plating is 100W/cm
2.
The structure of the organic electroluminescence device that the present embodiment provides is: IZO glass/V
2o
5/ TCTA/Alq
3/ TPBi/CsF/TiO
2/ Pt/TiO
2.
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 first metal oxide layer, metal level and the second metal oxide layer that stack gradually;
The preparation of composite cathode layer: first prepare by the mode of electron beam evaporation plating the first metal oxide layer that a layer thickness is 25nm on described electron injecting layer, material is TiO
2, particle diameter is 50nm, evaporation speed is 5nm/s, described TiO before evaporation
2be handled as follows: the titanium tetrachloride (TiCl that titanium dioxide is joined to 30mmol/L
4) in solution, the mass fraction that makes titanium dioxide is 10%, fully stirs, and in 60 DEG C of insulation 40min, filters, and then at 550 DEG C, calcines 35min; On described the first metal oxide layer, prepare by the mode of vacuum evaporation the metal level that a layer thickness is 25nm again, material is Au, and evaporation speed is 5nm/s, and the vacuum degree of vacuum evaporation process is 5 × 10
-4pa; Finally on metal level, prepare by the mode of electron beam evaporation plating the second metal oxide layer that a layer thickness is 400nm, material is TiO
2, particle diameter is 150nm, and evaporation speed is 5nm/s, and the energy density of electron beam evaporation plating is 80W/cm
2.
The structure of the organic electroluminescence device that the present embodiment provides is: IZO glass/MoO
3/ TAPC/DCJTB/Bphen/Cs
2cO
3/ TiO
2/ Au/TiO
2.
Comparative example
For being presented as 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 120nm, and the concrete structure of comparative example's organic electroluminescence device is: ito glass/WO
3/ TAPC/BCzVBi/Bphen/LiF/Ag, respectively corresponding conductive anode substrate of glass, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode.
Adopt the USB4000 fiber spectrometer testing electroluminescent spectrum of U.S. marine optics Ocean Optics, the current-voltage tester Keithley2400 test electric property of Keithley company of the U.S., CS-100A colorimeter test brightness and the colourity of Konica Minolta company of Japan, obtain the current efficiency of organic electroluminescence device with brightness change curve, to investigate the luminous efficiency of device, tested object is organic electroluminescence device prepared by embodiment 1 and comparative example.Test result as shown in Figure 2.
Fig. 2 is the brightness of organic electroluminescence device and the graph of a relation of current efficiency prepared by embodiment 1 and comparative example.Wherein, curve 1 is prepared for embodiment 1 the brightness of organic electroluminescence device and the graph of a relation of current efficiency; The brightness of organic electroluminescence device and the graph of a relation of current efficiency that curve 2 is prepared for comparative example.As can see from Figure 2, under different brightness, all large than comparative example of the current efficiency of organic electroluminescence device prepared by embodiment 1, the maximum current efficiency of embodiment 1 is 25.31cd/A, and that comparative example is only 16.83cd/A, this explanation, on electron injecting layer, first prepare the first metal oxide layer, make film surface form microspheric structure, change the refraction angle of light, reduce to the light of device both sides transmitting, metal level is mainly the effect of playing conduction and printing opacity, the second metal oxide layer plays the effect of reflection, this composite cathode layer has finally effectively improved 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 metal oxide layer, metal level and the second metal oxide layer that lamination arranges successively
The material of described the first metal oxide layer is titanium dioxide, and the material of described metal level is silver, aluminium, platinum or gold, and the material of described the second metal oxide layer is titanium dioxide.
2. organic electroluminescence device as claimed in claim 1, is characterized in that, the thickness of described the first metal oxide layer is 10～40nm.
3. organic electroluminescence device as claimed in claim 1, is characterized in that, the thickness of described metal level is 5～30nm.
4. organic electroluminescence device as claimed in claim 1, is characterized in that, the thickness of described the second metal oxide layer is 200～1000nm.
5. 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 metal oxide layer by the mode of electron beam evaporation plating, on described the first metal oxide layer, prepare metal level by the mode of vacuum evaporation again, finally on metal level, prepare the second metal oxide layer by the mode of electron beam evaporation plating, obtain organic electroluminescence device;
The material of described the first metal oxide layer is titanium dioxide, and the material of described metal level is silver, aluminium, platinum or gold, and the material of described the second metal oxide layer is titanium dioxide;
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 metal oxide layer, metal level and the second metal oxide layer is 1～10nm/s.
6. the preparation method of organic electroluminescence device as claimed in claim 5, is characterized in that, the thickness of described the first metal oxide layer is 10～40nm.
7. the preparation method of organic electroluminescence device as claimed in claim 5, is characterized in that, the thickness of described metal level is 5～30nm.
8. the preparation method of organic electroluminescence device as claimed in claim 5, is characterized in that, the thickness of described the second metal oxide layer is 200～1000nm.
9. the preparation method of organic electroluminescence device as claimed in claim 5, is characterized in that, the particle diameter of described titanium dioxide is 20～200nm.
10. the preparation method of organic electroluminescence device as claimed in claim 5, it is characterized in that, before the first metal oxide layer described in evaporation, further comprise following operating procedure: the material titanium dioxide of described the first metal oxide layer is joined in the titanium tetrachloride solution of 20～60mmol/L, the mass fraction that makes titanium dioxide is 5～30%, fully stirs, in 50～100 DEG C of insulation 20～60min, filter, then at 400～600 DEG C, calcine 20～40min.
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Application publication date: 20141029 |