CN103633250A - Organic electroluminescent device and preparation method thereof - Google Patents

Organic electroluminescent device and preparation method thereof Download PDF

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CN103633250A
CN103633250A CN201210305556.2A CN201210305556A CN103633250A CN 103633250 A CN103633250 A CN 103633250A CN 201210305556 A CN201210305556 A CN 201210305556A CN 103633250 A CN103633250 A CN 103633250A
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phenyl
light emitting
red
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周明杰
王平
冯小明
钟铁涛
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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]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H10K50/125—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers specially adapted for multicolour light emission, e.g. for emitting white light
    • C—CHEMISTRY; METALLURGY
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    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • 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
    • H10K85/311—Phthalocyanine
    • 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]
    • 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
    • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • 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
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole

Abstract

The invention provides an organic electroluminescent device which comprises a substrate, an anode, a hole transmitting layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transmitting layer and a cathode, wherein the substrate, the anode, the hole transmitting layer, the electron blocking layer, the light emitting layer, the hole blocking layer, the electron transmitting layer and the cathode are sequentially stacked. The light emitting layer comprises a red and green mixed light emitting layer, an exciton blocking layer, a yellow light emitting layer and a blue light emitting layer, wherein the red and green mixed light emitting layer, the exciton blocking layer, the yellow light emitting layer and the blue light emitting layer are sequentially stacked on the electron blocking layer. The light emitting layer is a compound layer structure which is formed by sequentially stacking the red and green mixed light emitting layer, the exciton blocking layer, the yellow light emitting layer and the blue light emitting layer. The red and green mixed light emitting layer can expand an exciton composite region. The exciton blocking layer can control and regulate the energy transfer between a blue light and a green light. The combination of the red and green mixed light emitting layer, the yellow light emitting layer and the blue light emitting layer can acquire abundant spectra. The color rendering index of the organic electroluminescent device is high. The invention further provides a preparation method of the organic electroluminescent device.

Description

Organic electroluminescence device and preparation method thereof
Technical field
The present invention relates to luminescence display technical field, particularly relate to a kind of organic electroluminescence device and preparation method thereof.
Background technology
Organic electroluminescent (Organic Light Emission Diode), hereinafter to be referred as OLED, have that brightness is high, material range of choice is wide, driving voltage is low, entirely solidify the characteristics such as active illuminating, have high definition, wide viewing angle simultaneously, and the advantage such as fast response time, be a kind of Display Technique and light source that has potentiality, meet the development trend that information age mobile communication and information show, and the requirement of green lighting technique, be current lot of domestic and foreign researcher's focal point.
Organic electroluminescent LED has a kind of structure of similar sandwich, it is respectively negative electrode and anode up and down, the organic material functional layer that clips single or multiple lift different materials and different structure between two electrodes, is followed successively by hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer.Organic electroluminescence device is carrier injection type luminescent device, at anode and negative electrode, add after operating voltage, hole is from anode, electronics is injected into respectively organic material functional layer from negative electrode, it is luminous that two kinds of charge carriers form hole-duplet in organic luminous layer, and then light sends from electrode one side.
At present, organic electroluminescent LED has a wide range of applications at lighting field.In some specific lighting environments, sometimes need a kind of illuminating product of high color rendering index (CRI) that illumination is provided, gallery for example, indoor gardens, the organic electroluminescence device of preparation conventionally, its color rendering index is in 75 ~ 80 left and right.Yet in these special application places, need the more lighting device of high color rendering index (CRI).Therefore, exploitation is high shows that the organic electroluminescence device of index has great importance.
Summary of the invention
Based on this, be necessary for the not high problem of the demonstration index of existing organic electroluminescence device, a kind of organic electroluminescence device that index is higher and preparation method thereof that shows is provided.
A kind of organic electroluminescence device, comprise the substrate, anode, hole transmission layer, electronic barrier layer, luminescent layer, hole blocking layer, electron transfer layer and the negative electrode that stack gradually, described luminescent layer comprises red-green glow hybrid illuminating layer, exciton barrier-layer, Yellow light emitting layer and the blue light-emitting stacking gradually on described electronic barrier layer.
Therein in an embodiment, described red-green glow hybrid illuminating layer is formed in material of main part by red emitting material and green light luminescent material co-doped, described red emitting material is two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanedione) close iridium, described green light luminescent material is that three (2-phenylpyridines) close iridium, described material of main part is 4, two (9H-carbazole) biphenyl or 9 of 4'-, 9'-(1, 3-phenyl) two-9H-carbazole, the mass percent that described red emitting material accounts for described red-green glow hybrid illuminating layer is 2 ~ 10%, the mass percent that described green light luminescent material accounts for described red-green glow hybrid illuminating layer is 2 ~ 10%.
In an embodiment, the material of described exciton barrier-layer is N therein, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine, 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene and 4,4', at least one in 4 ＂-tri-(carbazole-9-yl) triphenylamine.
In an embodiment, the material of described Yellow light emitting layer is 5,6,11,12-tetraphenyl naphthonaphthalene therein.
Therein in an embodiment, described blue light-emitting is doped in 1 by blue light emitting material, 3, in 5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene, form, described blue light emitting material is selected from two (4, the fluoro-5-cyano-phenyl of 6-bis-pyridine-N, C2) pyridine carboxylic acid closes iridium, two (4, 6-difluorophenyl pyridine-N, C2) pyridine formyl closes iridium, two (4, 6-difluorophenyl pyridine)-tetra-(1-pyrazolyl) boric acid closes iridium and two (2', 4'-difluorophenyl) pyridine] (tetrazolium pyridine) close a kind of in iridium, the mass percent that described blue light emitting material accounts for described blue light-emitting is 2 ~ 10%.
In an embodiment, the thickness of described red-green glow hybrid illuminating layer is 20 ~ 30 nanometers therein, and the thickness of described exciton barrier-layer is 2 ~ 5 nanometers, and the thickness of described Yellow light emitting layer is 0.2 ~ 1 nanometer, and the thickness of described blue light-emitting is 5 ~ 10 nanometers.
In an embodiment, described substrate is clear glass therein;
Described anode is indium tin oxide films;
Described hole transmission layer is formed by hole mobile material or is doped in described hole mobile material and is formed by the first dopant, wherein, described hole mobile material is selected from Phthalocyanine Zinc, CuPc, 4, 4', 4 ＂-tri-(2-naphthyl phenyl amino) triphenylamine, N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1, 1'-biphenyl-4, 4'-diamines), (4, 4', 4 ＂-tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine, N, N'-diphenyl-N, N'-bis-(3-aminomethyl phenyl)-1, 1 ＇-biphenyl-4, 4'-diamines, N, N, N', N'-tetramethoxy phenyl)-benzidine, 4, 4', 4 ＂-tri-(carbazole-9-yl) triphenylamine and 1, 1-bis-(4-(N, N'-bis-(p-tolyl) amino) phenyl) a kind of in cyclohexane, described the first dopant is selected from 2,3,5,6-tetrafluoro-7,7 ', 8,8 '-tetra-cyanogen quinone-bismethanes, 1,3,4,5,7,8-hexafluoro-tetra-cyanogen-diformazan is to naphthoquinones and 2,2'-(2,5-dicyano-3,6-difluoro cyclohexane-2,5-diene-Isosorbide-5-Nitrae-bis-subunit) a kind of in two malononitrile, the mass percent that described the first dopant accounts for described hole transmission layer is 1 ~ 10%,
Described electronic barrier layer is by Phthalocyanine Zinc, CuPc, 4,4', 4 ＂-tri-(2-naphthyl phenyl amino) triphenylamine, N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines), (4,4', 4 ＂-tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine, N, N'-diphenyl-N, N'-bis-(3-aminomethyl phenyl)-1,1'-biphenyl-4,4'-diamines, N, N, N', N'-tetramethoxy phenyl)-benzidine, 4,4', 4 ＂-tri-(carbazole-9-yl) triphenylamine and 1,1-bis-(4-(N, N'-bis-(p-tolyl) amino) phenyl) a kind of material in cyclohexane forms,
Described hole blocking layer is by 2-(4-xenyl)-5-(4-the tert-butyl group) phenyl-1,3,4-oxadiazole, (oxine)-aluminium, 4,7-diphenyl-o-phenanthroline, 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene, 2,9-dimethyl-4,7-biphenyl-1, two (2-methyl-oxine-the N1 of 10-phenanthrolene and 1,2,4-triazole derivative, O8)-(1,1'-biphenyl-4-hydroxyl) a kind of material in aluminium forms;
Described electron transfer layer is formed by electron transport material or is doped in described electron transport material and is formed by the second dopant, wherein, described electron transport material is selected from 2-(4-xenyl)-5-(4-the tert-butyl group) phenyl-1,3,4-oxadiazole, (oxine)-aluminium, 4,7-diphenyl-o-phenanthroline, 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene, 2,9-dimethyl-4,7-biphenyl-1, two (2-methyl-oxine-the N1 of 10-phenanthrolene and 1,2,4-triazole derivative, O8)-(1,1'-biphenyl-4-hydroxyl) aluminium; Described the second dopant is selected from a kind of in lithium carbonate, Lithium Azide, lithium fluoride, cesium azide, cesium carbonate and cesium fluoride, and the mass percent that described the second dopant accounts for described electron transfer layer is 5 ~ 30%;
Described negative electrode is silver layer.
In an embodiment, the thickness of described anode is 70 ~ 200 nanometers therein; The thickness of described hole transmission layer is 10 ~ 80 nanometers; The thickness of described electronic barrier layer is 5 ~ 20 nanometers; The thickness of described hole blocking layer is 5 ~ 20 nanometers; The thickness of described electron transfer layer is 20 ~ 100 nanometers; The thickness of described negative electrode is 70 ~ 200 nanometers.
A preparation method for organic electroluminescence device, comprises the steps:
Substrate is provided;
Adopt magnetron sputtering to form anode on described substrate;
Adopt vacuum evaporation to form hole transmission layer on described anode;
Adopt vacuum evaporation to form electronic barrier layer on described hole transmission layer;
Adopt vacuum evaporation on described electronic barrier layer, to form red-green glow hybrid illuminating layer, exciton barrier-layer, Yellow light emitting layer and the blue light-emitting stacking gradually, described in the red-green glow hybrid illuminating layer, exciton barrier-layer, Yellow light emitting layer and the blue light-emitting composition luminescent layer that stack gradually;
Adopt vacuum evaporation to form hole blocking layer on described blue light-emitting;
Adopt vacuum evaporation to form electron transfer layer on described hole barrier;
Adopt vacuum evaporation to form negative electrode on described electron transfer layer, obtain described organic electroluminescence device.
Therein in an embodiment, also comprise described substrate is carried out to cleaning-drying and the step to described anode plasma treatment, the step that described substrate is carried out to cleaning-drying is carried out ultrasonic cleaning for described substrate is placed in the deionized water that contains washing agent, after cleaning up, use successively isopropyl alcohol, acetone is processed 20 minutes in ultrasonic wave, and then dries up with nitrogen; The step that described anode is carried out to plasma treatment is for to be positioned over the anode that is laminated in described substrate in plasma processing chamber and to process 10 minutes.
The luminescent layer of above-mentioned organic electroluminescence device is the lamination layer structure that the red-green glow hybrid illuminating layer that stacks gradually, exciton barrier-layer, Yellow light emitting layer and blue light-emitting form, red-green glow hybrid illuminating layer can be widened the recombination region of exciton, exciton barrier-layer can control and regulate the energy between blue light and green glow to shift, red-green glow hybrid illuminating layer, Yellow light emitting layer and blue light-emitting combination can obtain the spectrum compared with horn of plenty, thereby make the color rendering index of organic electroluminescence device higher.
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;
Fig. 3 is the CIE1931 chromaticity coordinates figure of the organic electroluminescence device of embodiment 1;
Fig. 4 is the luminescent spectrum of the organic electroluminescence device of embodiment 1.
Embodiment
By embodiment, above-mentioned organic electroluminescence device and preparation method thereof is further set forth below.
Refer to Fig. 1, the organic electroluminescence device 100 of an execution mode, comprises and stacks gradually substrate 110, anode 120, hole transmission layer 130, electronic barrier layer 140, luminescent layer 150, hole blocking layer 160, electron transfer layer 170 and negative electrode 180.
Substrate 110 is transparent substrates, can adopt clear glass or polyethersulfone resin substrate.Present embodiment adopts clear glass.
Anode 120 is tin indium oxide (ITO) film, and the thickness of anode 120 is 70 ~ 200 nanometers.In other embodiments, anode 120 can be also indium doping zinc-oxide (IZO) film, aluminium-doped zinc oxide (AZO) film or Ga-doped zinc oxide (GZO) film.
Hole transmission layer 130 is formed by hole mobile material, or is doped in hole mobile material and is formed by the first dopant.
Hole mobile material is selected from Phthalocyanine Zinc (ZnPc), CuPc (CuPc), 4, 4', 4 ＂-tri-(2-naphthyl phenyl amino) triphenylamine (2-TNATA), N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1, 1'-biphenyl-4, 4'-diamines (NPB), (4, 4', 4 ＂-tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine (m-MTDATA), N, N'-diphenyl-N, N'-bis-(3-aminomethyl phenyl)-1, 1'-biphenyl-4, 4'-diamines (TPD), N, N, N', N'-tetramethoxy phenyl)-benzidine (MeO-TPD), 4, 4', 4 ＂-tri-(carbazole-9-yl) triphenylamine (TCTA) and 1, 1-bis-(4-(N, N'-bis-(p-tolyl) amino) phenyl) a kind of in cyclohexane (TAPC).
The first dopant is p-type material, is selected from 2,3,5,6-tetrafluoro-7,7', 8,8'-, tetra-cyanogen quinone-bismethanes (F4-TCNQ), 1,3,4,5,7,8-hexafluoro-tetra-cyanogen-diformazan is to naphthoquinones (F6-TNAP) and 2,2'-(2,5-dicyano-3,6-difluoro cyclohexane-2,5-diene-Isosorbide-5-Nitrae-bis-subunit) a kind of in two malononitrile (F2-HCNQ).The mass percent that the first dopant accounts for hole transmission layer 130 is 1 ~ 10%;
Preferably, hole transmission layer 130 is by 2,3,5,6-tetrafluoro-7, and 7', 8,8'-, tetra-cyanogen quinone-bismethanes (F4-TCNQ) are doped in N, N, N', N'-tetramethoxy phenyl) form in-benzidine (MeO-TPD).
The thickness of hole transmission layer 130 is 10 ~ 80 nanometers.
Electronic barrier layer 140 is by Phthalocyanine Zinc (ZnPc), CuPc (CuPc), 4, 4', 4 ＂-tri-(2-naphthyl phenyl amino) triphenylamine (2-TNATA), N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1, 1'-biphenyl-4, 4'-diamines) (NPB), (4, 4', 4 ＂-tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine (m-MTDATA), N, N'-diphenyl-N, N'-bis-(3-aminomethyl phenyl)-1, 1'-biphenyl-4, 4'-diamines (TPD), N, N, N', N'-tetramethoxy phenyl)-benzidine (MeO-TPD), 4, 4', 4 ＂-tri-(carbazole-9-yl) triphenylamine (TCTA) and 1, 1-bis-(4-(N, N'-bis-(p-tolyl) amino) phenyl) a kind of material in cyclohexane (TAPC) forms.
The thickness of electronic barrier layer 140 is 5 ~ 20 nanometers.
Luminescent layer 150 comprises red-green glow hybrid illuminating layer 151, exciton barrier-layer 152, Yellow light emitting layer 153 and the blue light-emitting 154 stacking gradually on electronic barrier layer 140.
Red-green glow hybrid illuminating layer 151 is formed in material of main part by red emitting material and green light luminescent material co-doped.Red emitting material is that two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanediones) close iridium (Ir (MDQ) 2 (acac)).Green light luminescent material is that three (2-phenylpyridines) close iridium (Ir (ppy) 3).Material of main part is two (9H-carbazole) biphenyl (CBP) of 4,4'-or 9,9'-(1,3-phenyl) two-9H-carbazole (mCP).The mass percent that red emitting material accounts for red-green glow hybrid illuminating layer 151 is 2 ~ 10%, and the mass percent that green light luminescent material accounts for red-green glow hybrid illuminating layer 151 is 2 ~ 10%.
Red-green glow hybrid illuminating layer 151 in same material of main part, can be widened the recombination region of exciton by red emitting material and green light luminescent material co-doped.
The thickness of red-green glow hybrid illuminating layer 151 is 20 ~ 30 nanometers.
Exciton barrier-layer 152 is by N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine (TPD), 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi) and 4,4', at least one material in 4 ＂-tri-(carbazole-9-yl) triphenylamine (TCTA) forms.
The thickness of exciton barrier-layer 152 is 2 ~ 5 nanometers.
Yellow light emitting layer 153 is formed by 5,6,11,12-tetraphenyl naphthonaphthalene (Rubrene).The thickness of Yellow light emitting layer 153 is 0.2 ~ 1 nanometer.
Blue light-emitting 154 is doped in 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi) and is formed by blue light emitting material.Blue light emitting material is selected from two (4, the fluoro-5-cyano-phenyl of 6-bis-pyridine-N, C2) pyridine carboxylic acid closes iridium (FCNIrpic), 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) and two (2', 4'-difluorophenyl) pyridine] (tetrazolium pyridine) close a kind of in iridium (FIrN4).The mass percent that blue light emitting material accounts for blue light-emitting 154 is 6%.
The thickness of blue light-emitting 154 is 5 ~ 15 nanometers.
Red-green glow hybrid illuminating layer 151, Yellow light emitting layer 153 and blue light-emitting 154 interact and make organic electroluminescence device 100 send white light.Exciton barrier-layer 152 can control and regulate the energy between green glow and blue light to shift, red-green glow hybrid illuminating layer 151, Yellow light emitting layer 153 and blue light-emitting 154 combinations can obtain the spectrum compared with horn of plenty, make the luminescent spectrum of organic electroluminescence device 100 wider, thereby improved color rendering index.
Hole blocking layer 160 is by 2-(4-xenyl)-5-(4-the tert-butyl group) phenyl-1,3,4-oxadiazole (PBD), (oxine)-aluminium) (Alq3), 4,7-diphenyl-o-phenanthroline (Bphen), (1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene) (TPBi), 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene (BCP), 1,2,4-triazole derivative (TAZ) and two (2-methyl-oxine-N1, O8)-(1,1'-biphenyl-4-hydroxyl) aluminium) a kind of material in (BAlq) forms.
The thickness of hole blocking layer 160 is 5 ~ 20 nanometers.
Electron transfer layer 170 is formed by electron transport material or is doped in electron transport material and is formed by the second dopant.
Electron transport material is selected from 2-(4-xenyl)-5-(4-the tert-butyl group) phenyl-1,3,4-oxadiazole (PBD), (oxine)-aluminium (Alq3), 4,7-diphenyl-o-phenanthroline (Bphen), (1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene) (TPBi), 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene (BCP), 1,2,4-triazole derivative (TAZ) and two (2-methyl-oxine-N1, O8)-(1,1'-biphenyl-4-hydroxyl) aluminium) a kind of in (BAlq).
The second dopant is N-shaped material, is selected from lithium carbonate (Li 2cO 3), Lithium Azide (LiN 3), lithium fluoride (LiF), cesium azide (CsN 3), cesium carbonate (Cs 2cO 3) and cesium fluoride (CsF) in a kind of.The mass percent that the second dopant accounts for electron transfer layer 170 is 5 ~ 30%.
Preferably, electron transfer layer 170 is by cesium azide (CsN 3) be doped in 4,7-diphenyl-o-phenanthroline (Bphen) and form.
The thickness of electron transfer layer 170 is 20 ~ 100 nanometers.
Negative electrode 180 is metal level.The negative electrode 180 of present embodiment is silver layer.In other embodiments, also can adopt work function is lower, performance is more stable magnesium layer, aluminium lamination, magnesium-aluminum alloy layer etc.The thickness of negative electrode 180 is 70 ~ 200 nanometers.
The luminescent layer 150 of above-mentioned organic electroluminescence device 100 comprises the red-green glow hybrid illuminating layer 151 stacking gradually on electronic barrier layer 140, exciton barrier-layer 152, Yellow light emitting layer 153 and blue light-emitting 154, red-green glow hybrid illuminating layer 151 can be widened the recombination region of exciton, red-green glow hybrid illuminating layer 151, the arrangement mode of Yellow light emitting layer 153 and blue light-emitting 154 can obtain wider luminescent spectrum, exciton barrier-layer 152 can control and regulate the energy between green glow and blue light to shift, thereby make the luminescent spectrum of organic electroluminescence device 100 wider, thereby improved color rendering index.
Electroluminescent device is charge carrier (electronics or hole) injection type electroluminescence device, and the injection of charge carrier, transmission and balance thereof restrict charge carrier radiation recombination efficiency, have determined efficiency and the life-span of electroluminescent device.Organic electroluminescence device 100 arranges electronic barrier layer 140 between hole transmission layer 130 and luminescent layer 150, between luminescent layer 150 and electron transfer layer 170, hole blocking layer 160 is set, electronic barrier layer 140 and hole blocking layer 160 for by electronics and hole confinement in certain region, to improve charge carrier at the compound probability of luminescent layer 150, can effectively regulate injection and the transmission in electronics and hole, hole and electronics in balance organic electroluminescence device 100, thereby efficiency and the life-span of improving organic electroluminescence device 100.
Refer to Fig. 2, the preparation method of the organic electroluminescence device of an execution mode, comprises the steps:
Step S110: substrate is provided.
Substrate can adopt clear glass or polyethersulfone resin substrate.
First clean substrate, to avoid the pollutant on substrate to produce harmful effect to the performance of organic electroluminescence device.Substrate is placed in the deionized water that contains washing agent and carries out ultrasonic cleaning, use successively isopropyl alcohol after cleaning up, acetone is processed 20 minutes in ultrasonic wave, and then dries up with nitrogen, standby.
Step S120: adopt magnetron sputtering to form anode on substrate.
After substrate cleaning-drying, adopt magnetron sputtering on substrate, to deposit tin indium oxide (ITO), form ito thin film as anode.
Also can on substrate, form indium doping zinc-oxide (IZO) film, aluminium-doped zinc oxide (AZO) film or Ga-doped zinc oxide (GZO) film as anode.
The thickness of anode is 70 ~ 200 nanometers.
The anode that is laminated in clear glass surface is put into plasma processing chamber and process 10 minutes, to improve the work content of anode, reduce hole injection barrier, be conducive to more hole and enter in luminescent layer and electron recombination, improve luminous efficiency.
Step S130: adopt vacuum evaporation to form hole transmission layer on anode.
Vacuum degree is 5 * 10 -4pa.
Hole transmission layer is formed by hole mobile material, or is doped in hole mobile material and is formed by the first dopant.
Hole mobile material is selected from Phthalocyanine Zinc (ZnPc), CuPc (CuPc), 4, 4', 4 ＂-tri-(2-naphthyl phenyl amino) triphenylamine (2-TNATA), N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1, 1'-biphenyl-4, 4'-diamines (NPB), (4, 4', 4 ＂-tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine (m-MTDATA), N, N'-diphenyl-N, N'-bis-(3-aminomethyl phenyl)-1, 1'-biphenyl-4, 4'-diamines (TPD), N, N, N', N'-tetramethoxy phenyl)-benzidine (MeO-TPD), 4, 4', 4 ＂-tri-(carbazole-9-yl) triphenylamine (TCTA) and 1, 1-bis-(4-(N, N'-bis-(p-tolyl) amino) phenyl) a kind of in cyclohexane (TAPC).
The first dopant is selected from 2,3, and 5,6-tetrafluoro-7,7', 8,8'-tetra-cyanogen quinone-bismethanes (F4-TCNQ), 1,3,4,5,7,8-hexafluoro-tetra-cyanogen-diformazan is to naphthoquinones (F6-TNAP) and 2,2'-(2,5-dicyano-3,6-difluoro cyclohexane-2,5-diene-Isosorbide-5-Nitrae-bis-subunit) a kind of in two malononitrile (F2-HCNQ).The mass percent that the first dopant accounts for hole transmission layer 130 is 1 ~ 10%;
The thickness of hole transmission layer 130 is 10 ~ 80 nanometers.
Step S140: adopt vacuum evaporation to form electronic barrier layer on hole transmission layer.
Vacuum degree is 5 * 10 -4pa.
Electronic barrier layer is by Phthalocyanine Zinc (ZnPc), CuPc (CuPc), 4, 4', 4 ＂-tri-(2-naphthyl phenyl amino) triphenylamine (2-TNATA), N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1, 1'-biphenyl-4, 4'-diamines) (NPB), (4, 4', 4 ＂-tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine (m-MTDATA), N, N'-diphenyl-N, N'-bis-(3-aminomethyl phenyl)-1, 1'-biphenyl-4, 4'-diamines (TPD), N, N, N', N'-tetramethoxy phenyl)-benzidine (MeO-TPD), 4, 4', 4 ＂-tri-(carbazole-9-yl) triphenylamine (TCTA) and 1, 1-bis-(4-(N, N'-bis-(p-tolyl) amino) phenyl) a kind of material in cyclohexane (TAPC) forms.
The thickness of electronic barrier layer 140 is 5 ~ 20 nanometers.
Step S150: adopt vacuum evaporation to form red-green glow hybrid illuminating layer, exciton barrier-layer, Yellow light emitting layer and the blue light-emitting stacking gradually on electronic barrier layer.
Vacuum degree is 5 * 10 -4pa.
Adopt vacuum evaporation on electronic barrier layer, to form red-green glow hybrid illuminating layer.Red-green glow hybrid illuminating layer is formed in material of main part by red emitting material and green light luminescent material co-doped.Red emitting material is that two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanediones) close iridium (Ir (MDQ) 2(acac)).Green light luminescent material is that three (2-phenylpyridines) close iridium (Ir (ppy) 3).Material of main part is two (9H-carbazole) biphenyl (CBP) of 4,4'-or 9,9'-(1,3-phenyl) two-9H-carbazole (mCP).The mass percent that red emitting material accounts for red-green glow hybrid illuminating layer is 2 ~ 10%, and the mass percent that green light luminescent material accounts for red-green glow hybrid illuminating layer is 2 ~ 10%.The thickness of red-green glow hybrid illuminating layer 151 is 20 ~ 30 nanometers.
Adopt vacuum evaporation to form exciton barrier-layer on red-green glow hybrid illuminating layer.Exciton barrier-layer is by N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine (TPD), 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi) and 4,4', at least one material in 4 ＂-tri-(carbazole-9-yl) triphenylamine (TCTA) forms.The thickness of exciton barrier-layer is 2 ~ 5 nanometers.
Adopt vacuum evaporation on exciton barrier-layer, to form Yellow light emitting layer.Yellow light emitting layer is formed by 5,6,11,12-tetraphenyl naphthonaphthalene.The thickness of Yellow light emitting layer is 0.2 ~ 1 nanometer.
Adopt vacuum evaporation to form blue light-emitting on Yellow light emitting layer.Blue light-emitting is doped in 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi) and is formed by blue light emitting material.Blue light emitting material is selected from two (4, the fluoro-5-cyano-phenyl of 6-bis-pyridine-N, C2) pyridine carboxylic acid closes iridium (FCNIrpic), 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) and two (2', 4'-difluorophenyl) pyridine] (tetrazolium pyridine) close a kind of in iridium (FIrN4).The mass percent that blue light emitting material accounts for blue light-emitting is 2 ~ 10%.The thickness of blue light-emitting is 5 ~ 15 nanometers.
Red-green glow hybrid illuminating layer, exciton barrier-layer, Yellow light emitting layer and blue light-emitting stack gradually the luminescent layer that is formed with organic electroluminescence devices on electronic barrier layer.
Step S160: adopt vacuum evaporation to form hole blocking layer on blue light-emitting.
Vacuum degree is 5 * 10 -4pa.
Hole blocking layer is by 2-(4-xenyl)-5-(4-the tert-butyl group) phenyl-1,3,4-oxadiazole (PBD), (oxine)-aluminium (Alq3), 4,7-diphenyl-o-phenanthroline (Bphen), (1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene) (TPBi), 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene (BCP), 1,2,4-triazole derivative (TAZ) and two (2-methyl-oxine-N1, O8)-(1,1'-biphenyl-4-hydroxyl) aluminium) a kind of material in (BAlq) forms.The thickness of hole blocking layer is 5 ~ 20 nanometers.
Step S170: adopt vacuum evaporation to form electron transfer layer on hole barrier.
Vacuum degree is 5 * 10 -4pa.
Electron transfer layer is formed by electron transport material or is doped in electron transport material and is formed by the second dopant.
Electron transport material is selected from 2-(4-xenyl)-5-(4-the tert-butyl group) phenyl-1,3,4-oxadiazole (PBD), (oxine)-aluminium (Alq3), 4,7-diphenyl-o-phenanthroline (Bphen), (1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene) (TPBi), 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene (BCP), 1,2,4-triazole derivative (TAZ) and two (2-methyl-oxine-N1, O8)-(1,1'-biphenyl-4-hydroxyl) aluminium) a kind of in (BAlq).
The second dopant is selected from lithium carbonate (Li 2cO 3), Lithium Azide (LiN 3), lithium fluoride (LiF), cesium azide (CsN 3), cesium carbonate (Cs 2cO 3) and cesium fluoride (CsF) in a kind of.The mass percent that the second dopant accounts for electron transfer layer is 5 ~ 30%.
The thickness of electron transfer layer is 20 ~ 100 nanometers.
Step S180: adopt vacuum evaporation to form negative electrode on electron transfer layer, obtain organic electroluminescence device.
Vacuum degree is 5 * 10 -4pa.
Negative electrode is metal level.Present embodiment vacuum evaporation silver forms silver layer as negative electrode on electron transfer layer.The thickness of negative electrode is 70 ~ 200 nanometers.
The substrate stacking gradually, anode, hole transmission layer, electronic barrier layer, luminescent layer, hole blocking layer, electron transfer layer and negative electrode form organic electroluminescence device.
The preparation method of above-mentioned organic electroluminescence device adopts magnetron sputtering ito anode in clear glass preparation, then adopts vacuum evaporation to prepare each functional layer.This preparation method's technique is simple, is easy to extensive preparation.
Vacuum evaporation is prepared each functional layer all in vacuum degree 5 * 10 -4under Pa, carry out evaporation.In higher vacuum degree 5 * 10 -4under Pa, can avoid the film that deposition forms to produce defect, be conducive to improve quality of forming film, thereby obtain the organic electroluminescence device of stable performance.
It is below specific embodiment.
Embodiment 1
Structure is: Glass/ITO/F6-TNAP:MeO-TPD/ZnPc/Ir (MDQ) 2(acac): Ir (ppy) 3: CBP/TPD/Rubrene/FIrpic:TPBi/BAlq/CsN 3: the organic electroluminescence device of Bphen/Ag;
The preparation technology of this device is as follows:
(1) provide clear glass as substrate, be expressed as Glass.Clear glass is placed in the deionized water that contains washing agent and carries out ultrasonic cleaning, use successively isopropyl alcohol after cleaning up, acetone is processed 20 minutes in ultrasonic wave, then dries up with nitrogen;
(2) adopt clear glass surface deposition tin indium oxide (ITO) film of magnetron sputtering after cleaning-drying as anode, thickness is 100nm.Prepare after anode, the anode that is laminated in clear glass surface is put into plasma processing chamber and process 10 minutes;
(3) adopt vacuum evaporation to form hole transmission layer on the surface of anode.Vacuum degree is 5 * 10 -4pa.Hole transmission layer is doped in N by 1,3,4,5,7,8-hexafluoro-tetra-cyanogen-diformazan to naphthoquinones (F6-TNAP), N, N', N'-tetramethoxy phenyl) the middle formation of-benzidine (MeO-TPD), be expressed as F6-TNAP:MeO-TPD.F6-TNAP account for hole transmission layer gross mass 5%.The thickness of hole transmission layer is 60nm;
(4) adopt vacuum evaporation to form electronic barrier layer on the surface of hole transmission layer.Vacuum degree is 5 * 10 -4pa.Electronic barrier layer is formed by Phthalocyanine Zinc (ZnPc).The thickness of electronic barrier layer is 10nm.
(5) adopt vacuum evaporation to form on the surface of electronic barrier layer the red-green glow hybrid illuminating layer, exciton barrier-layer, Yellow light emitting layer and the blue light-emitting that stack gradually and form luminescent layer, vacuum degree is 5 * 10 -4pa;
Red-green glow hybrid illuminating layer closes iridium (Ir (MDQ) by red emitting material two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanedione) 2(acac)) and green light luminescent material three (2-phenylpyridine) close iridium (Ir (ppy) 3) co-doped formation in 4,4'-bis-(9-carbazole) biphenyl (CBP), be expressed as Ir (MDQ) 2(acac): Ir (ppy) 3: CBP.Ir (MDQ) 2(acac) account for 6% of red-green glow hybrid illuminating layer gross mass, Ir (ppy) 3account for 8% of red-green glow hybrid illuminating layer gross mass.The thickness of red-green glow hybrid illuminating layer is 30nm;
Exciton barrier-layer is by N, N'-bis-(3-aminomethyl phenyl)-N, and N'-diphenyl-4,4'-benzidine (TPD) forms, and the thickness of exciton barrier-layer is 3nm;
Yellow light emitting layer is formed by 5,6,11,12-tetraphenyl naphthonaphthalene (Rubrene), and the thickness of Yellow light emitting layer is 1nm;
Blue light-emitting closes iridium (FIrpic) by two (4,6-difluorophenyl pyridine-N, C2) pyridine formyl and is doped in formation in 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi), is expressed as FIrpic:TPBi.FIrpic accounts for 6% of blue light-emitting gross mass.The thickness of blue light-emitting is 10nm;
(6) adopt vacuum evaporation to form hole blocking layer on the surface of luminescent layer.Hole blocking layer is by two (2-methyl-oxine-N1, O8)-(1,1'-biphenyl-4-hydroxyl) aluminium) (BAlq) form.The thickness of hole blocking layer is 10nm;
(7) adopt vacuum evaporation to form electron transfer layer on the surface of hole blocking layer, vacuum degree is 5 * 10 -4pa.Electron transfer layer is by cesium azide (CsN 3) be doped in formation in 4,7-diphenyl-o-phenanthroline (Bphen), be expressed as CsN 3: Bphen.CsN 3account for 15% of electron transfer layer gross mass.The thickness of electron transfer layer is 50 nanometers;
(8) adopt vacuum evaporation to form negative electrode on the surface of electron transfer layer and obtain organic electroluminescence device.Vacuum degree is 5 * 10 -4pa.Negative electrode is silver layer, and the thickness of negative electrode is 100nm.
Fig. 3 is the organic electroluminescence device of the embodiment 1 CIE1931 chromaticity coordinates figure when 3.5V, and its chromaticity coordinates is (0.31,0.38), differs less with standard white luminous point (0.33,0.33), and this organic electroluminescence device can be launched comparatively desirable white light.
Fig. 4 is the luminescent spectrum of embodiment 1 organic electroluminescence device, the luminescent spectrum coverage of the organic electroluminescence device of embodiment 1 is wide, luminous by Yellow light emitting layer, making originally red, greenly luminously peak-to-peakly also has luminous compared with weak light region, obviously make luminescent spectrum scope widen, therefore its color rendering is better, and color rendering index is high.
Embodiment 2
Structure is: Glass/ITO/F4-TCNQ:MeO-TPD/CuPc/Ir (MDQ) 2(acac): Ir (ppy) 3: mCP/TCTA/Rubrene/FCNIrpic:TPBi/PBD/Li 2cO 3: the organic electroluminescence device of PBD/Ag;
The preparation technology of this device is as follows:
(1) provide clear glass as substrate, be expressed as Glass.Clear glass is placed in the deionized water that contains washing agent and carries out ultrasonic cleaning, use successively isopropyl alcohol after cleaning up, acetone is processed 20 minutes in ultrasonic wave, then dries up with nitrogen;
(2) adopt clear glass surface deposition tin indium oxide (ITO) film of magnetron sputtering after cleaning-drying as anode, thickness is 70nm.Prepare after anode, the anode that is laminated in clear glass surface is put into plasma processing chamber and process 10 minutes;
(3) adopt vacuum evaporation to form hole transmission layer on the surface of anode.Vacuum degree is 5 * 10 -4pa.Hole transmission layer is by 2,3,5,6-tetrafluoro-7, and 7', 8,8'-, tetra-cyanogen quinone-bismethanes (F4-TCNQ) are doped in N, N, N', N'-tetramethoxy phenyl) form in-benzidine (MeO-TPD), be expressed as F4-TCNQ:MeO-TPD.F4-TCNQ account for hole transmission layer gross mass 1%.The thickness of hole transmission layer is 10nm;
(4) adopt vacuum evaporation to form electronic barrier layer on the surface of hole transmission layer.Vacuum degree is 5 * 10 -4pa.Electronic barrier layer is formed by CuPc (CuPc).The thickness of electronic barrier layer is 20nm.
(5) adopt vacuum evaporation to form on the surface of electronic barrier layer the red-green glow hybrid illuminating layer, exciton barrier-layer, Yellow light emitting layer and the blue light-emitting that stack gradually and form luminescent layer, vacuum degree is 5 * 10 -4pa;
Red-green glow hybrid illuminating layer closes iridium (Ir (MDQ) by red emitting material two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanedione) 2(acac)) and green light luminescent material three (2-phenylpyridine) close iridium (Ir (ppy) 3) co-doped formation in 9,9'-(1,3-phenyl) two-9H-carbazole (mCP), be expressed as Ir (MDQ) 2(acac): Ir (ppy) 3: mCP.Ir (MDQ) 2(acac) account for 2% of red-green glow hybrid illuminating layer gross mass, Ir (ppy) 3account for 2% of red-green glow hybrid illuminating layer gross mass.The thickness of red-green glow hybrid illuminating layer is 20nm;
Exciton barrier-layer is by 4,4', and 4 ＂-tri-(carbazole-9-yl) triphenylamine (TCTA) forms, and the thickness of exciton barrier-layer is 2nm;
Yellow light emitting layer is formed by 5,6,11,12-tetraphenyl naphthonaphthalene (Rubrene), and the thickness of Yellow light emitting layer is 0.2nm;
Blue light-emitting is by two (4, the fluoro-5-cyano-phenyl of 6-bis-pyridine-N, C2) pyridine carboxylic acid closes iridium (FCNIrpic) and is doped in 1,3, in 5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi), form, be expressed as FCNIrpic:TPBi.FCNIrpic accounts for 2% of blue light-emitting gross mass.The thickness of blue light-emitting is 5nm;
(6) adopt vacuum evaporation to form hole blocking layer on the surface of luminescent layer.Hole blocking layer is by 2-(4-xenyl)-5-(4-the tert-butyl group) phenyl-1,3,4-oxadiazole (PBD) forms.The thickness of hole blocking layer is 20nm;
(7) adopt vacuum evaporation to form electron transfer layer on the surface of hole blocking layer, vacuum degree is 5 * 10 -4pa.Electron transfer layer is by lithium carbonate (Li 2cO 3) be doped in 2-(4-xenyl)-5-(4-the tert-butyl group) phenyl-1, in 3,4-oxadiazole (PBD), form, be expressed as Li 2cO 3: PBD.Li 2cO 3account for 5% of electron transfer layer gross mass.The thickness of electron transfer layer is 20nm;
(8) adopt vacuum evaporation to form negative electrode on the surface of electron transfer layer and obtain organic electroluminescence device.Vacuum degree is 5 * 10 -4pa.Negative electrode is silver layer, and the thickness of negative electrode is 170nm.
Embodiment 3
Structure is: Glass/ITO/F2-HCNQ:MeO-TPD/2-TNATA/Ir (MDQ) 2(acac): Ir (ppy) 3: mCP/TPBi/Rubrene/FIr6:TPBi/Alq3/LiN 3: the organic electroluminescence device of BCP/Ag;
The preparation technology of this device is as follows:
(1) provide clear glass as substrate, be expressed as Glass.Clear glass is placed in the deionized water that contains washing agent and carries out ultrasonic cleaning, use successively isopropyl alcohol after cleaning up, acetone is processed 20 minutes in ultrasonic wave, then dries up with nitrogen;
(2) adopt clear glass surface deposition tin indium oxide (ITO) film of magnetron sputtering after cleaning-drying as anode, thickness is 200nm.Prepare after anode, the anode that is laminated in clear glass surface is put into plasma processing chamber and process 10 minutes;
(3) adopt vacuum evaporation to form hole transmission layer on the surface of anode.Vacuum degree is 5 * 10 -4pa.Hole transmission layer is by 2,2'-(2,5-dicyano-3,6-difluoro cyclohexane-2,5-diene-Isosorbide-5-Nitrae-bis-subunit) two malononitrile (F2-HCNQ) are doped in N, N, N', N'-tetramethoxy phenyl) the middle formation of-benzidine (MeO-TPD), be expressed as F2-HCNQ:MeO-TPD.F2-HCNQ account for hole transmission layer gross mass 10%.The thickness of hole transmission layer is 80nm;
(4) adopt vacuum evaporation to form electronic barrier layer on the surface of hole transmission layer.Vacuum degree is 5 * 10 -4pa.Electronic barrier layer is by 4,4', and 4 ＂-tri-(2-naphthyl phenyl amino) triphenylamine (2-TNATA) forms.The thickness of electronic barrier layer is 5nm.
(5) adopt vacuum evaporation to form on the surface of electronic barrier layer the red-green glow hybrid illuminating layer, exciton barrier-layer, Yellow light emitting layer and the blue light-emitting that stack gradually and form luminescent layer, vacuum degree is 5 * 10 -4pa;
Red-green glow hybrid illuminating layer closes iridium (Ir (MDQ) by red emitting material two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanedione) 2(acac)) and green light luminescent material three (2-phenylpyridine) close iridium (Ir (ppy) 3) co-doped formation in 9,9'-(1,3-phenyl) two-9H-carbazole (mCP), be expressed as Ir (MDQ) 2(acac): Ir (ppy) 3: mCP.Ir (MDQ) 2(acac) account for 10% of red-green glow hybrid illuminating layer gross mass, Ir (ppy) 3account for 10% of red-green glow hybrid illuminating layer gross mass.The thickness of red-green glow hybrid illuminating layer is 25nm;
Exciton barrier-layer is formed by 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi), and the thickness of exciton barrier-layer is 5nm;
Yellow light emitting layer is formed by 5,6,11,12-tetraphenyl naphthonaphthalene (Rubrene), and the thickness of Yellow light emitting layer is 0.5nm;
Blue light-emitting is by two (4; 6-difluorophenyl pyridine)-tetra-(1-pyrazolyl) boric acid closes iridium (FIr6) and is doped in 1; 3; in 5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi), form; FIr6 accounts for 10% of blue light-emitting gross mass, and the thickness of blue light-emitting is 12nm;
(6) adopt vacuum evaporation to form hole blocking layer on the surface of luminescent layer.Hole blocking layer is formed by (oxine)-aluminium (Alq3).The thickness of hole blocking layer is 5nm;
(7) adopt vacuum evaporation to form electron transfer layer on the surface of hole blocking layer, vacuum degree is 5 * 10 -4pa.Electron transfer layer is by Lithium Azide (LiN 3) being doped in 2,9-dimethyl-4,7-biphenyl-1, forms in 10-phenanthrolene (BCP), is expressed as LiN 3: BCP.LiN 3account for 30% of electron transfer layer gross mass.The thickness of electron transfer layer is 100nm;
(8) adopt vacuum evaporation to form negative electrode on the surface of electron transfer layer and obtain organic electroluminescence device.Vacuum degree is 5 * 10 -4pa.Negative electrode is silver layer, and the thickness of negative electrode is 200nm.
Embodiment 4
Structure is: Glass/ITO/F6-TNAP:TAPC/NPB/Ir (MDQ) 2(acac): Ir (ppy) 3: the organic electroluminescence device of CBP/TCTA:TPBi/Rubrene/FIrN4:TPBi/Bphen/LiF:TPBi/Ag;
The preparation technology of this device is as follows:
(1) provide clear glass as substrate, be expressed as Glass.Clear glass is placed in the deionized water that contains washing agent and carries out ultrasonic cleaning, use successively isopropyl alcohol after cleaning up, acetone is processed 20 minutes in ultrasonic wave, then dries up with nitrogen;
(2) adopt clear glass surface deposition tin indium oxide (ITO) film of magnetron sputtering after cleaning-drying as anode, thickness is 100nm.Prepare after anode, the anode that is laminated in clear glass surface put into plasma processing chamber and processes?
(3) adopt vacuum evaporation to form hole transmission layer on the surface of anode.Vacuum degree is 5 * 10 -4pa.Hole transmission layer is by 1,3, and 4,5,7,8-hexafluoro-tetra-cyanogen-diformazan is doped in 1 to naphthoquinones (F6-TNAP), in 1-bis-(4-(N, N'-bis-(p-tolyl) amino) phenyl) cyclohexane (TAPC), form, be expressed as F6-TNAP:TAPC.F6-TNAP account for hole transmission layer gross mass 5%.The thickness of hole transmission layer is 60nm;
(4) adopt vacuum evaporation to form electronic barrier layer on the surface of hole transmission layer.Vacuum degree is 5 * 10 -4pa.Electronic barrier layer is by N, N'-diphenyl-N, and N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB) forms.The thickness of electronic barrier layer is 10nm.
(5) adopt vacuum evaporation to form on the surface of electronic barrier layer the red-green glow hybrid illuminating layer, exciton barrier-layer, Yellow light emitting layer and the blue light-emitting that stack gradually and form luminescent layer, vacuum degree is 5 * 10 -4pa;
Red-green glow hybrid illuminating layer closes iridium (Ir (MDQ) by red emitting material two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanedione) 2(acac)) and green light luminescent material three (2-phenylpyridine) close iridium (Ir (ppy) 3) co-doped formation in 9,9'-, bis-carbazole biphenyl (CBP), be expressed as Ir (MDQ) 2(acac): Ir (ppy) 3: CBP.Ir (MDQ) 2(acac) account for 6% of red-green glow hybrid illuminating layer gross mass, Ir (ppy) 3account for 8% of red-green glow hybrid illuminating layer gross mass.The thickness of red-green glow hybrid illuminating layer is 25nm;
Exciton barrier-layer is by 4,4', and 4 ＂-tri-(carbazole-9-yl) triphenylamine (TCTA) and 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi) mixture forms, and the mass ratio of TCTA and TPBi is 1:3.The thickness of exciton barrier-layer is 3nm;
Yellow light emitting layer is formed by 5,6,11,12-tetraphenyl naphthonaphthalene (Rubrene), and the thickness of Yellow light emitting layer is 0.3nm;
Blue light-emitting is by two (2', 4'-difluorophenyl) pyridine] (tetrazolium pyridine) close iridium (FIrN4) and be doped in 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi) and form, and is expressed as FIrN4:TPBi.FIrN4 accounts for 6% of blue light-emitting gross mass, and the thickness of blue light-emitting is 8nm;
(6) adopt vacuum evaporation to form hole blocking layer on the surface of luminescent layer.Hole blocking layer is formed by 4,7-diphenyl-o-phenanthroline (Bphen).The thickness of hole blocking layer is 10nm;
(7) adopt vacuum evaporation to form electron transfer layer on the surface of hole blocking layer, vacuum degree is 5 * 10 -4pa.Electron transfer layer is doped in 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi) and is formed by lithium fluoride (LiF), is expressed as LiF:TPBi.LiF accounts for 15% of electron transfer layer gross mass.The thickness of electron transfer layer is 50 nanometers;
(8) adopt vacuum evaporation to form negative electrode on the surface of electron transfer layer and obtain organic electroluminescence device.Vacuum degree is 5 * 10 -4pa.Negative electrode is silver layer, and the thickness of negative electrode is 100nm.
Table 1 is the organic electroluminescence device of embodiment 1 ~ 4 preparation color rendering index and the luminous efficiency when 3.6V
Embodiment Color rendering index Luminous efficiency (lm/W)
Embodiment 1 88 19.5
Embodiment 2 87 20.1
Embodiment 3 92 16.8
Embodiment 4 90 16.5
As can be seen from Table 1, the organic electroluminescence device of embodiment 1 ~ 4, owing to having adopted the device architecture of p-i-n, coordinates the collocation of red, green, blue and yellow four-color luminescent material, therefore can obtain efficient luminous efficiency.In addition, the organic electroluminescence device of embodiment 1 ~ 4 has adopted red, green, blue, yellow four look material adapteds, make luminescent spectrum wider, by being provided with exciton barrier-layer, the energy of controlling between blue light and green light luminescent material shifts, therefore can the Effective Regulation curve of spectrum, make its requirement that meets high color rendering index (CRI), thereby obtain the white light emitting device of high color rendering index (CRI), can be widely used in and need the illumination of high color rendering index (CRI) place.
The demonstration index of existing white light organic electroluminescent device, generally in 75 ~ 80 left and right, is restricted in the illumination of the high demonstration of needs index or the application in demonstration place.The demonstration index of embodiment 1 ~ 4, more than 87, has wide range of applications.
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, it is characterized in that, comprise the substrate, anode, hole transmission layer, electronic barrier layer, luminescent layer, hole blocking layer, electron transfer layer and the negative electrode that stack gradually, described luminescent layer comprises red-green glow hybrid illuminating layer, exciton barrier-layer, Yellow light emitting layer and the blue light-emitting stacking gradually on described electronic barrier layer.
2. organic electroluminescence device according to claim 1, it is characterized in that, described red-green glow hybrid illuminating layer is formed in material of main part by red emitting material and green light luminescent material co-doped, described red emitting material is two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanedione) close iridium, described green light luminescent material is that three (2-phenylpyridines) close iridium, described material of main part is 4, two (9H-carbazole) biphenyl or 9 of 4'-, 9'-(1, 3-phenyl) two-9H-carbazole, the mass percent that described red emitting material accounts for described red-green glow hybrid illuminating layer is 2 ~ 10%, the mass percent that described green light luminescent material accounts for described red-green glow hybrid illuminating layer is 2 ~ 10%.
3. organic electroluminescence device according to claim 1, it is characterized in that, the material of described exciton barrier-layer is N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine, 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene and 4,4', at least one in 4 ＂-tri-(carbazole-9-yl) triphenylamine.
4. organic electroluminescence device according to claim 1, is characterized in that, the material of described Yellow light emitting layer is 5,6,11,12-tetraphenyl naphthonaphthalene.
5. organic electroluminescence device according to claim 1, it is characterized in that, described blue light-emitting is doped in 1 by blue light emitting material, 3, in 5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene, form, described blue light emitting material is selected from two (4, the fluoro-5-cyano-phenyl of 6-bis-pyridine-N, C2) pyridine carboxylic acid closes iridium, two (4, 6-difluorophenyl pyridine-N, C2) pyridine formyl closes iridium, two (4, 6-difluorophenyl pyridine)-tetra-(1-pyrazolyl) boric acid closes iridium and two (2', 4'-difluorophenyl) pyridine] (tetrazolium pyridine) close a kind of in iridium, the mass percent that described blue light emitting material accounts for described blue light-emitting is 2 ~ 10%.
6. organic electroluminescence device according to claim 1, it is characterized in that, the thickness of described red-green glow hybrid illuminating layer is 20 ~ 30 nanometers, the thickness of described exciton barrier-layer is 2 ~ 5 nanometers, the thickness of described Yellow light emitting layer is 0.2 ~ 1 nanometer, and the thickness of described blue light-emitting is 5 ~ 10 nanometers.
7. organic electroluminescence device according to claim 1, is characterized in that,
Described substrate is clear glass;
Described anode is indium tin oxide films;
Described hole transmission layer is formed by hole mobile material or is doped in described hole mobile material and is formed by the first dopant, wherein, described hole mobile material is selected from Phthalocyanine Zinc, CuPc, 4, 4', 4 ＂-tri-(2-naphthyl phenyl amino) triphenylamine, N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1, 1'-biphenyl-4, 4'-diamines), (4, 4', 4 ＂-tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine, N, N'-diphenyl-N, N'-bis-(3-aminomethyl phenyl)-1, 1 ＇-biphenyl-4, 4'-diamines, N, N, N', N'-tetramethoxy phenyl)-benzidine, 4, 4', 4 ＂-tri-(carbazole-9-yl) triphenylamine and 1, 1-bis-(4-(N, N'-bis-(p-tolyl) amino) phenyl) a kind of in cyclohexane, described the first dopant is selected from 2,3,5,6-tetrafluoro-7,7 ', 8,8 '-tetra-cyanogen quinone-bismethanes, 1,3,4,5,7,8-hexafluoro-tetra-cyanogen-diformazan is to naphthoquinones and 2,2'-(2,5-dicyano-3,6-difluoro cyclohexane-2,5-diene-Isosorbide-5-Nitrae-bis-subunit) a kind of in two malononitrile, the mass percent that described the first dopant accounts for described hole transmission layer is 1 ~ 10%,
Described electronic barrier layer is by Phthalocyanine Zinc, CuPc, 4,4', 4 ＂-tri-(2-naphthyl phenyl amino) triphenylamine, N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines), (4,4', 4 ＂-tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine, N, N'-diphenyl-N, N'-bis-(3-aminomethyl phenyl)-1,1'-biphenyl-4,4'-diamines, N, N, N', N'-tetramethoxy phenyl)-benzidine, 4,4', 4 ＂-tri-(carbazole-9-yl) triphenylamine and 1,1-bis-(4-(N, N'-bis-(p-tolyl) amino) phenyl) a kind of material in cyclohexane forms,
Described hole blocking layer is by 2-(4-xenyl)-5-(4-the tert-butyl group) phenyl-1,3,4-oxadiazole, (oxine)-aluminium, 4,7-diphenyl-o-phenanthroline, 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene, 2,9-dimethyl-4,7-biphenyl-1, two (2-methyl-oxine-the N1 of 10-phenanthrolene and 1,2,4-triazole derivative, O8)-(1,1'-biphenyl-4-hydroxyl) a kind of material in aluminium forms;
Described electron transfer layer is formed by electron transport material or is doped in described electron transport material and is formed by the second dopant, wherein, described electron transport material is selected from 2-(4-xenyl)-5-(4-the tert-butyl group) phenyl-1,3,4-oxadiazole, (oxine)-aluminium, 4,7-diphenyl-o-phenanthroline, 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene, 2,9-dimethyl-4,7-biphenyl-1, two (2-methyl-oxine-the N1 of 10-phenanthrolene and 1,2,4-triazole derivative, O8)-(1,1'-biphenyl-4-hydroxyl) aluminium; Described the second dopant is selected from a kind of in lithium carbonate, Lithium Azide, lithium fluoride, cesium azide, cesium carbonate and cesium fluoride, and the mass percent that described the second dopant accounts for described electron transfer layer is 5 ~ 30%;
Described negative electrode is silver layer.
8. organic electroluminescence device according to claim 1, is characterized in that, the thickness of described anode is 70 ~ 200 nanometers; The thickness of described hole transmission layer is 10 ~ 80 nanometers; The thickness of described electronic barrier layer is 5 ~ 20 nanometers; The thickness of described hole blocking layer is 5 ~ 20 nanometers; The thickness of described electron transfer layer is 20 ~ 100 nanometers; The thickness of described negative electrode is 70 ~ 200 nanometers.
9. a preparation method for organic electroluminescence device, is characterized in that, comprises the steps:
Substrate is provided;
Adopt magnetron sputtering to form anode on described substrate;
Adopt vacuum evaporation to form hole transmission layer on described anode;
Adopt vacuum evaporation to form electronic barrier layer on described hole transmission layer;
Adopt vacuum evaporation on described electronic barrier layer, to form red-green glow hybrid illuminating layer, exciton barrier-layer, Yellow light emitting layer and the blue light-emitting stacking gradually, described in the red-green glow hybrid illuminating layer, exciton barrier-layer, Yellow light emitting layer and the blue light-emitting composition luminescent layer that stack gradually;
Adopt vacuum evaporation to form hole blocking layer on described blue light-emitting;
Adopt vacuum evaporation to form electron transfer layer on described hole barrier;
Adopt vacuum evaporation to form negative electrode on described electron transfer layer, obtain described organic electroluminescence device.
10. the preparation method of organic electroluminescence device according to claim 9, it is characterized in that, also comprise described substrate is carried out to cleaning-drying and the step to described anode plasma treatment, the step that described substrate is carried out to cleaning-drying is carried out ultrasonic cleaning for described substrate is placed in the deionized water that contains washing agent, after cleaning up, use successively isopropyl alcohol, acetone is processed 20 minutes in ultrasonic wave, and then dries up with nitrogen; The step that described anode is carried out to plasma treatment is for to be positioned over the anode that is laminated in described substrate in plasma processing chamber and to process 10 minutes.
CN201210305556.2A 2012-08-24 2012-08-24 Organic electroluminescent device and preparation method thereof Pending CN103633250A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
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CN105045023A (en) * 2014-04-25 2015-11-11 日立乐金光科技株式会社 Light source module and image projection device
CN105336872A (en) * 2015-10-09 2016-02-17 北京大学深圳研究生院 White-light organic light-emitting diode device and preparation method thereof
CN110459688A (en) * 2019-07-29 2019-11-15 云谷（固安）科技有限公司 Blue light emitting device and display device
WO2020119556A1 (en) * 2018-12-12 2020-06-18 惠科股份有限公司 Light-emitting device and display device

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105045023A (en) * 2014-04-25 2015-11-11 日立乐金光科技株式会社 Light source module and image projection device
CN105336872A (en) * 2015-10-09 2016-02-17 北京大学深圳研究生院 White-light organic light-emitting diode device and preparation method thereof
WO2020119556A1 (en) * 2018-12-12 2020-06-18 惠科股份有限公司 Light-emitting device and display device
CN110459688A (en) * 2019-07-29 2019-11-15 云谷（固安）科技有限公司 Blue light emitting device and display device
CN110459688B (en) * 2019-07-29 2023-03-24 云谷（固安）科技有限公司 Blue light emitting device and display apparatus

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