CN104051650A - Organic electroluminescent device and preparation method thereof - Google Patents

Organic electroluminescent device and preparation method thereof Download PDF

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Publication number
CN104051650A
CN104051650A CN201310084448.1A CN201310084448A CN104051650A CN 104051650 A CN104051650 A CN 104051650A CN 201310084448 A CN201310084448 A CN 201310084448A CN 104051650 A CN104051650 A CN 104051650A
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layer
bis
phenyl
diphenyl
biphenyl
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周明杰
王平
钟铁涛
冯小明
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/17—Carrier injection layers
    • H10K50/171—Electron injection 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
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/321—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3]
    • H10K85/324—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3] comprising aluminium, e.g. Alq3
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/624—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing six or more rings
    • 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

Abstract

The invention discloses an organic electroluminescent device and a preparation method thereof. The device comprises an anode, a cavity injection layer, a cavity transmission layer, a luminescent layer, an electron transmission layer, an electron injection layer and a cathode which are successively stacked. The electron injection layer comprises a main material, and a first object material and a second object material which are doped in the main material. The main material is 4,7- diphenyl-1,10-phenanthroline, 4,7-diphenyl-1,10-o-phenanthroline, 4-biphenyl phenolic-di(2-methyl-8-hydroxyquinoline) aluminum, 8-hydroxyquinoline, 3-(diphenyl-4-ly)-5-(4- tert-butyl phenyl)-4-pheyl-4H-1,2,4-triazole or 1,3,5-(1-pheyl-1H- benzimidazole-2-ly)benzene. The first object material is lithium acetate, sodium acetate, potassium acetate, rubidium acetate or caesium acetate. The second object material is lithium fluoride, lithium azide, lithium nitride, cesium fluoride, caesium azide or caesium nitride. The life of the device is longer.

Description

Organic electroluminescence device and preparation method thereof
Technical field
The present invention relates to electroluminescent technology field, particularly relate to 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.
Yet the luminous efficiency of current organic electroluminescence device is lower, be difficult to meet user demand.
Summary of the invention
Based on this, be necessary the organic electroluminescence device that provides a kind of luminous efficiency higher.
A kind of organic electroluminescence device, comprise the anode stacking gradually, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode, described electron injecting layer comprises material of main part and is doped in the first guest materials and the second guest materials in described material of main part, described material of main part is 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 or 1, 3, 5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene, described the first guest materials is lithium acetate, sodium acetate, potassium acetate, rubidium acetate or cesium acetate, described the second guest materials is lithium fluoride, Lithium Azide, lithium nitride, cesium fluoride, cesium azide or nitrogenize caesium.
In an embodiment, the mass ratio of described the first guest materials and described material of main part is 3:100～15:100 therein.
In an embodiment, the mass ratio of described the second guest materials and described material of main part is 25:100～35:100 therein.
In an embodiment, the thickness of described electron injecting layer is 10～30 nanometers therein.
In an embodiment, described hole injection layer is formed in hole mobile material by doped metallic oxide therein, and described metal oxide is molybdenum trioxide, tungstic acid, vanadic oxide or rhenium trioxide; Described hole mobile material is 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 or 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane;
Described hole transmission layer is by 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 or 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane formation;
Described luminescent layer is doped in luminous material of main part and is formed by luminous guest materials, described luminous guest materials is two (4,6-difluorophenyl pyridine-N, C2) pyridine formyl closes iridium), two (4,6-difluorophenyl pyridine)-tetra-(1-pyrazolyl) boric acid closes iridium, three (2-(4', the fluoro-5 '-cyano group of 6'-bis-) phenylpyridine-N, C2') close iridium, two (4,6-difluorophenyl pyridine)-(3-(trifluoromethyl)-5-(pyridine-2-yl)-1,2,4-triazole) close iridium or two (4,6-difluorophenyl pyridines) (5-(pyridine-2-yl)-tetrazolium) and close iridium; Described luminous material of main part is 4,4'-bis-(9-carbazole) biphenyl, 9,9'-(1,3-phenyl) two-9H-carbazole, 9-(4-2-methyl-2-phenylpropane base)-3, two (triphenyl the silicon)-9H-carbazoles of 6-), 2, two (3-(9H-carbazole-9-yl) phenyl) pyridines, 3 of 6-, two (3-(9H-carbazole-9-yl) phenyl) pyridine or Isosorbide-5-Nitrae--two (triphenyl silicon) benzene of 5-;
Described electron transfer layer is by 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 or 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene forms;
Described negative electrode is formed by silver, aluminium or gold.
In an embodiment, the mass percent that described metal oxide accounts for described hole injection layer is 25～35% therein;
The mass ratio of described luminous guest materials and described luminous material of main part is 5:100～20:100.
Therein in an embodiment, the thickness of described hole injection layer is 10～15 nanometers, and the thickness of described hole transmission layer is 30～50 nanometers, and the thickness of described luminescent layer is 5～15 nanometers, the thickness of described electron transfer layer is 10～60 nanometers, and the thickness of described negative electrode is 50～200 nanometers.
A preparation method for organic electroluminescence device, comprises the steps:
Anode is provided, and on described anode, vacuum evaporation forms hole injection layer;
On described hole injection layer, vacuum evaporation forms hole transmission layer;
On described hole transmission layer, vacuum evaporation forms luminescent layer;
On described luminescent layer, vacuum evaporation forms electron transfer layer;
On described electron transfer layer, vacuum evaporation forms electron injecting layer, described electron injecting layer comprises material of main part and is doped in the first guest materials and the second guest materials in described material of main part, described material of main part is 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 or 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene; Described the first guest materials is lithium acetate, sodium acetate, potassium acetate, rubidium acetate or cesium acetate; Described the second guest materials is lithium fluoride, Lithium Azide, lithium nitride, cesium fluoride, cesium azide or nitrogenize caesium;
On described electron injecting layer, vacuum evaporation forms negative electrode, obtains organic electroluminescence device.
Therein in an embodiment, described vacuum evaporation vacuum degree be 1 * 10 -5pa～1 * 10 -3pa.
In an embodiment, on described electron transfer layer, vacuum evaporation forms in the step of electron injecting layer therein, and the evaporation rate of described vacuum evaporation is
A kind of and the acetate co-doped of the electron injecting layer of above-mentioned organic electroluminescence device in lithium salts and cesium salt forms in electron injection material, can improve electron injection efficiency, makes hole and electronics reach balance, thereby improves luminous efficiency.
Accompanying drawing explanation
Fig. 1 is the structural representation of the organic electroluminescence device of an execution mode;
Fig. 2 is preparation method's flow chart of the organic electroluminescence device of an execution mode;
Fig. 3 is the luminous efficiency curve figure of the organic electroluminescence device of embodiment 1～6 and comparative example 1.
Embodiment
For above-mentioned purpose of the present invention, feature and advantage can be become apparent more, below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in detail.A lot of details have been set forth in the following description so that fully understand the present invention.But the present invention can implement to be much different from alternate manner described here, and those skilled in the art can do similar improvement without prejudice to intension of the present invention in the situation that, so the present invention is not subject to the restriction of following public concrete enforcement.
Refer to Fig. 1, the organic electroluminescence device 100 of an execution mode, comprises the anode 10, hole injection layer 20, hole transmission layer 30, luminescent layer 40, electron transfer layer 50, electron injecting layer 60 and the negative electrode 70 that stack gradually.
Anode 10 can, for indium tin oxide glass (ITO), aluminium zinc oxide glass (AZO) or indium-zinc oxide glass (IZO), be preferably indium tin oxide glass (ITO).
Indium tin oxide glass (ITO), aluminium zinc oxide glass (AZO) or indium-zinc oxide glass (IZO) refer to the glass that is laminated with indium and tin oxide film, aluminium zinc oxide film or indium-zinc oxide film on surface, preferably, the thickness of indium and tin oxide film, aluminium zinc oxide film or indium-zinc oxide film is 100 nanometers.
Hole injection layer 20 is formed in hole mobile material by doped metallic oxide.
Metal oxide is molybdenum trioxide (MoO 3), tungstic acid (WO 3), vanadic oxide (V 2o 5) or rhenium trioxide (ReO 3); Hole mobile material is 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) or 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane (TAPC).
Preferably, to account for the mass percent of hole injection layer 20 be 25～35% to metal oxide.
Preferably, the thickness of hole injection layer 20 is 10～15 nanometers.
Hole transmission layer 30 is by 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) or 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane (TAPC) formation.
Preferably, the thickness of hole transmission layer 30 is 30～50 nanometers.
Luminescent layer 40 is doped in luminous material of main part and is formed by luminous guest materials.
Luminous guest materials is two (4,6-difluorophenyl pyridine-N, C2) pyridine formyl closes iridium) (FIrpic), two (4,6-difluorophenyl pyridine)-tetra-(1-pyrazolyl) boric acid closes iridium (FIr6), three (2-(4', the fluoro-5 '-cyano group of 6'-bis-) phenylpyridine-N, C2') close iridium (FCNIr), two (4,6-difluorophenyl pyridine)-(3-(trifluoromethyl)-5-(pyridine-2-yl)-1,2,4-triazole) close iridium (FIrtaz) or two (4,6-difluorophenyl pyridines) (5-(pyridine-2-yl)-tetrazolium) and close iridium (FIrN4); Luminous material of main part is 4,4'-bis-(9-carbazole) biphenyl (CBP), 9,9'-(1,3-phenyl) two-9H-carbazole (mCP), 9-(4-2-methyl-2-phenylpropane base)-3, two (triphenyl the silicon)-9H-carbazoles of 6-) (CzSi), 2, two (3-(9H-carbazole-9-yl) phenyl) pyridines (26DCzPPY), 3 of 6-, two (3-(9H-carbazole-9-yl) phenyl) pyridine (35DCzPPY) or Isosorbide-5-Nitrae--two (triphenyl silicon) benzene (UGH2) of 5-.
Preferably, the mass ratio of luminous guest materials and luminous material of main part is 5:100～20:100.
Preferably, the thickness of luminescent layer 40 is 5～15 nanometers.
Electron transfer layer 50 is by 4,7-diphenyl-1,10-phenanthroline (Bphen), 4,7-diphenyl-1,10-Phen (BCP), 4-biphenyl phenolic group-bis-(2-methyl-oxine) close aluminium (BAlq), oxine aluminium (Alq3), 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole (TAZ) or 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBI) forms.
Preferably, the thickness of electron transfer layer 50 is 10～60 nanometers.
Electron injecting layer 60 comprises material of main part and is doped in the first guest materials and the second guest materials in material of main part.
Material of main part is 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-1,2,4-triazole (TAZ) or 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBI).
The first guest materials is lithium acetate (CH 3cOOLi), sodium acetate (CH 3cOONa), potassium acetate (CH 3cOOK), rubidium acetate (CH 3cOORb) or cesium acetate (CH 3cOOCs).
The second guest materials is lithium fluoride (LiF), Lithium Azide (LiN 3), lithium nitride (Li 3n), cesium fluoride (CsF), cesium azide (CsN 3) or nitrogenize caesium (Cs 3n).
Preferably, the mass ratio of the first guest materials and material of main part is 3:100～15:100.
Preferably, the mass ratio of the second guest materials and material of main part is 25:100～35:100.
Preferably, the thickness of electron injecting layer 60 is 10～30 nanometers.
Negative electrode 70 is formed by argent (Ag), aluminium (Al) or gold (Au).
Preferably, the thickness of negative electrode 70 is 50～200 nanometers.
Electroluminescent device is charge carrier (electronics or hole) injection type electroluminescence device, and the injection in electronics and hole, transmission and balance thereof have determined the luminous efficiency of electroluminescent device.In organic electroluminescence device, hole mobility is more much bigger than electron mobility, therefore, improves electron injection efficiency and electron transport ability, makes hole and electronics reach balance, most important for luminous efficiency.
A kind of and the acetate co-doped of the electron injecting layer 60 of organic electroluminescence device 100 in lithium salts and cesium salt forms in electron injection material, be conducive to improve electron injection efficiency, thereby making hole and electronic equilibrium, improve luminous efficiency, is 1000cd/cm in brightness 2under, luminous efficiency has improved 30%.
The mass percent that a kind of doping content in lithium salts and cesium salt accounts for material of main part is 25～35%, and when the mass percent that doping content of acetate accounts for material of main part is 3～15%, luminous efficiency is the highest.
Refer to Fig. 2, the preparation method of the organic electroluminescence device of an execution mode, comprises the steps:
Step S110: anode is provided, and vacuum evaporation forms hole injection layer on anode.
Anode can, for indium tin oxide glass, aluminium zinc oxide glass or indium-zinc oxide glass, be preferably indium tin oxide glass.
Preferably, the thickness of the indium and tin oxide film of anode, aluminium zinc oxide film or indium-zinc oxide film is 100 nanometers.
First employing vacuum evaporation carried out ultrasonic cleaning with liquid detergent, deionized water, acetone and ethanol antianode form hole injection layer on anode before, each ultrasonic cleaning 5 minutes, stop 5 minutes, repeat respectively 3 times, then use oven for drying, obtain cleaning, dry anode.Further anode is carried out to surface-active-treatment, to increase the oxygen content of anode surface, improve the work function of anode.Carry out the step of surface activation process for adopting ultraviolet-ozone (UV-ozone) to process 30～50 minutes the anode after cleaning-drying.
Hole injection layer is formed in hole mobile material by doped metallic oxide.
Metal oxide is molybdenum trioxide (MoO 3), tungstic acid (WO 3), vanadic oxide (V 2o 5) or rhenium trioxide (ReO 3); Hole mobile material is 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) or 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane (TAPC).
Preferably, to account for the mass percent of hole injection layer be 25～35% to metal oxide.
Preferably, the thickness of hole injection layer is 10～15 nanometers.
The vacuum degree of vacuum evaporation is preferably 1 * 10 -5pa～1 * 10 -3pa, evaporation rate is
Step S120: vacuum evaporation forms hole transmission layer on hole injection layer.
Hole transmission layer is by 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) or 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane (TAPC) formation.
Preferably, the thickness of hole transmission layer is 30～50 nanometers.
The vacuum degree of vacuum evaporation is preferably 1 * 10 -5pa～1 * 10 -3pa, evaporation rate is
Step S130: vacuum evaporation forms luminescent layer on hole transmission layer.
Luminescent layer is doped in luminous material of main part and is formed by luminous guest materials.
Luminous guest materials is two (4,6-difluorophenyl pyridine-N, C2) pyridine formyl closes iridium) (FIrpic), two (4,6-difluorophenyl pyridine)-tetra-(1-pyrazolyl) boric acid closes iridium (FIr6), three (2-(4', the fluoro-5 '-cyano group of 6'-bis-) phenylpyridine-N, C2') close iridium (FCNIr), two (4,6-difluorophenyl pyridine)-(3-(trifluoromethyl)-5-(pyridine-2-yl)-1,2,4-triazole) close iridium (FIrtaz) or two (4,6-difluorophenyl pyridines) (5-(pyridine-2-yl)-tetrazolium) and close iridium (FIrN4); Luminous material of main part is 4,4'-bis-(9-carbazole) biphenyl (CBP), 9,9'-(1,3-phenyl) two-9H-carbazole (mCP), 9-(4-2-methyl-2-phenylpropane base)-3, two (triphenyl the silicon)-9H-carbazoles of 6-) (CzSi), 2, two (3-(9H-carbazole-9-yl) phenyl) pyridines (26DCzPPY), 3 of 6-, two (3-(9H-carbazole-9-yl) phenyl) pyridine (35DCzPPY) or Isosorbide-5-Nitrae--two (triphenyl silicon) benzene (UGH2) of 5-.
Preferably, the mass ratio of luminous guest materials and luminous material of main part is 5:100～20:100.
Preferably, the thickness of luminescent layer is 5～15 nanometers.
The vacuum degree 1 * 10 of vacuum evaporation -5pa～1 * 10 -3pa, evaporation rate
Step S140: vacuum evaporation forms electron transfer layer on luminescent layer.
Electron transfer layer is by 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-1,2,4-triazole (TAZ) or 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBI) forms.
Preferably, the thickness of electron transfer layer is 10～60 nanometers.
The vacuum degree 1 * 10 of vacuum evaporation -5pa～1 * 10 -3pa, evaporation rate
Step S150: vacuum evaporation forms electron injecting layer on electron transfer layer.
Electron injecting layer comprises material of main part and is doped in the first guest materials and the second guest materials in material of main part.
Material of main part is 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-1,2,4-triazole (TAZ) or 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBI).
The first guest materials is lithium acetate (CH 3cOOLi), sodium acetate (CH 3cOONa), potassium acetate (CH 3cOOK), rubidium acetate (CH 3cOORb) or cesium acetate (CH 3cOOCs).
The second guest materials is lithium fluoride (LiF), Lithium Azide (LiN 3), lithium nitride (Li 3n), cesium fluoride (CsF), cesium azide (CsN 3) or nitrogenize caesium (Cs 3n).
Preferably, the mass ratio of the first guest materials and material of main part is 3:100～15:100.
Preferably, the mass ratio of the second guest materials and material of main part is 25:100～35:100.
Preferably, the thickness of electron injecting layer is 10～30 nanometers.
The vacuum degree 1 * 10 of vacuum evaporation -5pa～1 * 10 -3pa, evaporation rate
Step S160: vacuum evaporation forms negative electrode on electron injecting layer, obtains organic electroluminescence device.
Negative electrode is formed by argent (Ag), aluminium (Al) or gold (Au).
Preferably, the thickness of negative electrode 70 is 50～200 nanometers.
The vacuum degree 1 * 10 of vacuum evaporation -5pa～1 * 10 -3pa, evaporation rate
The preparation method of above-mentioned organic electroluminescence device adopts vacuum evaporation on anode, to form the hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the negative electrode that stack gradually and obtains organic electroluminescence device, preparation technology is simple, is easy to extensive preparation.
The vacuum degree of vacuum evaporation is 1 * 10 -5pa～1 * 10 -3pa, the evaporation rate of preparing hole injection layer and luminescent layer is 0.1 the evaporation rate of preparing hole transmission layer, electron transfer layer and electron injecting layer is the evaporation rate of preparing negative electrode is select suitable vacuum degree, and adopt different evaporation rates according to different materials, be conducive to improve quality of forming film, thereby obtain the organic electroluminescence device of stable performance.
Especially, in vacuum degree, be 1 * 10 -5pa～1 * 10 -3under Pa, with evaporation rate evaporation lithium acetate, sodium acetate, potassium acetate, a kind of in rubidium acetate and cesium acetate, lithium fluoride, Lithium Azide, lithium nitride, cesium fluoride, a kind of in cesium azide and nitrogenize caesium and 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, the lumo energy that can reduce electron injecting layer and electron transfer layer is poor, accelerate electronic injection speed, improve electron-hole recombination rate, thereby improve device luminous efficiency.
It is below specific embodiment.
Embodiment 1
Structure is ITO/MoO 3: NPB/NPB/FIrpic:CBP/Bphen/CH 3the preparation of the organic electroluminescence device of COOLi:LiF:Bphen/Ag
(1) using indium tin oxide glass as anode, be expressed as ITO.First with liquid detergent, deionized water, acetone and ethanol antianode, carry out ultrasonic cleaning, each ultrasonic cleaning 5 minutes, stops 5 minutes, repeats respectively 3 times, then uses oven for drying, obtains cleaning, dry anode.Further adopt ultraviolet-ozone (UV-ozone) to carry out surface activation process 30 minutes to the anode after cleaning-drying;
(2) in the anode surface vacuum evaporation through surface activation process, form hole injection layer, vacuum degree is 1 * 10 -5pa, evaporation rate hole injection layer is doped in N by molybdenum trioxide, N'-diphenyl-N, and N'-bis-(1-naphthyl)-1,1'-biphenyl-4, form in 4'-diamines, are expressed as MoO 3: NPB; Wherein, MoO 3the mass percent that accounts for hole injection layer is 30%, and the thickness of hole injection layer is 12.5 nanometers;
(3) on hole injection layer, vacuum evaporation forms hole transmission layer, and vacuum degree is 1 * 10 -5pa, evaporation rate hole transmission layer is by N, N'-diphenyl-N, and N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines forms, and is expressed as NPB; The thickness of hole transmission layer is 40 nanometers;
(4) on hole transmission layer, vacuum evaporation forms luminescent layer, and vacuum degree is 1 * 10 -5pa, evaporation rate luminescent layer closes iridium by two (4,6-difluorophenyl pyridine-N, C2) pyridine formyl and is doped in 4,4'-bis-(9-carbazole) biphenyl and forms, and is expressed as FIrpic:CBP; Wherein, the mass ratio of FIrpic and CBP is 12.5:100; The thickness of luminescent layer is 10 nanometers;
(5) on luminescent layer, vacuum evaporation forms electron transfer layer, and vacuum degree is 1 * 10 -5pa, evaporation rate electron transfer layer is by 4,7-diphenyl-1, and 10-phenanthroline forms, and is expressed as Bphen; The thickness of electron transfer layer is 35 nanometers;
(6) on electron transfer layer, vacuum evaporation forms electron injecting layer, and vacuum degree is 1 * 10 -5pa, evaporation rate electron injecting layer is doped in 4,7-diphenyl-1 by lithium acetate and lithium fluoride, in 10-phenanthroline, forms, and is expressed as CH 3cOOLi:LiF:Bphen; Wherein, CH 3the mass ratio of COOLi and Bphen is 10:100, and the mass ratio of LiF and Bphen is 30:100; The thickness of electron injecting layer is 20 nanometers;
(7) on electron injecting layer, vacuum evaporation forms negative electrode, and vacuum degree is 1 * 10 -5pa, evaporation rate negative electrode is formed by argent (Ag), is expressed as Ag, and the thickness of negative electrode is 125 nanometers.
It is ITO/MoO that the anode stacking gradually, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode form structure 3: NPB/NPB/FIrpic:CBP/Bphen/CH 3the organic electroluminescence device of COOLi:LiF:Bphen/Ag.
Embodiment 2
Structure is ITO/WO 3: TCTA/TCTA/FIr6:mCP/BCP/CH 3cOONa:LiN 3: the preparation of the organic electroluminescence device of BCP/Al
(1) using indium tin oxide glass as anode, be expressed as ITO.First with liquid detergent, deionized water, acetone and ethanol antianode, carry out ultrasonic cleaning, each ultrasonic cleaning 5 minutes, stops 5 minutes, repeats respectively 3 times, then uses oven for drying, obtains cleaning, dry anode.Further adopt ultraviolet-ozone (UV-ozone) to carry out surface activation process 50 minutes to the anode after cleaning-drying;
(2) in the anode surface vacuum evaporation through surface activation process, form hole injection layer, vacuum degree is 5 * 10 -5pa, evaporation rate hole injection layer is doped in 4,4' by tungstic acid, in 4''-tri-(carbazole-9-yl) triphenylamine, forms, and is expressed as WO 3: TCTA; Wherein, WO 3the mass percent that accounts for hole injection layer is 25%, and the thickness of hole injection layer is 10 nanometers;
(3) on hole injection layer, vacuum evaporation forms hole transmission layer, and vacuum degree is 5 * 10 -5pa, evaporation rate hole transmission layer is by 4,4', and 4''-tri-(carbazole-9-yl) triphenylamine forms, and is expressed as TCTA; The thickness of hole transmission layer is 30 nanometers;
(4) on hole transmission layer, vacuum evaporation forms luminescent layer, and vacuum degree is 5 * 10 -5pa, evaporation rate luminescent layer closes iridium by two (4,6-difluorophenyl pyridines)-tetra-(1-pyrazolyl) boric acid and is doped in 9,9'-(1,3-phenyl), two-9H-carbazole and forms, and is expressed as FIr6:mCP; Wherein, the mass ratio of FIr6 and mCP is 5:100; The thickness of luminescent layer is 5 nanometers;
(5) on luminescent layer, vacuum evaporation forms electron transfer layer, and vacuum degree is 5 * 10 -5pa, evaporation rate electron transfer layer is by 4,7-diphenyl-1, and 10-Phen forms, and is expressed as BCP; The thickness of electron transfer layer is 10 nanometers;
(6) on electron transfer layer, vacuum evaporation forms electron injecting layer, and vacuum degree is 5 * 10 -5pa, evaporation rate electron injecting layer is doped in 4,7-diphenyl-1 by sodium acetate and Lithium Azide, in 10-Phen, forms, and is expressed as CH 3cOONa:LiN 3: BCP; Wherein, CH 3the mass ratio of COONa and BCP is 15:100, LiN 3with the mass ratio of BCP be 25:100; The thickness of electron injecting layer is 30 nanometers;
(7) on electron injecting layer, vacuum evaporation forms negative electrode, and vacuum degree is 5 * 10 -5pa, evaporation rate negative electrode is formed by metallic aluminium (Al), is expressed as Al, and the thickness of negative electrode is 50 nanometers.
It is ITO/WO that the anode stacking gradually, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode form structure 3: TCTA/TCTA/FIr6:mCP/BCP/CH 3cOONa:LiN 3: the organic electroluminescence device of BCP/Al.
Embodiment 3
Structure is ITO/V 2o 5: CBP/CBP/FCNIr:CzSi/BAlq/CH 3cOOK:Li 3the preparation of the organic electroluminescence device of N:BAlq/Au
(1) using indium tin oxide glass as anode, be expressed as ITO.First with liquid detergent, deionized water, acetone and ethanol antianode, carry out ultrasonic cleaning, each ultrasonic cleaning 5 minutes, stops 5 minutes, repeats respectively 3 times, then uses oven for drying, obtains cleaning, dry anode.Further adopt ultraviolet-ozone (UV-ozone) to carry out surface activation process 40 minutes to the anode after cleaning-drying;
(2) in the anode surface vacuum evaporation through surface activation process, form hole injection layer, vacuum degree is 5 * 10 -5pa, evaporation rate hole injection layer is doped in 4,4'-bis-(9-carbazole) biphenyl and is formed by vanadic oxide, is expressed as V 2o 5: CBP; Wherein, V 2o 5the mass percent that accounts for hole injection layer is 35%, and the thickness of hole injection layer is 15 nanometers;
(3) on hole injection layer, vacuum evaporation forms hole transmission layer, and vacuum degree is 5 * 10 -5pa, evaporation rate hole transmission layer is formed by 4,4'-bis-(9-carbazole) biphenyl, is expressed as CBP; The thickness of hole transmission layer is 50 nanometers;
(4) on hole transmission layer, vacuum evaporation forms luminescent layer, and vacuum degree is 5 * 10 -5pa, evaporation rate luminescent layer is by three (2-(4', the fluoro-5 '-cyano group of 6'-bis-) phenylpyridine-N, C2') close iridium and be doped in 9-(4-2-methyl-2-phenylpropane base)-3, in two (triphenyl the silicon)-9H-carbazoles of 6-, form, be expressed as FCNIr:CzSi; Wherein, the mass ratio of FCNIr and CzSi is 20:100; The thickness of luminescent layer is 15 nanometers;
(5) on luminescent layer, vacuum evaporation forms electron transfer layer, and vacuum degree is 5 * 10 -5pa, evaporation rate electron transfer layer closes aluminium by 4-biphenyl phenolic group-bis-(2-methyl-oxine) and forms, and is expressed as BAlq; The thickness of electron transfer layer is 60 nanometers;
(6) on electron transfer layer, vacuum evaporation forms electron injecting layer, and vacuum degree is 5 * 10 -5pa, evaporation rate electron injecting layer is doped in 4-biphenyl phenolic group-bis-(2-methyl-oxine) by potassium acetate and lithium nitride and closes in aluminium and form, and is expressed as CH 3cOOK:Li 3n:BAlq; Wherein, CH 3the mass ratio of COOK and BAlq is 3:100, Li 3the mass ratio of N and BAlq is 35:100; The thickness of electron injecting layer is 10 nanometers;
(7) on electron injecting layer, vacuum evaporation forms negative electrode, and vacuum degree is 5 * 10 -5pa, evaporation rate negative electrode is formed by metallic gold (Au), is expressed as Au, and the thickness of negative electrode is 200 nanometers.
It is ITO/V that the anode stacking gradually, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode form structure 2o 5: CBP/CBP/FCNIr:CzSi/BAlq/CH 3cOOK:Li 3the organic electroluminescence device of N:BAlq/Au.
Embodiment 4
Structure is ITO/ReO 3: TPD/TPD/FIrtaz:26DCzPPY/Alq 3/ CH 3cOORb:CsF:Alq 3the preparation of the organic electroluminescence device of //Ag
(1) using indium tin oxide glass as anode, be expressed as ITO.First with liquid detergent, deionized water, acetone and ethanol antianode, carry out ultrasonic cleaning, each ultrasonic cleaning 5 minutes, stops 5 minutes, repeats respectively 3 times, then uses oven for drying, obtains cleaning, dry anode.Further adopt ultraviolet-ozone (UV-ozone) to carry out surface activation process 30 minutes to the anode after cleaning-drying;
(2) in the anode surface vacuum evaporation through surface activation process, form hole injection layer, vacuum degree is 5 * 10 -5pa, evaporation rate hole injection layer is doped in N by rhenium trioxide, N'-bis-(3-aminomethyl phenyl)-N, and N'-diphenyl-4, form in 4'-benzidine, are expressed as ReO 3: TPD; Wherein, ReO 3the mass percent that accounts for hole injection layer is 30%, and the thickness of hole injection layer is 13 nanometers;
(3) on hole injection layer, vacuum evaporation forms hole transmission layer, and vacuum degree is 5 * 10 -5pa, evaporation rate hole transmission layer is by N, N'-bis-(3-aminomethyl phenyl)-N, and N'-diphenyl-4,4'-benzidine forms, and is expressed as TPD; The thickness of hole transmission layer is 40 nanometers;
(4) on hole transmission layer, vacuum evaporation forms luminescent layer, and vacuum degree is 5 * 10 -5pa, evaporation rate luminescent layer is by two (4,6-difluorophenyl pyridine)-(3-(trifluoromethyl)-5-(pyridine-2-yl)-1,2,4-triazole is closed iridium) is doped in 2, in two (3-(9H-carbazole-9-yl) phenyl) pyridines of 6-, form, be expressed as FIrtaz:26DCzPPY; Wherein, the mass ratio of FIrtaz and 26DCzPPY is 12:100; The thickness of luminescent layer is 10 nanometers;
(5) on luminescent layer, vacuum evaporation forms electron transfer layer, and vacuum degree is 5 * 10 -5pa, evaporation rate electron transfer layer is formed by oxine aluminium, is expressed as Alq 3; The thickness of electron transfer layer is 30 nanometers;
(6) on electron transfer layer, vacuum evaporation forms electron injecting layer, and vacuum degree is 5 * 10 -5pa, evaporation rate electron injecting layer is doped in oxine aluminium and is formed by rubidium acetate and cesium fluoride, is expressed as CH 3cOORb:CsF:Alq 3; Wherein, CH 3cOORb and Alq 3mass ratio be 10:100, CsF and Alq 3mass ratio be 30:100; The thickness of electron injecting layer is 30 nanometers;
(7) on electron injecting layer, vacuum evaporation forms negative electrode, and vacuum degree is 5 * 10 -5pa, evaporation rate negative electrode is formed by argent (Ag), is expressed as Ag, and the thickness of negative electrode is 100 nanometers.
It is ITO/ReO that the anode stacking gradually, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode form structure 3: TPD/TPD/FIrtaz:26DCzPPY/Alq 3/ CH 3cOORb:CsF:Alq 3the organic electroluminescence device of //Ag.
Embodiment 5
Structure is ITO/MoO 3: TAPC/TAPC/FIrN4:35DCzPPY/TAZ/CH 3cOOCs:CsN 3: the preparation of the organic electroluminescence device of TAZ/Al
(1) using indium tin oxide glass as anode, be expressed as ITO.First with liquid detergent, deionized water, acetone and ethanol antianode, carry out ultrasonic cleaning, each ultrasonic cleaning 5 minutes, stops 5 minutes, repeats respectively 3 times, then uses oven for drying, obtains cleaning, dry anode.Further adopt ultraviolet-ozone (UV-ozone) to carry out surface activation process 30 minutes to the anode after cleaning-drying;
(2) in the anode surface vacuum evaporation through surface activation process, form hole injection layer, vacuum degree is 5 * 10 -5pa, evaporation rate hole injection layer is doped in 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl by molybdenum trioxide] form in cyclohexane, be expressed as MoO 3: TAPC; Wherein, MoO 3the mass percent that accounts for hole injection layer is 25%, and the thickness of hole injection layer is 10 nanometers;
(3) on hole injection layer, vacuum evaporation forms hole transmission layer, and vacuum degree is 5 * 10 -5pa, evaporation rate hole transmission layer is by 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane formation, be expressed as TAPC; The thickness of hole transmission layer is 40 nanometers;
(4) on hole transmission layer, vacuum evaporation forms luminescent layer, and vacuum degree is 5 * 10 -5pa, evaporation rate luminescent layer closes iridium by two (4,6-difluorophenyl pyridines) (5-(pyridine-2-yl)-tetrazolium) and is doped in two (3-(9H-carbazole-9-yl) phenyl) pyridines of 3,5-and forms, and is expressed as FIrN4:35DCzPPY; Wherein, the mass ratio of FIrN4 and 35DCzPPY is 12:100; The thickness of luminescent layer is 10 nanometers;
(5) on luminescent layer, vacuum evaporation forms electron transfer layer, and vacuum degree is 5 * 10 -5pa, evaporation rate electron transfer layer is by 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1, and 2,4-triazole forms, and is expressed as TAZ; The thickness of electron transfer layer is 50 nanometers;
(6) on electron transfer layer, vacuum evaporation forms electron injecting layer, and vacuum degree is 5 * 10 -5pa, evaporation rate electron injecting layer is doped in 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1 by cesium acetate and cesium azide, in 2,4-triazole, forms, and is expressed as CH 3cOOCs:CsN 3: TAZ; Wherein, CH 3the mass ratio of COOCs and TAZ is 10:100, CsN 3with the mass ratio of TAZ be 30:100; The thickness of electron injecting layer is 30 nanometers;
(7) on electron injecting layer, vacuum evaporation forms negative electrode, and vacuum degree is 5 * 10 -5pa, evaporation rate negative electrode is formed by metallic aluminium (Al), is expressed as Al, and the thickness of negative electrode is 100 nanometers.
It is ITO/MoO that the anode stacking gradually, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode form structure 3: TAPC/TAPC/FIrN4:35DCzPPY/TAZ/CH 3cOOCs:CsN 3: the organic electroluminescence device of TAZ/Al.
Embodiment 6
Structure is ITO/WO 3: NPB/NPB/FIrpic:UGH2/TPBI/CH 3cOOCs:Cs 3the preparation of the organic electroluminescence device of N:TPBI/Al
(1) using indium tin oxide glass as anode, be expressed as ITO.First with liquid detergent, deionized water, acetone and ethanol antianode, carry out ultrasonic cleaning, each ultrasonic cleaning 5 minutes, stops 5 minutes, repeats respectively 3 times, then uses oven for drying, obtains cleaning, dry anode.Further adopt ultraviolet-ozone (UV-ozone) to carry out surface activation process 30 minutes to the anode after cleaning-drying;
(2) in the anode surface vacuum evaporation through surface activation process, form hole injection layer, vacuum degree is 1 * 10 -3pa, evaporation rate hole injection layer is doped in N by tungstic acid, N'-diphenyl-N, and N'-bis-(1-naphthyl)-1,1'-biphenyl-4, form in 4'-diamines, are expressed as WO 3: NPB; Wherein, WO 3the mass percent that accounts for hole injection layer is 30%, and the thickness of hole injection layer is 12 nanometers;
(3) on hole injection layer, vacuum evaporation forms hole transmission layer, and vacuum degree is 1 * 10 -3pa, evaporation rate hole transmission layer is by N, N'-diphenyl-N, and N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines forms, and is expressed as NPB; The thickness of hole transmission layer is 40 nanometers;
(4) on hole transmission layer, vacuum evaporation forms luminescent layer, and vacuum degree is 1 * 10 -3pa, evaporation rate luminescent layer is closed iridium and is doped in Isosorbide-5-Nitrae by two (4,6-difluorophenyl pyridine-N, C2) pyridine formyl--and in two (triphenyl silicon) benzene, form, be expressed as FIrpic:UGH2; Wherein, the mass ratio of FIrpic and UGH2 is 12:100; The thickness of luminescent layer is 10 nanometers;
(5) on luminescent layer, vacuum evaporation forms electron transfer layer, and vacuum degree is 1 * 10 -3pa, evaporation rate electron transfer layer is formed by 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene, is expressed as TPBI; The thickness of electron transfer layer is 30 nanometers;
(6) on electron transfer layer, vacuum evaporation forms electron injecting layer, and vacuum degree is 1 * 10 -3pa, evaporation rate electron injecting layer is doped in 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene and is formed by cesium acetate and nitrogenize caesium, is expressed as CH 3cOOCs:Cs 3n:TPBI; Wherein, CH 3the mass ratio of COOCs and TPBI is 10:100, Cs 3the mass ratio of N and TPBI is 30:100; The thickness of electron injecting layer is 30 nanometers;
(7) on electron injecting layer, vacuum evaporation forms negative electrode, and vacuum degree is 1 * 10 -5pa, evaporation rate negative electrode is formed by metallic aluminium (Al), is expressed as Al, and the thickness of negative electrode is 100 nanometers.
It is ITO/WO that the anode stacking gradually, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode form structure 3: NPB/NPB/FIrpic:UGH2/TPBI/CH 3cOOCs:Cs 3the organic electroluminescence device of N:TPBI/Al.
Comparative example 1
Structure is ITO/MoO 3: NPB/NPB/FIrpic:CBP/Bphen/Cs 3the preparation of the organic electroluminescence device of N:Bphen/Ag
(1) using indium tin oxide glass as anode, be expressed as ITO.First with liquid detergent, deionized water, acetone and ethanol antianode, carry out ultrasonic cleaning, each ultrasonic cleaning 5 minutes, stops 5 minutes, repeats respectively 3 times, then uses oven for drying, obtains cleaning, dry anode.Further adopt ultraviolet-ozone (UV-ozone) to carry out surface activation process 30 minutes to the anode after cleaning-drying;
(2) in the anode surface vacuum evaporation through surface activation process, form hole injection layer, vacuum degree is 1 * 10 -5pa, evaporation rate hole injection layer is doped in N by molybdenum trioxide, N'-diphenyl-N, and N'-bis-(1-naphthyl)-1,1'-biphenyl-4, form in 4'-diamines, are expressed as MoO 3: NPB; Wherein, MoO 3the mass percent that accounts for hole injection layer is 30%, and the thickness of hole injection layer is 12.5 nanometers;
(3) on hole injection layer, vacuum evaporation forms hole transmission layer, and vacuum degree is 1 * 10 -5pa, evaporation rate hole transmission layer is by N, N'-diphenyl-N, and N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines forms, and is expressed as NPB; The thickness of hole transmission layer is 40 nanometers;
(4) on hole transmission layer, vacuum evaporation forms luminescent layer, and vacuum degree is 1 * 10 -5pa, evaporation rate luminescent layer closes iridium by two (4,6-difluorophenyl pyridine-N, C2) pyridine formyl and is doped in 4,4'-bis-(9-carbazole) biphenyl and forms, and is expressed as FIrpic:CBP; Wherein, the mass ratio of FIrpic and CBP is 12.5:100; The thickness of luminescent layer is 10 nanometers;
(5) on luminescent layer, vacuum evaporation forms electron transfer layer, and vacuum degree is 1 * 10 -5pa, evaporation rate electron transfer layer is by 4,7-diphenyl-1, and 10-phenanthroline forms, and is expressed as Bphen; The thickness of electron transfer layer is 35 nanometers;
(6) on electron transfer layer, vacuum evaporation forms electron injecting layer, and vacuum degree is 1 * 10 -5pa, evaporation rate electron injecting layer is doped in 4,7-diphenyl-1 by nitrogenize caesium, in 10-phenanthroline, forms, and is expressed as Cs 3n:Bphen; Wherein, Cs 3the mass percent that N accounts for Bphen is 29%; The thickness of electron injecting layer is 20 nanometers;
(7) on electron injecting layer, vacuum evaporation forms negative electrode, and vacuum degree is 1 * 10 -5pa, evaporation rate negative electrode is formed by argent (Ag), is expressed as Ag, and the thickness of negative electrode is 125 nanometers.
It is ITO/MoO that the anode stacking gradually, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode form structure 3: NPB/NPB/FIrpic:CBP/Bphen/Cs 3the organic electroluminescence device of N:Bphen/Ag.
Table 1 is that the organic electroluminescence device of embodiment 1～6 and comparative example 1 is 200.0～1800.0cd/m in brightness 2under luminous efficiency.
Fig. 3 is that the organic electroluminescence device of embodiment 1～6 and comparative example 1 is the luminous efficiency curve under 200.0～1800.0cd/m2 in brightness.
The luminous efficiency of the organic electroluminescence device of table 1 embodiment 1～6 and comparative example 1
By Fig. 3 and table 1, can be found out, because the electron injecting layer of the organic electroluminescence device of embodiment 1～the 6 a kind of and acetate co-doped in lithium salts and cesium salt forms in electron injection material, electron injection efficiency is higher, makes hole and electronics reach balance, thereby has improved luminous efficiency.In brightness, be 200.0～1800.0cd/m 2under, the luminous efficiency of the organic electroluminescence device of embodiment 1～6 is all higher than the luminous efficiency of the organic electroluminescence device of comparative example 1.
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 (10)

1. an organic electroluminescence device, comprise the anode stacking gradually, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode, it is characterized in that, described electron injecting layer comprises material of main part and is doped in the first guest materials and the second guest materials in described material of main part, described material of main part is 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 or 1, 3, 5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene, described the first guest materials is lithium acetate, sodium acetate, potassium acetate, rubidium acetate or cesium acetate, described the second guest materials is lithium fluoride, Lithium Azide, lithium nitride, cesium fluoride, cesium azide or nitrogenize caesium.
2. organic electroluminescence device according to claim 1, is characterized in that, the mass ratio of described the first guest materials and described material of main part is 3:100～15:100.
3. organic electroluminescence device according to claim 1, is characterized in that, the mass ratio of described the second guest materials and described material of main part is 25:100～35:100.
4. organic electroluminescence device according to claim 1, is characterized in that, the thickness of described electron injecting layer is 10～30 nanometers.
5. organic electroluminescence device according to claim 1, is characterized in that,
Described hole injection layer is formed in hole mobile material by doped metallic oxide, and described metal oxide is molybdenum trioxide, tungstic acid, vanadic oxide or rhenium trioxide; Described hole mobile material is 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 or 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane;
Described hole transmission layer is by 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 or 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane formation;
Described luminescent layer is doped in luminous material of main part and is formed by luminous guest materials, described luminous guest materials is two (4,6-difluorophenyl pyridine-N, C2) pyridine formyl closes iridium), two (4,6-difluorophenyl pyridine)-tetra-(1-pyrazolyl) boric acid closes iridium, three (2-(4', the fluoro-5 '-cyano group of 6'-bis-) phenylpyridine-N, C2') close iridium, two (4,6-difluorophenyl pyridine)-(3-(trifluoromethyl)-5-(pyridine-2-yl)-1,2,4-triazole) close iridium or two (4,6-difluorophenyl pyridines) (5-(pyridine-2-yl)-tetrazolium) and close iridium; Described luminous material of main part is 4,4'-bis-(9-carbazole) biphenyl, 9,9'-(1,3-phenyl) two-9H-carbazole, 9-(4-2-methyl-2-phenylpropane base)-3, two (triphenyl the silicon)-9H-carbazoles of 6-), 2, two (3-(9H-carbazole-9-yl) phenyl) pyridines, 3 of 6-, two (3-(9H-carbazole-9-yl) phenyl) pyridine or Isosorbide-5-Nitrae--two (triphenyl silicon) benzene of 5-;
Described electron transfer layer is by 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 or 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene forms;
Described negative electrode is formed by silver, aluminium or gold.
6. organic electroluminescence device according to claim 5, is characterized in that,
The mass percent that described metal oxide accounts for described hole injection layer is 25～35%;
The mass ratio of described luminous guest materials and described luminous material of main part is 5:100～20:100.
7. organic electroluminescence device according to claim 1, it is characterized in that, the thickness of described hole injection layer is 10～15 nanometers, the thickness of described hole transmission layer is 30～50 nanometers, the thickness of described luminescent layer is 5～15 nanometers, the thickness of described electron transfer layer is 10～60 nanometers, and the thickness of described negative electrode is 50～200 nanometers.
8. a preparation method for organic electroluminescence device, is characterized in that, comprises the steps:
Anode is provided, and on described anode, vacuum evaporation forms hole injection layer;
On described hole injection layer, vacuum evaporation forms hole transmission layer;
On described hole transmission layer, vacuum evaporation forms luminescent layer;
On described luminescent layer, vacuum evaporation forms electron transfer layer;
On described electron transfer layer, vacuum evaporation forms electron injecting layer, described electron injecting layer comprises material of main part and is doped in the first guest materials and the second guest materials in described material of main part, described material of main part is 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 or 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene; Described the first guest materials is lithium acetate, sodium acetate, potassium acetate, rubidium acetate or cesium acetate; Described the second guest materials is lithium fluoride, Lithium Azide, lithium nitride, cesium fluoride, cesium azide or nitrogenize caesium;
On described electron injecting layer, vacuum evaporation forms negative electrode, obtains organic electroluminescence device.
9. the preparation method of organic electroluminescence device according to claim 8, is characterized in that, described vacuum evaporation vacuum degree be 1 * 10 -5pa～1 * 10 -3pa.
10. the preparation method of organic electroluminescence device according to claim 8, is characterized in that, on described electron transfer layer, vacuum evaporation forms in the step of electron injecting layer, and the evaporation rate of described vacuum evaporation is 0.1
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Application publication date: 20140917