CN103311448A - Organic electroluminescent device and preparation method thereof - Google Patents
Organic electroluminescent device and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the field of organic electroluminescent devices and discloses an organic electroluminescent device and a preparation method thereof. The organic electroluminescent device comprises an anode conductive glass substrate, a hole injection layer, a hole transport layer, a luminescent layer, a hole blocking layer, an electron transport layer, an electron injection layer and a cathode layer which are sequentially stacked, wherein the hole blocking layer is made of zinc-oxide-doped hole blocking material. As the organic electroluminescent device provided by the invention is made by doping a metal oxide in the hole blocking material, light emitted from two sides can be concentrated to the middle of the device through scattering and be reflected back to the bottom of the device by the cathode, and the light efficiency is improved. The material has good electron transport capability, can be used for improving the electron transport rate inside the device, has stable properties and is conducive to the improvement of stability of the device.
Description
Technical field
The present invention relates to organic electroluminescence device, 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 current density, high efficiency double-deck organic electroluminescence device (OLED).In this double-deck device, current density 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 the radiation inactivation, release luminous energy.
In traditional organic electroluminescence device, all be to be exiting surface with the ito glass substrate, this device technology of preparing maturation, research is many, the light that luminescent layer sends, will be through the reflection of top negative electrode, thus shine in the ito glass, and the only outgoing from all directions of luminescent layer, part light can be from the outgoing of device both sides before arriving negative electrode, cause out light loss, light emission rate is reduced, finally reduce luminous efficiency.
Summary of the invention
The organic electroluminescence device that provides a kind of luminance higher is provided one of problem to be solved by this invention.
A kind of organic electroluminescence device comprises the anode conducting substrate of glass, hole injection layer, hole transmission layer, luminescent layer, hole blocking layer, electron transfer layer, electron injecting layer and the cathode layer that stack gradually; Wherein, the material of described hole blocking layer is the hole barrier materials doping zinc-oxide, and the doping mass percent of zinc oxide is 1～20%; Described hole barrier materials is selected from two (triphenyl silicon) benzene of 1,4-, two (2-methyl-oxine-N1, O8)-(1,1 '-biphenyl-4-hydroxyl) aluminium or three (1-Phenylpyrazole) closes iridium.
In the described organic electroluminescence device, the material of each functional layer is as follows:
Described anode conducting substrate of glass is selected from indium tin oxide glass, mix the zinc oxide glass of aluminium or mix the zinc oxide glass of indium;
The material of described hole injection layer is selected from molybdenum trioxide, tungstic acid or vanadic oxide;
The material of described hole transmission layer is selected from 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;
To be dopant material be doped to the composite material of forming in the material of main part according to the ratio of mass percent 1～20% to the material of described luminescent layer; Wherein, dopant material is selected from 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); Material of main part is selected from 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 material of described electron transfer layer is selected from 4,7-diphenyl-1,10-phenanthroline, 1,2,4-triazole derivative or N-aryl benzimidazole;
The material of described electron injecting layer is selected from cesium carbonate, cesium fluoride, nitrine caesium or lithium fluoride;
The material of described cathode layer is selected from silver, aluminium, platinum or gold.
Two of problem to be solved by this invention is to provide the preparation method of above-mentioned organic electroluminescence device, comprises the steps;
S1, the anode conducting substrate of glass is carried out photoetching treatment, use liquid detergent, deionized water, acetone, ethanol, each ultrasonic cleaning 15min of isopropyl alcohol subsequently successively, remove organic pollution;
S2, will clean up back antianode electro-conductive glass suprabasil anode layer and carry out oxygen plasma treatment, the processing time is 5-15min, and power is 10-50W;
S3, employing evaporation process stack gradually evaporation hole injection layer, hole transmission layer, luminescent layer, hole blocking layer, electron transfer layer, electron injecting layer and cathode layer on the anode layer surface of anode conducting substrate of glass; Wherein, the material of described hole blocking layer is the hole barrier materials doping zinc-oxide, and the doping mass percent of zinc oxide is 1～20%; The thickness of described hole blocking layer is 2～20nm; Described hole barrier materials be selected from two (triphenyl silicon) benzene of 1,4-, two (2-methyl-oxine-N1, O8)-(1,1 '-biphenyl-4-hydroxyl) aluminium or three (1-Phenylpyrazole) closes iridium;
After above-mentioned processing step is finished, make organic electroluminescence device.
Organic electroluminescence device provided by the invention, mix with metal oxide and hole barrier materials, make focus on device by scattering to the light of both sides emissions in the middle of, reflected back into the device bottom by negative electrode, improve light extraction efficiency, material has electron transport ability preferably, can improve the electric transmission speed of device inside, and stable in properties, be conducive to improve the stability of device.
The preparation method of organic electroluminescence device provided by the invention, its preparation technology is simple, processing cost is low, is fit to commercially produce.
Description of drawings
Fig. 1 is the concrete organic electroluminescence device structural representation of implementing;
Current density and luminous efficiency graph of a relation between the organic electroluminescence device that Fig. 2 makes for embodiment 1 and the organic electroluminescence device of Comparative Examples.
Embodiment
The organic electroluminescence device that this embodiment provides, as shown in Figure 1, comprise anode conducting substrate of glass 11, hole injection layer 12, hole transmission layer 13, luminescent layer 14, hole blocking layer 15, electron transfer layer 16, electron injecting layer 17 and the cathode layer 18 that stacks gradually; Wherein, anode conducting substrate of glass 11 comprises anode layer 112 and substrate of glass 111; The material of described hole blocking layer is the hole barrier materials doping zinc-oxide, and zinc oxide (be that hole barrier materials is material of main part, zinc oxide is dopant material), and the doping mass percent of zinc oxide is 1～20% (preferred 15%); Described hole barrier materials is selected from two (triphenyl silicon) benzene (UGH2) of 1,4-, two (2-methyl-oxine-N1, O8)-(1,1 '-biphenyl-4-hydroxyl) aluminium (BAlq) or three (1-Phenylpyrazole) closes iridium (Ir (ppz)
3); The thickness of described hole blocking layer is 2～20nm, and preferred thickness is 10nm.
Organic electroluminescence device described above, material and the thickness of each functional layer are as follows:
Anode conducting substrate of glass 11 is selected from indium tin oxide glass, mix the zinc oxide glass of aluminium or mix the zinc oxide glass of indium, and its anode layer 112 is respectively indium tin oxide (ITO), mix the zinc oxide (AZO) of aluminium, mix the zinc oxide (IZO) of indium; Therefore, indium tin oxide glass, the zinc oxide glass of mixing aluminium, the zinc oxide glass of mixing indium are called for short ito glass, AZO glass, IZO glass respectively;
The material of hole injection layer 12 is selected from molybdenum trioxide (MoO
3), tungstic acid (WO
3) or vanadic oxide (V
2O
5); The thickness of hole injection layer is 10-40nm, and preferred thickness is 20nm;
The material of hole transmission layer 13 is selected from 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, the preferred NPB of 4 '-benzidine (NPB); The thickness of hole transmission layer is 20-60nm, and preferred thickness is 40nm;
The material of luminescent layer 14 is selected from two (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); Perhaps
To be dopant material be doped to the composite material of forming in the material of main part according to the ratio of mass percent 1～20% to the material of luminescent layer 14; Wherein, dopant material is selected from two (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); Material of main part is selected from 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 '-benzidines (NPB);
The thickness of luminescent layer 14 is 2-30nm;
The material of luminescent layer 14 is preferably Ir (ppy)
3Be doped among the TCTA, and the doping mass percent is 10% that at this moment, the thickness of luminescent layer is preferably 20nm;
The material of electron transfer layer 16 is selected from 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2, the 4-triazole derivative (as, TAZ) or N-aryl benzimidazole (TPBi); The thickness of electron transfer layer 15 is 40-80nm, preferred 60nm;
The material of electron injecting layer 17 is selected from 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 17 is 0.5-10nm, and preferred thickness is 0.7nm;
The material of cathode layer 17 is selected from silver (Ag), aluminium (Al), platinum (Pt) or gold (Au), is preferably Ag; The thickness of cathode layer is 80～250nm, and preferred thickness is 100nm.
The preparation method of above-mentioned organic electroluminescence device comprises the steps;
S1, the anode conducting substrate of glass is carried out photoetching treatment, use liquid detergent, deionized water, acetone, ethanol, each ultrasonic cleaning 15min of isopropyl alcohol subsequently successively, remove organic pollution;
S2, will clean up back antianode electro-conductive glass suprabasil anode layer and carry out oxygen plasma treatment, the processing time is 5-15min, and power is 10-50W;
S3, employing evaporation process stack gradually evaporation hole injection layer, hole transmission layer, luminescent layer, hole blocking layer, electron transfer layer, electron injecting layer and cathode layer on the anode layer surface of anode conducting substrate of glass; Wherein, the material of described hole blocking layer is the hole barrier materials doping zinc-oxide, and the doping mass percent of zinc oxide is 1～10%; Described hole barrier materials be selected from two (triphenyl silicon) benzene of 1,4-, two (2-methyl-oxine-N1, O8)-(1,1 '-biphenyl-4-hydroxyl) aluminium or three (1-Phenylpyrazole) closes iridium; The thickness of described hole blocking layer is 2～20nm;
After above-mentioned processing step is finished, make organic electroluminescence device.
Above-mentioned organic electroluminescence device, mix with metal oxide and hole barrier materials, on the one hand, used metal oxide has stronger reflection and scattering process to light, can make focus on device by scattering to the light of both sides emissions in the middle of, reflected back into the device bottom by negative electrode, improve light extraction efficiency, on the other hand, this material has electronic transmission performance preferably, can improve the electric transmission speed of device inside, thereby improve the recombination probability of hole and electronics, finally improve luminous efficiency.This material purity height, the source is simple, and is cheap, and stable in properties is conducive to improve the stability of device.
Below in conjunction with accompanying drawing, preferred embodiment of the present invention is described in further detail.
Following examples, its evaporation process are all in high vacuum coating equipment (scientific instrument development center, Shenyang Co., Ltd, pressure＜1 * 10
-3Pa) carry out in.
Embodiment 1
Earlier ito glass is carried out photoetching treatment, be cut into needed size, use liquid detergent successively, deionized water, acetone, ethanol, each ultrasonic 15min of isopropyl alcohol removes the organic pollution on ito glass surface; Clean up the back ito glass is carried out suitable processing: oxygen plasma treatment ITO layer, the processing time is 5min, power is 30W; (material is MoO to the evaporation hole injection layer successively
3, thickness is 20nm), hole transmission layer (material is NPB, and thickness is 40nm), (material is TCTA:Ir (ppy) to luminescent layer
3, Ir (ppy)
3Be dopant material, TCTA is material of main part, Ir (ppy)
3The doping mass percent be 10%; The thickness of this luminescent layer is 20nm), hole blocking layer (material is BAlq:ZnO, and BAlq is material of main part, and ZnO is dopant material, and the doping mass percent is 10%, and the hole barrier layer thickness is 10nm), electron transfer layer (material is TAZ, and thickness is 60nm); At last on electron transfer layer successively the evaporation electron injecting layer (material is LiF; Thickness is 10nm) and cathode layer (material is Ag, and thickness is 100nm).Obtain needed organic electroluminescence device at last, its structure is: ito glass/MoO
3/ NPB/TCTA:Ir (ppy)
3/ BAlq:ZnO/TAZ/LiF/Ag.
Current density and luminous efficiency graph of a relation between the organic electroluminescence device that Fig. 2 makes for embodiment 1 and the organic electroluminescence device of Comparative Examples; The organic electroluminescence device structure of Comparative Examples is: ito glass/MoO
3/ NPB/TCTA:Ir (ppy)
3/ BAlq/TAZ/LiF/Ag; Wherein, curve 1 is the current density of organic electroluminescence device of embodiment 1 and the graph of a relation of luminous efficiency; Curve 2 is the current density of organic electroluminescence device of Comparative Examples and the graph of a relation of luminous efficiency; 2602), electroluminescent spectrum tester (U.S. photo research company, model: PR650) and screen current density design (Beijing Normal University, model: ST-86LA) current-voltage tester (U.S. Keithly company, model:.
From accompanying drawing 2, can see, under different current densities, the current density of the electron luminescence device that embodiment 1 makes is big than Comparative Examples all, maximum energy efficiency is 22.4lm/W, and that Comparative Examples only is 16.3lm/W, this explanation, utilize metal oxide and hole barrier materials to mix, can make focus on device by scattering to the light of both sides emissions in the middle of, reflected back into the device bottom by negative electrode, improve light extraction efficiency, and material good electron transmission performance, can improve the electric transmission speed of device inside, and then improve the recombination probability of hole and electronics, finally improve luminous efficiency.
Earlier IZO glass is carried out photoetching treatment, be cut into needed size, use liquid detergent successively, deionized water, acetone, ethanol, each ultrasonic 15min of isopropyl alcohol, the organic pollution of removal IZO glass surface; Clean up the back IZO glass is carried out suitable processing: oxygen plasma treatment IZO layer, the processing time is 5min, power is 50W; (material is WO to the evaporation hole injection layer successively
3Thickness is 10nm), hole transmission layer (material is TCTA, and thickness is 60nm), (material is NPB:Firpic to luminescent layer, and NPB is material of main part, Firpic is dopant material, very than being 20%, light emitting layer thickness is 30nm to the doping quality), (material is UGH2:ZnO to hole blocking layer, and UGH2 is material of main part, ZnO is dopant material, the doping mass percent is 1%, and the hole barrier layer thickness is 2nm), electron transfer layer (material is Bphen, and thickness is 80nm); At last on electron transfer layer successively the evaporation electron injecting layer (material is CsF; Thickness is 10nm) and cathode layer (material is Al, and thickness is 250nm), obtaining needed organic electroluminescence device at last, its structure is: IZO glass/WO
3/ TCTA/NPB:Firpic/UGH2:ZnO/Bphen/CsF/Al.
Embodiment 3
Earlier AZO glass is carried out photoetching treatment, be cut into needed size, use liquid detergent successively, deionized water, acetone, ethanol, each ultrasonic 15min of isopropyl alcohol, the organic pollution of removal AZO glass surface; Clean up the back AZO glass is carried out suitable processing: oxygen plasma treatment AZO layer, the processing time is 15min, power is 10W; (material is V to the evaporation hole injection layer successively
2O
5, thickness is 20nm), hole transmission layer (material is NPB, and thickness is 40nm), (material is TCTA:Ir (MDQ) to luminescent layer
2(acac), TCTA is material of main part, Ir (MDQ)
2(acac) for dopant material doping quality very than being 1%, light emitting layer thickness is 2nm), (material is Ir (ppz) to hole blocking layer
3: ZnO, Ir (ppz)
3Be material of main part, ZnO is dopant material, and the doping mass percent is 10%, and the hole barrier layer thickness is 20nm), electron transfer layer (material is TAZ, and thickness is 40nm); At last on electron transfer layer successively the evaporation electron injecting layer (material is Cs
2CO
3Thickness is 0.5nm) and cathode layer (material is Au, and thickness is 80nm), obtaining needed organic electroluminescence device at last, its structure is: AZO glass/V
2O
5/ NPB/TCTA:Ir (MDQ)
2(acac)/r (ppz)
3: ZnO/TAZ/Cs
2CO
3/ Au.
Earlier ito glass is carried out photoetching treatment, be cut into needed size, use liquid detergent successively, deionized water, acetone, ethanol, each ultrasonic 15min of isopropyl alcohol removes the organic pollution on ito glass surface; Clean up the back to carrying out suitable processing at the bottom of the ito glass: oxygen plasma treatment ITO layer, the processing time is 15min, power is 10W; (material is WO to the evaporation hole injection layer successively
3, thickness is 40nm), hole transmission layer (material is TAPC, and thickness is 20nm), (material is TAPC:Ir (ppy) to luminescent layer
3, TAPC is material of main part, Ir (ppy)
3Be dopant material, the doping quality is very than being 8%, light emitting layer thickness is 12nm), (material is UGH2:ZnO to hole blocking layer, UGH2 is material of main part, ZnO is dopant material, the doping mass percent is 8%, and the hole barrier layer thickness is 5nm), electron transfer layer (material is TPBi, and thickness is 70nm); At last on electron transfer layer successively the evaporation electron injecting layer (material is CsN
3Thickness is 7nm) and cathode layer (material is Pt, and thickness is 180nm), obtaining needed organic electroluminescence device at last, its structure is: ito glass/WO
3/ TAPC/TAPC:Ir (ppy)
3/ TPBi/UGH2:ZnO/CsN
3/ Pt.
Embodiment 5
Earlier ito glass is carried out photoetching treatment, be cut into needed size, use liquid detergent successively, deionized water, acetone, ethanol, each ultrasonic 15min of isopropyl alcohol removes the organic pollution on ito glass surface; Clean up the back ito glass is carried out suitable processing: oxygen plasma treatment ITO layer, the processing time is 12min, power is 15W; (material is MoO to the evaporation hole injection layer successively
3Thickness is 30nm), hole transmission layer (material is TCTA, and thickness is 35nm), (material is TCTA:Firpic to luminescent layer, and TCTA is material of main part, Firpic is dopant material, very than being 15%, light emitting layer thickness is 20nm to the doping quality), (material is BAlq:ZnO to hole blocking layer, and BAlq is material of main part, ZnO is dopant material, the doping mass percent is 15%, and the hole barrier layer thickness is 8nm), electron transfer layer (material is TAZ, and thickness is 50nm); At last on electron transfer layer successively the evaporation electron injecting layer (material is Cs
2CO
3Thickness is 1nm) and cathode layer (material is Ag, and thickness is 200nm), obtaining needed organic electroluminescence device at last, its structure is: ito glass/MoO
3/ TCTA/TCTA:Firpic/BAlq:ZnO/TAZ/Cs
2CO
3/ Ag.
Earlier ito glass is carried out photoetching treatment, be cut into needed size, use liquid detergent successively, deionized water, acetone, ethanol, each ultrasonic 15min of isopropyl alcohol removes the organic pollution on ito glass surface; Clean up the back to carrying out suitable processing at the bottom of the ito glass: oxygen plasma treatment ITO layer, the processing time is 15min, power is 10W; (material is WO to the evaporation hole injection layer successively
3, thickness is 40nm), hole transmission layer (material is TAPC, and thickness is 20nm), (material is NPB:Ir (ppy) to luminescent layer
3, NPB is material of main part, Ir (ppy)
3Be dopant material, the doping quality is very than being 8%, light emitting layer thickness is 12nm), (material is UGH2:ZnO to hole blocking layer, UGH2 is material of main part, ZnO is dopant material, the doping mass percent is 8%, and the hole barrier layer thickness is 5nm), electron transfer layer (material is TPBi, and thickness is 70nm); At last on electron transfer layer successively the evaporation electron injecting layer (material is CsN
3Thickness is 7nm) and cathode layer (material is Pt, and thickness is 180nm), obtaining needed organic electroluminescence device at last, its structure is: ito glass/WO
3/ TAPC/NPB:Ir (ppy)
3/ TPBi/UGH2:ZnO/CsN
3/ Pt.
Embodiment 7
Earlier ito glass is carried out photoetching treatment, be cut into needed size, use liquid detergent successively, deionized water, acetone, ethanol, each ultrasonic 15min of isopropyl alcohol removes the organic pollution on ito glass surface; Clean up the back ito glass is carried out suitable processing: oxygen plasma treatment ITO layer, the processing time is 12min, power is 15W; (material is MoO to the evaporation hole injection layer successively
3Thickness is 30nm), hole transmission layer (material is TCTA, and thickness is 35nm), (material is TAPC:Firpic to luminescent layer, and TAPC is material of main part, Firpic is dopant material, very than being 20%, light emitting layer thickness is 20nm to the doping quality), (material is BAlq:ZnO to hole blocking layer, and BAlq is material of main part, ZnO is dopant material, the doping mass percent is 15%, and the hole barrier layer thickness is 8nm), electron transfer layer (material is TAZ, and thickness is 50nm); At last on electron transfer layer successively the evaporation electron injecting layer (material is Cs
2CO
3Thickness is 1nm) and cathode layer (material is Ag, and thickness is 200nm), obtaining needed organic electroluminescence device at last, its structure is: ito glass/MoO
3/ TCTA/TAPC:Firpic/BAlq:ZnO/TAZ/Cs
2CO
3/ Ag.
Embodiment 8
Earlier AZO glass is carried out photoetching treatment, be cut into needed size, use liquid detergent successively, deionized water, acetone, ethanol, each ultrasonic 15min of isopropyl alcohol, the organic pollution of removal AZO glass surface; Clean up the back AZO glass is carried out suitable processing: oxygen plasma treatment AZO layer, the processing time is 15min, power is 10W; (material is V to the evaporation hole injection layer successively
2O
5, thickness is 20nm), hole transmission layer (material is NPB, and thickness is 40nm), (material is TAPC:Ir (MDQ) to luminescent layer
2(acac), TAPC is material of main part, Ir (MDQ)
2(acac) for dopant material doping quality very than being 1%, light emitting layer thickness is 2nm), (material is Ir (ppz) to hole blocking layer
3: ZnO, Ir (ppz)
3Be material of main part, ZnO is dopant material, and the doping mass percent is 10%, and the hole barrier layer thickness is 20nm), electron transfer layer (material is TAZ, and thickness is 40nm); At last on electron transfer layer successively the evaporation electron injecting layer (material is Cs
2CO
3Thickness is 0.5nm) and cathode layer (material is Au, and thickness is 80nm), obtaining needed organic electroluminescence device at last, its structure is: AZO glass/V
2O
5/ NPB/TCTA:Ir (MDQ)
2(acac)/r (ppz)
3: ZnO/TAZ/Cs
2CO
3/ Au.
Embodiment 9
Earlier AZO glass is carried out photoetching treatment, be cut into needed size, use liquid detergent successively, deionized water, acetone, ethanol, each ultrasonic 15min of isopropyl alcohol, the organic pollution of removal AZO glass surface; Clean up the back AZO glass is carried out suitable processing: oxygen plasma treatment AZO layer, the processing time is 15min, power is 10W; (material is V to the evaporation hole injection layer successively
2O
5, thickness is 20nm), hole transmission layer (material is NPB, and thickness is 40nm), (material is NPB:Ir (MDQ) to luminescent layer
2(acac), NPB is material of main part, Ir (MDQ)
2(acac) for dopant material doping quality very than being 1%, light emitting layer thickness is 2nm), (material is Ir (ppz) to hole blocking layer
3: ZnO, Ir (ppz)
3Be material of main part, ZnO is dopant material, and the doping mass percent is 10%, and the hole barrier layer thickness is 20nm), electron transfer layer (material is TAZ, and thickness is 40nm); At last on electron transfer layer successively the evaporation electron injecting layer (material is Cs
2CO
3Thickness is 0.5nm) and cathode layer (material is Au, and thickness is 80nm), obtaining needed organic electroluminescence device at last, its structure is: AZO glass/V
2O
5/ NPB/NPB:Ir (MDQ)
2(acac)/r (ppz)
3: ZnO/TAZ/Cs
2CO
3/ Au.
Should be understood that above-mentioned statement at 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 anode conducting substrate of glass, hole injection layer, hole transmission layer, luminescent layer, hole blocking layer, electron transfer layer, electron injecting layer and the cathode layer that stack gradually; Wherein, the material of described hole blocking layer is the hole barrier materials doping zinc-oxide, and the doping mass percent of zinc oxide is 1～20%; Described hole barrier materials be selected from two (triphenyl silicon) benzene of 1,4-, two (2-methyl-oxine-N1, O8)-(1,1 '-biphenyl-4-hydroxyl) aluminium or three (1-Phenylpyrazole) closes iridium; The thickness of described hole blocking layer is 2～20nm.
2. organic electroluminescence device according to claim 1 is characterized in that, described anode conducting glass is selected from 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 selected from molybdenum trioxide, tungstic acid or vanadic oxide; The thickness of described hole injection layer is 10-40nm.
4. organic electroluminescence device according to claim 1, it is characterized in that, the material of described hole transmission layer is selected from 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, to be dopant material be doped to the composite material of forming in the material of main part according to the ratio of mass percent 1～20% to the material of described luminescent layer; Wherein, dopant material is selected from 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; Material of main part is selected from 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 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 selected from 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 selected from 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 selected from silver, aluminium, platinum or gold; The thickness of described cathode layer is 80～250nm.
9. the preparation method of the described organic electroluminescence device of claim 1 is characterized in that, comprises the steps;
S1, the anode conducting substrate of glass is carried out photoetching treatment, use liquid detergent, deionized water, acetone, ethanol, each ultrasonic cleaning 15min of isopropyl alcohol subsequently successively, remove organic pollution;
S2, will clean up back antianode electro-conductive glass suprabasil anode layer and carry out oxygen plasma treatment, the processing time is 5-15min, and power is 10-50W;
S3, employing evaporation process stack gradually evaporation hole injection layer, hole transmission layer, luminescent layer, hole blocking layer, electron transfer layer, electron injecting layer and cathode layer on the anode layer surface of anode conducting substrate of glass; Wherein, the material of described hole blocking layer is the hole barrier materials doping zinc-oxide, and the doping mass percent of zinc oxide is 1～20%; Described hole barrier materials be selected from two (triphenyl silicon) benzene of 1,4-, two (2-methyl-oxine-N1, O8)-(1,1 '-biphenyl-4-hydroxyl) aluminium or three (1-Phenylpyrazole) closes iridium; The thickness of described hole blocking layer is 2～20nm;
After above-mentioned processing step is finished, make organic electroluminescence device.
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Application publication date: 20130918 |