CN103579519A - Organic electroluminescence device and manufacturing method thereof - Google Patents

Organic electroluminescence device and manufacturing method thereof Download PDF

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Publication number
CN103579519A
CN103579519A CN201210264215.5A CN201210264215A CN103579519A CN 103579519 A CN103579519 A CN 103579519A CN 201210264215 A CN201210264215 A CN 201210264215A CN 103579519 A CN103579519 A CN 103579519A
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layer
thickness
electroluminescence device
organic electroluminescence
electron
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周明杰
王平
黄辉
陈吉星
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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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
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/16—Electron transporting layers
    • H10K50/166—Electron transporting layers comprising a multilayered structure
    • 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
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/18—Carrier blocking layers
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass

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Abstract

The invention belongs to the field of organic semiconductor materials and discloses an organic electroluminescence device and a manufacturing method of the organic electroluminescence device. The organic electroluminescence device comprises an anode substrate, a hole injection layer, a hole transmission layer, a light-emitting layer, a first electron transmission layer, a spacing layer, an auxiliary electron transmission layer, an electron injection layer and a cathode layer, wherein the anode substrate, the hole injection layer, the hole transmission layer, the light-emitting layer, the first electron transmission layer, the spacing layer, the auxiliary electron transmission layer, the electron injection layer and the cathode layer are sequentially stacked. The spacing layer is made of zinc oxide or titanium dioxide or magnesium oxide. According to the organic electroluminescence device, the auxiliary electron transmission layer is manufactured, so that transmission of electrons is enhanced; meanwhile, the spacing layer made of metallic oxide is arranged between the first electron transmission layer and the auxiliary electron transmission layer, photons are prevented from being coupled with the free electrons of metal electrodes to a certain degree, and therefore the light-emitting efficiency of the organic electroluminescence device is improved.

Description

A kind of organic electroluminescence device and preparation method thereof
Technical field
The present invention relates to organic semiconducting materials, relate in particular to a kind of organic electroluminescence device and preparation method thereof.
Background technology
The C.W.Tang of 1987 Nian， U.S. Eastman Kodak companies and VanSlyke have 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.
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 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 ground state transition to excitation state, excited energy, by Radiation-induced deactivation, produces photon, discharges luminous energy.
In traditional luminescent device, generally to prepare the transmission rate that one deck electron transfer layer improves electronics, prepare again the injection efficiency that one deck electron injecting layer improves electronics, and the transmission rate of electronics is conventionally than low two or three orders of magnitude of the transmission rate in hole, therefore, conventionally be all that electron transfer layer is carried out to n doping, that is to say electron transfer layer is carried out metal-doped, if Cs salt dopping is in Bphen, Li salt dopping is in TPBi, improve electric transmission speed, this method adopts more, and can effectively improve electric transmission speed, but, the amplitude that speed improves is not high, and thickness can not be done to obtain too thin (lower than 40nm), when luminescent material and metal electrode approach, luminescent material can produce coupling with metal electrode, exciton has been caused to loss (surface plasmon wave), thickness too thick (higher than 100nm), defect increases, the existence of electron trap, can make electronics or hole enter in trap, cause exciton recombination probability to reduce, all these so have influence on the raising of electric transmission speed, also just caused luminous efficiency low.
Summary of the invention
Problem to be solved by this invention is to provide a kind of organic electroluminescence device that can improve luminous efficiency.
Technical scheme of the present invention is as follows:
, comprise the anode substrate, hole injection layer, hole transmission layer, luminescent layer, the first electron transfer layer, wall, auxiliary electron transport layer, electron injecting layer and the cathode layer that stack gradually; The material of described wall is zinc oxide, titanium dioxide or magnesium oxide, and the thickness of this wall is 5-20nm.
Described organic electroluminescence device, wherein, described anode substrate is indium tin oxide glass, mix the zinc oxide glass of aluminium or mix the zinc oxide glass of indium.
Described organic electroluminescence device, wherein, the material of described hole injection layer is molybdenum trioxide, tungstic acid or vanadic oxide; The thickness of this hole injection layer is 20-60nm.
Described organic electroluminescence device, wherein, 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, N; N '-(1-naphthyl)-N, N '-diphenyl-4,4 '-benzidine; The thickness of this hole transmission layer is 20-60nm.
Described organic electroluminescence device, wherein, the material of described luminescent layer is two (4,6-difluorophenyl pyridine-N, C2) pyridine formyl closes iridium, two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanedione) and closes iridium or three (2-phenylpyridine) and close iridium and be doped in material of main part and form doping composite material according to the ratio of mass ratio 1 ~ 20%; Wherein, material of main part 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 thickness of this luminescent layer is 2-30nm.
Described organic electroluminescence device, wherein, the material of described the first electron transfer layer is 4,7-diphenyl-1,10-phenanthroline, 1,2,4-triazole derivative or N-aryl benzimidazole; The thickness of this first electron transfer layer is 40-80nm.
Described organic electroluminescence device, wherein, the material of described auxiliary electron transport layer is cadmium sulfide, calcium carbonate, cesium oxide or zinc sulphide; The thickness of described auxiliary electron transport layer is 20-80nm.
Described organic electroluminescence device, wherein, the material of described electron injecting layer is cesium carbonate, cesium fluoride, nitrine caesium or lithium fluoride; The thickness of this electron injecting layer is 0.5-10nm.
Described organic electroluminescence device, wherein, the material of described cathode layer is silver, aluminium, platinum or gold; The thickness of this cathode layer is 80-250nm.
The present invention also provides the preparation method of above-mentioned organic electroluminescence device, comprises the steps:
S1, first anode substrate is carried out to photoetching treatment, then clean, remove the organic pollution on anode substrate surface;
S2, the anode substrate after cleaning up is carried out to oxygen plasma treatment, the processing time is 5-15min, and the power of processing is 10-50W;
S3, on anode substrate surface, stack gradually evaporation hole injection layer, hole transmission layer, luminescent layer and the first electron transfer layer;
S4, utilize electron beam evaporation, the wall that is 5 ~ 20nm at described the first electron transfer layer surface evaporation thickness, the material of this wall is zinc oxide, titanium dioxide or magnesium oxide;
S5, then evaporation auxiliary electron transport layer, electron injecting layer and cathode layer successively on the surface of wall;
Finally, after above-mentioned processing step completes, make organic electroluminescence device.
Organic electroluminescence device provided by the invention, it strengthens the transmission of electronics by preparing auxiliary electron transport layer, between the first electron transfer layer and auxiliary electron transport layer, prepare the wall of layer of metal oxide simultaneously, avoid to a certain extent the coupling of the free electron of photon and metal electrode, improved light extraction efficiency; And this metal oxide has certain help to improving the transmission rate of electronics, and the transmission rate of electronics is than low two orders of magnitude of hole transport speed, therefore, improve electric transmission speed, to contribute to improve the recombination probability in electronics and hole, thereby improved the luminous efficiency of device.
Accompanying drawing explanation
Fig. 1 is the organic electroluminescence device structural representation that the present invention makes;
Fig. 2 is energy efficiency and the current density graph of a relation of the organic electroluminescence device that makes of the organic electroluminescence device that makes of embodiment 1 and comparative example 1; Wherein, curve 1 represents the energy efficiency that has electroluminescent device and the current density relation curve that embodiment 1 makes; Curve 2 represents the energy efficiency that has electroluminescent device and the current density relation curve that comparative example 1 makes.
Embodiment
Organic electroluminescence device provided by the invention, as shown in Figure 1, comprise anode substrate 101, hole injection layer 102, hole transmission layer 103, luminescent layer 104, the first electron transfer layer 105, wall 106, auxiliary electron transport layer 107, electron injecting layer 108 and cathode layer 109; The material of this wall 106 is zinc oxide (ZnO), titanium dioxide (TiO 2) or magnesium oxide (MgO), preferential oxidation zinc (ZnO); The thickness of this wall 106 is 5-20nm, and preferred thickness is 10nm.
In above-mentioned organic electroluminescence device, material and the thickness of other functional layer are as follows:
Anode substrate 101 for indium tin oxide glass (ITO), mix the zinc oxide glass (AZO) of aluminium or mix the zinc oxide glass (IZO) of indium, be preferably ITO; Wherein, indium tin oxide glass, is called for short ito glass, and glass is substrate, and ITO is conductive anode layer, and the usage of trade is written as ITO; The zinc oxide category of glass of mixing the zinc oxide glass of aluminium and mixing indium seemingly;
The material of hole injection layer 102 is molybdenum trioxide (MoO 3), tungstic acid (WO 3) or vanadic oxide (V 2o 5), be preferably WO 3; The thickness of hole injection layer 102 is 20-80nm, and preferred thickness is 40nm;
The material of hole transmission layer 103 is 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane (TAPC), 4,4', 4 " tri-(carbazole-9-yl) triphenylamine (TCTA), N, N '-(1-naphthyl)-N, N '-diphenyl-4; 4 '-benzidine (NPB), is preferably NPB; The thickness of hole transmission layer 103 is 20-60nm, and preferred thickness is 40nm;
Luminescent layer 104 materials are two (4,6-difluorophenyl pyridine-N, C 2) 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) according to the ratio of mass ratio 1%-20%, be doped to the doping composite material forming in material of main part; Wherein, material of main part 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); The material of luminescent layer 104 is preferably Ir (ppy) 3be doped to that in TCTA, (its representation is: TCTA:Ir (ppy) 3), Ir (ppy) 3doping mass percent be 10%; The thickness of luminescent layer 104 is 2-30nm, and thickness is preferably 20nm;
The material of the first electron transfer layer 105 adopts 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2, and 4-triazole derivative (as TAZ) or N-aryl benzimidazole (TPBI), be preferably TAZ; The thickness of the first electron transfer layer 105 is 40-80nm, and preferred thickness is 60nm;
The material of auxiliary electron transport layer 107 is cadmium sulfide (CdS), calcium carbonate (CaCO 3), cesium oxide (Cs 2o) or zinc sulphide (ZnS), be preferably ZnS; The thickness of auxiliary electron transport layer 107 is 20-80nm;
The material of electron injecting layer 108 is cesium carbonate (Cs 2cO 3), cesium fluoride (CsF), nitrine caesium (CsN 3) or lithium fluoride (LiF), be preferably CsF; The thickness of electron injecting layer 108 is 0.5-10nm, and preferred thickness is 2nm;
The material of cathode layer 109 is silver (Ag), aluminium (Al), platinum (Pt) or gold (Au), is preferably Ag; The thickness of cathode layer 109 is 80-250nm, and preferred thickness is 150nm.
The preparation method of above-mentioned organic electroluminescence device, comprises the steps:
S1, first anode substrate is carried out to photoetching treatment, be cut into needed size, then clean, cleaning process is for using successively liquid detergent, deionized water, acetone, ethanol, each ultrasonic 15min of isopropyl alcohol, the organic pollution on removal anode substrate surface;
S2, the conductive anode layer of the anode substrate after cleaning up is carried out to oxygen plasma treatment, to increase the conductive anode layer work function of anode substrate; Processing time is 5-15min, and processing power is 10-50W;
S3, in vacuum coating equipment, layer evaporation hole injection layer, hole transmission layer, luminescent layer and the first electron transfer layer successively in the conductive anode layer of the conductive anode layer of anode substrate;
S4, then on the first electron transfer layer surface, adopt electron beam evaporation plating wall, material is zinc oxide (ZnO), titanium dioxide (TiO 2) or magnesium oxide (MgO), thickness is 5-20nm;
S5, then on wall surface, stack gradually evaporation auxiliary electron transport layer, electron injecting layer and cathode layer;
Finally, after above-mentioned steps completes, make organic electroluminescence device.
In above-mentioned preparation technology, the evaporation of step S3 ~ S5 is vacuum thermal resistance evaporation, and pressure is 2 * 10 -3-2 * 10 -5pa.
Organic electroluminescence device provided by the invention, it strengthens the transmission of electronics by preparing auxiliary electron transport layer, between the first electron transfer layer and auxiliary electron transport layer, prepare the wall of layer of metal oxide simultaneously, beam projecting is after auxiliary electron transport layer, due to too near apart from negative electrode, the free electron coupling of understanding some photon and metal disappears, reduce light reflection and got back to the probability of anode outgoing, and this wall can carry out scattering to light, make, to the light of cathode emission, scattering or reflection occur when being less than auxiliary electron transport layer through the first electron transfer layer, get back to device bottom outgoing, avoided to a certain extent the coupling of the free electron of photon and metal electrode, improve light extraction efficiency.And this metal oxide has the feature of inorganic material high transfer rate, to improving the transmission rate of electronics, there is certain help, and the transmission rate of electronics is than low two orders of magnitude of hole transport speed, therefore, improve electric transmission speed, to contribute to improve the recombination probability in electronics and hole, thereby improved the luminous efficiency of device.
Below in conjunction with accompanying drawing, preferred embodiment of the present invention is described in further detail.
Following embodiment and comparative example, its preparation with test instrument used is: high vacuum coating equipment (scientific instrument development center, Shenyang Co., Ltd, pressure <1 * 10 -32602), electroluminescent spectrum tester (U.S. photo research company, model: PR650) and screen intensity meter (Beijing Normal University, model: ST-86LA) Pa), current-voltage tester (U.S. Keithly company, model:.
Embodiment 1
First ito glass is used to liquid detergent successively, deionized water, ultrasonic 15min, removes the organic pollution on ito glass surface, cleans up the rear ITO layer to ito glass and carries out oxygen plasma treatment, and the processing time is 5min, and power is 50W;
Secondly, (material is WO on the ITO layer surface after oxygen plasma treatment, to stack gradually evaporation hole injection layer 3, thickness is 40nm), hole transmission layer (material is NPB, and thickness is 40nm); (material is Ir (ppy) to luminescent layer 3be doped in TCTA, be expressed as TCTA:Ir (ppy) 3, Ir (ppy) 3doping mass percent be 10%; Thickness is 20nm), the first electron transfer layer (material is TAZ, and thickness is 60nm);
Then electron beam evaporation plating wall: material is ZnO, and thickness is 40nm;
Then on wall surface, stack gradually evaporation auxiliary electron transport layer (material is ZnS, and thickness is 40nm), electron injecting layer (material is CsF, and thickness is 2nm) and cathode layer (material is Ag, and thickness is 150nm);
Finally obtain needed organic electroluminescence device, its structure is: glass/ITO/WO 3/ NPB/TCTA:Ir (ppy) 3/ TAZ/ZnO/ZnS/CsF/Ag.
Embodiment 2
First ito glass is used to liquid detergent successively, deionized water, ultrasonic 15min, removes the organic pollution on ito glass surface, cleans up the rear ITO layer to ito glass and carries out oxygen plasma treatment, and the processing time is 15min, and power is 10W;
Subsequently, the ITO layer surface after oxygen plasma treatment stacks gradually evaporation hole injection layer (material is MoO 3, thickness is 20nm), hole transmission layer (material is TAPC, and thickness is 60nm), (material is Ir (MDQ) to luminescent layer 2(acac) be doped in NPB, be expressed as NPB:Ir (MDQ) 2(acac), Ir (MDQ) 2(acac) doping mass percent is 2%; Thickness is 20nm), the first electron transfer layer (material is TPBi, and thickness is 40nm)
Then electron beam evaporation plating wall, material is MgO, thickness is 20nm;
Then on wall surface, stack gradually evaporation auxiliary electron transport layer (material is CdS, and thickness is 20nm), (material is Cs to electron injecting layer 2cO 3, thickness is 10nm) and cathode layer (material is Au, and thickness is 80nm);
Finally obtain needed organic electroluminescence device, its structure is: glass/ITO/MoO 3/ TAPC/NPB:Ir (MDQ) 2(acac)/TPBi/MgO/CdS/Cs 2cO 3/ Au.
Embodiment 3
First AZO glass is used to liquid detergent successively, deionized water, ultrasonic 15min, the organic pollution of removal AZO glass surface, cleans up the rear AZO layer to AZO glass and carries out oxygen plasma treatment, and the processing time is 10min, and power is 30W;
Subsequently, the AZO surface after oxygen plasma treatment stacks gradually evaporation hole injection layer (material is WO 3, thickness is 80nm), hole transmission layer (material is TCTA, and thickness is 20nm), (material is that Firpic is doped in TCTA to luminescent layer, is expressed as TCTA:Firpic, and the doping mass percent of Firpic is 20%; Thickness is 30nm), the first electron transfer layer (material is TAZ, and thickness is 80nm);
Then electron beam evaporation plating wall, material is TiO 2, thickness is 5nm
Then in wall surface evaporation auxiliary electron transport layer, (material is CaCO 3, thickness is 80nm), (material is CsN to electron injecting layer 3, thickness 0.5nm) and cathode layer (material is Al, and thickness is 250nm);
Finally obtain needed organic electroluminescence device, its structure is: glass/AZO/WO 3/ TCTA/TCTA:Firpic/TAZ/TiO 2/ CaCO 3/ CsN 3/ Al.
Embodiment 4
First IZO glass is used to liquid detergent successively, deionized water, ultrasonic 15min, the organic pollution of removal IZO glass surface, cleans up the rear IZO layer to IZO glass and carries out oxygen plasma treatment, and the processing time is 12min, and power is 20W;
Subsequently, the IZO layer surface after oxygen plasma treatment stacks gradually evaporation hole injection layer (material is V 2o 5, thickness is 25nm); Hole transmission layer (material is NPB, and thickness is 55nm), (material is Ir (ppy) to luminescent layer 3be doped in TAPC, be expressed as TAPC:Ir (ppy) 3, Ir (ppy) 3doping mass percent be 9%; Thickness is 16nm), the first electron transfer layer (material is Bphen, and thickness is 50nm);
Then electron beam evaporation plating wall, material is ZnO, thickness is 15nm.
Then (material is Cs on wall surface, to stack gradually evaporation auxiliary electron transport layer 2o, thickness is 65nm), electron injecting layer (material is LiF, and thickness is 1nm) and cathode layer (material is Pt, and thickness is 100nm);
Finally obtain needed organic electroluminescence device, its structure is: glass/IZO/V 2o 5/ NPB/TAPC:Ir (ppy) 3/ Bphen/ZnO/Cs 2o/LiF/Pt.
Embodiment 5
First AZO glass is used to liquid detergent successively, deionized water, ultrasonic 15min, the organic pollution of removal AZO glass surface, cleans up the rear AZO layer to AZO glass and carries out oxygen plasma treatment, and the processing time is 10min, and power is 30W;
Subsequently, the AZO layer surface after oxygen plasma treatment stacks gradually evaporation hole injection layer (material is WO 3, thickness is 80nm); Hole transmission layer (material is TCTA, and thickness is 20nm); (material is Ir (MDQ) to luminescent layer 2(acac) be doped in TCTA, be expressed as TCTA:Ir (MDQ) 2(acac), Ir (MDQ) 2(acac) doping mass percent is 5%; Thickness is 30nm), the first electron transfer layer (material is TAZ, and thickness is 80nm);
Then electron beam evaporation plating wall, material is TiO 2, thickness is 5nm;
Then (material is Cs on wall surface, to stack gradually evaporation auxiliary electron transport layer 2o, thickness is 80nm), (material is CsN to electron injecting layer 3, thickness 0.5nm) and cathode layer (material is Ag, and thickness is 200nm);
Finally obtain needed organic electroluminescence device, its structure is: glass/AZO/WO 3/ TCTA/TCTA:Firpic/TAZ/TiO 2/ Cs 2o/CsN 3/ Ag.
Embodiment 6
First IZO glass is used to liquid detergent successively, deionized water, ultrasonic 15min, the organic pollution of removal IZO glass surface, cleans up the rear IZO layer to IZO glass and carries out oxygen plasma treatment, and the processing time is 10min, and power is 30W;
Subsequently, the IZO layer surface after oxygen plasma treatment stacks gradually evaporation hole injection layer (material is MoO 3, thickness is 60nm), hole transmission layer (material is TCTA, and thickness is 20nm), (material is that Firpic is doped in NPB to luminescent layer, is expressed as NPB:Firpic, and the doping mass percent of Firpic is 20%; Thickness is 30nm), the first electron transfer layer (material is TAZ, and thickness is 80nm);
Then electron beam evaporation plating wall, material is TiO 2, thickness is 5nm
Then (material is CaCO on wall surface, to stack gradually evaporation auxiliary electron transport layer 3, thickness is 80nm), (material is CsN to electron injecting layer 3, thickness 0.5nm) and cathode layer (material is Al, and thickness is 250nm);
Finally obtain needed organic electroluminescence device, its structure is: glass/IZO/MoO 3/ TCTA/NPB:Firpic/TAZ/TiO 2/ CaCO 3/ CsN 3/ Al.
Embodiment 7
First AZO glass is used to liquid detergent successively, deionized water, ultrasonic 15min, the organic pollution of removal AZO glass surface, cleans up the rear AZO layer to AZO glass and carries out oxygen plasma treatment, and the processing time is 10min, and power is 30W;
Subsequently, the AZO layer surface after oxygen plasma treatment stacks gradually evaporation hole injection layer (material is WO 3, thickness is 80nm), hole transmission layer (material is TCTA, and thickness is 20nm), (material is that Firpic is doped in TAPC to luminescent layer, is expressed as TAPC:Firpic, and the doping mass percent of Firpic is 20%; Thickness is 30nm), the first electron transfer layer (material is TAZ, and thickness is 80nm);
Then electron beam evaporation plating wall, material is MgO, thickness is 10nm
Then (material is CaCO on wall surface, to stack gradually evaporation auxiliary electron transport layer 3, thickness is 80nm), electron injecting layer (material is CsF, thickness 0.5nm) and cathode layer (material is Au, and thickness is 150nm);
Finally obtain needed organic electroluminescence device, its structure is: glass/AZO/WO 3/ TCTA/TAPC:Firpic/TAZ/MgO/CaCO 3/ CsF/Au.
Embodiment 8
First ito glass is used to liquid detergent successively, deionized water, ultrasonic 15min, removes the organic pollution on ito glass surface, cleans up the rear ITO layer to ito glass and carries out oxygen plasma treatment, and the processing time is 10min, and power is 30W;
Subsequently, the ITO laminate surface after oxygen plasma treatment stacks gradually evaporation hole injection layer (material is WO 3, thickness is 50nm), hole transmission layer (material is TAPC, and thickness is 40nm), (material is Ir (ppy) to luminescent layer 3be doped in NPB, be expressed as NPB:Ir (ppy) 3, Ir (ppy) 3doping mass percent be 20%; Thickness is 30nm), the first electron transfer layer (material is TAZ, and thickness is 80nm);
Then electron beam evaporation plating wall, material is TiO 2, thickness is 5nm
Then on wall surface, stack gradually evaporation auxiliary electron transport layer (material is CdS, and thickness is 60nm), (material is CsN to electron injecting layer 3, thickness 0.5nm) and cathode layer (material is Al, and thickness is 250nm);
Finally obtain needed organic electroluminescence device, its structure is: glass/ITO/WO 3/ TAPC/NPB:Ir (ppy) 3/ TAZ/TiO 2/ CdS/CsN 3/ Al.
Embodiment 9
First ito glass is used to liquid detergent successively, deionized water, ultrasonic 15min, removes the organic pollution on ito glass surface, cleans up the rear ITO layer to ito glass and carries out oxygen plasma treatment, and the processing time is 10min, and power is 30W;
Subsequently, the ITO layer surface after oxygen plasma treatment stacks gradually evaporation hole injection layer (material is WO 3, thickness is 80nm), hole transmission layer (material is TCTA, and thickness is 20nm), (material is Ir (MDQ) to luminescent layer 2(acac) be doped in TAPC, be expressed as TAPC:Ir (MDQ) 2(acac), Ir (MDQ) 2(acac) doping mass percent is 10%; Thickness is 10nm); The first electron transfer layer (material is Bphen, and thickness is 70nm);
Then electron beam evaporation plating wall, material is TiO 2, thickness is 5nm
(material is CaCO on wall surface, to stack gradually evaporation auxiliary electron transport layer 3, thickness is 80nm); (material is CsN to electron injecting layer 3, thickness 0.5nm) and cathode layer (material is Pt, and thickness is 250nm);
Finally obtain needed organic electroluminescence device, its structure is: glass/ITO/WO 3/ TCTA/TAPC:Ir (MDQ) 2(acac)/Bphen/TiO 2/ CaCO 3/ CsN 3/ Pt.
Comparative example 1
First ito glass is used to liquid detergent successively, deionized water, ultrasonic 15min, removes the organic pollution on ito glass surface, cleans up the rear ITO layer to ito glass and carries out oxygen plasma treatment, and the processing time is 5min, and power is 50W;
Secondly, the ITO layer surface after oxygen plasma treatment stacks gradually evaporation hole injection layer, and (material is WO 3, thickness is 40nm), hole transmission layer (material is NPB, and thickness is 40nm); (material is Ir (ppy) to luminescent layer 3be doped in TCTA, be expressed as TCTA:Ir (ppy) 3, Ir (ppy) 3doping mass percent be 10%; Thickness is 20nm); Electron transfer layer (material is TAZ, and thickness is 60nm);
Then on electron transfer layer surface, stack gradually evaporation electron injecting layer (material is CsF, and thickness is 2nm) and cathode layer (material is Ag, and thickness is 150nm);
Finally make organic electroluminescence device, its structure is: glass/ITO/WO 3/ NPB/TCTA:Ir (ppy) 3/ TAZ/CsF/Ag
Fig. 2 is energy efficiency and the current density graph of a relation of the organic electroluminescence device that makes of the organic electroluminescence device that makes of embodiment 1 and comparative example 1; Wherein, curve 1 represents the energy efficiency that has electroluminescent device and the current density relation curve that embodiment 1 makes; Curve 2 represents the energy efficiency that has electroluminescent device and the current density relation curve that comparative example 1 makes.
From accompanying drawing 2, can see, under different current densities, the energy efficiency of the organic electroluminescence device that embodiment 1 makes is all large than the energy efficiency of the organic electroluminescence device making of comparative example 1, maximum luminous efficiency is 30.7lm/W, and that comparative example 1 is only 18.8lm/W, this explanation, the wall of preparing layer of metal oxide between the first electron transfer layer and auxiliary electron transport layer, avoid to a certain extent the coupling of the free electron of photon and metal electrode, improved light extraction efficiency.And this metal oxide has certain help to improving the transmission rate of electronics, contribute to improve the recombination probability in electronics and hole, thereby improved the luminous efficiency of organic electroluminescence device.
Should be understood that, the 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, and scope of patent protection of the present invention should be as the criterion with claims.

Claims (10)

1. an organic electroluminescence device, is characterized in that, comprises the anode substrate, hole injection layer, hole transmission layer, luminescent layer, the first electron transfer layer, wall, auxiliary electron transport layer, electron injecting layer and the cathode layer that stack gradually; The material of described wall is zinc oxide, titanium dioxide or magnesium oxide, and the thickness of this wall is 5-20nm.
2. organic electroluminescence device according to claim 1, is characterized in that, described anode substrate is indium tin oxide glass, mix the zinc oxide glass of aluminium or mix the zinc oxide glass of indium.
3. organic electroluminescence device according to claim 1, is characterized in that, the material of described hole injection layer is molybdenum trioxide, tungstic acid or vanadic oxide; The thickness of this hole injection layer is 20-60nm.
4. organic electroluminescence device according to claim 1, it is characterized in that, 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, N; N '-(1-naphthyl)-N, N '-diphenyl-4,4 '-benzidine; The thickness of this 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 two (4,6-difluorophenyl pyridine-N, C 2) 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 and be doped in material of main part and form doping composite material according to the ratio of mass ratio 1 ~ 20%; Wherein, material of main part 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 thickness of this luminescent layer is 2-30nm.
6. organic electroluminescence device according to claim 1, is characterized in that, the material of described the first electron transfer layer is 4,7-diphenyl-1,10-phenanthroline, 1,2,4-triazole derivative or N-aryl benzimidazole; The thickness of this first electron transfer layer is 40-80nm.
7. organic electroluminescence device according to claim 1, is characterized in that, the material of described auxiliary electron transport layer is cadmium sulfide, calcium carbonate, cesium oxide or zinc sulphide; The thickness of described auxiliary electron transport layer is 20-80nm.
8. 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 this electron injecting layer is 0.5-10nm.
9. 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 this cathode layer is 80-250nm.
10. the preparation method of organic electroluminescence device claimed in claim 1, is characterized in that, comprises the steps:
S1, first anode substrate is carried out to photoetching treatment, then clean, remove the organic pollution on anode substrate surface;
S2, the anode substrate after cleaning up is carried out to oxygen plasma treatment, the processing time is 5-15min, and the power of processing is 10-50W;
S3, on anode substrate surface, stack gradually evaporation hole injection layer, hole transmission layer, luminescent layer and the first electron transfer layer;
S4, utilize electron beam evaporation, the wall that is 5 ~ 20nm at described the first electron transfer layer surface evaporation thickness, the material of this wall is zinc oxide, titanium dioxide or magnesium oxide;
S5, then evaporation auxiliary electron transport layer, electron injecting layer and cathode layer successively on the surface of wall;
Finally, after above-mentioned processing step completes, make organic electroluminescence device.
CN201210264215.5A 2012-07-27 2012-07-27 Organic electroluminescence device and manufacturing method thereof Pending CN103579519A (en)

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CN105226199A (en) * 2015-10-14 2016-01-06 上海大学 Be applied to the bielectron implanted layer structure of organic electroluminescence device, be inverted organic electroluminescence device and preparation method thereof
CN112970130A (en) * 2018-10-30 2021-06-15 夏普株式会社 Light-emitting element and method for manufacturing light-emitting element
CN112970130B (en) * 2018-10-30 2024-02-09 夏普株式会社 Light-emitting element and method for manufacturing light-emitting element
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Application publication date: 20140212