CN103378308A - Organic light-emitting device and manufacturing method thereof - Google Patents
Organic light-emitting device and manufacturing method thereof Download PDFInfo
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- CN103378308A CN103378308A CN201210132342XA CN201210132342A CN103378308A CN 103378308 A CN103378308 A CN 103378308A CN 201210132342X A CN201210132342X A CN 201210132342XA CN 201210132342 A CN201210132342 A CN 201210132342A CN 103378308 A CN103378308 A CN 103378308A
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Abstract
The invention belongs to the field of organic light-emitting devices and discloses an organic light-emitting device and a manufacturing method thereof. The organic light-emitting device comprises a glass substrate, a conductive anode layer, a hole transmission layer, a luminous layer, an electron transmission layer, an electron injection layer and a cathode layer, wherein the glass substrate, the conductive anode layer, the hole transmission layer, the luminous layer, the electron transmission layer, the electron injection layer and the cathode layer are stacked sequentially, the conductive anode layer comprises a metal layer and an activated carbon layer, the metal layer is stacked on the surface of the glass substrate, and the activated carbon layer is stacked on the surface of the metal layer. According to the organic light-emitting device, a mixed material of activated carbon suspension liquid and metal replaces ITO to be used as the anode of the organic light-emitting device, activated carbon can enhance the electrical conductivity of the organic light-emitting device and can further enhance the scattering of light, the incident angle of the light on a glass surface is changed, the probability of total reflection of the light is reduced, the light extraction rate and the front light-emitting strength are improved, and meanwhile the activated carbon is low in price, non-toxic and free of pollution.
Description
Technical field
The present invention relates to the electroluminescent device field, relate in particular to a kind of organic electroluminescence device and preparation method thereof.
Background technology
1987, the C.W.Tang of U.S. Eastman Kodak company and VanSlyke reported the breakthrough in the organic electroluminescent research.Utilize the ultrathin film technology to prepare high brightness, high efficiency double-deck organic electroluminescence device (OLED).In this double-deck device, brightness reaches 1000cd/m under the 10V
2, its luminous efficiency is that 1.51lm/W, life-span were greater than 100 hours.
The principle of luminosity of OLED is based under the effect of extra electric field, and electronics is injected into organic lowest unocccupied molecular orbital (LUMO) from negative electrode, and the hole is injected into organic highest occupied molecular orbital (HOMO) from anode.Electronics and hole meet at luminescent layer, compound, form exciton, exciton moves under electric field action, and energy is passed to luminescent material, and excitation electron is from the ground state transition to excitation state, excited energy produces photon by Radiation-induced deactivation, discharges luminous energy.
In traditional electroluminescent device, most study be exactly end ballistic device structure, take the ito glass substrate as exiting surface, this device technology of preparing is ripe, research and comparison is many, because the outgoing meeting of light is reflected through the absorption of ITO electric conducting material first, to carry out subvitreous absorption and a reflection again, just can shine in the air at last, and because glass surface is more smooth, and thickness of glass is larger, light path is strengthened, thereby more light is reflected away toward the glass both sides, cause the probability of the light that shines device in the glass to descend, finally affect luminous efficiency, therefore, it is very low that light shines airborne exitance, and most light has all lost, and the luminous efficiency of this class device is all on the low side.And the ITO cost is expensive, and indium tin composition wherein all is rare metal, and output is few, is not suitable for the volume production of product.
Summary of the invention
Based on the problems referred to above, problem to be solved by this invention be to provide a kind of preparation cost low, be suitable for commercialization volume production and the high organic electroluminescence device of luminous efficiency.
Technical scheme of the present invention is as follows:
A kind of organic electroluminescence device comprises the substrate of glass, conductive anode layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the cathode layer that stack gradually; Described conductive anode layer comprises metal and active carbon layer, and described metal level is layered in described glass basic surface, and described active carbon layer is layered in described layer on surface of metal; The thickness of described metal level is 5～20nm, and the thickness of described active carbon layer is 1～100 μ m; Wherein, the material of metal level is aluminium, silver or golden.
In the described organic electroluminescence device, the material of described active carbon layer is the mixture of active carbon and polytetrafluoroethylene; In the described active carbon layer, the mass percent of described active carbon is 5.21～35.69%.
In the described organic electroluminescence device, material and the thickness of other each functional layers are as follows:
The material of described hole transmission layer is 1,1-two [4-[N, N '-two (p-tolyl) amino] phenyl] cyclohexane, 4,4 ', 4 " three (carbazole-9-yl) triphenylamine, N, N '-(1-naphthyl)-N, N '-diphenyl-4,4 '-benzidines; The thickness of described hole transmission layer is 20～60nm;
The material of described luminescent layer is two (4,6-difluorophenyl pyridine-N, C
2) the pyridine formyl closes iridium, two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanedione) and close iridium or three (2-phenylpyridine) and close iridium;
The material of described luminescent layer is that guest materials is doped to the composite material in the material of main part, and the doping mass percent of described guest materials is 1～20%; Wherein, described guest materials is two (4,6-difluorophenyl pyridine-N, C
2) the pyridine formyl closes iridium, two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanedione) and close iridium or three (2-phenylpyridine) and close iridium, described material of main part is 4,7-diphenyl-1,10-phenanthroline, 1,2,4-triazole derivative (or N-aryl benzimidazole;
The thickness of described luminescent layer is 2～30nm;
The material of described electron transfer layer is 4,7-diphenyl-1,10-phenanthroline, 1,2,4-triazole derivative or N-aryl benzimidazole; The thickness of described electron transfer layer is 40～80nm;
The material of described electron injecting layer is cesium carbonate, cesium fluoride, nitrine caesium or lithium fluoride; The thickness of described electron injecting layer is 0.5-10nm;
The material of described cathode layer is silver, aluminium, platinum or gold; The thickness of described cathode layer is 80-300nm;
The present invention also provides a kind of preparation method of above-mentioned organic electroluminescence device, comprises the steps:
S1, substrate of glass is used liquid detergent, deionized water, acetone, ethanol, each ultrasonic cleaning 15min of isopropyl alcohol successively;
S2, utilize evaporation process, the glass basic surface evaporation thickness after cleaning up is the metal level of 5～20nm;
S3, utilize spin coating proceeding, at layer on surface of metal spin coating active carbon aaerosol solution, preparation thickness is the active carbon layer of 1～100 μ m;
S4, again utilize evaporation process, stack gradually evaporation hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and cathode layer on the active carbon layer surface;
After described processing step is finished, make described organic electroluminescence device.
Organic electroluminescence device provided by the invention, it utilizes the composite material of active carbon suspension and metal to replace ITO as the anode of luminescent device, and active carbon has very high conductivity, the large and pore-size distribution homogeneous in aperture; Active carbon also has the characteristics of high-specific surface area, this characteristics are except can strengthening its electric conductivity, can also be in to a certain degree lower enhancing scattering of light, make the light generation scattering of luminescent layer, change incidence angle, its probability that total reflection occurs is reduced, improve light extraction efficiency and positive luminous intensity, thereby strengthen luminous efficiency; Simultaneously, active carbon is cheap, and the source is abundant, and nontoxic pollution-free is fit to commercialization.
The preparation method of organic electroluminescence device provided by the invention, the mixing and doping technique of active carbon suspension and metal is simple, need not be through evaporation operation repeatedly.
Description of drawings
Fig. 1 is the structural representation of organic electroluminescence device of the present invention;
Fig. 2 is the luminous efficiency of the organic electroluminescence device that makes of the organic electroluminescence device that makes of embodiment 1 and Comparative Examples 1 and the comparison diagram of brightness; Wherein, curve 1 is the luminous efficiency of embodiment 1 and the graph of a relation of brightness; Curve 2 is the luminous efficiency of Comparative Examples 1 and the graph of a relation of brightness.
Embodiment
Organic electroluminescence device provided by the invention is realized in such a way:
A kind of organic electroluminescence device as shown in Figure 1, comprises the substrate of glass 11, conductive anode layer 12, hole transmission layer 13, luminescent layer 14, electron transfer layer 15, electron injecting layer 16 and the cathode layer 17 that stack gradually; Conductive anode layer 12 comprises metal 121 and active carbon layer 122, and metal level 121 is layered in described substrate of glass 11 surfaces, and described active carbon layer 122 is layered in described metal level 121 surfaces; The thickness of described metal level 121 is 5～20nm, and the thickness of described active carbon layer 122 is 1～100 μ m; Wherein, the material of metal level 121 is aluminium (Al), silver (Ag) or gold (Au); The material of active carbon layer 122 is the mixture of active carbon and polytetrafluoroethylene; In the active carbon layer, the mass percent of active carbon is 5.21～35.69%.
For the mass percent of above-mentioned active carbon, convert in the following way and get:
Polytetrafluoroethylene (PTFE) is added to the water, is configured to mass percent concentration and is 20% the PTFE aqueous solution; Active carbon is added in the PTFE aqueous solution, obtain active carbon suspension, and the mass percent of the shared PTFE solution of active carbon is 1～10%;
Suppose the quality of active carbon suspension according to 100 parts of calculating, PTFE is 20 parts, and active carbon then becomes 1.1～11.1 parts; Like this, in organic electroluminescence device, moisture is to be removed, remaining is exactly PTFE and active carbon, both gross mass umbers are 21.1～31.1, and this moment, the mass percent scope of active carbon was 5.21% (being 1.1/21.1*100%=5.21%)～35.69% (being 11.1/31.1*100%=35.69%).
The preferred silver of the material of metal level 121 (Ag), the preferred 10nm of thickness; The preferred 10 μ m of the thickness of active carbon layer 122, in the active carbon layer 122, the mass percent of active carbon is preferably 20%.
Above-mentioned organic electroluminescence device, material and the thickness of its each functional layer are as follows:
The material of hole transmission layer 13 all adopts 1,1-two [4-[N, N '-two (p-tolyl) amino] phenyl] cyclohexane (TAPC), 4,4 ', 4 " three (carbazole-9-yl) triphenylamine (TCTA), N, N '-(1-naphthyl)-N, N '-diphenyl-4; 4 '-benzidine (NPB) is preferably TCTA; The thickness of hole transmission layer 13 is 20-60nm, and preferred thickness is 50nm;
The material of luminescent layer 14 is with (4,6-difluorophenyl pyridine-N, C
2) the pyridine formyl closes iridium (FIrpic), two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanedione) and close iridium (Ir (MDQ)
2(acac)) or three (2-phenylpyridines) close iridium (Ir (ppy)
3) for guest materials is doped to the composite material that obtains in the material of main part, the doping mass percent of described guest materials is 1～20%; Wherein, material of main part is 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2,4-triazole derivative (such as TAZ) or N-aryl benzimidazole (TPBI); The material of preferred luminescent layer is Ir (ppy)
3Being doped among the TPBi (is TPBi:Ir (ppy)
3), and Ir (ppy)
3The doping mass percent is 10%; The thickness of luminescent layer is 2～30nm, and preferred thickness is 20nm;
The material of electron transfer layer 15 is 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2, and 4-triazole derivative (such as TAZ) or N-aryl benzimidazole (TPBI) are preferably TAZ; The thickness of electron transfer layer 15 is 40-80nm, and preferred thickness is 60nm;
The material of electron injecting layer 16 is cesium carbonate (Cs
2CO
3), cesium fluoride (CsF), nitrine caesium (CsN
3) or lithium fluoride (LiF), be preferably LiF; The thickness of electron injecting layer 16 is 0.5-10nm, and preferred thickness is 1nm;
The material of cathode layer 17 is silver (Ag), aluminium (Al), platinum (Pt) or gold (Au), is preferably Ag; The thickness of cathode layer is 80-300nm, and preferred thickness is 100nm.
The above-mentioned preparation method who is laminated with organic electroluminescence devices comprises the steps:
S1, substrate of glass is used liquid detergent, deionized water, acetone, ethanol, each ultrasonic cleaning 15min of isopropyl alcohol successively, remove the organic pollution of glass surface
S2, utilize evaporation process, the glass basic surface evaporation thickness after cleaning up is the metal level of 5～20nm;
S3, utilize spin coating proceeding, at layer on surface of metal spin coating active carbon aaerosol solution, preparation thickness is the active carbon layer of 1～100 μ m;
S4, again utilize evaporation process, stack gradually evaporation hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and cathode layer on the active carbon layer surface;
After described processing step is finished, make described organic electroluminescence device.
Among the above-mentioned preparation method's who is laminated with organic electroluminescence devices the step S3, the active carbon aaerosol solution adopts following technique to make:
Polytetrafluoroethylene (PTFE) is added to the water, is configured to mass percent concentration and is 20% the PTFE aqueous solution; Polytetrafluoroethylene is mainly used in strengthening caking property, and it is tightr that active carbon layer is combined with adjacent organic;
Active carbon is added in the PTFE aqueous solution, obtain active carbon suspension, and the mass percent of the shared PTFE solution of active carbon is 1～10%.
Organic electroluminescence device provided by the invention, it utilizes the composite material of active carbon suspension and metal to replace ITO as the anode of luminescent device, and active carbon has very high conductivity, the large and pore-size distribution homogeneous in aperture; Active carbon also has the characteristics of high-specific surface area, this characteristics are except can strengthening its electric conductivity, can also be in to a certain degree lower enhancing scattering of light, make the light generation scattering of luminescent layer, change incidence angle, its probability that total reflection occurs is reduced, improve light extraction efficiency and positive luminous intensity, thereby strengthen luminous efficiency; Simultaneously, active carbon is cheap, and the source is abundant, and nontoxic pollution-free is fit to commercialization.
The preparation method of organic electroluminescence device provided by the invention, the mixing and doping technique of active carbon suspension and metal is simple, need not be through evaporation operation repeatedly.
The below is described in further detail preferred embodiment of the present invention.
The used preparation of following embodiment and tester are: high vacuum coating equipment (scientific instrument development center, Shenyang Co., Ltd, pressure＜1 * 10
-3Pa), current-voltage tester (U.S. Keithly company, 2602), the electroluminescent spectrum tester (U.S. photo research company model:, model: PR650) and screen intensity meter (Beijing Normal University, model: ST-86LA).
Embodiment 1
The organic electroluminescence device structure of present embodiment: glass/(Ag/ active carbon)/TCTA/TPBi:Ir (ppy)
3/ TAZ/LiF/Ag.
The preparation technology of organic electroluminescence device is as follows:
First substrate of glass is used liquid detergent successively, deionized water, acetone, ethanol, each ultrasonic 15min of isopropyl alcohol, the organic pollution of removal glass surface;
Glass basic surface evaporated metal layer after cleaning up (material is Ag, and thickness is 10nm); Then layer on surface of metal spin coating active carbon aaerosol solution (mass percent of active carbon is 20%), make the active carbon layer that thickness is 10 μ m;
Time stack gradually evaporation hole transmission layer (material is TCTA, and thickness is 50nm) on active carbon layer surface subsequently, (material is TPBi:Ir (ppy) to luminescent layer
3, i.e. Ir (ppy)
3Be doped among the TPBi, and Ir (ppy)
3The doping mass percent is 10%, and thickness is 20nm), electron transfer layer (material is TAZ, and thickness is 60nm), electron injecting layer (material is LiF, and thickness is 1nm) and cathode layer (materials A g, thickness are 100nm);
After above-mentioned technique is finished, make the organic electroluminescence devices that is laminated with that needs.
The organic electroluminescence device structure of present embodiment: glass/(Al/ active carbon)/TCTA/TPBi:Ir (MDQ)
2(acac)/Bphen/Cs
2CO
3/ Au.
The preparation technology of organic electroluminescence device is as follows:
First substrate of glass is used liquid detergent successively, deionized water, acetone, ethanol, each ultrasonic 15min of isopropyl alcohol, the organic pollution of removal glass surface;
Glass basic surface evaporated metal layer after cleaning up (material is Al, and thickness is 5nm); Then layer on surface of metal spin coating active carbon aaerosol solution (mass percent of active carbon is 5.21%), make the active carbon layer that thickness is 1 μ m;
Time stack gradually evaporation hole transmission layer (material is TCTA, and thickness is 60nm) on active carbon layer surface subsequently, (material is TPBi:Ir (MDQ) to luminescent layer
2(acac), i.e. Ir (MDQ)
2(acac) be doped among the TPBi, and Ir (MDQ)
2(acac) the doping mass percent is 2%, and thickness is 20nm), electron transfer layer (material is Bphen, and thickness is 80nm), (material is Cs to electron injecting layer
2CO
3, thickness is 10nm) and cathode layer (materials A u, thickness are 120nm);
After above-mentioned technique is finished, make the organic electroluminescence devices that is laminated with that needs.
Embodiment 3
The organic electroluminescence device structure of present embodiment: glass/(Au/ active carbon)/NPB/TAZ:Firpic/TPBi/CsF/Pt.
The preparation technology of organic electroluminescence device is as follows:
First substrate of glass is used liquid detergent successively, deionized water, acetone, ethanol, each ultrasonic 15min of isopropyl alcohol, the organic pollution of removal glass surface;
Glass basic surface evaporated metal layer after cleaning up (material is Au, and thickness is 20nm); Then layer on surface of metal spin coating active carbon aaerosol solution (mass percent of active carbon is 35.69%), make the active carbon layer that thickness is 100 μ m;
(material is NPB to stack gradually the evaporation hole transmission layer surperficial time at active carbon layer subsequently, thickness is 20nm), (material is TAZ:Firpic to luminescent layer, be that Firpic is doped among the TAZ, and Firpic doping mass percent is 20%, thickness is 30nm), (material is TPBi to electron transfer layer, thickness is 35nm), electron injecting layer (material is CsF, and thickness is 0.5nm) and cathode layer (material Pt, thickness are 80nm);
After above-mentioned technique is finished, make the organic electroluminescence devices that is laminated with that needs.
The organic electroluminescence device structure of present embodiment: glass/(Ag/ active carbon)/TAPCBphen:Ir (ppy)
3/ TAZ/CsN
3/ Al.
The preparation technology of organic electroluminescence device is as follows:
First substrate of glass is used liquid detergent successively, deionized water, acetone, ethanol, each ultrasonic 15min of isopropyl alcohol, the organic pollution of removal glass surface;
Glass basic surface evaporated metal layer after cleaning up (material is Ag, and thickness is 15nm); Then layer on surface of metal spin coating active carbon aaerosol solution (mass percent of active carbon is 28.5%), make the active carbon layer that thickness is 50 μ m;
Time stack gradually evaporation hole transmission layer (material is TAPC, and thickness is 45nm) on active carbon layer surface subsequently, (material is Bphen:Ir (ppy) to luminescent layer
3, i.e. Ir (ppy)
3Be doped among the Bphen, and Ir (ppy)
3The doping mass percent is 6%, and thickness is 12nm), electron transfer layer (material is TAZ, and thickness is 75nm), (material is CsN to electron injecting layer
3, thickness is 0.7nm) and cathode layer (materials A l, thickness are 120nm);
After above-mentioned technique is finished, make the organic electroluminescence devices that is laminated with that needs.
Embodiment 5
The organic electroluminescence device structure of present embodiment: glass/(Ag/ active carbon)/TCTA/TPBi:Firpic/TAZ/LiF/Ag.
The preparation technology of organic electroluminescence device is as follows:
First substrate of glass is used liquid detergent successively, deionized water, acetone, ethanol, each ultrasonic 15min of isopropyl alcohol, the organic pollution of removal glass surface;
Glass basic surface evaporated metal layer after cleaning up (material is Ag, and thickness is 10nm); Then layer on surface of metal spin coating active carbon aaerosol solution (mass percent of active carbon is 7%), make the active carbon layer that thickness is 35 μ m;
(material is TCTA to stack gradually the evaporation hole transmission layer surperficial time at active carbon layer subsequently, thickness is 50nm), (material is TPBi:Firpic to luminescent layer, be that Firpic is doped among the TPBi, and Firpic doping mass percent is 20%, thickness is 20nm), (material is TAZ to electron transfer layer, thickness is 60nm), electron injecting layer (material is LiF, and thickness is 1nm) and cathode layer (materials A g, thickness are 100nm);
After above-mentioned technique is finished, make the organic electroluminescence devices that is laminated with that needs.
Embodiment 6
The organic electroluminescence device structure of present embodiment: glass/(Au/ active carbon)/TCTA/Bphen:Ir (MDQ)
2(acac)/TAZ/CsN
3/ Al.
The preparation technology of organic electroluminescence device is as follows:
First substrate of glass is used liquid detergent successively, deionized water, acetone, ethanol, each ultrasonic 15min of isopropyl alcohol, the organic pollution of removal glass surface;
Glass basic surface evaporated metal layer after cleaning up (material is Au, and thickness is 15nm); Then layer on surface of metal spin coating active carbon aaerosol solution (mass percent of active carbon is 18.5%), make the active carbon layer that thickness is 80 μ m;
Time stack gradually evaporation hole transmission layer (material is TCTA, and thickness is 45nm) on active carbon layer surface subsequently, (material is Bphen:Ir (MDQ) to luminescent layer
2(acac), i.e. Ir (MDQ)
2(acac) be doped among the Bphen, and Ir (MDQ)
2(acac) the doping mass percent is 3%, and thickness is 5nm), electron transfer layer (material is TAZ, and thickness is 75nm), (material is CsN to electron injecting layer
3, thickness is 0.7nm) and cathode layer (materials A l, thickness are 120nm);
After above-mentioned technique is finished, make the organic electroluminescence devices that is laminated with that needs.
Embodiment 7
The organic electroluminescence device structure of present embodiment: glass/(Pt/ active carbon)/NPB/Bphen:Firpic/TAZ/LiF/Ag.
The preparation technology of organic electroluminescence device is as follows:
First substrate of glass is used liquid detergent successively, deionized water, acetone, ethanol, each ultrasonic 15min of isopropyl alcohol, the organic pollution of removal glass surface;
Glass basic surface evaporated metal layer after cleaning up (material is Pt, and thickness is 15nm); Then layer on surface of metal spin coating active carbon aaerosol solution (mass percent of active carbon is 32%), make the active carbon layer that thickness is 80 μ m;
(material is NPB to stack gradually the evaporation hole transmission layer surperficial time at active carbon layer subsequently, thickness is 50nm), (material is Bphen:Firpic to luminescent layer, be that Firpic is doped among the Bphen, and Firpic doping mass percent is 12%, thickness is 15nm), (material is TAZ to electron transfer layer, thickness is 75nm), electron injecting layer (material is LiF, and thickness is 1.2nm) and cathode layer (materials A g, thickness are 150nm);
After above-mentioned technique is finished, make the organic electroluminescence devices that is laminated with that needs.
The organic electroluminescence device structure of present embodiment: glass/(Ag/ active carbon)/TAPC/TAZ:Ir (MDQ)
2(acac)/TPBi/LiF/Ag.
The preparation technology of organic electroluminescence device is as follows:
First substrate of glass is used liquid detergent successively, deionized water, acetone, ethanol, each ultrasonic 15min of isopropyl alcohol, the organic pollution of removal glass surface;
Glass basic surface evaporated metal layer after cleaning up (material is Ag, and thickness is 10nm); Then layer on surface of metal spin coating active carbon aaerosol solution (mass percent of active carbon is 24%), make the active carbon layer that thickness is 100 μ m;
Time stack gradually evaporation hole transmission layer (material is TAPC, and thickness is 55nm) on active carbon layer surface subsequently, (material is TAZ:Ir (MDQ) to luminescent layer
2(acac), i.e. Ir (MDQ)
2(acac) be doped among the TAZ, and Ir (MDQ)
2(acac) the doping mass percent is 2.5%, and thickness is 4nm), electron transfer layer (material is TPBi, and thickness is 65nm), electron injecting layer (material is LiF, and thickness is 1nm) and cathode layer (materials A g, thickness are 150nm);
After above-mentioned technique is finished, make the organic electroluminescence devices that is laminated with that needs.
Embodiment 9
The organic electroluminescence device structure of present embodiment: glass/(Ag/ active carbon)/TAPC/TAZ:Ir (ppy)
3/ Bphen/LiF/Ag.
The preparation technology of organic electroluminescence device is as follows:
First substrate of glass is used liquid detergent successively, deionized water, acetone, ethanol, each ultrasonic 15min of isopropyl alcohol, the organic pollution of removal glass surface;
Glass basic surface evaporated metal layer after cleaning up (material is Ag, and thickness is 10nm); Then layer on surface of metal spin coating active carbon aaerosol solution (mass percent of active carbon is 15.5%), make the active carbon layer that thickness is 25 μ m;
Time stack gradually evaporation hole transmission layer (material is TAPC, and thickness is 55nm) on active carbon layer surface subsequently, (material is TAZ:Ir (ppy) to luminescent layer
3, i.e. Ir (ppy)
3Be doped among the TAZ, and Ir (ppy)
3The doping mass percent is 18%, and thickness is 8nm), electron transfer layer (material is Bphen, and thickness is 70nm), electron injecting layer (material is LiF, and thickness is 1nm) and cathode layer (materials A g, thickness are 90nm);
After above-mentioned technique is finished, make the organic electroluminescence devices that is laminated with that needs.
Comparative Examples 1
The organic electroluminescence device structure of this Comparative Examples: glass/ITO/TCTA/TPBi:Ir (ppy)
3/ TAZ/LiF/Ag.
The preparation technology of organic electroluminescence device is as follows:
First substrate of glass is used liquid detergent successively, deionized water, acetone, ethanol, each ultrasonic 15min of isopropyl alcohol, the organic pollution of removal glass surface;
Glass basic surface sputter evaporation ITO after cleaning up, thickness 120nm is; Then
Evaporation hole transmission layer (material is TCTA, and thickness is 50nm), (material is TPBi:Ir (ppy) to luminescent layer
3, i.e. Ir (ppy)
3Be doped among the TPBi, and Ir (ppy)
3The doping mass percent is 10%, and thickness is 20nm), electron transfer layer (material is TAZ, and thickness is 60nm), electron injecting layer (material is LiF, and thickness is 1nm) and cathode layer (materials A g, thickness are 100nm);
After above-mentioned technique is finished, make the organic electroluminescence devices that is laminated with that needs.
Fig. 2 is the luminous efficiency of the organic electroluminescence device that makes of the organic electroluminescence device that makes of embodiment 1 and Comparative Examples 1 and the comparison diagram of brightness; Wherein, curve 1 is the luminous efficiency of embodiment 1 and the graph of a relation of brightness; Curve 2 is the luminous efficiency of Comparative Examples 1 and the graph of a relation of brightness.
Fig. 2 can see, under different current densities, the luminous efficiency of embodiment 1 is large than Comparative Examples 1 all, and maximum luminous efficiency is 17.1lm/W, and that Comparative Examples 1 only is 9.6lm/W, and the luminous efficiency rate of Comparative Examples 1 along with the increase of current density fast-descending; This all illustrates, utilize active carbon suspension and metal to replace ITO as the anode of luminescent device, can be in to a certain degree lower enhancing scattering of light, make the light generation scattering of luminescent layer, change incidence angle, its probability that total reflection occurs is reduced, improve light extraction efficiency and positive luminous intensity, thereby strengthen luminous efficiency.
Should be understood that above-mentioned statement for preferred embodiment of the present invention is comparatively detailed, can not therefore think the restriction to scope of patent protection of the present invention, scope of patent protection of the present invention should be as the criterion with claims.
Claims (9)
1. an organic electroluminescence device is characterized in that, comprises the substrate of glass, conductive anode layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the cathode layer that stack gradually; Described conductive anode layer comprises metal and active carbon layer, and described metal level is layered in described glass basic surface, and described active carbon layer is layered in described layer on surface of metal; The thickness of described metal level is 5～20nm, and the thickness of described active carbon layer is 1～100 μ m.
2. organic electroluminescence device according to claim 1 is characterized in that, the material of described metal level is aluminium, silver or golden.
3. organic electroluminescence device according to claim 1 is characterized in that, the material of described active carbon layer is the mixture of active carbon and polytetrafluoroethylene; In the described active carbon layer, the mass percent of active carbon is 5.21～35.69%.
4. organic electroluminescence device according to claim 1, it is characterized in that, the material of described hole transmission layer is 1,1-two [4-[N, N '-two (p-tolyl) amino] phenyl] cyclohexane, 4,4 ', 4 " three (carbazole-9-yl) triphenylamine, N; N '-(1-naphthyl)-N, N '-diphenyl-4,4 '-benzidine; The thickness of described hole transmission layer is 20～60nm.
5. organic electroluminescence device according to claim 1 is characterized in that, the material of described luminescent layer is that guest materials is doped to the composite material in the material of main part, and the doping mass percent of described guest materials is 1～20%; Wherein, described guest materials is two (4,6-difluorophenyl pyridine-N, C
2) the pyridine formyl closes iridium, two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanedione) and close iridium or three (2-phenylpyridine) and close iridium, described material of main part is 4,7-diphenyl-1,10-phenanthroline, 1,2,4-triazole derivative (or N-aryl benzimidazole; The thickness of described luminescent layer is 2～30nm.
6. organic electroluminescence device according to claim 1 is characterized in that, the material of described electron transfer layer is 4,7-diphenyl-1,10-phenanthroline, 1,2,4-triazole derivative or N-aryl benzimidazole; The thickness of described electron transfer layer is 40～80nm.
7. organic electroluminescence device according to claim 1 is characterized in that, the material of described electron injecting layer is cesium carbonate, cesium fluoride, nitrine caesium or lithium fluoride; The thickness of described electron injecting layer is 0.5-10nm.
8. organic electroluminescence device according to claim 1 is characterized in that, the material of described cathode layer is silver, aluminium, platinum or gold; The thickness of described cathode layer is 80-300nm.
9. the preparation method of organic electroluminescence device claimed in claim 1 is characterized in that, comprises the steps:
S1, substrate of glass is used liquid detergent, deionized water, acetone, ethanol, each ultrasonic cleaning 15min of isopropyl alcohol successively;
S2, utilize evaporation process, the glass basic surface evaporation thickness after cleaning up is the metal level of 5～20nm;
S3, utilize spin coating proceeding, at layer on surface of metal spin coating active carbon aaerosol solution, preparation thickness is the active carbon layer of 1～100 μ m;
S4, again utilize evaporation process, stack gradually evaporation hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and cathode layer on the active carbon layer surface;
After described processing step is finished, make described organic electroluminescence device.
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