CN104078622A - Organic light-emitting diode device and manufacturing method thereof - Google Patents

Organic light-emitting diode device and manufacturing method thereof Download PDF

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CN104078622A
CN104078622A CN201310109551.7A CN201310109551A CN104078622A CN 104078622 A CN104078622 A CN 104078622A CN 201310109551 A CN201310109551 A CN 201310109551A CN 104078622 A CN104078622 A CN 104078622A
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layer
bis
aluminium
metal
nanometers
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周明杰
王平
钟铁涛
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
    • H10K50/80—Constructional details
    • H10K50/805—Electrodes
    • H10K50/82—Cathodes
    • 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
    • H10K50/805—Electrodes
    • H10K50/82—Cathodes
    • H10K50/828—Transparent cathodes, e.g. comprising thin metal layers
    • 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
    • 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
    • H10K2102/10—Transparent electrodes, e.g. using graphene
    • H10K2102/101—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO]
    • 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
    • H10K2102/10—Transparent electrodes, e.g. using graphene
    • H10K2102/101—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO]
    • H10K2102/102—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO] comprising tin oxides, e.g. fluorine-doped SnO2
    • 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
    • H10K2102/10—Transparent electrodes, e.g. using graphene
    • H10K2102/101—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO]
    • H10K2102/103—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO] comprising indium oxides, e.g. ITO

Abstract

An organic light-emitting diode device comprises a glass substrate, a hole injection layer, a hole transmission layer, a green light-emitting layer, an electron transmission layer, an electron injection layer and a cathode layer which are sequentially stacked, wherein the cathode layer comprises a metal layer, a metal oxide mixed layer, a metal doped layer and a transparent conductive layer which are sequentially stacked. The metal layer is stacked on the electron injection layer and made from aluminum, nickel, gold or silver, the metal oxide mixed layer is made from a mixture formed by mixing, by same mass, two of neodymium pentoxide, vanadium pentoxide and tantalum pentoxide, the metal doped layer is made from silver doped magnesium or lithium doped aluminum, and the transparent conductive layer is made from an indium-tin oxide, an aluminum-zinc oxide or an indium-zinc oxide. The organic light-emitting diode device has high luminous efficiency. In addition, the invention further relates to a manufacturing method of the organic light-emitting diode device.

Description

Organic electroluminescence device and preparation method thereof
Technical field
The present invention relates to field of electronic devices, particularly a kind of organic electroluminescence device and preparation method thereof.
Background technology
Organic electroluminescence device (OLED) has advantages of that some are unique: (1) OLED belongs to diffused area source, does not need by extra light-conducting system, to obtain large-area white light source as light-emitting diode (LED); (2) due to the diversity of luminous organic material, OLED illumination is the light of design color as required, no matter be little Molecule OLEDs at present, or polymer organic LED (PLED) has all obtained and has comprised white-light spectrum at the light of interior all colours; (3) OLED can make on as glass, pottery, metal, plastic or other material at multiple substrate, freer when this makes to design lighting source; (4) adopt the mode of making OLED demonstration to make OLED illumination panel, can in illumination, show information; (5) OLED also can be used as controlled look in illuminator, allows user to regulate light atmosphere according to individual demand.But there is the lower problem of luminous efficiency in traditional organic electroluminescence device.
Summary of the invention
Given this, be necessary to provide organic electroluminescence device that a kind of luminous efficiency is higher and preparation method thereof.
A kind of organic electroluminescence device, comprise the glass substrate stacking gradually, hole injection layer, hole transmission layer, green light emitting layer, electron transfer layer, electron injecting layer and cathode layer, described cathode layer comprises the metal level stacking gradually, metal oxide mixed layer, metal-doped layer and transparency conducting layer, described metal level is laminated on described electron injecting layer, the material of described metal level is aluminium, nickel, golden or silver-colored, the material of described metal oxide mixed layer is five oxidation two neodymiums, two kinds of mixtures that form according to identical mass mixing in vanadic oxide and tantalum pentoxide, the material of described metal-doped layer is the magnesium of silver doping or the aluminium of lithium doping, described in the magnesium of described silver doping, silver is 5:1～20:1 with the mass ratio of described magnesium, the mass ratio of lithium and described aluminium described in the aluminium of described lithium doping is 0.001:1～0.001:0.1, the material of described transparency conducting layer is indium tin oxide, aluminium zinc oxide or indium-zinc oxide.
In an embodiment, the thickness of described metal level is 5 nanometer～20 nanometers therein; The thickness of described metal oxide mixed layer is 40 nanometer～60 nanometers; The thickness of described metal-doped layer is 10 nanometer～20 nanometers; The thickness of described transparency conducting layer is 20 nanometer～40 nanometers.
Therein in an embodiment, the material of described hole injection layer comprises hole mobile material and is doped in the p-type dopant in described hole mobile material, and the mass ratio of described p-type dopant and described hole mobile material is 0.25～0.35:1, described hole mobile material is selected from N, N '-diphenyl-N, N '-bis-(1-naphthyl)-1, 1 '-biphenyl-4, 4 '-diamines, 4, 4 ', 4 " tri-(carbazole-9-yl) triphenylamine, 4, 4 '-bis-(9-carbazole) biphenyl, N, N '-bis-(3-aminomethyl phenyl)-N, N '-diphenyl-4, 4 '-benzidine and 1, 1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] a kind of in cyclohexane, described p-type dopant is selected from molybdenum trioxide, tungstic acid, a kind of in vanadic oxide and rhenium trioxide,
The material of described hole transmission layer is selected from N, N '-diphenyl-N, N '-bis-(1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines, 4,4 ', 4 " tri-(carbazole-9-yl) triphenylamine, 4; 4 '-bis-(9-carbazole) biphenyl, N; N '-bis-(3-aminomethyl phenyl)-N, N '-diphenyl-4,4 '-benzidine and 1; 1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] a kind of in cyclohexane;
The material of described green light emitting layer comprises material of main part and is doped in the green guest material in described material of main part, the mass ratio of described green guest material and described material of main part is 0.02～0.1:1, described material of main part is selected from 4, 4 ', 4 " tri-(carbazole-9-yl) triphenylamine, 9, 9 '-(1, 3-phenyl) two-9H-carbazole, 4, 4 '-bis-(9-carbazole) biphenyl, N, N '-bis-(3-aminomethyl phenyl)-N, N '-diphenyl-4, 4 '-benzidine, 1, 1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane and 9, a kind of in two (1-naphthyl) anthracenes of 10-, described green guest material is that three (2-phenylpyridines) close iridium, acetopyruvic acid two (2-phenylpyridine) iridium and three [2-(p-methylphenyl) pyridine] closes a kind of in iridium (III),
The material of described electron transfer layer is selected from 4,7-diphenyl-1,10-phenanthroline, 4,7-diphenyl-1,10-Phen, 4-biphenyl phenolic group-bis-(2-methyl-oxine) close aluminium, oxine aluminium, 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole and 1, a kind of in 3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene;
The material of described electron injecting layer comprises electron transport material and co-doped sulfate and the alkali metal salt in described electron transport material, the mass ratio of described sulfate and described electron transport material is 0.06～0.25:1, the mass ratio of described alkali metal salt and described electron transport material is 0.25～0.35:1, described electron transport material is selected from 4, 7-diphenyl-1, 10-phenanthroline, 4, 7-diphenyl-1, 10-Phen, 4-biphenyl phenolic group-bis-(2-methyl-oxine) close aluminium, oxine aluminium, 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1, 2, 4-triazole and 1, 3, a kind of in 5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene, described sulfate is selected from lithium sulfate, sodium sulphate, potassium sulfate, a kind of in rubidium sulfate and cesium sulfate, described alkali metal salt is selected from lithium fluoride, Lithium Azide, lithium nitride, cesium fluoride, a kind of in cesium azide and nitrogenize caesium.
In an embodiment, the thickness of described hole injection layer is 10 nanometer～15 nanometers therein; The thickness of described hole transmission layer is 30 nanometer～50 nanometers; The thickness of described green light emitting layer is 10 nanometer～30 nanometers; The thickness of described electron transfer layer is 10 nanometer～60 nanometers; The thickness of described electron injecting layer is 15 nanometer～45 nanometers.
A preparation method for organic electroluminescence device, comprises the steps:
On glass substrate, vacuum evaporation forms hole injection layer, hole transmission layer, green light emitting layer, electron transfer layer and electron injecting layer successively; And
On described electron injecting layer, form cathode layer, described cathode layer comprises the metal level stacking gradually, metal oxide mixed layer, metal-doped layer and transparency conducting layer, described metal level is formed on described electron injecting layer, and described metal level and described metal-doped layer are prepared by vacuum evaporation, described metal oxide mixed layer and described transparency conducting layer are prepared by magnetron sputtering, obtain organic electroluminescence device, wherein, the material of described metal level is aluminium, nickel, golden or silver-colored, the material of described metal oxide mixed layer is five oxidation two neodymiums, two kinds of mixtures that form according to identical mass mixing in vanadic oxide and tantalum pentoxide, the material of described metal-doped layer is the magnesium of silver doping or the aluminium of lithium doping, described in the magnesium of described silver doping, silver is 5:1～20:1 with the mass ratio of described magnesium, the mass ratio of lithium and described aluminium described in the aluminium of described lithium doping is 0.001:1～0.001:0.1, the material of described transparency conducting layer is indium tin oxide, aluminium zinc oxide or indium-zinc oxide.
Therein in an embodiment, on described glass substrate, vacuum evaporation also comprises the step that described glass substrate is cleaned before forming described hole injection layer: described glass substrate is adopted to liquid detergent, deionized water, acetone and ethanol ultrasonic cleaning successively, and then dry.
In an embodiment, vacuum evaporation after described cleaning glass substrate, on described glass substrate is also comprised to the step of the surface of described glass substrate being carried out to activation processing before forming described hole injection layer therein.
In an embodiment, the vacuum degree that vacuum evaporation forms described hole injection layer is 1 * 10 therein -5pa～1 * 10 -3pa, evaporation rate is
The vacuum degree that vacuum evaporation forms described hole transmission layer is 1 * 10 -5pa～1 * 10 -3pa, evaporation rate is
The vacuum degree that vacuum evaporation forms described green light emitting layer is 1 * 10 -5pa～1 * 10 -3pa, evaporation rate is
The vacuum degree that vacuum evaporation forms described electron transfer layer is 1 * 10 -5pa～1 * 10 -3pa, evaporation rate is
The vacuum degree that vacuum evaporation forms described electron injecting layer is 1 * 10 -5pa～1 * 10 -3pa, evaporation rate is
The vacuum degree that vacuum evaporation forms described metal level is 1 * 10 -5pa～1 * 10 -3pa, evaporation rate is
The base vacuum degree that magnetron sputtering forms described metal oxide mixed layer is 1 * 10 -5pa～1 * 10 -3pa;
The vacuum degree that vacuum evaporation forms described metal-doped layer is 1 * 10 -5pa～1 * 10 -3pa, evaporation rate is
The base vacuum degree that magnetron sputtering forms described transparency conducting layer is 1 * 10 -5pa～1 * 10 -3pa.
The cathode layer of above-mentioned organic electroluminescence device comprises metal level, metal oxide mixed layer, metal-doped layer and the transparency conducting layer stacking gradually, the material of metal level is aluminium (Al), nickel (Ni), gold (Au) or silver (Ag), these materials can improve conductivity, their work content is on the low side simultaneously, and electronics easily injects; The material of metal oxide mixed layer is for being tantalum pentoxide (Ta 2o 5), niobium pentaoxide (Nb 2o 5) and vanadic oxide (V 2o 5) in two kinds of mixtures that form according to identical mass mixing, tantalum pentoxide (Ta 2o 5), niobium pentaoxide (Nb 2o 5) and vanadic oxide (V 2o 5) be good insulating material, can prevent that metal ion is diffused into the distortion of lattice that causes film in organic film, the phenomenon that there will be crystallization and recrystallization in more serious situation, can obviously improve the effect that prevents rete crystallization after they are mixed to form to mixture; The material of metal-doped layer is the magnesium (Mg) of silver (Ag) doping or the aluminium (Al) of lithium (Li) doping, and these materials can improve conductivity, strengthen the injection of electronics; And the material of transparency conducting layer is indium tin oxide (ITO), aluminium zinc oxide (AZO) or indium-zinc oxide (IZO), these materials can guarantee light transmittance, certain conductive capability is provided simultaneously, the cathode layer of this structure can improve electron injection efficiency, make both hole and electron reach balance, thereby effectively improve the luminous efficiency of organic electroluminescence device, and in brightness at 1000cd/m 2when lower, the luminous efficiency of organic electroluminescence device has improved more than 0.6 times.
Accompanying drawing explanation
Fig. 1 is the structural representation of the organic electroluminescence device of an execution mode;
Fig. 2 is preparation method's the flow chart of the organic electroluminescence device of an execution mode.
Embodiment
Mainly in conjunction with the drawings and the specific embodiments organic electroluminescence device and preparation method thereof is described in further detail below.
As shown in Figure 1, the organic electroluminescence device 100 of an execution mode, comprises the substrate of glass 110, hole injection layer 120, hole transmission layer 130, green light emitting layer 140, electron transfer layer 150, electron injecting layer 160 and the cathode layer 170 that stack gradually.
Glass substrate 110 materials can be the conventional baseplate material in this area, are preferably indium tin oxide glass (ITO).Preferably, the thickness of glass substrate 110 is 100 nanometers.
The material of hole injection layer 120 comprises hole mobile material and is doped in the p-type dopant in hole mobile material, and the mass ratio of p-type dopant and hole mobile material is 0.25～0.35:1.Hole mobile material is selected from N, N '-diphenyl-N, N '-bis-(1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines (NPB), 4,4 ', 4 " tri-(carbazole-9-yl) triphenylamine (TCTA), 4; 4 '-bis-(9-carbazole) biphenyl (CBP), N; N '-bis-(3-aminomethyl phenyl)-N, N '-diphenyl-4,4 '-benzidine (TPD) and 1; 1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] a kind of in cyclohexane (TAPC).P-type dopant is molybdenum trioxide (MoO 3), tungstic acid (WO 3), vanadic oxide (V 2o 5) and rhenium trioxide (ReO 3) in a kind of.Preferably, the thickness of hole injection layer 120 is 10 nanometer～15 nanometers.
The material of hole transmission layer 130 is selected from N, N '-diphenyl-N, N '-bis-(1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines (NPB), 4,4 ', 4 " tri-(carbazole-9-yl) triphenylamine (TCTA), 4; 4 '-bis-(9-carbazole) biphenyl (CBP), N; N '-bis-(3-aminomethyl phenyl)-N, N '-diphenyl-4,4 '-benzidine (TPD) and 1; 1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] a kind of in cyclohexane (TAPC).Preferably, the thickness of hole transmission layer 130 is 30 nanometer～50 nanometers.
The material of green light emitting layer 140 comprises material of main part and is doped in the green guest material in material of main part, and the mass ratio of green guest material and material of main part is 0.02～0.1:1.Material of main part is selected from 4,4 ', 4 " tri-(carbazole-9-yl) triphenylamine (TCTA), 9,9 '-(1; 3-phenyl) two-9H-carbazole (mCP), 4; 4 '-bis-(9-carbazole) biphenyl (CBP), N, N '-bis-(3-aminomethyl phenyl)-N, N '-diphenyl-4; 4 '-benzidine (TPD), 1; 1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] a kind of in two (1-naphthyl) anthracenes (ADN) of cyclohexane (TAPC) and 9,10-.Green guest material is that three (2-phenylpyridines) close iridium (Ir (ppy) 3), acetopyruvic acid two (2-phenylpyridine) iridium (Ir (ppy) 2(acac)) and three [2-(p-methylphenyl) pyridines] close iridium (III) (Ir (mppy) 3) in a kind of.Preferably, the thickness of green light emitting layer 140 is 10 nanometer～30 nanometers.
The material of electron transfer layer 150 is selected from 4,7-diphenyl-1,10-phenanthroline (Bphen), 4, and 7-diphenyl-1,10-Phen (BCP), 4-biphenyl phenolic group-bis-(2-methyl-oxine) close aluminium (BAlq), oxine aluminium (Alq 3), 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1, a kind of in 2,4-triazole (TAZ) and 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBI).Preferably, the thickness of electron transfer layer 150 is 10 nanometer～60 nanometers.
The material of electron injecting layer 160 comprises electron transport material and co-doped sulfate and the alkali metal salt in electron transport material, the mass ratio of sulfate and electron transport material is 0.06～0.25:1, and the mass ratio of alkali metal salt and electron transport material is 0.25～0.35:1.The material of electron transport material is selected from 4,7-diphenyl-1,10-phenanthroline (Bphen), 4, and 7-diphenyl-1,10-Phen (BCP), 4-biphenyl phenolic group-bis-(2-methyl-oxine) close aluminium (BAlq), oxine aluminium (Alq 3), 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1, a kind of in 2,4-triazole (TAZ) and 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBI).Sulfate is selected from lithium sulfate (Li 2sO 4), sodium sulphate (Na 2sO 4), potassium sulfate (K 2sO 4), rubidium sulfate (Rb 2sO 4) and cesium sulfate (Cs 2sO 4) in a kind of.Alkali metal salt is selected from lithium fluoride (LiF), Lithium Azide (LiN 3), lithium nitride (Li 3n), cesium fluoride (CsF), cesium azide (CsN 3) and nitrogenize caesium (Cs 3n) a kind of in.
Electron injecting layer 160 adopts the electron transport material of sulfate and alkali metal salt co-doped as material, can make the poor reduction of lumo energy surpass 0.1eV, strengthens electronic injection.Wherein, sulfate is selected from lithium sulfate (Li 2sO 4), sodium sulphate (Na 2sO 4), potassium sulfate (K 2sO 4), rubidium sulfate (Rb 2sO 4) and cesium sulfate (Cs 2sO 4) in a kind of, these sulfate can improve the thermal stability of electron injecting layer 160, the defect state at clearing electrode and organic layer interface makes to form between electrode and organic layer good interface performance.And alkali metal salt is selected from lithium fluoride (LiF), Lithium Azide (LiN 3), lithium nitride (Li 3n), cesium fluoride (CsF), cesium azide (CsN 3) and nitrogenize caesium (Cs 3n) a kind of in, these alkali metal salts can evaporation, and electron donation is strong, can strengthen electronics speed.
Preferably, the thickness of electron injecting layer 160 is 15 nanometer～45 nanometers.
Cathode layer 170 comprises metal level 172, metal oxide mixed layer 174, metal-doped layer 176 and the transparency conducting layer 178 stacking gradually.Metal level 172 is laminated on electron injecting layer 160.The material of metal level 172 is aluminium (Al), nickel (Ni), gold (Au) or silver (Ag).The material of metal oxide mixed layer 174 is tantalum pentoxide (Ta 2o 5), niobium pentaoxide (Nb 2o 5) and vanadic oxide (V 2o 5) in two kinds of mixtures that form according to identical mass mixing.The material of metal-doped layer 176 is the magnesium (Mg) of silver (Ag) doping or the aluminium (Al) of lithium (Li) doping.The magnesium (Mg) of silver (Ag) doping is expressed as: Mg:Ag, in the magnesium (Mg) of silver (Ag) doping, silver (Ag) is 5:1～20:1 with the mass ratio of magnesium (Mg).The aluminium (Al) of lithium (Li) doping is expressed as: Al:Li, in the aluminium (Al) of lithium (Li) doping, lithium (Li) is 0.001:1～0.001:0.1 with the mass ratio of aluminium (Al).The material of transparency conducting layer 178 is indium tin oxide (ITO), aluminium zinc oxide (AZO) or indium-zinc oxide (IZO).
The material of metal level 172 is aluminium (Al), nickel (Ni), gold (Au) or silver (Ag), and these materials can improve conductivity, and their work content is on the low side simultaneously, and electronics easily injects.
The material of metal oxide mixed layer 172 is tantalum pentoxide (Ta 2o 5), niobium pentaoxide (Nb 2o 5) and vanadic oxide (V 2o 5) at least two kinds of mixtures that form according to identical mass mixing, tantalum pentoxide (Ta 2o 5), niobium pentaoxide (Nb 2o 5) and vanadic oxide (V 2o 5) be and there is higher refractive index, and transmitance is high, and tantalum pentoxide (Ta 2o 5), niobium pentaoxide (Nb 2o 5) and vanadic oxide (V 2o 5) be insulating material, can prevent that metal ion is diffused into the distortion of lattice that causes film in organic film, the phenomenon that there will be crystallization and recrystallization in more serious situation, can obviously improve the effect that prevents rete crystallization after they are mixed to form to mixture.
The material of metal-doped layer 174 is the magnesium (Mg) of silver (Ag) doping or the aluminium (Al) of lithium (Li) doping, in the magnesium (Mg) of silver (Ag) doping, magnesium (Mg) work content is low, and silver (Ag) is not oxidizable, in the aluminium (Al) of lithium (Li) doping, lithium (Li) and aluminium (Al) can form LiAl complex compound, make the magnesium (Mg) of silver (Ag) doping there is suitable work content and conductivity with the aluminium (Al) of lithium (Li) doping, can improve conductivity, strengthen the injection of electronics.
The material of transparency conducting layer 176 is indium tin oxide (ITO), aluminium zinc oxide (AZO) or indium-zinc oxide (IZO), and these materials can guarantee light transmittance, and certain conductive capability is provided simultaneously.
Preferably, the thickness of metal level 172 is 5 nanometer～20 nanometers; The thickness of metal oxide mixed layer 174 is 40 nanometer～60 nanometers; The thickness of metal-doped layer 176 is 10 nanometer～20 nanometers; The thickness of transparency conducting layer 178 is 20 nanometer～40 nanometers.
The cathode layer 170 of above-mentioned organic electroluminescence device 100 comprises metal level 172, metal oxide mixed layer 174, metal-doped layer 176 and the transparency conducting layer 178 stacking gradually, the material of metal level 172 is aluminium (Al), nickel (Ni), gold (Au) or silver (Ag), these materials can improve conductivity, their work content is on the low side simultaneously, and electronics easily injects; The material of metal oxide mixed layer 174 is for being tantalum pentoxide (Ta 2o 5), niobium pentaoxide (Nb 2o 5) and vanadic oxide (V 2o 5) in two kinds of mixtures that form according to identical mass mixing, tantalum pentoxide (Ta 2o 5), niobium pentaoxide (Nb 2o 5) and vanadic oxide (V 2o 5) be good insulating material, can prevent that metal ion is diffused into the distortion of lattice that causes film in organic film, the phenomenon that there will be crystallization and recrystallization in more serious situation, can obviously improve the effect that prevents rete crystallization after they are mixed to form to mixture; The material of metal-doped layer 176 is the magnesium (Mg) of silver (Ag) doping or the aluminium (Al) of lithium (Li) doping, and these materials can improve conductivity, strengthen the injection of electronics; And the material of transparency conducting layer 178 is indium tin oxide (ITO), aluminium zinc oxide (AZO) or indium-zinc oxide (IZO), these materials can guarantee light transmittance, certain conductive capability is provided simultaneously, the cathode layer 170 of this structure can improve electron injection efficiency, make both hole and electron reach balance, thereby effectively improve the luminous efficiency of organic electroluminescence device 100, and in brightness at 1000cd/m 2when lower, the luminous efficiency of organic electroluminescence device has improved more than 0.6 times.
As shown in Figure 2, the preparation method of the organic electroluminescence device of an execution mode, comprises the steps:
Step S210: vacuum evaporation forms hole injection layer, hole transmission layer, green light emitting layer, electron transfer layer and electron injecting layer successively on glass substrate.
Preferably, on glass substrate, vacuum evaporation also comprises the step that glass substrate is cleaned before forming hole injection layer: glass substrate is adopted to liquid detergent, deionized water, acetone and ethanol ultrasonic cleaning successively, and then dry.In specific embodiment, clean 5 minutes at every turn, stop 5 minutes, repeat respectively 3 times, and then use oven for drying.
Preferably, will after cleaning glass substrate, on glass substrate, before vacuum evaporation formation hole injection layer, also comprise the step of the surface of glass substrate being carried out to activation processing.By the glass substrate to after cleaning, carry out surface activation process, can increase the oxygen content of glass baseplate surface, improve the work function of glass baseplate surface.
Preferably, the vacuum degree of vacuum evaporation formation hole injection layer is 1 * 10 -5pa～1 * 10 -3pa, evaporation rate is
Preferably, the vacuum degree of vacuum evaporation formation hole transmission layer is 1 * 10 -5pa～1 * 10 -3pa, evaporation rate is
Preferably, the vacuum degree of vacuum evaporation formation green light emitting layer is 1 * 10 -5pa～1 * 10 -3pa, evaporation rate is
Preferably, the vacuum degree of vacuum evaporation formation electron transfer layer is 1 * 10 -5pa～1 * 10 -3pa, evaporation rate is
Preferably, the vacuum degree of vacuum evaporation formation electron injecting layer is 1 * 10 -5pa～1 * 10 -3pa, evaporation rate is
Step S220: form cathode layer on electron injecting layer, cathode layer comprises metal level, metal oxide mixed layer, metal-doped layer and the transparency conducting layer stacking gradually, metal level is formed on electron injecting layer, and metal level and metal-doped layer are prepared by vacuum evaporation, metal oxide mixed layer and transparency conducting layer are prepared by magnetron sputtering, obtain organic electroluminescence device.Wherein, the material of metal level is aluminium (Al), nickel (Ni), gold (Au) or silver (Ag).The material of metal oxide mixed layer is tantalum pentoxide (Ta 2o 5), niobium pentaoxide (Nb 2o 5) and vanadic oxide (V 2o 5) in two kinds of mixtures that form according to identical mass mixing.The material of metal-doped layer is the magnesium (Mg) of silver (Ag) doping or the aluminium (Al) of lithium (Li) doping.In the magnesium (Mg) of silver (Ag) doping, silver (Ag) is 5:1～20:1 with the mass ratio of magnesium (Mg).In the aluminium (Al) of lithium (Li) doping, lithium (Li) is 0.001:1～0.001:0.1 with the mass ratio of aluminium (Al).The material of transparency conducting layer is indium tin oxide (ITO), aluminium zinc oxide (AZO) or indium-zinc oxide (IZO).
Preferably, the vacuum degree of vacuum evaporation formation metal level is 1 * 10 -5pa～1 * 10 -3pa, evaporation rate is
Preferably, the base vacuum degree of magnetron sputtering formation metal oxide mixed layer is 1 * 10 -5pa～1 * 10 -3pa.
Preferably, to form the vacuum degree of metal-doped layer be 1 * 10 in vacuum evaporation -5pa～1 * 10 -3pa, evaporation rate is
Preferably, the base vacuum degree of magnetron sputtering formation transparency conducting layer is 1 * 10 -5pa～1 * 10 -3pa.
The preparation method of above-mentioned organic electroluminescence device is simple, and easily operation, and the organic electroluminescence device of preparing has higher luminous efficiency, is conducive to industrialization and produces.
Be below specific embodiment part:
Embodiment 1
The structure of the organic electroluminescence device of the present embodiment is: ITO/NPB:MoO 3/ NPB/TCTA:Ir (ppy) 3/ Bphen/Bphen:LiF:Li 2sO 4/ Al/Nb 2o 5: V 2o 5/ Mg:Ag/IZO.
Being prepared as follows of the organic electroluminescence device of this embodiment:
(1) ito glass substrate is adopted successively to liquid detergent, deionized water, acetone and ethanol ultrasonic cleaning, clean 5 minutes at every turn, stop 5 minutes, repeat respectively 3 times, then use oven for drying, the glass substrate after drying is carried out to surface activation process; Wherein, the thickness of ito glass substrate is 100 nanometers.
(2) on glass substrate, vacuum evaporation forms hole injection layer, hole transmission layer, green light emitting layer, electron transfer layer and electron injecting layer successively: the material of hole injection layer is molybdenum trioxide (MoO 3) doping N, N '-diphenyl-N, N '-bis-(1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines (NPB), is expressed as: NPB:MoO 3, wherein, molybdenum trioxide (MoO 3) and N, N '-diphenyl-N, N '-bis-(1-naphthyl)-1,1 '-biphenyl-4, the mass ratio of 4 '-diamines (NPB) is 0.3:1, and the thickness of hole injection layer is 12.5 nanometers, and the vacuum degree of vacuum evaporation is 1 * 10 -5pa, evaporation rate is the material of hole transmission layer is N, N '-diphenyl-N, and N '-bis-(1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines (NPB), thickness is 40 nanometers, the vacuum degree of vacuum evaporation is 1 * 10 -5pa, evaporation rate is the material of green light emitting layer is that three (2-phenylpyridines) close iridium (Ir (ppy) 3) doping 4,4 ', 4 " tri-(carbazole-9-yl) triphenylamine (TCTA), is expressed as: TCTA:Ir (ppy) 3, wherein, three (2-phenylpyridines) close iridium (Ir (ppy) 3) with 4,4 ', 4 " mass ratio of tri-(carbazole-9-yl) triphenylamine (TCTA) is 0.06:1, and the thickness of green light emitting layer is 20 nanometers, and the vacuum degree of vacuum evaporation is 1 * 10 -5pa, evaporation rate is the material of electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (Bphen), and thickness is 35 nanometers, the vacuum degree of vacuum evaporation is 1 * 10 -5pa, evaporation rate is the material of electron injecting layer is lithium fluoride (LiF) and lithium sulfate (Li 2sO 4) co-doped 4,7-diphenyl-1,10-phenanthroline (Bphen), is expressed as: Bphen:LiF:Li 2sO 4, wherein, lithium fluoride (LiF) and 4,7-diphenyl-1,10-phenanthroline (Bphen) mass ratio is 0.3:1, lithium sulfate (Li 2sO 4) with 4,7-diphenyl-1, the mass ratio of 10-phenanthroline (Bphen) is 0.15:1, and the thickness of electron injecting layer is 35 nanometers, and the vacuum degree of vacuum evaporation is 1 * 10 -5pa, evaporation rate is
(3) on electron injecting layer, form cathode layer, cathode layer comprises metal level, metal oxide mixed layer, metal-doped layer and the transparency conducting layer stacking gradually, metal level is formed on electron injecting layer, and metal level and metal-doped layer are prepared by vacuum evaporation, metal oxide mixed layer and transparency conducting layer are prepared by magnetron sputtering, obtain organic electroluminescence device: the material of metal level is aluminium (Al), and thickness is 5 nanometers, and the vacuum degree of vacuum evaporation is 1 * 10 -5pa, evaporation rate is the material of metal oxide mixed layer is niobium pentaoxide (Nb 2o 5) and vanadic oxide (V 2o 5) mixture that is mixed to form, be expressed as: Nb 2o 5: V 2o 5, and niobium pentaoxide (Nb 2o 5) and vanadic oxide (V 2o 5) mass ratio be 1:1, the thickness of metal oxide mixed layer is 50 nanometers, base vacuum degree is 1 * 10 -5pa; The material of metal-doped layer is that the magnesium (Mg) of silver (Ag) doping is expressed as: Mg:Ag, and the middle silver of magnesium (Mg) (Ag) of silver (Ag) doping is 5:1 with the mass ratio of magnesium (Mg), and the thickness of metal-doped layer is 15 nanometers, and the vacuum degree of vacuum evaporation is 1 * 10 -5pa, evaporation rate is the material of transparency conducting layer is indium-zinc oxide (IZO), and thickness is 30 nanometers, and base vacuum degree is 1 * 10 -5pa; Cathode layer is expressed as: Al/Nb 2o 5: V 2o 5/ Mg:Ag/IZO.The structure that obtains the present embodiment is: ITO/NPB:MoO 3/ NPB/TCTA:Ir (ppy) 3/ Bphen/Bphen:LiF:Li 2sO 4/ Al/Nb 2o 5: V 2o 5the organic electroluminescence device of/Mg:Ag/IZO.Wherein, brace "/" represents layer structure, TCTA:Ir (ppy) 3in colon ": " represent that doping mixes, lower with.
The luminous efficiency of organic electroluminescence device prepared by the present embodiment is in Table 1.
Embodiment 2
The structure of the organic electroluminescence device of the present embodiment is: ITO/TCTA:WO 3/ TCTA/mCP:Ir (ppy) 2(acac)/BCP/BCP:LiN 3: Na 2sO 4/ Ni/Ta 2o 5: V 2o 5/ Al:Li/ITO.
Being prepared as follows of the organic electroluminescence device of this embodiment:
(1) ito glass substrate is adopted successively to liquid detergent, deionized water, acetone and ethanol ultrasonic cleaning, clean 5 minutes at every turn, stop 5 minutes, repeat respectively 3 times, then use oven for drying, the glass substrate after drying is carried out to surface activation process; Wherein, the thickness of ito glass substrate is 100 nanometers.
(2) on glass substrate, vacuum evaporation forms hole injection layer, hole transmission layer, green light emitting layer, electron transfer layer and electron injecting layer successively: the material of hole injection layer is tungstic acid (WO 3) doping 4,4 ', 4 " tri-(carbazole-9-yl) triphenylamine (TCTA), is expressed as: TCTA:WO 3, wherein, tungstic acid (WO 3) with 4,4 ', 4 " tri-(carbazole-9-yl) triphenylamine (TCTA) mass ratio is 0.25:1, and the thickness of hole injection layer is 10 nanometers, and the vacuum degree of vacuum evaporation is 5 * 10 -5pa, evaporation rate is the material of hole transmission layer is 4,4 ', 4 " tri-(carbazole-9-yl) triphenylamine (TCTA), thickness is 30 nanometers, the vacuum degree of vacuum evaporation is 5 * 10 -5pa, evaporation rate is the material of green light emitting layer is acetopyruvic acid two (2-phenylpyridine) iridium (Ir (ppy) 2(acac)) 9,9 '-(1,3-phenyl) two-9H-carbazole (mCP) of doping, is expressed as: mCP:Ir (ppy) 2(acac), wherein, acetopyruvic acid two (2-phenylpyridine) iridium (Ir (ppy) 2(acac) be) 0.02:1 with the mass ratio of 9,9 '-(1,3-phenyl) two-9H-carbazole (mCP), the thickness of green light emitting layer is 10 nanometers, and the vacuum degree of vacuum evaporation is 5 * 10 -5pa, evaporation rate is the material of electron transfer layer is 4,7-diphenyl-1,10-Phen (BCP), and thickness is 10 nanometers, the vacuum degree of vacuum evaporation is 5 * 10 -5pa, evaporation rate is the material of electron injecting layer is Lithium Azide (LiN 3) and sodium sulphate (Na 2sO 4) co-doped 4,7-diphenyl-1,10-Phen (BCP), is expressed as: BCP:LiN 3: Na 2sO 4, wherein, Lithium Azide (LiN 3) with 4,7-diphenyl-1, the mass ratio of 10-Phen (BCP) is 0.25:1, sodium sulphate (Na 2sO 4) with 4,7-diphenyl-1, the mass ratio of 10-Phen (BCP) is 0.25:1, and the thickness of electron injecting layer is 45 nanometers, and the vacuum degree of vacuum evaporation is 5 * 10 -5pa, evaporation rate is
(3) on electron injecting layer, form cathode layer, cathode layer comprises metal level, metal oxide mixed layer, metal-doped layer and the transparency conducting layer stacking gradually, metal level is formed on electron injecting layer, and metal level and metal-doped layer are prepared by vacuum evaporation, metal oxide mixed layer and transparency conducting layer are prepared by magnetron sputtering, obtain organic electroluminescence device: the material of metal level is nickel (Ni), and thickness is 20 nanometers, and the vacuum degree of vacuum evaporation is 1 * 10 -3pa, evaporation rate is the material of metal oxide mixed layer is tantalum pentoxide (Ta 2o 5) and vanadic oxide (V 2o 5) mixture that is mixed to form, be expressed as: Ta 2o 5: V 2o 5, and tantalum pentoxide (Ta 2o 5) and vanadic oxide (V 2o 5) mass ratio be 1:1, thickness is 40 nanometers, base vacuum degree is 1 * 10 -3pa; The material of metal-doped layer is that the aluminium (Al) of lithium (Li) doping is expressed as: Al:Li, in the aluminium (Al) of lithium (Li) doping, lithium (Li) is 0.006:1 with the mass ratio of aluminium (Al), the thickness of metal-doped layer is 10 nanometers, and the vacuum degree of vacuum evaporation is 1 * 10 -3pa, evaporation rate is the material of transparency conducting layer is indium tin oxide (ITO), and thickness is 40 nanometers, and base vacuum degree is 1 * 10 -3pa; Cathode layer is expressed as: Ni/Ta 2o 5: V 2o 5/ Al:Li/ITO.The structure that obtains the present embodiment is: ITO/TCTA:WO 3/ TCTA/mCP:Ir (ppy) 2(acac)/BCP/BCP:LiN 3: Na 2sO 4/ Ni/Ta 2o 5: V 2o 5the organic electroluminescence device of/Al:Li/ITO.
The luminous efficiency of organic electroluminescence device prepared by the present embodiment is in Table 1.
Embodiment 3
The structure of the organic electroluminescence device of the present embodiment is: ITO/CBP:V 2o 5/ CBP/CBP:Ir (mppy) 3/ BAlq/BAlq:Li 3n:K 2sO 4/ Au/Nb 2o 5: Ta 2o 5/ Al:Li/AZO.
Being prepared as follows of the organic electroluminescence device of this embodiment:
(1) ito glass substrate is adopted successively to liquid detergent, deionized water, acetone and ethanol ultrasonic cleaning, clean 5 minutes at every turn, stop 5 minutes, repeat respectively 3 times, then use oven for drying, the glass substrate after drying is carried out to surface activation process; Wherein, the thickness of ito glass substrate is 100 nanometers.
(2) on glass substrate, vacuum evaporation forms hole injection layer, hole transmission layer, green light emitting layer, electron transfer layer and electron injecting layer successively: the material of hole injection layer is vanadic oxide (V 2o 5) doping 4,4 '-bis-(9-carbazole) biphenyl (CBP), be expressed as: CBP:V 2o 5, wherein, vanadic oxide (V 2o 5) with 4,4 '-bis-(9-carbazole) biphenyl (CBP) mass ratioes be 0.35:1, the thickness of hole injection layer is 15 nanometers, the vacuum degree of vacuum evaporation is 5 * 10 -5pa, evaporation rate is the material of hole transmission layer is 4,4 '-bis-(9-carbazole) biphenyl (CBP), and thickness is 50 nanometers, and the vacuum degree of vacuum evaporation is 5 * 10 -5pa, evaporation rate is the material of green light emitting layer is that three [2-(p-methylphenyl) pyridines] close iridium (III) (Ir (mppy) 3) doping 4,4 '-bis-(9-carbazole) biphenyl (CBP), be expressed as: CBP:Ir (mppy) 3, wherein, three [2-(p-methylphenyl) pyridines] close iridium (III) (Ir (mppy) 3) with the mass ratio of 4,4 '-bis-(9-carbazole) biphenyl (CBP) be 0.1:1, the thickness of green light emitting layer is 30 nanometers, the vacuum degree of vacuum evaporation is 5 * 10 -5pa, evaporation rate is the material of electron transfer layer is that 4-biphenyl phenolic group-bis-(2-methyl-oxine) close aluminium (BAlq), and thickness is 60 nanometers, and the vacuum degree of vacuum evaporation is 5 * 10 -5pa, evaporation rate is the material of electron injecting layer is lithium nitride (Li 3n) with potassium sulfate (K 2sO 4) 4-biphenyl phenolic group-bis-(2-methyl-oxine) of co-doped close aluminium (BAlq), be expressed as: BAlq:Li 3n:K 2sO 4, wherein, lithium nitride (Li 3n) mass ratio that closes aluminium (BAlq) with 4-biphenyl phenolic group-bis-(2-methyl-oxine) is 0.35:1, potassium sulfate (K 2sO 4) mass ratio that closes aluminium (BAlq) with 4-biphenyl phenolic group-bis-(2-methyl-oxine) is 0.06:1, the thickness of electron injecting layer is 15 nanometers, the vacuum degree of vacuum evaporation is 5 * 10 -5pa, evaporation rate is
(3) on electron injecting layer, form cathode layer, cathode layer comprises metal level, metal oxide mixed layer, metal-doped layer and the transparency conducting layer stacking gradually, metal level is formed on electron injecting layer, and metal level and metal-doped layer are prepared by vacuum evaporation, metal oxide mixed layer and transparency conducting layer are prepared by magnetron sputtering, obtain organic electroluminescence device: the material of metal level is gold (Au), and thickness is 10 nanometers, and the vacuum degree of vacuum evaporation is 1 * 10 -4pa, evaporation rate is the material of metal oxide mixed layer is niobium pentaoxide (Nb 2o 5) and tantalum pentoxide (Ta 2o 5) mixture that is mixed to form, be expressed as: Nb 2o 5: Ta 2o 5, and niobium pentaoxide (Nb 2o 5) and tantalum pentoxide (Ta 2o 5) mass ratio be 1:1, the thickness of metal oxide mixed layer is 60 nanometers, base vacuum degree is 1 * 10 -4pa; The material of metal-doped layer is that the aluminium (Al) of lithium (Li) doping is expressed as: Al:Li, in the aluminium (Al) of lithium (Li) doping, lithium (Li) is 0.001:0.1 with the mass ratio of aluminium (Al), the thickness of metal-doped layer is 20 nanometers, and the vacuum degree of vacuum evaporation is 1 * 10 -4pa, evaporation rate is the material of transparency conducting layer is aluminium zinc oxide (AZO), and thickness is 20 nanometers, and base vacuum degree is 1 * 10 -4pa; Cathode layer is expressed as: Au/Nb 2o 5: Ta 2o 5/ Al:Li/AZO.The structure that obtains the present embodiment is: ITO/CBP:V 2o 5/ CBP/CBP:Ir (mppy) 3/ BAlq/BAlq:Li 3n:K 2sO 4/ Au/Nb 2o 5: Ta 2o 5the organic electroluminescence device of/Al:Li/AZO.
The luminous efficiency of organic electroluminescence device prepared by the present embodiment is in Table 1.
Embodiment 4
The structure of the organic electroluminescence device of the present embodiment is: ITO/TPD:ReO 3/ TPD/TPD:Ir (ppy) 3/ Alq 3/ Alq 3: CsF:Rb 2sO 4/ Ag/Nb 2o 5: V 2o 5/ Mg:Ag/IZO.
Being prepared as follows of the organic electroluminescence device of this embodiment:
(1) ito glass substrate is adopted successively to liquid detergent, deionized water, acetone and ethanol ultrasonic cleaning, clean 5 minutes at every turn, stop 5 minutes, repeat respectively 3 times, then use oven for drying, the glass substrate after drying is carried out to surface activation process; Wherein, the thickness of ito glass substrate is 100 nanometers.
(2) on glass substrate, vacuum evaporation forms hole injection layer, hole transmission layer, green light emitting layer, electron transfer layer and electron injecting layer successively: the material of hole injection layer is rhenium trioxide (ReO 3) doping N, N '-bis-(3-aminomethyl phenyl)-N, N '-diphenyl-4,4 '-benzidine (TPD), is expressed as: TPD:ReO 3, wherein, rhenium trioxide (ReO 3) and N, N '-bis-(3-aminomethyl phenyl)-N, N '-diphenyl-4,4 '-benzidine (TPD) mass ratio is 0.3:1, and the thickness of hole injection layer is 13 nanometers, and the vacuum degree of vacuum evaporation is 5 * 10 -5pa, evaporation rate is the material of hole transmission layer is N, N '-bis-(3-aminomethyl phenyl)-N, and N '-diphenyl-4,4 '-benzidine (TPD), thickness is 40 nanometers, the vacuum degree of vacuum evaporation is 5 * 10 -5pa, evaporation rate is the material of green light emitting layer is that three (2-phenylpyridines) close iridium (Ir (ppy) 3) doping N, N '-bis-(3-aminomethyl phenyl)-N, N '-diphenyl-4,4 '-benzidine (TPD), is expressed as: TPD:Ir (ppy) 3, wherein, three (2-phenylpyridines) close iridium (Ir (ppy) 3) and N, N '-bis-(3-aminomethyl phenyl)-N, N '-diphenyl-4, the mass ratio of 4 '-benzidine (TPD) is 0.05:1, and the thickness of green light emitting layer is 20 nanometers, and the vacuum degree of vacuum evaporation is 5 * 10 -5pa, evaporation rate is the material of electron transfer layer is oxine aluminium (Alq 3), thickness is 30 nanometers, the vacuum degree of vacuum evaporation is 5 * 10 -5pa, evaporation rate is the material of electron injecting layer is cesium fluoride (CsF) and rubidium sulfate (Rb 2sO 4) the oxine aluminium (Alq of co-doped 3), be expressed as: Alq 3: CsF:Rb 2sO 4, wherein, cesium fluoride (CsF) and oxine aluminium (Alq 3) mass ratio be 0.3:1, rubidium sulfate (Rb 2sO 4) and oxine aluminium (Alq 3) mass ratio be 0.1:1, the thickness of electron injecting layer is 30 nanometers, the vacuum degree of vacuum evaporation is 5 * 10 -5pa, evaporation rate is
(3) on electron injecting layer, form cathode layer, cathode layer comprises metal level, metal oxide mixed layer, metal-doped layer and the transparency conducting layer stacking gradually, metal level is formed on electron injecting layer, and metal level and metal-doped layer are prepared by vacuum evaporation, metal oxide mixed layer and transparency conducting layer are prepared by magnetron sputtering, obtain organic electroluminescence device: the material of metal level is silver (Ag), and thickness is 5 nanometers, and the vacuum degree of vacuum evaporation is 1 * 10 -5pa, evaporation rate is the material of metal oxide mixed layer is niobium pentaoxide (Nb 2o 5) and vanadic oxide (V 2o 5) mixture that is mixed to form, be expressed as: Nb 2o 5: V 2o 5, and niobium pentaoxide (Nb 2o 5) and vanadic oxide (V 2o 5) mass ratio be 1:1, the thickness of metal oxide mixed layer is 60 nanometers, base vacuum degree is 1 * 10 -5pa; The material of metal-doped layer is that the magnesium (Mg) of silver (Ag) doping is expressed as: Mg:Ag, and the middle silver of magnesium (Mg) (Ag) of silver (Ag) doping is 20:1 with the mass ratio of magnesium (Mg), and the thickness of metal-doped layer is 10 nanometers, and the vacuum degree of vacuum evaporation is 1 * 10 -5pa, evaporation rate is the material of transparency conducting layer is indium-zinc oxide (IZO), and thickness is 20 nanometers, and base vacuum degree is 1 * 10 -5pa; Cathode layer is expressed as: Ag/Nb 2o 5: V 2o 5/ Mg:Ag/IZO.The structure that obtains the present embodiment is: ITO/TPD:ReO 3/ TPD/TPD:Ir (ppy) 3/ Alq 3/ Alq 3: CsF:Rb 2sO 4/ Ag/Nb 2o 5: V 2o 5the organic electroluminescence device of/Mg:Ag/IZO.
The luminous efficiency of organic electroluminescence device prepared by the present embodiment is in Table 1.
Embodiment 5
The structure of the organic electroluminescence device of the present embodiment is: ITO/TAPC:MoO 3/ TAPC/TAPC:Ir (ppy) 2(acac)/TAZ/TAZ:CsN 3: Cs 2sO 4/ Al/V 2o 5: Ta 2o 5/ Al:Li/AZO.
Being prepared as follows of the organic electroluminescence device of this embodiment:
(1) ito glass substrate is adopted successively to liquid detergent, deionized water, acetone and ethanol ultrasonic cleaning, clean 5 minutes at every turn, stop 5 minutes, repeat respectively 3 times, then use oven for drying, the glass substrate after drying is carried out to surface activation process; Wherein, the thickness of ito glass substrate is 100 nanometers.
(2) on glass substrate, vacuum evaporation forms hole injection layer, hole transmission layer, green light emitting layer, electron transfer layer and electron injecting layer successively: the material of hole injection layer is molybdenum trioxide (MoO 3) doping 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane (TAPC), be expressed as: TAPC:MoO 3, wherein, molybdenum trioxide (MoO 3) with 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] mass ratio of cyclohexane (TAPC) is 0.25:1, and the thickness of hole injection layer is 10 nanometers, and the vacuum degree of vacuum evaporation is 5 * 10 -5pa, evaporation rate is the material of hole transmission layer is 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane (TAPC), thickness is 40 nanometers, the vacuum degree of vacuum evaporation is 5 * 10 -5pa, evaporation rate is the material of green light emitting layer is (Ir (ppy) 2(acac)) 1 of doping, 1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane (TAPC), be expressed as: TAPC:Ir (ppy) 2(acac), wherein, (Ir (ppy) 2(acac)) with 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] mass ratio of cyclohexane (TAPC) is 0.07:1, and the thickness of green light emitting layer is 20 nanometers, and the vacuum degree of vacuum evaporation is 5 * 10 -5pa, evaporation rate is the material of electron transfer layer is 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole (TAZ), and thickness is 50 nanometers, the vacuum degree of vacuum evaporation is 5 * 10 -5pa, evaporation rate is the material of electron injecting layer is cesium azide (CsN 3) and cesium sulfate (Cs 2sO 4) 3-(biphenyl-4-yl)-5-(4-the tert-butyl-phenyl)-4-phenyl-4H-1 of co-doped, 2,4-triazole (TAZ), is expressed as: TAZ:CsN 3: Cs 2sO 4, wherein, cesium azide (CsN 3) and 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1, the mass ratio of 2,4-triazole (TAZ) is 0.3:1, cesium sulfate (Cs 2sO 4) and 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1, the mass ratio of 2,4-triazole (TAZ) is 0.1:1, and the thickness of electron injecting layer is 30 nanometers, and the vacuum degree of vacuum evaporation is 5 * 10 -5pa, evaporation rate is
(3) on electron injecting layer, form cathode layer, cathode layer comprises metal level, metal oxide mixed layer, metal-doped layer and the transparency conducting layer stacking gradually, metal level is formed on electron injecting layer, and metal level and metal-doped layer are prepared by vacuum evaporation, metal oxide mixed layer and transparency conducting layer are prepared by magnetron sputtering, obtain organic electroluminescence device: the material of metal level is aluminium (Al), and thickness is 20 nanometers, and the vacuum degree of vacuum evaporation is 1 * 10 -3pa, evaporation rate is the material of metal oxide mixed layer is vanadic oxide (V 2o 5) and tantalum pentoxide (Ta 2o 5) mixture that is mixed to form, be expressed as: V 2o 5: Ta 2o 5, and vanadic oxide (V 2o 5) and tantalum pentoxide (Ta 2o 5) mass ratio be 1:1, the thickness of metal oxide mixed layer is 40 nanometers, base vacuum degree is 1 * 10 -3pa; The material of metal-doped layer is that the aluminium (Al) of lithium (Li) doping is expressed as: Al:Li, in the aluminium (Al) of lithium (Li) doping, lithium (Li) is 0.001:1 with the mass ratio of aluminium (Al), the thickness of metal-doped layer is 20 nanometers, and the vacuum degree of vacuum evaporation is 1 * 10 -3pa, evaporation rate is the material of transparency conducting layer is aluminium zinc oxide (AZO), and thickness is 40 nanometers, and base vacuum degree is 1 * 10 -3pa; Cathode layer is expressed as: Al/V 2o 5: Ta 2o 5/ Al:Li/AZO.The structure that obtains the present embodiment is: ITO/TAPC:MoO 3/ TAPC/TAPC:Ir (ppy) 2(acac)/TAZ/TAZ:CsN 3: Cs 2sO 4/ Al/V 2o 5: Ta 2o 5the organic electroluminescence device of/Al:Li/AZO.
Organic electroluminescence device prepared by the present embodiment is at 1000cd/m 2under luminous efficiency in Table 1.
Embodiment 6
The structure of the organic electroluminescence device of the present embodiment is: ITO/NPB:WO 3/ NPB/ADN:Ir (mppy) 3/ TPBI/TPBI:Cs 3n:Cs 2sO 4/ Ni/Nb 2o 5: Ta 2o 5/ Mg:Ag/IZO.
Being prepared as follows of the organic electroluminescence device of this embodiment:
(1) ito glass substrate is adopted successively to liquid detergent, deionized water, acetone and ethanol ultrasonic cleaning, clean 5 minutes at every turn, stop 5 minutes, repeat respectively 3 times, then use oven for drying, the glass substrate after drying is carried out to surface activation process; Wherein, the thickness of ito glass substrate is 100 nanometers.
(2) on glass substrate, vacuum evaporation forms hole injection layer, hole transmission layer, green light emitting layer, electron transfer layer and electron injecting layer successively: the material of hole injection layer is tungstic acid (WO 3) doping N, N '-diphenyl-N, N '-bis-(1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines (NPB), is expressed as: NPB:WO 3, wherein, tungstic acid (WO 3) and N, N '-diphenyl-N, N '-bis-(1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines (NPB) mass ratio is 0.3:1, and the thickness of hole injection layer is 12 nanometers, and the vacuum degree of vacuum evaporation is 1 * 10 -3pa, evaporation rate is the material of hole transmission layer is N, N '-diphenyl-N, and N '-bis-(1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines (NPB), thickness is 40 nanometers, the vacuum degree of vacuum evaporation is 1 * 10 -3pa, evaporation rate is the material of green light emitting layer is that three [2-(p-methylphenyl) pyridines] close iridium (III) (Ir (mppy) 3) doping 9, two (1-naphthyl) anthracenes (ADN) of 10-, are expressed as: ADN:Ir (mppy) 3, wherein, three [2-(p-methylphenyl) pyridines] close iridium (III) (Ir (mppy) 3) with 9, the mass ratio of two (1-naphthyl) anthracenes (ADN) of 10-is 0.06:1, the thickness of green light emitting layer is 20 nanometers, the vacuum degree of vacuum evaporation is 1 * 10 -3pa, evaporation rate is the material of electron transfer layer is 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBI), and thickness is 30 nanometers, and the vacuum degree of vacuum evaporation is 1 * 10 -3pa, evaporation rate is the material of electron injecting layer is nitrogenize caesium (Cs 3n) with cesium sulfate (Cs 2sO 4) co-doped 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBI), is expressed as: TPBI:Cs 3n:Cs 2sO 4, wherein, nitrogenize caesium (Cs 3n) with 1,3, the mass ratio of 5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBI) is 0.3:1, cesium sulfate (Cs 2sO 4) with 1,3, the mass ratio of 5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBI) is 0.1:1, the thickness of electron injecting layer is 30 nanometers, the vacuum degree of vacuum evaporation is 1 * 10 -3pa, evaporation rate is
(3) on electron injecting layer, form cathode layer, cathode layer comprises metal level, metal oxide mixed layer, metal-doped layer and the transparency conducting layer stacking gradually, metal level is formed on electron injecting layer, and metal level and metal-doped layer are prepared by vacuum evaporation, metal oxide mixed layer and transparency conducting layer are prepared by magnetron sputtering, obtain organic electroluminescence device: the material of metal level is nickel (Ni), and thickness is 10 nanometers, and the vacuum degree of vacuum evaporation is 1 * 10 -5pa, evaporation rate is the material of metal oxide mixed layer is niobium pentaoxide (Nb 2o 5) and tantalum pentoxide (Ta 2o 5) mixture that is mixed to form, be expressed as: Nb 2o 5: Ta 2o 5, and niobium pentaoxide (Nb 2o 5) and tantalum pentoxide (Ta 2o 5) mass ratio be 1:1, the thickness of metal oxide mixed layer is 40 nanometers, base vacuum degree is 1 * 10 -5pa; The material of metal-doped layer is that the magnesium (Mg) of silver (Ag) doping is expressed as: Mg:Ag, and the middle silver of magnesium (Mg) (Ag) of silver (Ag) doping is 10:1 with the mass ratio of magnesium (Mg), and the thickness of metal-doped layer is 15 nanometers, and the vacuum degree of vacuum evaporation is 1 * 10 -4pa, evaporation rate is the material of transparency conducting layer is indium-zinc oxide (IZO), and thickness is 30 nanometers, and base vacuum degree is 1 * 10 -4pa; Cathode layer is expressed as: Ni/Nb 2o 5: Ta 2o 5/ Mg:Ag/IZO.The structure that obtains the present embodiment is: ITO/NPB:WO 3/ NPB/ADN:Ir (mppy) 3/ TPBI/TPBI:Cs 3n:Cs 2sO 4/ Ni/Nb 2o 5: Ta 2o 5the organic electroluminescence device of/Mg:Ag/IZO.
Organic electroluminescence device prepared by the present embodiment is at 1000cd/m 2under luminous efficiency in Table 1.
Comparative example 1
The structure of the organic electroluminescence device of comparative example 1 is: ITO/NPB:MoO 3/ NPB/TCTA:Ir (ppy) 3/ Bphen/Bphen:LiF:Li 2sO 4/ Ag.
Being prepared as follows of the organic electroluminescence device of comparative example 1:
(1) ito glass substrate is adopted successively to liquid detergent, deionized water, acetone and ethanol ultrasonic cleaning, clean 5 minutes at every turn, stop 5 minutes, repeat respectively 3 times, then use oven for drying, the glass substrate after drying is carried out to surface activation process; Wherein, the thickness of ito glass substrate is 100 nanometers.
(2) on glass substrate, vacuum evaporation forms hole injection layer, hole transmission layer, green light emitting layer, electron transfer layer, electron injecting layer and cathode layer successively: the material of hole injection layer is molybdenum trioxide (MoO 3) doping N, N '-diphenyl-N, N '-bis-(1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines (NPB), is expressed as: NPB:MoO 3, wherein, molybdenum trioxide (MoO 3) and N, N '-diphenyl-N, N '-bis-(1-naphthyl)-1,1 '-biphenyl-4, the mass ratio of 4 '-diamines (NPB) is 0.3:1, and the thickness of hole injection layer is 12.5 nanometers, and the vacuum degree of vacuum evaporation is 1 * 10 -5pa, evaporation rate is the material of hole transmission layer is N, N '-diphenyl-N, and N '-bis-(1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines (NPB), thickness is 40 nanometers, the vacuum degree of vacuum evaporation is 1 * 10 -5pa, evaporation rate is the material of green light emitting layer is that three (2-phenylpyridines) close iridium (Ir (ppy) 3) doping 4,4 ', 4 " tri-(carbazole-9-yl) triphenylamine (TCTA), is expressed as: TCTA:Ir (ppy) 3, wherein, three (2-phenylpyridines) close iridium (Ir (ppy) 3) with 4,4 ', 4 " mass ratio of tri-(carbazole-9-yl) triphenylamine (TCTA) is 0.06:1, and the thickness of green light emitting layer is 20 nanometers, and the vacuum degree of vacuum evaporation is 1 * 10 -5pa, evaporation rate is the material of electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (Bphen), and thickness is 35 nanometers, the vacuum degree of vacuum evaporation is 1 * 10 -5pa, evaporation rate is the material of electron injecting layer is lithium fluoride (LiF) and lithium sulfate (Li 2sO 4) co-doped 4,7-diphenyl-1,10-phenanthroline (Bphen), is expressed as: Bphen:LiF:Li 2sO 4, wherein, lithium fluoride (LiF) and 4,7-diphenyl-1,10-phenanthroline (Bphen) mass ratio is 0.3:1, lithium sulfate (Li 2sO 4) with 4,7-diphenyl-1, the mass ratio of 10-phenanthroline (Bphen) is 0.15:1, and the thickness of electron injecting layer is 35 nanometers, and the vacuum degree of vacuum evaporation is 1 * 10 -5pa, evaporation rate is the material of cathode layer is silver (Ag), and thickness is 138 nanometers.Vacuum degree is 5 * 10 -5pa, evaporation rate is the structure that obtains comparative example 1 preparation is: ITO/NPB:MoO 3/ NPB/TCTA:Ir (ppy) 3/ Bphen/Bphen:LiF:Li 2sO 4the organic electroluminescence device of/Ag.
The organic electroluminescence device of comparative example 1 preparation is at 1000cd/m 2under luminous efficiency in Table 1.
Table 1 represents is that the organic electroluminescence device prepared of organic electroluminescence device and the comparative example 1 of embodiment 1～embodiment 6 preparations is at 1000cd/m 2under the data of luminous efficiency.
Table 1
From table 1, can learn, the organic electroluminescence device of embodiment 1～embodiment 6 preparations is at 1000cd/m 2under luminous efficiency be at least 26.5m/W, and the organic electroluminescence device of embodiment 1 preparation is at 1000cd/m 2under luminous efficiency maximum can reach 27.2lm/W, and comparative example 1 preparation organic electroluminescence device at 1000cd/m 2under luminous efficiency be 15lm/W to the maximum, the luminous efficiency that is the organic electroluminescence device of embodiment 1 preparation has improved 0.81 times than the luminous efficiency of the organic electroluminescence device of comparative example 1, and significantly, the luminous efficiency of the organic electroluminescence device of embodiment 1～embodiment 6 preparations has at least improved more than 0.6 times, and organic electroluminescence device of the present invention has higher luminous efficiency.
The above embodiment has only expressed several execution mode of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection range of patent of the present invention should be as the criterion with claims.

Claims (8)

1. an organic electroluminescence device, it is characterized in that, comprise the glass substrate stacking gradually, hole injection layer, hole transmission layer, green light emitting layer, electron transfer layer, electron injecting layer and cathode layer, described cathode layer comprises the metal level stacking gradually, metal oxide mixed layer, metal-doped layer and transparency conducting layer, described metal level is laminated on described electron injecting layer, the material of described metal level is aluminium, nickel, golden or silver-colored, the material of described metal oxide mixed layer is five oxidation two neodymiums, two kinds of mixtures that form according to identical mass mixing in vanadic oxide and tantalum pentoxide, the material of described metal-doped layer is the magnesium of silver doping or the aluminium of lithium doping, described in the magnesium of described silver doping, silver is 5:1～20:1 with the mass ratio of described magnesium, the mass ratio of lithium and described aluminium described in the aluminium of described lithium doping is 0.001:1～0.001:0.1, the material of described transparency conducting layer is indium tin oxide, aluminium zinc oxide or indium-zinc oxide.
2. organic electroluminescence device according to claim 1, is characterized in that, the thickness of described metal level is 5 nanometer～20 nanometers; The thickness of described metal oxide mixed layer is 40 nanometer～60 nanometers; The thickness of described metal-doped layer is 10 nanometer～20 nanometers; The thickness of described transparency conducting layer is 20 nanometer～40 nanometers.
3. organic electroluminescence device according to claim 1, it is characterized in that, the material of described hole injection layer comprises hole mobile material and is doped in the p-type dopant in described hole mobile material, and the mass ratio of described p-type dopant and described hole mobile material is 0.25～0.35:1, described hole mobile material is selected from N, N '-diphenyl-N, N '-bis-(1-naphthyl)-1, 1 '-biphenyl-4, 4 '-diamines, 4, 4 ', 4 " tri-(carbazole-9-yl) triphenylamine, 4, 4 '-bis-(9-carbazole) biphenyl, N, N '-bis-(3-aminomethyl phenyl)-N, N '-diphenyl-4, 4 '-benzidine and 1, 1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] a kind of in cyclohexane, described p-type dopant is selected from molybdenum trioxide, tungstic acid, a kind of in vanadic oxide and rhenium trioxide,
The material of described hole transmission layer is selected from N, N '-diphenyl-N, N '-bis-(1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines, 4,4 ', 4 " tri-(carbazole-9-yl) triphenylamine, 4; 4 '-bis-(9-carbazole) biphenyl, N; N '-bis-(3-aminomethyl phenyl)-N, N '-diphenyl-4,4 '-benzidine and 1; 1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] a kind of in cyclohexane;
The material of described green light emitting layer comprises material of main part and is doped in the green guest material in described material of main part, the mass ratio of described green guest material and described material of main part is 0.02～0.1:1, described material of main part is selected from 4, 4 ', 4 " tri-(carbazole-9-yl) triphenylamine, 9, 9 '-(1, 3-phenyl) two-9H-carbazole, 4, 4 '-bis-(9-carbazole) biphenyl, N, N '-bis-(3-aminomethyl phenyl)-N, N '-diphenyl-4, 4 '-benzidine, 1, 1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane and 9, a kind of in two (1-naphthyl) anthracenes of 10-, described green guest material is that three (2-phenylpyridines) close iridium, acetopyruvic acid two (2-phenylpyridine) iridium and three [2-(p-methylphenyl) pyridine] closes a kind of in iridium (III),
The material of described electron transfer layer is selected from 4,7-diphenyl-1,10-phenanthroline, 4,7-diphenyl-1,10-Phen, 4-biphenyl phenolic group-bis-(2-methyl-oxine) close aluminium, oxine aluminium, 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole and 1, a kind of in 3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene;
The material of described electron injecting layer comprises electron transport material and co-doped sulfate and the alkali metal salt in described electron transport material, the mass ratio of described sulfate and described electron transport material is 0.06～0.25:1, the mass ratio of described alkali metal salt and described electron transport material is 0.25～0.35:1, described electron transport material is selected from 4, 7-diphenyl-1, 10-phenanthroline, 4, 7-diphenyl-1, 10-Phen, 4-biphenyl phenolic group-bis-(2-methyl-oxine) close aluminium, oxine aluminium, 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1, 2, 4-triazole and 1, 3, a kind of in 5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene, described sulfate is selected from lithium sulfate, sodium sulphate, potassium sulfate, a kind of in rubidium sulfate and cesium sulfate, described alkali metal salt is selected from lithium fluoride, Lithium Azide, lithium nitride, cesium fluoride, a kind of in cesium azide and nitrogenize caesium.
4. organic electroluminescence device according to claim 1, is characterized in that, the thickness of described hole injection layer is 10 nanometer～15 nanometers; The thickness of described hole transmission layer is 30 nanometer～50 nanometers; The thickness of described green light emitting layer is 10 nanometer～30 nanometers; The thickness of described electron transfer layer is 10 nanometer～60 nanometers; The thickness of described electron injecting layer is 15 nanometer～45 nanometers.
5. a preparation method for organic electroluminescence device, is characterized in that, comprises the steps:
On glass substrate, vacuum evaporation forms hole injection layer, hole transmission layer, green light emitting layer, electron transfer layer and electron injecting layer successively; And
On described electron injecting layer, form cathode layer, described cathode layer comprises the metal level stacking gradually, metal oxide mixed layer, metal-doped layer and transparency conducting layer, described metal level is formed on described electron injecting layer, and described metal level and described metal-doped layer are prepared by vacuum evaporation, described metal oxide mixed layer and described transparency conducting layer are prepared by magnetron sputtering, obtain organic electroluminescence device, wherein, the material of described metal level is aluminium, nickel, golden or silver-colored, the material of described metal oxide mixed layer is five oxidation two neodymiums, two kinds of mixtures that form according to identical mass mixing in vanadic oxide and tantalum pentoxide, the material of described metal-doped layer is the magnesium of silver doping or the aluminium of lithium doping, described in the magnesium of described silver doping, silver is 5:1～20:1 with the mass ratio of described magnesium, the mass ratio of lithium and described aluminium described in the aluminium of described lithium doping is 0.001:1～0.001:0.1, the material of described transparency conducting layer is indium tin oxide, aluminium zinc oxide or indium-zinc oxide.
6. the preparation method of organic electroluminescence device according to claim 5, it is characterized in that, on described glass substrate, vacuum evaporation also comprises the step that described glass substrate is cleaned before forming described hole injection layer: described glass substrate is adopted to liquid detergent, deionized water, acetone and ethanol ultrasonic cleaning successively, and then dry.
7. the preparation method of organic electroluminescence device according to claim 6, it is characterized in that, vacuum evaporation after described cleaning glass substrate, on described glass substrate is also comprised to the step of the surface of described glass substrate being carried out to activation processing before forming described hole injection layer.
8. the preparation method of organic electroluminescence device according to claim 5, is characterized in that, the vacuum degree that vacuum evaporation forms described hole injection layer is 1 * 10 -5pa～1 * 10 -3pa, evaporation rate is
The vacuum degree that vacuum evaporation forms described hole transmission layer is 1 * 10 -5pa～1 * 10 -3pa, evaporation rate is
The vacuum degree that vacuum evaporation forms described green light emitting layer is 1 * 10 -5pa～1 * 10 -3pa, evaporation rate is
The vacuum degree that vacuum evaporation forms described electron transfer layer is 1 * 10 -5pa～1 * 10 -3pa, evaporation rate is
The vacuum degree that vacuum evaporation forms described electron injecting layer is 1 * 10 -5pa～1 * 10 -3pa, evaporation rate is
The vacuum degree that vacuum evaporation forms described metal level is 1 * 10 -5pa～1 * 10 -3pa, evaporation rate is
The base vacuum degree that magnetron sputtering forms described metal oxide mixed layer is 1 * 10 -5pa～1 * 10 -3pa;
The vacuum degree that vacuum evaporation forms described metal-doped layer is 1 * 10 -5pa～1 * 10 -3pa, evaporation rate is
The base vacuum degree that magnetron sputtering forms described transparency conducting layer is 1 * 10 -5pa～1 * 10 -3pa.
CN201310109551.7A 2013-03-29 2013-03-29 Organic light-emitting diode device and manufacturing method thereof Pending CN104078622A (en)

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CN110098347A (en) * 2019-04-29 2019-08-06 武汉华星光电半导体显示技术有限公司 OLED display panel and preparation method
CN112635691A (en) * 2020-12-31 2021-04-09 Tcl华星光电技术有限公司 Array substrate and manufacturing method thereof
CN113964279A (en) * 2020-07-20 2022-01-21 咸阳彩虹光电科技有限公司 Top-emitting organic electroluminescent element and top-emitting organic electroluminescent device

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CN110098347A (en) * 2019-04-29 2019-08-06 武汉华星光电半导体显示技术有限公司 OLED display panel and preparation method
CN113964279A (en) * 2020-07-20 2022-01-21 咸阳彩虹光电科技有限公司 Top-emitting organic electroluminescent element and top-emitting organic electroluminescent device
CN112635691A (en) * 2020-12-31 2021-04-09 Tcl华星光电技术有限公司 Array substrate and manufacturing method thereof
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Application publication date: 20141001