CN103904234B - A kind of organic electroluminescence device and preparation method thereof - Google Patents
A kind of organic electroluminescence device and preparation method thereof Download PDFInfo
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- CN103904234B CN103904234B CN201210571794.8A CN201210571794A CN103904234B CN 103904234 B CN103904234 B CN 103904234B CN 201210571794 A CN201210571794 A CN 201210571794A CN 103904234 B CN103904234 B CN 103904234B
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- 238000005401 electroluminescence Methods 0.000 title claims abstract description 100
- 238000002360 preparation method Methods 0.000 title claims abstract description 46
- 239000010410 layer Substances 0.000 claims abstract description 568
- 230000004888 barrier function Effects 0.000 claims abstract description 379
- 239000000463 material Substances 0.000 claims abstract description 177
- 239000000758 substrate Substances 0.000 claims abstract description 125
- 239000002131 composite material Substances 0.000 claims abstract description 123
- 239000011241 protective layer Substances 0.000 claims abstract description 71
- 230000005540 biological transmission Effects 0.000 claims abstract description 49
- 238000002347 injection Methods 0.000 claims abstract description 49
- 239000007924 injection Substances 0.000 claims abstract description 49
- 230000027756 respiratory electron transport chain Effects 0.000 claims abstract description 49
- 238000007738 vacuum evaporation Methods 0.000 claims description 76
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 67
- 229910052782 aluminium Inorganic materials 0.000 claims description 67
- 239000004411 aluminium Substances 0.000 claims description 67
- -1 polytetrafluoroethylene Polymers 0.000 claims description 57
- 229910052757 nitrogen Inorganic materials 0.000 claims description 40
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 28
- 150000001875 compounds Chemical class 0.000 claims description 24
- 239000000113 methacrylic resin Substances 0.000 claims description 20
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 18
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 18
- 239000011353 cycloaliphatic epoxy resin Substances 0.000 claims description 18
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 18
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 18
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 18
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical group [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- 238000005566 electron beam evaporation Methods 0.000 claims description 14
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000011261 inert gas Substances 0.000 claims description 11
- 239000011572 manganese Substances 0.000 claims description 10
- 238000004806 packaging method and process Methods 0.000 claims description 10
- 239000011701 zinc Substances 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 9
- 238000004528 spin coating Methods 0.000 claims description 9
- 239000004033 plastic Substances 0.000 claims description 8
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 claims description 7
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 6
- 239000005083 Zinc sulfide Substances 0.000 claims description 6
- WDEQGLDWZMIMJM-UHFFFAOYSA-N benzyl 4-hydroxy-2-(hydroxymethyl)pyrrolidine-1-carboxylate Chemical compound OCC1CC(O)CN1C(=O)OCC1=CC=CC=C1 WDEQGLDWZMIMJM-UHFFFAOYSA-N 0.000 claims description 6
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 claims description 6
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 claims description 6
- 229910001635 magnesium fluoride Inorganic materials 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 5
- IBHBKWKFFTZAHE-UHFFFAOYSA-N n-[4-[4-(n-naphthalen-1-ylanilino)phenyl]phenyl]-n-phenylnaphthalen-1-amine Chemical class C1=CC=CC=C1N(C=1C2=CC=CC=C2C=CC=1)C1=CC=C(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C3=CC=CC=C3C=CC=2)C=C1 IBHBKWKFFTZAHE-UHFFFAOYSA-N 0.000 claims description 4
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 29
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 22
- 239000001301 oxygen Substances 0.000 abstract description 22
- 229910052760 oxygen Inorganic materials 0.000 abstract description 22
- 230000003628 erosive effect Effects 0.000 abstract description 9
- 238000001704 evaporation Methods 0.000 description 109
- 230000008020 evaporation Effects 0.000 description 109
- 229920002799 BoPET Polymers 0.000 description 38
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 32
- 239000011521 glass Substances 0.000 description 31
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 30
- 239000010408 film Substances 0.000 description 29
- DHDHJYNTEFLIHY-UHFFFAOYSA-N 4,7-diphenyl-1,10-phenanthroline Chemical group C1=CC=CC=C1C1=CC=NC2=C1C=CC1=C(C=3C=CC=CC=3)C=CN=C21 DHDHJYNTEFLIHY-UHFFFAOYSA-N 0.000 description 20
- 238000005538 encapsulation Methods 0.000 description 19
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 16
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 239000004743 Polypropylene Substances 0.000 description 15
- 229920001155 polypropylene Polymers 0.000 description 15
- AWXGSYPUMWKTBR-UHFFFAOYSA-N 4-carbazol-9-yl-n,n-bis(4-carbazol-9-ylphenyl)aniline Chemical compound C12=CC=CC=C2C2=CC=CC=C2N1C1=CC=C(N(C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=C1 AWXGSYPUMWKTBR-UHFFFAOYSA-N 0.000 description 14
- 101000837344 Homo sapiens T-cell leukemia translocation-altered gene protein Proteins 0.000 description 14
- 102100028692 T-cell leukemia translocation-altered gene protein Human genes 0.000 description 14
- 238000001994 activation Methods 0.000 description 14
- 229920006267 polyester film Polymers 0.000 description 14
- 239000004593 Epoxy Substances 0.000 description 12
- 239000003292 glue Substances 0.000 description 12
- 239000007789 gas Substances 0.000 description 11
- 150000005360 2-phenylpyridines Chemical class 0.000 description 10
- 229910052741 iridium Inorganic materials 0.000 description 10
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 10
- 125000006617 triphenylamine group Chemical class 0.000 description 10
- 229910052786 argon Inorganic materials 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 239000002344 surface layer Substances 0.000 description 8
- 238000004506 ultrasonic cleaning Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- GEQBRULPNIVQPP-UHFFFAOYSA-N 2-[3,5-bis(1-phenylbenzimidazol-2-yl)phenyl]-1-phenylbenzimidazole Chemical compound C1=CC=CC=C1N1C2=CC=CC=C2N=C1C1=CC(C=2N(C3=CC=CC=C3N=2)C=2C=CC=CC=2)=CC(C=2N(C3=CC=CC=C3N=2)C=2C=CC=CC=2)=C1 GEQBRULPNIVQPP-UHFFFAOYSA-N 0.000 description 6
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- 239000000084 colloidal system Substances 0.000 description 6
- 238000010894 electron beam technology Methods 0.000 description 6
- 229910052756 noble gas Inorganic materials 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 230000035699 permeability Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000005286 illumination Methods 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000006378 damage Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical group [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 3
- 230000002045 lasting effect Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 230000035882 stress Effects 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- QVLNJJLJVMLHFO-UHFFFAOYSA-N [F].[O-2].[Zn+2] Chemical compound [F].[O-2].[Zn+2] QVLNJJLJVMLHFO-UHFFFAOYSA-N 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 238000004770 highest occupied molecular orbital Methods 0.000 description 2
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229910021332 silicide Inorganic materials 0.000 description 2
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 2
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 238000004776 molecular orbital Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/84—Passivation; Containers; Encapsulations
- H10K50/844—Encapsulations
- H10K50/8445—Encapsulations multilayered coatings having a repetitive structure, e.g. having multiple organic-inorganic bilayers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention discloses a kind of organic electroluminescence device; comprise the anode conducting substrate, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the negative electrode that stack gradually; negative electrode is also provided with protective layer and barrier layer; barrier layer comprises composite barrier, inorganic barrier layer and inorganic barrier layer; composite barrier, inorganic barrier layer and inorganic barrier layer form a basic structure, and barrier layer is that multiple basic structure repeats to be formed.The invention also discloses the preparation method of this organic electroluminescence device.The present invention arranges barrier layer on organic electroluminescence device, effectively can reduce water, oxygen isoreactivity material to the erosion of organic electroluminescence device, improve the life-span of organic electroluminescence device.
Description
Technical field
The present invention relates to electronic device association area, particularly relate to a kind of organic electroluminescence device and preparation method thereof.
Background technology
Organic electroluminescence device (Organiclight-emittingDevices, be called for short OLEDs) be a kind of multilayer luminescent device using luminous organic material, comprise the anode layer, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and the negative electrode that stack gradually.Under the principle of luminosity of OLED is based on the effect of extra electric field, electronics is injected into organic lowest unocccupied molecular orbital (LUMO) from negative electrode, and hole is injected into organic highest occupied molecular orbital (HOMO) from anode, meet at luminescent layer in electronics and hole, compound, formation exciton, and exciton moves under electric field action, by energy transferring to luminescent material, excitation electron is from ground state transition to excitation state, excited energy, by Radiation-induced deactivation, produces photon, release luminous energy.Luminous efficiency is high, driving voltage is low, visual angle is wide, glow color range of choice is wide, manufacture craft is simple because it has for OLED, and easily realize the features such as panchromatic and Flexible Displays, cause increasing concern in illumination and flat display field, and be considered to be most likely at the device of new generation following illumination and display device market occupying dominance.
At present, there is life-span shorter problem in organic electroluminescence device, and this occurs rapidly aging mainly because organic material film is very loose after easily being infiltrated by compositions such as the steam in air and oxygen.Therefore, organic electroluminescence device must encapsulate before entering actual use, and the quality of encapsulation is directly connected to the life-span of organic electroluminescence device.
Summary of the invention
The object of the invention is to the defect overcoming above-mentioned prior art, a kind of organic electroluminescence device and preparation method thereof is provided.This organic electroluminescence device is provided with protective layer and barrier layer; effectively can reduce water, oxygen isoreactivity material to the erosion of organic electroluminescence device, improve the life-span of organic electroluminescence device, preparation method is simple to operation; cost of material is low, is applicable to suitability for industrialized production.
First aspect, the invention provides a kind of organic electroluminescence device, comprise the anode conducting substrate, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the negative electrode that stack gradually, it is characterized in that, described negative electrode is also provided with protective layer and barrier layer, described barrier layer comprises composite barrier, inorganic barrier layer and inorganic barrier layer, described composite barrier, inorganic barrier layer and inorganic barrier layer form a basic structure, and described barrier layer is that multiple described basic structure repeats to be formed;
The material of described protective layer is CuPc, N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines, oxine aluminium, silicon monoxide, magnesium fluoride or zinc sulphide;
The material of described composite barrier is the oxide of doping phthalocyanine-like compound, and described oxide is SiO
2, Al
2o
3, TiO
2, ZrO
2, HfO
2or Ta
2o
5;
The material of described inorganic barrier layer is the oxide in described composite barrier;
The material of described inorganic barrier layer is polytetrafluoroethylene, methacrylic resin or cycloaliphatic epoxy resin.
Phthalocyanine-like compound has good conductivity and acid-proof alkaline, it also shows excellent stability under the illumination and intensification of light fixture simultaneously, therefore adulterate phthalocyanine-like compound in the oxide, and the water resistant of described composite barrier, oxidation resistant ability can be made more stable lasting.
Preferably, described phthalocyanine-like compound is CuPc, Phthalocyanine Zinc, FePC, Cobalt Phthalocyanine, manganese phthalocyanine or Nickel Phthalocyanine, and the doping mass fraction of phthalocyanine-like compound described in composite barrier is 10% ~ 30%.
Preferably, described barrier layer is that 3 ~ 4 basic structures repeat to be formed.
Barrier layer of the present invention is divided into three layers, can reduce single inorganic barrier layer, single inorganic barrier layer defect on the impact of packaging effect, extend water, Oxygen permeation path, make water, path that oxygen is with organic electroluminescence devices is more complicated, the outside water of effective minimizing, oxygen isoreactivity material are to the erosion of organic electroluminescence device, ensure the pliability on barrier layer, to reach encapsulation requirement simultaneously.
The existence of protective layer can stop that outside water, oxygen isoreactivity material are to the erosion of organic electroluminescence device, improve the life-span of organic electroluminescence device.Preferably, the thickness of described protective layer is 200nm ~ 300nm.
Preferably, the thickness of described composite barrier is 100nm ~ 150nm, and the thickness of described inorganic barrier layer is 100nm ~ 150nm, and the thickness of described inorganic barrier layer is 1 ~ 1.5 μm.
Wherein, described anode conducting substrate is conducting glass substrate or conduction organic film substrate.Preferably, described anode conducting substrate is conduction organic film substrate.Organic film substrate is soft, using organic film substrate as anode, can make flexible organic electroluminescent device.
Wherein, described anode conducting substrate comprises substrate and magnetron sputtering in suprabasil conductive anode layer.Preferably, the material of described conductive anode layer is indium tin oxide (ITO).
Preferably, the material of described hole injection layer is MoO
3n is doped into, the doping composite material formed in N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines according to the doping content of 30wt%; The material of described hole transmission layer is 4,4', 4 "-three (carbazole-9-base) triphenylamines; The material of described luminescent layer is that three (2-phenylpyridines) close iridium and are doped into the doping composite material formed in 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene according to the doping content of 5wt%; The material of described electron transfer layer is 4,7-diphenyl-1,10-phenanthroline; The material of described electron injecting layer is CsN
3the composite material formed in 4,7-diphenyl-1,10-phenanthroline is mixed according to the doping content of 30wt%.
Preferably, the thickness of described hole injection layer is 10nm, and the thickness of described hole transmission layer is 30nm, and the thickness of described luminescent layer is 20nm, and the thickness of described electron transfer layer is 10nm, and the thickness of described electron injecting layer is 20nm.
Preferably; described barrier layer is also provided with cap; described cap and described anode conducting substrate form enclosure space, and described hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer, negative electrode, protective layer and barrier layer are contained in described enclosure space.Cap is set, forms enclosure space with anode conducting substrate, protection can be formed to organic electroluminescence device better.
Wherein, described cap can, for containing aluminium high temperature resistance polyester film (being abbreviated as containing aluminium PET film), also can be tinsel.Preferably, described cap is for containing aluminium high temperature resistance polyester film.Flexible containing aluminium PET film, more suitable for prepare flexible organic electroluminescent device.
Organic electroluminescence device of the present invention, negative electrode is provided with barrier layer, outside water, oxygen isoreactivity material can be effectively reduced to the erosion of organic electroluminescence device, meet sealing and the requirement of encapsulation, considerably improve the life-span of organic electroluminescence device.According to test, the water vapour permeability (WVTR) of organic electroluminescence device of the present invention reaches as high as 1.6 × 10
-5g/m
2day, useful life reaches 15, and more than 000 hour (at T701000cd/m
2luminescent condition under).
Second aspect, the invention provides a kind of preparation method of organic electroluminescence device, comprises the steps:
(1) provide clean dry anode conducting substrate, and in conductive anode layer on described anode conducting substrate successively vacuum evaporation prepare hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode;
(2) method of vacuum evaporation is adopted to prepare protective layer on negative electrode, the material of described protective layer is CuPc, N, N'-diphenyl-N, N'-bis-(1-naphthyls)-1,1'-biphenyl-4,4'-diamines, oxine aluminium, silicon monoxide, magnesium fluoride or zinc sulphide;
(3) on described protective layer, prepare barrier layer, obtain organic electroluminescence device; Wherein, the concrete preparation method on described barrier layer is as follows:
A () adopts the mode of electron beam evaporation to make composite barrier;
B () adopts the mode of magnetron sputtering to make inorganic barrier layer on described composite barrier;
(c) under the atmosphere of inert gas on described second silicide layer spin coating prepare inorganic barrier layer;
D () described composite barrier, inorganic barrier layer and inorganic barrier layer form a basic structure, repeat step (a) and (b) after step (c) and prepare multiple described basic structure with (c), obtain the barrier layer containing multiple described basic structure;
Wherein, the material of described composite barrier is the oxide of doping phthalocyanine-like compound, and described oxide is SiO
2, Al
2o
3, TiO
2, ZrO
2, HfO
2or Ta
2o
5, the material of described inorganic barrier layer is the oxide in described composite barrier, and the material of described inorganic barrier layer is polytetrafluoroethylene, methacrylic resin or cycloaliphatic epoxy resin.
Preferably, adopt the mode of electron beam evaporation to make composite barrier described in step (a), background vacuum is 1 × 10
-4~ 1 × 10
-3pa, the thickness of described composite barrier is 100nm ~ 150nm.
Preferably, described phthalocyanine-like compound is CuPc, Phthalocyanine Zinc, FePC, Cobalt Phthalocyanine, manganese phthalocyanine or Nickel Phthalocyanine, and the doping mass fraction of phthalocyanine-like compound described in described composite barrier is 10% ~ 30%.
Preferably, adopt the mode of magnetron sputtering to prepare inorganic barrier layer described in step (b) on described composite barrier, concrete operations are: using oxide as target, pass into argon gas as atmosphere of inert gases, with 1 × 10
-4~ 1 × 10
-3background vacuum magnetron sputtering on described composite barrier of Pa forms inorganic barrier layer, and the described oxide in the material composite barrier of described inorganic barrier layer, for being selected from SiO
2, Al
2o
3, TiO
2, ZrO
2, HfO
2and Ta
2o
5in any one; The thickness of described inorganic barrier layer is 100nm ~ 150nm.
Preferably, carry out exposure curing described in step (c) with ultraviolet light, the wavelength of ultraviolet light is 360nm, and light intensity is 10 ~ 15mW/cm
2, the time for exposure is 150 ~ 200 seconds.
Preferably, the thickness of described inorganic barrier layer is 1 ~ 1.5 μm.
Preferably, described barrier layer is that 3 ~ 4 basic structures repeat to be formed.
Preferably, the vacuum evaporation of step (2) described protective layer, vacuum degree is 1 × 10
-5pa ~ 1 × 10
-3pa, evaporation rate is
the thickness of described protective layer is 200nm ~ 300nm.
Particularly, the clean drying of described anode conducting substrate, concrete operations are, anode conducting substrate is put into successively acetone, ethanol, deionized water, ethanol carries out ultrasonic cleaning, then adopt nitrogen to dry up, and put into baking oven and dry stand-by.
Wherein, described anode conducting substrate is conducting glass substrate or conduction organic film substrate.Preferably, described anode conducting substrate is conduction organic film substrate.Organic film substrate is soft, using organic film substrate as anode, can make flexible organic electroluminescent device.
Wherein, described anode conducting substrate comprises substrate and magnetron sputtering in suprabasil conductive anode layer.Preferably, the material of described conductive anode layer is indium tin oxide (ITO).
Preferably, the thickness of described conductive anode layer is 100nm.
Preferably, in the preparation method of described organic electroluminescence device, after clean dry anode conducting substrate is provided, goes back antianode electrically-conductive backing plate and carried out surface activation process.The oxygen content of conductive surface layer can be increased like this, improve the work function of conductive layer surface.
Preferably, the material of described hole injection layer is MoO
3n is doped into, the doping composite material formed in N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines according to the doping content of 30wt%; The material of described hole transmission layer is 4,4', 4 "-three (carbazole-9-base) triphenylamines; The material of described luminescent layer is that three (2-phenylpyridines) close iridium and are doped into the doping composite material formed in 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene according to the doping content of 5wt%; The material of described electron transfer layer is 4,7-diphenyl-1,10-phenanthroline; The material of described electron injecting layer is CsN
3the composite material formed in 4,7-diphenyl-1,10-phenanthroline is mixed according to the doping content of 30wt%.
Preferably, the thickness of described hole injection layer is 10nm, and the thickness of described hole transmission layer is 30nm, and the thickness of described luminescent layer is 20nm, and the thickness of described electron transfer layer is 10nm, and the thickness of described electron injecting layer is 20nm.
Preferably, described hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer adopt the method for vacuum evaporation to be prepared, and during vacuum evaporation, vacuum degree is 3 × 10
-5pa, evaporation rate
Preferably, the material of described negative electrode is aluminium, and thickness is 100nm, and described negative electrode adopts the method for vacuum evaporation to be prepared, and during vacuum evaporation, vacuum degree is 3 × 10
-5pa, evaporation rate
Preferably; described preparation method also comprises the steps: to provide cap after step (3); at cap edge-coating packaging plastic; then cap is covered on described barrier layer; by UV-irradiation, packaging plastic is solidified; sealing forms enclosure space, is contained in described enclosure space in described hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer, negative electrode, protective layer and barrier layer, obtains the organic electroluminescence device sealed.
Wherein, described cap can, for containing aluminium high temperature resistance polyester film (being abbreviated as containing aluminium PET film), also can be tinsel.Preferably, described cap is for containing aluminium high temperature resistance polyester film.Flexible containing aluminium PET film, more suitable for prepare flexible organic electroluminescent device.
Preferably, described packaging plastic is epoxy resin.
First on negative electrode, prepare layer protective layer prepares barrier layer to preparation method of the present invention again, effectively prevent the destruction that in the preparation process of barrier layer, target produces; Preparation method of the present invention also adopts the electron beam evaporation technique different with magnetron sputtering two kinds to prepare the barrier layer of continuous two-layer similar material respectively simultaneously, has both improve the barrier properties on barrier layer, and has effectively released slow stress in thin film again.It is organic electroluminescence device prepared by anode substrate with electro-conductive glass that preparation method of the present invention is applicable to encapsulation, is also applicable to flexible organic electroluminescent device.
Compared to prior art, a kind of organic electroluminescence device of the present invention and preparation method thereof has following beneficial effect:
(1) described organic electroluminescence device, negative electrode is provided with barrier layer, effectively reduces outside water, oxygen isoreactivity material to the erosion of organic electroluminescence device, improves the life-span of organic electroluminescence device;
(2) adulterate phthalocyanine-like compound in the oxide as barrier layer, the water resistant on barrier layer, oxidation resistant ability can be made more stable lasting;
(3) first on negative electrode, prepare layer protective layer prepares barrier layer to described preparation method again, effectively prevent the destruction that in the preparation process of barrier layer, target produces;
(4) adopt the electron beam evaporation technique different with magnetron sputtering two kinds to prepare the barrier layer of continuous two-layer similar material respectively, both improve the barrier properties on barrier layer, and effectively released slow stress in thin film again.
Accompanying drawing explanation
In order to be illustrated more clearly in technical scheme of the present invention, be briefly described to the accompanying drawing used required in execution mode below, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to these accompanying drawings.
Fig. 1 is the structural representation of the organic electroluminescence device that the embodiment of the present invention 1 obtains.
Embodiment
Below in conjunction with the accompanying drawing in embodiment of the present invention, the technical scheme in embodiment of the present invention is clearly and completely described.
A kind of organic electroluminescence device, comprise the anode conducting substrate, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the negative electrode that stack gradually, it is characterized in that, described negative electrode is also provided with protective layer and barrier layer, described barrier layer comprises composite barrier, inorganic barrier layer and inorganic barrier layer, described composite barrier, inorganic barrier layer and inorganic barrier layer form a basic structure, and described barrier layer is that multiple described basic structure repeats to be formed;
The material of described protective layer is CuPc (molecular formula is CuPc), N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (being expressed as NPB), oxine aluminium (are expressed as Alq
3), silicon monoxide (molecular formula is SiO), (molecular formula is MgF to magnesium fluoride
2) or zinc sulphide (molecular formula is ZnS);
The material of described composite barrier is the oxide of doping phthalocyanine-like compound, and described oxide is SiO
2, Al
2o
3, TiO
2, ZrO
2, HfO
2or Ta
2o
5;
The material of described inorganic barrier layer is the oxide in described composite barrier;
The material of described inorganic barrier layer is polytetrafluoroethylene, methacrylic resin or cycloaliphatic epoxy resin.
Phthalocyanine-like compound has good conductivity and acid-proof alkaline, it also shows excellent stability under the illumination and intensification of light fixture simultaneously, therefore adulterate phthalocyanine-like compound in the oxide, and the water resistant of described composite barrier, oxidation resistant ability can be made more stable lasting.
Described phthalocyanine-like compound is CuPc, Phthalocyanine Zinc, FePC, Cobalt Phthalocyanine, manganese phthalocyanine or Nickel Phthalocyanine, and the doping mass fraction of phthalocyanine-like compound described in composite barrier is 10% ~ 30%.
Described barrier layer is that 3 ~ 4 basic structures repeat to be formed.
Barrier layer of the present invention is divided into three layers, can reduce single inorganic barrier layer, single inorganic barrier layer defect on the impact of packaging effect, extend water, Oxygen permeation path, make water, path that oxygen is with organic electroluminescence devices is more complicated, the outside water of effective minimizing, oxygen isoreactivity material are to the erosion of organic electroluminescence device, ensure the pliability on barrier layer, to reach encapsulation requirement simultaneously.
The existence of protective layer can stop that outside water, oxygen isoreactivity material are to the erosion of organic electroluminescence device, improve the life-span of organic electroluminescence device.The thickness of described protective layer is 200nm ~ 300nm.
The thickness of described composite barrier is 100nm ~ 150nm, and the thickness of described inorganic barrier layer is 100nm ~ 150nm, and the thickness of described inorganic barrier layer is 1 ~ 1.5 μm.
Wherein, anode conducting substrate comprises anode conductive layer and substrate, its substrate can be glass substrate or organic film substrate, the material of anode conductive layer can be conductive oxide, as, tin indium oxide (ITO), Al-Doped ZnO (AZO), mix indium zinc oxide (IZO) or mix fluorine zinc oxide (FTO), these conductive oxides are produced on the glass substrate, are called for short ito glass, AZO glass, IZO glass, FTO glass.Anode conducting substrate can be made by oneself, also can commercially obtain.In actual applications, the material can other being selected as required suitable is as anode conducting substrate.In actual applications, the anode pattern of required organic electroluminescence device can be prepared on anode conducting substrate.Anode conducting substrate is prior art, does not repeat them here.
Described anode conducting substrate is conduction organic film substrate.Organic film substrate is soft, using organic film substrate as anode, can make flexible organic electroluminescent device.
Wherein, described anode conducting substrate comprises substrate and evaporation in suprabasil conductive anode layer.The material of described conductive anode layer is indium tin oxide (ITO).
The material of described hole injection layer is MoO
3be doped into N according to the doping content of 30wt%, the doping composite material formed in N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (is expressed as MoO
3-NPB); The material of described hole transmission layer is 4,4', 4 "-three (carbazole-9-base) triphenylamines (being expressed as TCTA); The material of described luminescent layer is that three (2-phenylpyridines) close iridium and are doped into according to the doping content of 5wt% the doping composite material formed in 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene and (are expressed as Ir (ppy)
3-TPBI); The material of described electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (being expressed as Bphen); The material of described electron injecting layer is CsN
3mix according to the doping content of 30wt% the composite material formed in 4,7-diphenyl-1,10-phenanthroline and (be expressed as CsN
3-Bphen).
The thickness of described hole injection layer is 10nm, and the thickness of described hole transmission layer is 30nm, and the thickness of described luminescent layer is 20nm, and the thickness of described electron transfer layer is 10nm, and the thickness of described electron injecting layer is 20nm.
Described barrier layer is also provided with cap; described cap and described anode conducting substrate form enclosure space, and described hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer, negative electrode, protective layer and barrier layer are contained in described enclosure space.Cap is set, forms enclosure space with anode conducting substrate, protection can be formed to organic electroluminescence device better.
Wherein, described cap can, for containing aluminium high temperature resistance polyester film (being abbreviated as containing aluminium PET film), also can be tinsel.
Described cap is for containing aluminium high temperature resistance polyester film.Flexible containing aluminium PET film, more suitable for prepare flexible organic electroluminescent device.
Organic electroluminescence device of the present invention, negative electrode is provided with barrier layer, outside water, oxygen isoreactivity material can be effectively reduced to the erosion of organic electroluminescence device, meet sealing and the requirement of encapsulation, considerably improve the life-span of organic electroluminescence device.According to test, the water vapour permeability (WVTR) of organic electroluminescence device of the present invention reaches as high as 1.6 × 10
-5g/m
2day, useful life reaches 15, and more than 000 hour (at T701000cd/m
2luminescent condition under).
Second aspect, the invention provides a kind of preparation method of organic electroluminescence device, comprises the steps:
(1) provide clean dry anode conducting substrate, and in conductive anode layer on described anode conducting substrate successively vacuum evaporation prepare hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode;
(2) method of vacuum evaporation is adopted to prepare protective layer on negative electrode, the material of described protective layer is CuPc, N, N'-diphenyl-N, N'-bis-(1-naphthyls)-1,1'-biphenyl-4,4'-diamines, oxine aluminium, silicon monoxide, magnesium fluoride or zinc sulphide;
(3) on described protective layer, prepare barrier layer, obtain organic electroluminescence device; Wherein, the concrete preparation method on described barrier layer is as follows:
A () adopts the mode of electron beam evaporation to make composite barrier;
B () adopts the mode of magnetron sputtering to make inorganic barrier layer on described composite barrier;
(c) under the atmosphere of inert gas on described second silicide layer spin coating prepare inorganic barrier layer;
D () described composite barrier, inorganic barrier layer and inorganic barrier layer form a basic structure, repeat step (a) and (b) after step (c) and prepare multiple described basic structure with (c), obtain the barrier layer containing multiple described basic structure;
Wherein, the material of described composite barrier is the oxide of doping phthalocyanine-like compound, and described oxide is SiO
2, Al
2o
3, TiO
2, ZrO
2, HfO
2or Ta
2o
5, the material of described inorganic barrier layer is the oxide in described composite barrier, and the material of described inorganic barrier layer is polytetrafluoroethylene, methacrylic resin or cycloaliphatic epoxy resin.
Adopt the mode of electron beam evaporation to make composite barrier described in step (a), background vacuum is 1 × 10
-4~ 1 × 10
-3pa, the thickness of described composite barrier is 100nm ~ 150nm.
Described phthalocyanine-like compound is CuPc, Phthalocyanine Zinc, FePC, Cobalt Phthalocyanine, manganese phthalocyanine or Nickel Phthalocyanine, and the doping mass fraction of phthalocyanine-like compound described in described composite barrier is 10% ~ 30%.
Adopt the mode of magnetron sputtering to prepare inorganic barrier layer described in step (b) on described composite barrier, concrete operations are: using oxide as target, pass into argon gas as atmosphere of inert gases, with 1 × 10
-4~ 1 × 10
-3background vacuum magnetron sputtering on described composite barrier of Pa forms inorganic barrier layer, and the described oxide in the material composite barrier of described inorganic barrier layer, for being selected from SiO
2, Al
2o
3, TiO
2, ZrO
2, HfO
2and Ta
2o
5in any one; The thickness of described inorganic barrier layer is 100nm ~ 150nm.
Carry out exposure curing with ultraviolet light described in step (c), the wavelength of ultraviolet light is 360nm, and light intensity is 10 ~ 15mW/cm
2, the time for exposure is 150 ~ 200 seconds.
The thickness of described inorganic barrier layer is 1 ~ 1.5 μm.
Described barrier layer is that 3 ~ 4 basic structures repeat to be formed.
The vacuum evaporation of step (2) described protective layer, vacuum degree is 1 × 10
-5pa ~ 1 × 10
-3pa, evaporation rate is
the thickness of described protective layer is 200nm ~ 300nm.
The clean drying of described anode conducting substrate, concrete operations are, anode conducting substrate is put into successively acetone, ethanol, deionized water, ethanol carries out ultrasonic cleaning, then adopt nitrogen to dry up, and put into baking oven and dry stand-by.
Wherein, anode conducting substrate comprises anode conductive layer and substrate, its substrate can be glass substrate or organic film substrate, the material of anode conductive layer can be conductive oxide, as, tin indium oxide (ITO), Al-Doped ZnO (AZO), mix indium zinc oxide (IZO) or mix fluorine zinc oxide (FTO), these conductive oxides are produced on the glass substrate, are called for short ito glass, AZO glass, IZO glass, FTO glass.Anode conducting substrate can be made by oneself, also can commercially obtain.In actual applications, the material can other being selected as required suitable is as anode conducting substrate.In actual applications, the anode pattern of required organic electroluminescence device can be prepared on anode conducting substrate.Anode conducting substrate is prior art, does not repeat them here.
The thickness of described conductive anode layer is 100nm.
In the preparation method of described organic electroluminescence device, after clean dry anode conducting substrate is provided, goes back antianode electrically-conductive backing plate and carried out surface activation process.The oxygen content of conductive surface layer can be increased like this, improve the work function of conductive layer surface.
The material of described hole injection layer is MoO
3be doped into N according to the doping content of 30wt%, the doping composite material formed in N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (is expressed as MoO
3-NPB); The material of described hole transmission layer is 4,4', 4 "-three (carbazole-9-base) triphenylamines (being expressed as TCTA); The material of described luminescent layer is that three (2-phenylpyridines) close iridium and are doped into according to the doping content of 5wt% the doping composite material formed in 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene and (are expressed as Ir (ppy)
3-TPBI); The material of described electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (being expressed as Bphen); The material of described electron injecting layer is CsN
3mix according to the doping content of 30wt% the composite material formed in 4,7-diphenyl-1,10-phenanthroline and (be expressed as CsN
3-Bphen).
The thickness of described hole injection layer is 10nm, and the thickness of described hole transmission layer is 30nm, and the thickness of described luminescent layer is 20nm, and the thickness of described electron transfer layer is 10nm, and the thickness of described electron injecting layer is 20nm.
Described hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer adopt the method for vacuum evaporation to be prepared, and during vacuum evaporation, vacuum degree is 3 × 10
-5pa, evaporation rate
The material of described negative electrode is aluminium, and thickness is 100nm, and described negative electrode adopts the method for vacuum evaporation to be prepared, and during vacuum evaporation, vacuum degree is 3 × 10
-5pa, evaporation rate
Described preparation method also comprises the steps: to provide cap after step (3); at cap edge-coating packaging plastic; then cap is covered on described barrier layer; by UV-irradiation, packaging plastic is solidified; sealing forms enclosure space; described hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer, negative electrode, protective layer and barrier layer are contained in described enclosure space, obtain the organic electroluminescence device sealed.
Wherein, described cap can, for containing aluminium high temperature resistance polyester film (being abbreviated as containing aluminium PET film), also can be tinsel.
Described cap is for containing aluminium high temperature resistance polyester film.Flexible containing aluminium PET film, more suitable for prepare flexible organic electroluminescent device.
Described packaging plastic is epoxy resin.
First on negative electrode, prepare layer protective layer prepares barrier layer to preparation method of the present invention again, effectively prevent the destruction that in the preparation process of barrier layer, target produces; Preparation method of the present invention also adopts the electron beam evaporation technique different with magnetron sputtering two kinds to prepare the barrier layer of continuous two-layer similar material respectively simultaneously, has both improve the barrier properties on barrier layer, and has effectively released slow stress in thin film again.It is organic electroluminescence device prepared by anode substrate with electro-conductive glass that preparation method of the present invention is applicable to encapsulation, is also applicable to flexible organic electroluminescent device.
Embodiment one
A preparation method for organic electroluminescence device, comprises the steps:
(1) select polypropylene film with ITO conductive layer as anode conducting substrate, anode conducting substrate is put into acetone, ethanol, deionized water, ethanol successively, each ultrasonic cleaning 5 minutes, then adopt nitrogen to dry up, and put into baking oven and dry stand-by; Then surface activation process is carried out to the anode conducting substrate after cleaning, to increase the oxygen content of anode conducting substrate surface layer, improve the work function of anode conducting substrate surface; The described polypropylene film with ITO conductive layer comprises polypropylene film substrate and the ITO conductive layer of evaporation on polypropylene film, and the thickness of described ITO conductive layer is 100nm.
(2) adopt the mode of vacuum evaporation in clean drying and conductive anode layer on anode conducting substrate after surface activation process prepares hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode successively, wherein:
The material of hole injection layer is doping MoO
3n, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (is expressed as MoO
3-NPB), MoO
3doping mass fraction 25%; Vacuum degree during vacuum evaporation is 3 × 10
-5pa, evaporation rate
evaporation thickness is 10nm;
The material of hole transmission layer is 4,4', 4 "-three (carbazole-9-base) triphenylamines (being expressed as TCTA); Vacuum degree during vacuum evaporation is 3 × 10
-5pa, evaporation rate
evaporation thickness is 40nm;
The material of luminescent layer comprises material of main part and guest materials.Material of main part is 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene (being expressed as TPBI), and guest materials is that three (2-phenylpyridines) close iridium and (are expressed as Ir (ppy)
3), and the doping mass fraction of guest materials is 5%; Vacuum degree during vacuum evaporation is 3 × 10
-5pa, evaporation rate
evaporation thickness is 20nm;
The material of electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (being expressed as Bphen); Vacuum degree during vacuum evaporation is 3 × 10
-5pa, evaporation rate
evaporation thickness is 30nm;
The material of electron injecting layer is doping CsN
34,7-diphenyl-1,10-phenanthrolines (be expressed as CsN
3-Bphen), CsN
3doping mass fraction be 25%; Vacuum degree during vacuum evaporation is 3 × 10
-5pa, evaporation rate
evaporation thickness is 20nm;
The material of negative electrode is aluminium (Al), and vacuum degree during vacuum evaporation is 3 × 10
-5pa, evaporation rate
evaporation thickness is 100nm.
(3) adopt the method for vacuum evaporation to prepare protective layer on negative electrode, wherein the material of protective layer is CuPc, and vacuum degree during vacuum evaporation is 3 × 10
-5pa, evaporation rate
evaporation thickness is 200nm.
(4) on described protective layer, prepare barrier layer, obtain organic electroluminescence device; Wherein, the specific solution on described barrier layer is:
A () adopts the mode of electron beam evaporation to make composite barrier on described protective layer, the material of described composite barrier is the SiO of doped with Cu Pc
2, wherein the doping mass fraction of CuPc is 20%, and concrete operations are, by the SiO of doped with Cu Pc
2be placed in the cold-crucible of vacuum evaporation instrument, utilize electron beam directly to heat the SiO making doped with Cu Pc
2carburation by evaporation also forms composite barrier on the protection layer, and background vacuum during evaporation is 1 × 10
-4pa, the thickness of composite barrier is 125nm;
B () adopts the mode of magnetron sputtering to prepare inorganic barrier layer on described composite barrier, the material of inorganic barrier layer is SiO
2, concrete operations are, with SiO
2for target, pass into argon gas as noble gas atmosphere, with 1 × 10
-4the background vacuum of Pa forms the inorganic barrier layer that thickness is 150nm on composite barrier;
C () adopts the mode of first spin coating post-exposure to prepare inorganic barrier layer on inorganic barrier layer, wherein the material of inorganic barrier layer is polytetrafluoroethylene, concrete operations are, under atmosphere of inert gases, polytetrafluoroethylene colloid is spin-coated on inorganic barrier layer, rubberization thickness is 1.5 μm, then uses ultraviolet light (wavelength is 365nm) with 15mW/cm
2intensity exposure solidify 200 seconds;
D () composite barrier, inorganic barrier layer and inorganic barrier layer form a basic structure, repeat step (a) and (b) and (c) three preparations three basic structures, form barrier layer.
(5) cap is selected containing aluminium high temperature resistance polyester film (being abbreviated as containing aluminium PET film); containing aluminium PET film edge-coating epoxy encapsulation glue; then described barrier layer is covered containing aluminium PET film; then epoxy encapsulation glue described in ultraviolet light polymerization is used; thus make to form enclosure space containing aluminium PET film and anode conducting base plate seals; hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer, negative electrode, protective layer and barrier layer are contained in this enclosure space, obtain the organic electroluminescence device sealed.
Fig. 1 is the structural representation of organic electroluminescence device prepared by the present embodiment, as shown in Figure 1, organic electroluminescence device prepared by this enforcement, comprise the anode conducting substrate 100 stacked gradually, hole injection layer 200, hole transmission layer 300, luminescent layer 400, electron transfer layer 500, electron injecting layer 600, negative electrode 700, protective layer 800, barrier layer 900 and cap 999, and this barrier layer 900 comprises composite barrier 901, 904, 907, inorganic barrier layer 902, 905, 908 and inorganic barrier layer 903, 906, 909, described composite barrier 901, inorganic barrier layer 902 and inorganic barrier layer 903 form a basic structure, described barrier layer is that 3 basic structures repeat to be formed,
The material of composite barrier is the SiO of doped with Cu Pc
2(be expressed as CuPc-SiO
2), the doping mass fraction of CuPc is 20%;
The material of inorganic barrier layer is SiO
2;
The material of inorganic barrier layer is polytetrafluoroethylene.
Organic electroluminescence device prepared by the present embodiment is flexible organic electroluminescent device, and concrete structure is:
Polypropylene film/ITO/ (MoO
3-NPB)/TCTA/ (TPBI-Ir (ppy)
3)/Bphen/ (CsN
3-Bphen)/Al/CuPc/CuPc-SiO
2/ SiO
2/ polytetrafluoroethylene/CuPc-SiO
2/ SiO
2/ polytetrafluoroethylene/CuPc-SiO
2/ SiO
2/ polytetrafluoroethylene/containing aluminium PET film.
Embodiment two
A preparation method for organic electroluminescence device, comprises the steps:
(1) select ito glass substrate as anode conducting substrate, anode conducting substrate is put into acetone, ethanol, deionized water, ethanol successively, each ultrasonic cleaning 5 minutes, then adopt nitrogen to dry up, and put into baking oven and dry stand-by; Then surface activation process is carried out to the anode conducting substrate after cleaning, to increase the oxygen content of anode conducting substrate surface layer, improve the work function of anode conducting substrate surface; Ito glass substrate comprises substrate of glass and evaporation ITO conductive layer on the glass substrate, and the thickness of ITO conductive layer is 100nm.
(2) adopt the mode of vacuum evaporation in clean drying and conductive anode layer on anode conducting substrate after surface activation process prepares hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode successively, wherein:
The material of hole injection layer is doping MoO
3n, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (is expressed as MoO
3-NPB), MoO
3doping mass fraction 25%; Vacuum degree during vacuum evaporation is 3 × 10
-5pa, evaporation rate
evaporation thickness is 10nm;
The material of hole transmission layer is 4,4', 4 "-three (carbazole-9-base) triphenylamines (being expressed as TCTA); Vacuum degree during vacuum evaporation is 3 × 10
-5pa, evaporation rate
evaporation thickness is 40nm;
The material of luminescent layer comprises material of main part and guest materials.Material of main part is 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene (being expressed as TPBI), and guest materials is that three (2-phenylpyridines) close iridium and (are expressed as Ir (ppy)
3), and the doping mass fraction of guest materials is 5%; Vacuum degree during vacuum evaporation is 3 × 10
-5pa, evaporation rate
evaporation thickness is 20nm;
The material of electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (being expressed as Bphen); Vacuum degree during vacuum evaporation is 3 × 10
-5pa, evaporation rate
evaporation thickness is 30nm;
The material of electron injecting layer is doping CsN
34,7-diphenyl-1,10-phenanthrolines (be expressed as CsN
3-Bphen), CsN
3doping mass fraction be 25%; Vacuum degree during vacuum evaporation is 3 × 10
-5pa, evaporation rate
evaporation thickness is 20nm;
The material of negative electrode is aluminium (Al), and vacuum degree during vacuum evaporation is 3 × 10
-5pa, evaporation rate
evaporation thickness is 100nm.
(3) adopt the method for vacuum evaporation to prepare protective layer on negative electrode, wherein the material of protective layer is N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (being expressed as NPB), and vacuum degree during vacuum evaporation is 3 × 10
-5pa, evaporation rate
evaporation thickness is 300nm.
(4) on described protective layer, prepare barrier layer, obtain organic electroluminescence device; Wherein, the specific solution on described barrier layer is:
A () adopts the mode of electron beam evaporation to make composite barrier on described protective layer, the material of described composite barrier is the Al of doping of Zn Pc
2o
3, wherein the doping mass fraction of ZnPc is 10%, and concrete operations are, by the Al of doping of Zn Pc
2o
3be placed in the cold-crucible of vacuum evaporation instrument, utilize electron beam directly to heat the Al making doping of Zn Pc
2o
3carburation by evaporation also forms composite barrier on the protection layer, and background vacuum during evaporation is 1 × 10
-4pa, the thickness of composite barrier is 100nm;
B () adopts the mode of magnetron sputtering to prepare inorganic barrier layer on described composite barrier, the material of inorganic barrier layer is Al
2o
3, concrete operations are, with Al
2o
3for target, pass into argon gas as noble gas gas, with 2 × 10
-4the background vacuum of Pa forms the inorganic barrier layer that thickness is 100nm on composite barrier;
C () adopts the mode of first spin coating post-exposure to prepare inorganic barrier layer on inorganic barrier layer, wherein the material of inorganic barrier layer is methacrylic resin, concrete operations are, under atmosphere of inert gases, methacrylic resin colloid is spin-coated on inorganic barrier layer, rubberization thickness is 1 μm, then uses ultraviolet light (wavelength is 365nm) with 10mW/cm
2intensity exposure solidify 150 seconds;
D () composite barrier, inorganic barrier layer and inorganic barrier layer form a basic structure, repeat step (a) and (b) and (c) four preparations four above-mentioned basic structures, form barrier layer.
(5) cap is selected containing aluminium high temperature resistance polyester film (being abbreviated as containing aluminium PET film); containing aluminium PET film edge-coating epoxy encapsulation glue; then described barrier layer is covered containing aluminium PET film; then epoxy encapsulation glue described in ultraviolet light polymerization is used; thus make to form enclosure space containing aluminium PET film and anode conducting base plate seals; hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer, negative electrode, protective layer and barrier layer are contained in this enclosure space, obtain the organic electroluminescence device sealed.
Organic electroluminescence device prepared by this enforcement, comprise stack gradually anode conducting substrate, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer, negative electrode, protective layer and barrier layer, and this barrier layer comprises composite barrier, inorganic barrier layer and inorganic barrier layer, described composite barrier, inorganic barrier layer and inorganic barrier layer form a basic structure, and described barrier layer is that 4 described basic structures repeat to be formed;
The material of composite barrier is the Al of doping of Zn Pc
2o
3(be expressed as ZnPc-Al
2o
3), the doping mass fraction of ZnPc is 10%.
The material of inorganic barrier layer is Al
2o
3.
The material of inorganic barrier layer is methacrylic resin.
Under normal conditions; this barrier layer is also provided with cap; cap and anode conducting substrate form enclosure space; be contained in hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer, negative electrode, protective layer and barrier layer in this enclosure space, the concrete structure of the organic electroluminescence device of final preparation is: the concrete structure of organic electroluminescence device prepared by the present embodiment is:
Glass/ITO/ (MoO
3-NPB)/TCTA/ (TPBI-Ir (ppy)
3)/Bphen/ (CsN
3-Bphen)/Al/NPB/ZnPc-Al
2o
3/ Al
2o
3/ methacrylic resin/ZnPc-Al
2o
3/ Al
2o
3/ methacrylic resin/ZnPc-Al
2o
3/ Al
2o
3/ methacrylic resin/ZnPc-Al
2o
3/ Al
2o
3/ methacrylic resin/containing aluminium PET film.
Embodiment three
A preparation method for organic electroluminescence device, comprises the steps:
(1) select polypropylene film with ITO conductive layer as anode conducting substrate, anode conducting substrate is put into acetone, ethanol, deionized water, ethanol successively, each ultrasonic cleaning 5 minutes, then adopt nitrogen to dry up, and put into baking oven and dry stand-by; Then surface activation process is carried out to the anode conducting substrate after cleaning, to increase the oxygen content of anode conducting substrate surface layer, improve the work function of anode conducting substrate surface; The described polypropylene film with ITO conductive layer comprises polypropylene film substrate and the ITO conductive layer of evaporation on polypropylene film, and the thickness of described ITO conductive layer is 100nm.
(2) adopt the mode of vacuum evaporation in clean drying and conductive anode layer on anode conducting substrate after surface activation process prepares hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode successively, wherein:
The material of hole injection layer is doping MoO
3n, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (is expressed as MoO
3-NPB), MoO
3doping mass fraction 25%; Vacuum degree during vacuum evaporation is 3 × 10
-5pa, evaporation rate
evaporation thickness is 10nm;
The material of hole transmission layer is 4,4', 4 "-three (carbazole-9-base) triphenylamines (being expressed as TCTA); Vacuum degree during vacuum evaporation is 3 × 10
-5pa, evaporation rate
evaporation thickness is 40nm;
The material of luminescent layer comprises material of main part and guest materials.Material of main part is 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene (being expressed as TPBI), and guest materials is that three (2-phenylpyridines) close iridium and (are expressed as Ir (ppy)
3), and the doping mass fraction of guest materials is 5%; Vacuum degree during vacuum evaporation is 3 × 10
-5pa, evaporation rate
evaporation thickness is 20nm;
The material of electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (being expressed as Bphen); Vacuum degree during vacuum evaporation is 3 × 10
-5pa, evaporation rate
evaporation thickness is 30nm;
The material of electron injecting layer is doping CsN
34,7-diphenyl-1,10-phenanthrolines (be expressed as CsN
3-Bphen), CsN
3doping mass fraction be 25%; Vacuum degree during vacuum evaporation is 3 × 10
-5pa, evaporation rate
evaporation thickness is 20nm;
The material of negative electrode is aluminium (Al), and vacuum degree during vacuum evaporation is 3 × 10
-5pa, evaporation rate
evaporation thickness is 100nm.
(3) adopt the method for vacuum evaporation to prepare protective layer on negative electrode, wherein the material of protective layer is that oxine aluminium (is expressed as Alq
3), vacuum degree during vacuum evaporation is 3 × 10
-5pa, evaporation rate
evaporation thickness is 250nm.
(4) on described protective layer, prepare barrier layer, obtain organic electroluminescence device; Wherein, the specific solution on described barrier layer is:
A () adopts the mode of electron beam evaporation to make composite barrier on described protective layer, the material of described composite barrier is the TiO of doped F ePc
2, wherein the doping mass fraction of FePc is 30%, and concrete operations are, by the TiO of doped F ePc
2be placed in the cold-crucible of vacuum evaporation instrument, utilize electron beam directly to heat the TiO making doped F ePc
2carburation by evaporation also forms composite barrier on the protection layer, and background vacuum during evaporation is 1 × 10
-4pa, the thickness of composite barrier is 125nm;
B () adopts the mode of magnetron sputtering to prepare inorganic barrier layer on described composite barrier, the material of inorganic barrier layer is TiO
2, concrete operations are, with TiO
2for target, pass into argon gas as noble gas atmosphere, with 2 × 10
-4the background vacuum of Pa forms the inorganic barrier layer that thickness is 120nm on composite barrier;
C () adopts the mode of first spin coating post-exposure to prepare inorganic barrier layer on inorganic barrier layer, wherein the material of inorganic barrier layer is cycloaliphatic epoxy resin, concrete operations are, under atmosphere of inert gases, cycloaliphatic epoxy resin colloid is spin-coated on inorganic barrier layer, rubberization thickness is 1.2 μm, then uses ultraviolet light (wavelength is 365nm) with 12mW/cm
2intensity exposure solidify 180 seconds;
D () composite barrier, inorganic barrier layer and inorganic barrier layer form a basic structure, repeat step (a) and (b) and (c) three preparations three basic structures, form barrier layer.
(5) cap is selected containing aluminium high temperature resistance polyester film (being abbreviated as containing aluminium PET film); containing aluminium PET film edge-coating epoxy encapsulation glue; then described barrier layer is covered containing aluminium PET film; then epoxy encapsulation glue described in ultraviolet light polymerization is used; thus make to form enclosure space containing aluminium PET film and anode conducting base plate seals; hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer, negative electrode, protective layer and barrier layer are contained in this enclosure space, obtain the organic electroluminescence device sealed.
Organic electroluminescence device prepared by this enforcement, comprise stack gradually anode conducting substrate, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer, negative electrode, protective layer, barrier layer and cap, and this barrier layer comprises composite barrier, inorganic barrier layer and inorganic barrier layer, described composite barrier, inorganic barrier layer and inorganic barrier layer form a basic structure, and described barrier layer is that 3 described basic structures repeat to be formed;
The material of composite barrier is the TiO of doped F ePc
2(be expressed as FePc-TiO
2), the doping mass fraction of FePc is 30%.
The material of inorganic barrier layer is TiO
2.
The material of inorganic barrier layer is cycloaliphatic epoxy resin.
Organic electroluminescence device prepared by the present embodiment is flexible organic electroluminescent device, and concrete structure is:
Polypropylene film/ITO/ (MoO
3-NPB)/TCTA/ (TPBI-Ir (ppy)
3)/Bphen/ (CsN
3-Bphen)/Al/Alq
3/ FePc-TiO
2/ TiO
2/ cycloaliphatic epoxy resin/FePc-TiO
2/ TiO
2/ cycloaliphatic epoxy resin/FePc-TiO
2/ TiO
2/ cycloaliphatic epoxy resin/containing aluminium PET film.
Embodiment four
A preparation method for organic electroluminescence device, comprises the steps:
(1) select ito glass substrate as anode conducting substrate, anode conducting substrate is put into acetone, ethanol, deionized water, ethanol successively, each ultrasonic cleaning 5 minutes, then adopt nitrogen to dry up, and put into baking oven and dry stand-by; Then surface activation process is carried out to the anode conducting substrate after cleaning, to increase the oxygen content of anode conducting substrate surface layer, improve the work function of anode conducting substrate surface; Ito glass substrate comprises substrate of glass and evaporation ITO conductive layer on the glass substrate, and the thickness of ITO conductive layer is 100nm.
(2) adopt the mode of vacuum evaporation in clean drying and conductive anode layer on anode conducting substrate after surface activation process prepares hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode successively, wherein:
The material of hole injection layer is doping MoO
3n, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (is expressed as MoO
3-NPB), MoO
3doping mass fraction 25%; Vacuum degree during vacuum evaporation is 3 × 10
-5pa, evaporation rate
evaporation thickness is 10nm;
The material of hole transmission layer is 4,4', 4 "-three (carbazole-9-base) triphenylamines (being expressed as TCTA); Vacuum degree during vacuum evaporation is 3 × 10
-5pa, evaporation rate
evaporation thickness is 40nm;
The material of luminescent layer comprises material of main part and guest materials.Material of main part is 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene (being expressed as TPBI), and guest materials is that three (2-phenylpyridines) close iridium and (are expressed as Ir (ppy)
3), and the doping mass fraction of guest materials is 5%; Vacuum degree during vacuum evaporation is 3 × 10
-5pa, evaporation rate
evaporation thickness is 20nm;
The material of electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (being expressed as Bphen); Vacuum degree during vacuum evaporation is 3 × 10
-5pa, evaporation rate
evaporation thickness is 30nm;
The material of electron injecting layer is doping CsN
34,7-diphenyl-1,10-phenanthrolines (be expressed as CsN
3-Bphen), CsN
3doping mass fraction be 25%; Vacuum degree during vacuum evaporation is 3 × 10
-5pa, evaporation rate
evaporation thickness is 20nm;
The material of negative electrode is aluminium (Al), and vacuum degree during vacuum evaporation is 3 × 10
-5pa, evaporation rate
evaporation thickness is 100nm.
(3) adopt the method for vacuum evaporation to prepare protective layer on negative electrode, wherein the material of protective layer is SiO, and vacuum degree during vacuum evaporation is 5 × 10
-5pa, evaporation rate
evaporation thickness is 200nm.
(4) on described protective layer, prepare barrier layer, obtain organic electroluminescence device; Wherein, the specific solution on described barrier layer is:
A () adopts the mode of electron beam evaporation to make composite barrier on described protective layer, the material of described composite barrier is the ZrO of doping CoPc
2, wherein the doping mass fraction of CoPc is 20%, and concrete operations are, by the ZrO of doping CoPc
2be placed in the cold-crucible of vacuum evaporation instrument, utilize electron beam directly to heat the ZrO making doping CoPc
2carburation by evaporation also forms composite barrier on the protection layer, and background vacuum during evaporation is 2 × 10
-4pa, the thickness of composite barrier is 120nm;
B () adopts the mode of magnetron sputtering to prepare inorganic barrier layer on described composite barrier, the material of inorganic barrier layer is ZrO
2, concrete operations are, with ZrO
2for target, pass into argon gas as noble gas gas, with 2 × 10
-4the background vacuum of Pa forms the inorganic barrier layer that thickness is 120nm on composite barrier;
C () adopts the mode of first spin coating post-exposure to prepare inorganic barrier layer on inorganic barrier layer, wherein the material of inorganic barrier layer is polytetrafluoroethylene, concrete operations are, under atmosphere of inert gases, polytetrafluoroethylene colloid is spin-coated on inorganic barrier layer, rubberization thickness is 1.2 μm, then uses ultraviolet light (wavelength is 365nm) with 12mW/cm
2intensity exposure solidify 180 seconds;
D () composite barrier, inorganic barrier layer and inorganic barrier layer form a basic structure, repeat step (a) and (b) and (c) three preparations three above-mentioned basic structures, form barrier layer.
(5) cap is selected containing aluminium high temperature resistance polyester film (being abbreviated as containing aluminium PET film); containing aluminium PET film edge-coating epoxy encapsulation glue; then described barrier layer is covered containing aluminium PET film; then epoxy encapsulation glue described in ultraviolet light polymerization is used; thus make to form enclosure space containing aluminium PET film and anode conducting base plate seals; hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer, negative electrode, protective layer and barrier layer are contained in this enclosure space, obtain the organic electroluminescence device sealed.
Organic electroluminescence device prepared by this enforcement, comprise stack gradually anode conducting substrate, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer, negative electrode, protective layer, barrier layer and cap, and this barrier layer comprises composite barrier, inorganic barrier layer and inorganic barrier layer, described composite barrier, inorganic barrier layer and inorganic barrier layer form a basic structure, and described barrier layer is that 3 described basic structures repeat to be formed;
The material of composite barrier is the ZrO of doping CoPc
2(CoPc-ZrO
2), the doping mass fraction of CoPc is 20%.
The material of inorganic barrier layer is ZrO
2.
The material of inorganic barrier layer is polytetrafluoroethylene.
The concrete structure of organic electroluminescence device prepared by the present embodiment is:
Glass/ITO/ (MoO
3-NPB)/TCTA/ (TPBI-Ir (ppy)
3)/Bphen/ (CsN
3-Bphen)/Al/SiO/CoPc-ZrO
2/ ZrO
2/ polytetrafluoroethylene/CoPc-ZrO
2/ ZrO
2/ polytetrafluoroethylene/CoPc-ZrO
2/ ZrO
2/ polytetrafluoroethylene/containing aluminium PET film.
Embodiment five
A preparation method for organic electroluminescence device, comprises the steps:
(1) select polypropylene film with ITO conductive layer as anode conducting substrate, anode conducting substrate is put into acetone, ethanol, deionized water, ethanol successively, each ultrasonic cleaning 5 minutes, then adopt nitrogen to dry up, and put into baking oven and dry stand-by; Then surface activation process is carried out to the anode conducting substrate after cleaning, to increase the oxygen content of anode conducting substrate surface layer, improve the work function of anode conducting substrate surface; The described polypropylene film with ITO conductive layer comprises polypropylene film substrate and the ITO conductive layer of evaporation on polypropylene film, and the thickness of described ITO conductive layer is 100nm.
(2) adopt the mode of vacuum evaporation in clean drying and conductive anode layer on anode conducting substrate after surface activation process prepares hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode successively, wherein:
The material of hole injection layer is doping MoO
3n, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (is expressed as MoO
3-NPB), MoO
3doping mass fraction 25%; Vacuum degree during vacuum evaporation is 3 × 10
-5pa, evaporation rate
evaporation thickness is 10nm;
The material of hole transmission layer is 4,4', 4 "-three (carbazole-9-base) triphenylamines (being expressed as TCTA); Vacuum degree during vacuum evaporation is 3 × 10
-5pa, evaporation rate
evaporation thickness is 40nm;
The material of luminescent layer comprises material of main part and guest materials.Material of main part is 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene (being expressed as TPBI), and guest materials is that three (2-phenylpyridines) close iridium and (are expressed as Ir (ppy)
3), and the doping mass fraction of guest materials is 5%; Vacuum degree during vacuum evaporation is 3 × 10
-5pa, evaporation rate
evaporation thickness is 20nm;
The material of electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (being expressed as Bphen); Vacuum degree during vacuum evaporation is 3 × 10
-5pa, evaporation rate
evaporation thickness is 30nm;
The material of electron injecting layer is doping CsN
34,7-diphenyl-1,10-phenanthrolines (be expressed as CsN
3-Bphen), CsN
3doping mass fraction be 25%; Vacuum degree during vacuum evaporation is 3 × 10
-5pa, evaporation rate
evaporation thickness is 20nm;
The material of negative electrode is aluminium (Al), and vacuum degree during vacuum evaporation is 3 × 10
-5pa, evaporation rate
evaporation thickness is 100nm.
(3) adopt the method for vacuum evaporation to prepare protective layer on negative electrode, wherein the material of protective layer is MgF
2, vacuum degree during vacuum evaporation is 5 × 10
-5pa, evaporation rate
evaporation thickness is 300nm.
(4) on described protective layer, prepare barrier layer, obtain organic electroluminescence device; Wherein, the specific solution on described barrier layer is:
A () adopts the mode of electron beam evaporation to make composite barrier on described protective layer, the material of described composite barrier is the HfO of doped with Mn Pc
2, wherein the doping mass fraction of MnPc is 20%, and concrete operations are, by the HfO of doped with Mn Pc
2be placed in the cold-crucible of vacuum evaporation instrument, utilize electron beam directly to heat the HfO making doped with Mn Pc
2carburation by evaporation also forms composite barrier on the protection layer, and background vacuum during evaporation is 2 × 10
-4pa, the thickness of composite barrier is 120nm;
B () adopts the mode of magnetron sputtering to prepare inorganic barrier layer on composite barrier, the material of inorganic barrier layer is HfO
2, concrete operations are, with HfO
2for target, pass into argon gas as noble gas atmosphere, with 2 × 10
-4the background vacuum of Pa forms the inorganic barrier layer that thickness is 120nm on composite barrier;
C () adopts the mode of first spin coating post-exposure to prepare inorganic barrier layer on inorganic barrier layer, wherein the material of inorganic barrier layer is methacrylic resin, concrete operations are, under atmosphere of inert gases, methacrylic resin colloid is spin-coated on inorganic barrier layer, rubberization thickness is 1.2 μm, then uses ultraviolet light (wavelength is 365nm) with 13mW/cm
2intensity exposure solidify 190 seconds;
D () composite barrier, inorganic barrier layer and inorganic barrier layer form a basic structure, repeat step (a) and (b) and (c) four preparations four above-mentioned basic structures, form barrier layer.
(5) cap is selected containing aluminium high temperature resistance polyester film (being abbreviated as containing aluminium PET film); containing aluminium PET film edge-coating epoxy encapsulation glue; then described barrier layer is covered containing aluminium PET film; then epoxy encapsulation glue described in ultraviolet light polymerization is used; thus make to form enclosure space containing aluminium PET film and anode conducting base plate seals; hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer, negative electrode, protective layer and barrier layer are contained in this enclosure space, obtain the organic electroluminescence device sealed.
Organic electroluminescence device prepared by this enforcement, comprise stack gradually anode conducting substrate, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer, negative electrode, protective layer, barrier layer and cap, and this barrier layer comprises composite barrier, inorganic barrier layer and inorganic barrier layer, described composite barrier, inorganic barrier layer and inorganic barrier layer form a basic structure, and described barrier layer is that 4 described basic structures repeat to be formed;
The material of composite barrier is the HfO of doped with Mn Pc
2(MnPc-HfO
2), the doping mass fraction of MnPc is 20%.
The material of inorganic barrier layer is HfO
2.
The material of inorganic barrier layer is methacrylic resin.
Organic electroluminescence device prepared by the present embodiment is flexible organic electroluminescent device, and concrete structure is:
Polypropylene film/ITO/ (MoO
3-NPB)/TCTA/ (TPBI-Ir (ppy)
3)/Bphen/ (CsN
3-Bphen)/Al/MgF
2/ MnPc-HfO
2/ HfO
2/ methacrylic resin/MnPc-HfO
2/ HfO
2/ methacrylic resin/MnPc-HfO
2/ HfO
2/ methacrylic resin/MnPc-HfO
2/ HfO
2/ methacrylic resin/containing aluminium PET film.
Embodiment six
A preparation method for organic electroluminescence device, comprises the steps:
(1) select ito glass substrate as anode conducting substrate, anode conducting substrate is put into acetone, ethanol, deionized water, ethanol successively, each ultrasonic cleaning 5 minutes, then adopt nitrogen to dry up, and put into baking oven and dry stand-by; Then surface activation process is carried out to the anode conducting substrate after cleaning, to increase the oxygen content of anode conducting substrate surface layer, improve the work function of anode conducting substrate surface; Ito glass substrate comprises substrate of glass and evaporation ITO conductive layer on the glass substrate, and the thickness of ITO conductive layer is 100nm.
(2) adopt the mode of vacuum evaporation in clean drying and conductive anode layer on anode conducting substrate after surface activation process prepares hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode successively, wherein:
The material of hole injection layer is doping MoO
3n, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (is expressed as MoO
3-NPB), MoO
3doping mass fraction 25%; Vacuum degree during vacuum evaporation is 3 × 10
-5pa, evaporation rate
evaporation thickness is 10nm;
The material of hole transmission layer is 4,4', 4 "-three (carbazole-9-base) triphenylamines (being expressed as TCTA); Vacuum degree during vacuum evaporation is 3 × 10
-5pa, evaporation rate
evaporation thickness is 40nm;
The material of luminescent layer comprises material of main part and guest materials.Material of main part is 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene (being expressed as TPBI), and guest materials is that three (2-phenylpyridines) close iridium and (are expressed as Ir (ppy)
3), and the doping mass fraction of guest materials is 5%; Vacuum degree during vacuum evaporation is 3 × 10
-5pa, evaporation rate
evaporation thickness is 20nm;
The material of electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (being expressed as Bphen); Vacuum degree during vacuum evaporation is 3 × 10
-5pa, evaporation rate
evaporation thickness is 30nm;
The material of electron injecting layer is doping CsN
34,7-diphenyl-1,10-phenanthrolines (be expressed as CsN
3-Bphen), CsN
3doping mass fraction be 25%; Vacuum degree during vacuum evaporation is 3 × 10
-5pa, evaporation rate
evaporation thickness is 20nm;
The material of negative electrode is aluminium (Al), and vacuum degree during vacuum evaporation is 3 × 10
-5pa, evaporation rate
evaporation thickness is 100nm.
(3) adopt the method for vacuum evaporation to prepare protective layer on negative electrode, wherein the material of protective layer is ZnS, and vacuum degree during vacuum evaporation is 1 × 10
-3pa, evaporation rate
evaporation thickness is 250nm.
(4) on described protective layer, prepare barrier layer, obtain organic electroluminescence device; Wherein, the specific solution on described barrier layer is:
A () adopts the mode of electron beam evaporation to make composite barrier on described protective layer, the material of described composite barrier is the Ta of Ni doped Pc
2o
5, wherein Ta
2o
5doping mass fraction be 20%, concrete operations are, by the Ta of Ni doped Pc
2o
5be placed in the cold-crucible of vacuum evaporation instrument, utilize electron beam directly to heat the Ta making Ni doped Pc
2o
5carburation by evaporation also forms composite barrier on the protection layer, and background vacuum during evaporation is 1 × 10
-3pa, the thickness of composite barrier is 130nm;
B () adopts the mode of magnetron sputtering to prepare inorganic barrier layer on described composite barrier, the material of inorganic barrier layer is Ta
2o
5, concrete operations are, with Ta
2o
5for target, pass into argon gas as noble gas gas, with 1 × 10
-3the background vacuum of Pa forms the inorganic barrier layer that thickness is 120nm on composite barrier;
C () adopts the mode of first spin coating post-exposure to prepare inorganic barrier layer on inorganic barrier layer, wherein the material of inorganic barrier layer is cycloaliphatic epoxy resin, concrete operations are, under atmosphere of inert gases, cycloaliphatic epoxy resin colloid is spin-coated on inorganic barrier layer, rubberization thickness is 1.2 μm, then uses ultraviolet light (wavelength is 365nm) with 12mW/cm
2intensity exposure solidify 150 seconds;
D () composite barrier, inorganic barrier layer and inorganic barrier layer form a basic structure, repeat step (a) and (b) and (c) three preparations three above-mentioned basic structures, form barrier layer.
(5) cap is selected containing aluminium high temperature resistance polyester film (being abbreviated as containing aluminium PET film); containing aluminium PET film edge-coating epoxy encapsulation glue; then described barrier layer is covered containing aluminium PET film; then epoxy encapsulation glue described in ultraviolet light polymerization is used; thus make to form enclosure space containing aluminium PET film and anode conducting base plate seals; hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer, negative electrode, protective layer and barrier layer are contained in this enclosure space, obtain the organic electroluminescence device sealed.
Organic electroluminescence device prepared by this enforcement, comprise stack gradually anode conducting substrate, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer, negative electrode, protective layer, barrier layer and cap, and this barrier layer comprises composite barrier, inorganic barrier layer and inorganic barrier layer, described composite barrier, inorganic barrier layer and inorganic barrier layer form a basic structure, and described barrier layer is that 3 described basic structures repeat to be formed;
The material of composite barrier is the Ta of Ni doped Pc
2o
5(NiPc-Ta
2o
5), the doping mass fraction of NiPc is 20%.
The material of inorganic barrier layer is Ta
2o
5.
The material of inorganic barrier layer is cycloaliphatic epoxy resin.
The concrete structure of organic electroluminescence device prepared by the present embodiment is:
Glass/ITO/ (MoO
3-NPB)/TCTA/ (TPBI-Ir (ppy)
3)/Bphen/ (CsN
3-Bphen)/Al/SiO/NiPc-Ta
2o
5/ Ta
2o
5/ cycloaliphatic epoxy resin/NiPc-Ta
2o
5/ Ta
2o
5/ cycloaliphatic epoxy resin/NiPc-Ta
2o
5/ Ta
2o
5/ cycloaliphatic epoxy resin/containing aluminium PET film.
Effect example
Water vapour permeability tester is adopted to measure the water vapour permeability (WVTR) of the organic electroluminescence device that embodiment one to six is finally prepared respectively, simultaneously at T701000cd/m
2luminescent condition under life-span of the respectively final organic electroluminescence device of preparation of testing example one to six, test result is as shown in table 1:
As can be seen from Table 1, the water vapour permeability of organic electroluminescence device of the present invention reaches as high as 1.6 × 10
-5g/m
2day, the life-span reaches 15, and more than 000 hour (at T701000cd/m
2luminescent condition under).
The above is the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications are also considered as protection scope of the present invention.
Claims (10)
1. an organic electroluminescence device, comprise the anode conducting substrate, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the negative electrode that stack gradually, it is characterized in that, described negative electrode is also provided with protective layer and barrier layer, described barrier layer comprises composite barrier, inorganic barrier layer and inorganic barrier layer, described composite barrier, inorganic barrier layer and inorganic barrier layer form a basic structure, and described barrier layer is that multiple described basic structure repeats to be formed;
The material of described protective layer is CuPc, N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines, oxine aluminium, silicon monoxide, magnesium fluoride or zinc sulphide;
The material of described composite barrier is the oxide of doping phthalocyanine-like compound, and described oxide is SiO
2, Al
2o
3, TiO
2, ZrO
2, HfO
2or Ta
2o
5;
The material of described inorganic barrier layer is the oxide in described composite barrier;
The material of described inorganic barrier layer is polytetrafluoroethylene, methacrylic resin or cycloaliphatic epoxy resin.
2. organic electroluminescence device as claimed in claim 1; it is characterized in that; described barrier layer is also provided with cap; described cap and described anode conducting substrate form enclosure space, and described hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer, negative electrode, protective layer and barrier layer are contained in described enclosure space.
3. organic electroluminescence device as claimed in claim 1, it is characterized in that, described phthalocyanine-like compound is CuPc, Phthalocyanine Zinc, FePC, Cobalt Phthalocyanine, manganese phthalocyanine or Nickel Phthalocyanine, and the doping mass fraction of phthalocyanine-like compound described in described composite barrier is 10% ~ 30%.
4. organic electroluminescence device as claimed in claim 1, is characterized in that, described barrier layer is that 3 ~ 4 described basic structures repeat to be formed.
5. organic electroluminescence device as claimed in claim 1, it is characterized in that, the thickness of described composite barrier is 100nm ~ 150nm, and the thickness of described inorganic barrier layer is 100nm ~ 150nm, and the thickness of described inorganic barrier layer is 1 ~ 1.5 μm.
6. a preparation method for organic electroluminescence device, is characterized in that, comprises the steps:
(1) provide clean dry anode conducting substrate, and in conductive anode layer on described anode conducting substrate successively vacuum evaporation prepare hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode;
(2) method of vacuum evaporation is adopted to prepare protective layer on negative electrode, the material of described protective layer is CuPc, N, N'-diphenyl-N, N'-bis-(1-naphthyls)-1,1'-biphenyl-4,4'-diamines, oxine aluminium, silicon monoxide, magnesium fluoride or zinc sulphide;
(3) on described protective layer, prepare barrier layer, obtain organic electroluminescence device; Wherein, the concrete preparation method on described barrier layer is as follows:
A () adopts the mode of electron beam evaporation to make composite barrier;
B () adopts the mode of magnetron sputtering to make inorganic barrier layer on described composite barrier;
(c) under the atmosphere of inert gas on described inorganic barrier layer spin coating prepare inorganic barrier layer;
D () described composite barrier, inorganic barrier layer and inorganic barrier layer form a basic structure, after step (c), repeat step (a), (b) and (c) prepares multiple described basic structure, obtain the barrier layer containing multiple described basic structure;
Wherein, the material of described composite barrier is the oxide of doping phthalocyanine-like compound, and described oxide is SiO
2, Al
2o
3, TiO
2, ZrO
2, HfO
2or Ta
2o
5, the material of described inorganic barrier layer is the oxide in described composite barrier, and the material of described inorganic barrier layer is polytetrafluoroethylene, methacrylic resin or cycloaliphatic epoxy resin.
7. the preparation method of organic electroluminescence device as claimed in claim 6; it is characterized in that; described preparation method also comprises the steps: to provide cap after step (3); at cap edge-coating packaging plastic; then cap is covered on described barrier layer; by UV-irradiation, packaging plastic is solidified; sealing forms enclosure space; described hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer, negative electrode, protective layer and barrier layer are contained in described enclosure space, obtain the organic electroluminescence device sealed.
8. the preparation method of organic electroluminescence device as claimed in claim 6, it is characterized in that, described phthalocyanine-like compound is CuPc, Phthalocyanine Zinc, FePC, Cobalt Phthalocyanine, manganese phthalocyanine or Nickel Phthalocyanine, and the doping mass fraction of phthalocyanine-like compound described in described composite barrier is 10% ~ 30%.
9. the preparation method of organic electroluminescence device as claimed in claim 6, is characterized in that, described barrier layer is that 3 ~ 4 described basic structures repeat to be formed.
10. the preparation method of organic electroluminescence device as claimed in claim 6, it is characterized in that, the thickness of described composite barrier is 100nm ~ 150nm, and the thickness of described inorganic barrier layer is 100nm ~ 150nm, and the thickness of described inorganic barrier layer is 1 ~ 1.5 μm.
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| CN1567554A (en) * | 2003-06-11 | 2005-01-19 | 胜华科技股份有限公司 | Packaging method of electronic components |
| CN101080121A (en) * | 2007-07-06 | 2007-11-28 | 清华大学 | An organic EL part and its making method |
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