CN103904230B - 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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- CN103904230B CN103904230B CN201210570666.1A CN201210570666A CN103904230B CN 103904230 B CN103904230 B CN 103904230B CN 201210570666 A CN201210570666 A CN 201210570666A CN 103904230 B CN103904230 B CN 103904230B
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- 238000005401 electroluminescence Methods 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title claims abstract description 43
- 239000010410 layer Substances 0.000 claims abstract description 391
- 239000000758 substrate Substances 0.000 claims abstract description 80
- 230000004888 barrier function Effects 0.000 claims abstract description 73
- 239000000463 material Substances 0.000 claims abstract description 64
- 239000011241 protective layer Substances 0.000 claims abstract description 42
- 238000010521 absorption reaction Methods 0.000 claims abstract description 36
- 230000005540 biological transmission Effects 0.000 claims abstract description 34
- 238000002347 injection Methods 0.000 claims abstract description 32
- 239000007924 injection Substances 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 32
- 230000027756 respiratory electron transport chain Effects 0.000 claims abstract description 31
- 229910052751 metal Inorganic materials 0.000 claims abstract description 24
- 239000002184 metal Substances 0.000 claims abstract description 24
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 22
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims abstract description 17
- CSSYLTMKCUORDA-UHFFFAOYSA-N barium(2+);oxygen(2-) Chemical compound [O-2].[Ba+2] CSSYLTMKCUORDA-UHFFFAOYSA-N 0.000 claims abstract description 17
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000292 calcium oxide Substances 0.000 claims abstract description 14
- 229910002665 PbTe Inorganic materials 0.000 claims abstract description 12
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 12
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 12
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 12
- OCGWQDWYSQAFTO-UHFFFAOYSA-N tellanylidenelead Chemical compound [Pb]=[Te] OCGWQDWYSQAFTO-UHFFFAOYSA-N 0.000 claims abstract description 12
- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910004613 CdTe Inorganic materials 0.000 claims abstract description 9
- 229910005642 SnTe Inorganic materials 0.000 claims abstract description 9
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical group [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000001704 evaporation Methods 0.000 claims description 38
- 230000008020 evaporation Effects 0.000 claims description 38
- 238000007738 vacuum evaporation Methods 0.000 claims description 31
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 22
- 229910052757 nitrogen Inorganic materials 0.000 claims description 21
- 239000003292 glue Substances 0.000 claims description 20
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 20
- 229910052782 aluminium Inorganic materials 0.000 claims description 18
- 239000004411 aluminium Substances 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 17
- 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 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 15
- 239000011248 coating agent Substances 0.000 claims description 14
- 238000000576 coating method Methods 0.000 claims description 14
- 239000002131 composite material Substances 0.000 claims description 14
- 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 claims description 10
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 10
- 239000010949 copper Substances 0.000 claims description 10
- 229910052709 silver Inorganic materials 0.000 claims description 10
- 239000004332 silver Substances 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 238000007789 sealing Methods 0.000 claims description 9
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 claims description 7
- 150000005360 2-phenylpyridines Chemical class 0.000 claims description 5
- 229910052741 iridium Inorganic materials 0.000 claims description 5
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 5
- QWODREODAXFISP-UHFFFAOYSA-N n-[4-(4-anilinophenyl)phenyl]-n-phenylnaphthalen-1-amine Chemical compound C=1C=C(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C3=CC=CC=C3C=CC=2)C=CC=1NC1=CC=CC=C1 QWODREODAXFISP-UHFFFAOYSA-N 0.000 claims description 5
- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical compound [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 claims description 5
- -1 negative electrode Substances 0.000 claims description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 4
- 208000034189 Sclerosis Diseases 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 18
- 239000001301 oxygen Substances 0.000 abstract description 18
- 229910052760 oxygen Inorganic materials 0.000 abstract description 18
- 230000003628 erosive effect Effects 0.000 abstract description 6
- 239000011521 glass Substances 0.000 description 59
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 32
- 238000004140 cleaning Methods 0.000 description 32
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 238000010926 purge Methods 0.000 description 16
- 238000001994 activation Methods 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 230000035699 permeability Effects 0.000 description 9
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- 239000008367 deionised water Substances 0.000 description 8
- 239000003822 epoxy resin Substances 0.000 description 8
- 229920000647 polyepoxide Polymers 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 229920006334 epoxy coating Polymers 0.000 description 6
- 230000006378 damage Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- DIVZFUBWFAOMCW-UHFFFAOYSA-N 4-n-(3-methylphenyl)-1-n,1-n-bis[4-(n-(3-methylphenyl)anilino)phenyl]-4-n-phenylbenzene-1,4-diamine Chemical compound CC1=CC=CC(N(C=2C=CC=CC=2)C=2C=CC(=CC=2)N(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=C(C)C=CC=2)C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=C(C)C=CC=2)=C1 DIVZFUBWFAOMCW-UHFFFAOYSA-N 0.000 description 4
- 238000005538 encapsulation Methods 0.000 description 4
- 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 3
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 description 3
- 239000002346 layers by function Substances 0.000 description 3
- 239000011368 organic material Substances 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- QVLNJJLJVMLHFO-UHFFFAOYSA-N [F].[O-2].[Zn+2] Chemical compound [F].[O-2].[Zn+2] QVLNJJLJVMLHFO-UHFFFAOYSA-N 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 2
- 230000009545 invasion Effects 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920006267 polyester film Polymers 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 150000004772 tellurides Chemical class 0.000 description 2
- 125000006617 triphenylamine group Chemical class 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
- 239000011787 zinc oxide Substances 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- HONWGFNQCPRRFM-UHFFFAOYSA-N 2-n-(3-methylphenyl)-1-n,1-n,2-n-triphenylbenzene-1,2-diamine Chemical class CC1=CC=CC(N(C=2C=CC=CC=2)C=2C(=CC=CC=2)N(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 HONWGFNQCPRRFM-UHFFFAOYSA-N 0.000 description 1
- 229910017767 Cu—Al Inorganic materials 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
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- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005525 hole transport Effects 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
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- 238000006116 polymerization reaction Methods 0.000 description 1
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- 239000002344 surface layer Substances 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
-
- 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
- H10K50/846—Passivation; Containers; Encapsulations comprising getter material or desiccants
-
- 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
- H10K50/87—Arrangements for heating or cooling
-
- 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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- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
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; also comprise the protective layer being arranged on cathode surface; protective layer comprises inorganic barrier layer, inorganic barrier layer and moisture absorption layer successively; the material of inorganic barrier layer is metal telluride, and metal telluride is Sb
2te
3, Bi
2te, CdTe, In
2te
3, one or more in SnTe and PbTe; The material of moisture absorption layer is calcium oxide, barium monoxide, strontium oxide strontia or magnesium oxide.Present invention also offers the preparation method of this organic electroluminescence device, the method effectively can reduce steam and oxygen to the erosion of electroluminescent device, improves the life-span of organic electroluminescence device.
Description
Technical field
The present invention relates to organic electroluminescence device, be specifically related to a kind of organic electroluminescence device and preparation method thereof.
Background technology
Organic electroluminescence device (OLED) is a kind of current mode light emitting semiconductor device based on organic material.Its typical structure is between transparent anode and metallic cathode, accompany multilayer organic material film (hole injection layer, hole transmission layer, luminescent layer, electron supplying layer and electron injecting layer), and apply certain voltage when between electrode after, luminescent layer will be luminous.In recent years, organic electroluminescence device because cost of manufacture own is low, the response time is short, luminosity is high, the feature such as wide viewing angle, low driving voltage and energy-conserving and environment-protective received extensive concern in fields such as total colouring, backlight and illuminations, and has been 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.
Glass cover or crown cap is adopted to encapsulate in conventional art, its edge ultraviolet polymerization resin seal, but the glass cover used in this method or crown cap volume are often comparatively large, add the weight of device, and the method can not be applied to flexible organic electroluminescence gives out light the encapsulation of device.
Summary of the invention
For overcoming the defect of above-mentioned prior art, the invention provides a kind of organic electroluminescence device and preparation method thereof.This organic electroluminescence device is provided with protective layer at cathode surface, effectively can reduce water, oxygen isoreactivity material to the erosion of device, thus improves the life-span of organic electroluminescence device significantly.Its preparation method technique is simple, and material is cheap and easy to get, is suitable for suitability for industrialized production.
On the one hand, the invention provides a kind of organic electroluminescence device, comprise the anode conducting substrate stacked gradually, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode, also comprise the protective layer being arranged on described cathode surface, described protective layer comprises inorganic barrier layer successively, inorganic barrier layer and moisture absorption layer, the material of described inorganic barrier layer is CuPc, N, N '-(1-naphthyl)-N, N '-diphenyl-4, 4 '-benzidine, 8-hydroxyquinoline aluminum, 4, 4', 4 "-three (N-3-methylphenyl-N-phenyl is amino) triphenylamine or 4, 7-diphenyl-1, 10-Phen, the material of described inorganic barrier layer is metal telluride, and described metal telluride is Sb
2te
3, Bi
2te, CdTe, In
2te
3, one or more in SnTe and PbTe, the material of described moisture absorption layer is calcium oxide, barium monoxide, strontium oxide strontia or magnesium oxide.
The effect of each functional layer is respectively anode conducting substrate (substrate and anode conducting effect), hole injection layer (injected hole, be conducive to hole to be injected into transferring material from anode), hole transmission layer (transporting holes, be conducive to hole transport in luminescent material), luminescent layer (electronics and hole compound in this layer, then energy trasfer is luminous to light emitting molecule), electron transfer layer (transmission electronic, be conducive to electric transmission in luminescent material), electron injecting layer (injects electronics, be conducive to electronics to be injected into transferring material from anode), negative electrode (power supply electronics is provided for device), the protective layer (protection negative electrode and organic layer) of cathode surface.
Preferably, the thickness of described inorganic barrier layer is 200 ~ 300nm.
Inorganic barrier layer material CuPc (CuPc), N, N '-(1-naphthyl)-N, N '-diphenyl-4,4 '-benzidine (NPB), 8-hydroxyquinoline aluminum (Alq
3), 4,4', 4 "-three (N-3-methylphenyl-N-phenyl amino) triphenylamines (m-MTDATA) or 4,7-diphenyl-1,10-Phen (BCP) are deposited on metal cathode surface by the mode of vacuum evaporation.The existence of inorganic barrier layer can protect each functional layer and negative electrode to exempt from destruction in subsequent operation process.
The material of described inorganic barrier layer is metal telluride, and described metal telluride is Sb
2te
3, Bi
2te, CdTe, In
2te
3, one or more in SnTe and PbTe.The inorganic barrier layer compactness be prepared into tellurides is high, and the ability of waterproof oxygen is strong, effectively can stop the erosion to device inside of external moisture, oxygen, extends the useful life of device.
Preferably, the thickness of inorganic barrier layer is 100 ~ 200nm.
Preferably, the material of described moisture absorption layer is calcium oxide, barium monoxide, strontium oxide strontia or magnesium oxide.Preferably, the thickness of described moisture absorption layer is 100 ~ 200nm.Calcium oxide (CaO), barium monoxide (BaO), strontium oxide strontia (SrO) and magnesium oxide (MgO) are high-hydroscopicity material, thus effectively can absorb the steam of invasion device, reduce the destruction that steam produces device.
Preferably, 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.
Preferably, the material of described hole injection layer is MoO
3adulterate the N of 30% mass fraction, the composite material that N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB) is formed; The material of described hole transmission layer is 4,4', 4 "-three (carbazole-9-base) triphenylamines (TCTA); The material of described luminescent layer is that adulterate three (2-phenylpyridines) of 5% mass fraction of 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene (TPBI) close iridium (Ir (ppy)
3) composite material that formed; The material of described electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (Bphen); The material of described electron injecting layer is that 4,7-diphenyl-1,10-phenanthroline (Bphen) adulterates the CsN of 30% mass fraction
3the composite material formed.
Negative electrode can be non-transparent metals negative electrode (aluminium, silver, gold etc.), also can be transparent cathode (dielectric layer/metal level/dielectric layer structure etc. that dielectric layer tramp metal layer is formed).
Preferably; described organic electroluminescence device also comprises and is arranged on heat dissipating layer on described protective layer and 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 heat dissipating layer are contained in described enclosure space.
Preferably, the material of described heat dissipating layer is one or more combinations in metallic aluminium, silver and copper.Preferably, the thickness of described heat dissipating layer is 200 ~ 500nm.Because device is in the course of the work along with the generation of amount of heat, heat dissipating layer metal has good heat conductivility, can rapidly the heat that device produces in luminescence process be conducted out from device inside in time, thus effectively prevent device over-heat inside and cause the situation of service life reduction, improve the useful life of device.
Cap is set, forms enclosure space with anode conducting substrate, protection can be formed to organic electroluminescence device better.Wherein, described cap is tinsel or contains aluminium high temperature resistance polyester film (being abbreviated as containing aluminium PET film).Preferably, described cap is tinsel.Using tinsel as cap, the heat-sinking capability of organic electroluminescence device can be improved, encapsulation is dropped to minimum on the impact of light efficiency.
Anode conducting substrate and cap can form enclosure space under the adhesive effect of UV glue.Preferably, UV glue is epoxy resin.
On the other hand, the invention provides a kind of preparation method of organic electroluminescence device, comprise the following steps:
(1) provide clean anode electrically-conductive backing plate, on anode substrate, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode are prepared in vacuum evaporation successively;
(2) prepare protective layer on the cathode, obtain organic electroluminescence device; Wherein, described protective layer comprises inorganic barrier layer, inorganic barrier layer and moisture absorption layer, concrete preparation method is as follows: prepare inorganic barrier layer by the mode of vacuum evaporation at described cathode surface evaporation, then adopts magnetron sputtering method to prepare inorganic barrier layer and moisture absorption layer successively on described inorganic barrier layer surface;
The material of described inorganic barrier layer is CuPc, N, N '-(1-naphthyl)-N, N '-diphenyl-4,4 '-benzidine, 8-hydroxyquinoline aluminum, 4,4', 4 "-three (N-3-methylphenyl-N-phenyl is amino) triphenylamine or 4; 7-diphenyl-1,10-Phen; The material of described inorganic barrier layer is metal telluride, and described metal telluride is Sb
2te
3, Bi
2te, CdTe, In
2te
3, one or more in SnTe and PbTe; The material of described moisture absorption layer is calcium oxide, barium monoxide, strontium oxide strontia or magnesium oxide.
Described inorganic barrier layer adopts the mode of vacuum evaporation to be prepared in cathode surface.Preferably, the vacuum degree in described vacuum evaporation process is 1 × 10
-5pa ~ 1 × 10
-3pa, evaporation rate is
Preferably, the thickness of described inorganic barrier layer is 200 ~ 300nm.The existence of inorganic barrier layer can protect each functional layer and negative electrode to exempt from destruction in subsequent operation process.
Described inorganic barrier layer adopts magnetron sputtering method to be prepared in inorganic barrier layer surface.Preferably, the background vacuum in described magnetron sputtering process is 1 × 10
-4pa ~ 1 × 10
-3pa.Preferably, the thickness of inorganic barrier layer is 100 ~ 200nm.The inorganic barrier layer compactness be prepared into tellurides is high, and the ability of waterproof oxygen is strong, effectively can stop the erosion to device inside of external moisture, oxygen, extends the useful life of device.
Described moisture absorption layer adopts magnetron sputtering method to be prepared in inorganic barrier layer surface.Preferably, the background vacuum in described magnetron sputtering process is 1 × 10
-4pa ~ 1 × 10
-3pa.Preferably, the thickness of described moisture absorption layer is 100 ~ 200nm.Calcium oxide, barium monoxide, strontium oxide strontia and magnesium oxide are high-hydroscopicity material, thus effectively can absorb the steam of invasion device, reduce the destruction that steam produces device.
Preferably, 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 substrate carries out following clean operation usually: carry out acetone cleaning → ethanol purge → washed with de-ionized water → ethanol purge successively, all clean with supersonic wave cleaning machine, individual event washing cleaning 5 minutes, and then dry up with nitrogen, stove-drying is stand-by; Again surface activation process is carried out to the substrate after cleaning, to increase the oxygen content of conductive surface layer, improve the work function of conductive layer surface.
Preferably, the material of described hole injection layer is MoO
3adulterate the N of 30% mass fraction, the composite material that N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB) is formed; The material of described hole transmission layer is 4,4', 4 "-three (carbazole-9-base) triphenylamines (TCTA); The material of described luminescent layer is that adulterate three (2-phenylpyridines) of 5% mass fraction of 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene (TPBI) close iridium (Ir (ppy)
3) composite material that formed; The material of described electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (Bphen); The material of described electron injecting layer is that 4,7-diphenyl-1,10-phenanthroline (Bphen) adulterates the CsN of 30% mass fraction
3the composite material formed.
Negative electrode can be non-transparent metals negative electrode (aluminium, silver, gold etc.), also can be transparent cathode (dielectric layer/metal level/dielectric layer structure etc. that dielectric layer tramp metal layer is formed).
Described hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode are prepared by vacuum evaporation.Preferably, the vacuum degree in described vacuum evaporation process is 1 × 10
-5pa ~ 1 × 10
-3pa, evaporation rate is
Preferably, described preparation method comprises further: prepare heat dissipating layer at described moisture absorption layer surface vacuum evaporation; At described heat dissipating layer surface coverage cap; at described cap edge-coating UV glue; by the described UV glue of mode drying sclerosis of ultraviolet curing; sealing forms enclosure space; described hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer, negative electrode, protective layer and heat dissipating layer are contained in described enclosure space, obtain the organic electroluminescence device sealed.
Described heat dissipating layer adopts the mode of vacuum evaporation to be prepared in moisture absorption layer surface.Preferably, the vacuum degree in described vacuum evaporation process is 1 × 10
-5pa ~ 1 × 10
-3pa, evaporation rate is
preferably, the material of described heat dissipating layer is one or more combinations in metallic aluminium, silver and copper.Preferably, the thickness of described heat dissipating layer is 200 ~ 500nm.Because device is in the course of the work along with the generation of amount of heat, heat dissipating layer metal has good heat conductivility, can rapidly the heat that device produces in luminescence process be conducted out from device inside in time, thus effectively prevent device over-heat inside and cause the situation of service life reduction, improve the useful life of device.
Wherein, described cap is tinsel or contains aluminium high temperature resistance polyester film (being abbreviated as containing aluminium PET film).Preferably, described cap is tinsel.Using tinsel as cap, the heat-sinking capability of organic electroluminescence device can be improved, encapsulation is dropped to minimum on the impact of light efficiency.
Anode conducting substrate and cap can form enclosure space under the adhesive effect of UV glue.Preferably, UV glue is epoxy resin.
Preferably, the light intensity of UV light is 15 ~ 25mW/cm
2, the time for exposure is 300 ~ 400s.
The invention provides a kind of organic electroluminescence device and preparation method thereof and there is following beneficial effect:
(1) organic electroluminescence device of the present invention is by arranging protective layer at cathode surface, greatly reduces steam, oxygen to the erosion of organic electroluminescence device, improves the life-span of organic electroluminescence device;
(2) preparation method of the present invention is applicable to the organic electroluminescence device that preparation take electro-conductive glass as anode substrate, is also applicable to prepare the flexible organic electroluminescent device being anode substrate with plastics or metal; And preparation method's technique is simple, easy large area preparation, is suitable for industrialization and uses on a large scale.
Accompanying drawing explanation
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 the embodiment of the present invention, be clearly and completely described the technical scheme in the embodiment of the present invention, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.
Embodiment 1
A preparation method for organic electroluminescence device, comprises the following steps:
(1) ito glass substrate is got, carry out acetone cleaning → ethanol purge → washed with de-ionized water → ethanol purge successively, all clean with supersonic wave cleaning machine, individual event washing cleaning 5 minutes, then dry up with nitrogen, stove-drying is stand-by, then carries out surface activation process to the ito glass substrate after cleaning, to increase the oxygen content of ito glass substrate superficial layer, improve the work function on ito glass substrate surface; ITO thickness 100nm;
(2) adopt the mode of vacuum evaporation in clean drying and ito glass 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 MoO
3the composite material that the NPB adulterating 30% mass fraction is formed (is expressed as MoO
3-NPB), vacuum degree during evaporation is 3 × 10
-5pa, evaporation rate is
evaporation thickness is 10nm;
The material of hole transmission layer is 4,4', 4 "-three (carbazole-9-base) triphenylamine (TCTA), the vacuum degrees 3 × 10 during evaporation
-5pa, evaporation rate is
evaporation thickness is 30nm;
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 is
evaporation thickness is 20nm;
The material of electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (Bphen), the vacuum degree 3 × 10 during vacuum evaporation
-5pa, evaporation rate is
evaporation thickness is 10nm;
The material of electron injecting layer is that 4,7-diphenyl-1,10-phenanthroline (Bphen) adulterates the CsN of 30% mass fraction
3the composite material formed, vacuum degree during vacuum evaporation is 3 × 10
-5pa, evaporation rate is
evaporation thickness is 20nm;
The material of metallic cathode is metallic aluminium (Al), and evaporation thickness is 100nm, and vacuum degree during vacuum evaporation is 3 × 10
-5pa, evaporation rate is
(3) prepare protective layer on the cathode, obtain organic electroluminescence device, wherein, described protective layer comprises inorganic barrier layer, inorganic barrier layer and moisture absorption layer, and concrete preparation method is as follows:
By the mode of vacuum evaporation cathode surface prepare a layer thickness be the CuPc film of 300nm as inorganic barrier layer, vacuum degree control is 1 × 10
-5pa, evaporation rate is
At CuPc film adopt magnetron sputtering method to prepare on the surface Sb that a layer thickness is 100nm
2te
3layer is as inorganic barrier layer, and background vacuum is 1 × 10
-4pa;
Adopt magnetron sputtering method at Sb again
2te
3layer surface preparation a layer thickness be the CaO layer of 100nm as moisture absorption layer, background vacuum is 1 × 10
-4pa.
In order to better protection device construction, improve waterproof oxygen performance, carry out following operation further:
(4) CaO layer surface evaporation prepare a layer thickness be the metallic aluminum of 200nm as heat dissipating layer, vacuum degree control is 1 × 10
-5pa, evaporation rate is
(5) on metallic aluminum, cover a tinsel as cap, at tinsel edge-coating UV glue, UV glue is epoxy resin, and coating thickness is 10 μm, is cured, light intensity 20mW/cm with UV light (λ=365nm)
2, time for exposure 350s, sealing forms enclosure space, is contained in this enclosure space by hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer, aluminium negative electrode, protective layer and heat dissipating layer, is formed and is sealed with organic electroluminescence devices.
Adopt water vapour permeability tester to measure the water vapour permeability of this organic electroluminescence device, record water vapour permeability (WVTR, the g/m of this organic electroluminescence device
2day) be 3.6 × 10
-4, at T701000cd/m
2luminescent condition under test this organic electroluminescence device life-span be 9001 hours.
Fig. 1 is the structural representation of the organic electroluminescence device that the embodiment of the present invention 1 obtains.As shown in Figure 1, the present embodiment organic electroluminescence device, comprises ito glass substrate 1, hole injection layer 2, hole transmission layer 3, luminescent layer 4, electron transfer layer 5, electron injecting layer 6, metallic cathode 7, protective layer 8, heat dissipating layer 9 and cap 10 successively.Ito glass substrate 1 and cap 10 form an enclosure space by epoxy sealing, and hole injection layer 2, hole transmission layer 3, luminescent layer 4, electron transfer layer 5, electron injecting layer 6, metallic cathode 7, protective layer 8 and heat dissipating layer 9 are contained in this enclosure space.Described protective layer 8 comprises the inorganic barrier layer CuPc film 81 that a layer thickness is 300nm successively, and a layer thickness is the Sb of 100nm
2te
3inorganic barrier layer 82 and a layer thickness are the CaO moisture absorption layer 83 of 100nm.
The structure of organic electroluminescence device prepared by the present embodiment is:
Ito glass substrate/(MoO
3-NPB)/TCTA/ (TPBI-Ir (ppy)
3)/Bphen/ (Bphen-CsN
3)/Al/CuPc/Sb
2te
3/ CaO/Al/ tinsel.
Embodiment 2
A preparation method for organic electroluminescence device, comprises the following steps:
(1) ito glass substrate is got, carry out acetone cleaning → ethanol purge → washed with de-ionized water → ethanol purge successively, all clean with supersonic wave cleaning machine, individual event washing cleaning 5 minutes, then dry up with nitrogen, stove-drying is stand-by, then carries out surface activation process to the ito glass substrate after cleaning, to increase the oxygen content of ito glass substrate superficial layer, improve the work function on ito glass substrate surface; ITO thickness 100nm;
(2) adopt the mode of vacuum evaporation in clean drying and ito glass 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, specifically prepare with embodiment 1;
(3) prepare protective layer on the cathode, obtain organic electroluminescence device, wherein, described protective layer comprises inorganic barrier layer, inorganic barrier layer and moisture absorption layer, and concrete preparation method is as follows:
By the mode of vacuum evaporation cathode surface prepare a layer thickness be the NPB film of 250nm as inorganic barrier layer, vacuum degree control is 5 × 10
-5pa, evaporation rate is
At NPB film adopt magnetron sputtering method to prepare on the surface Bi that a layer thickness is 120nm
2te layer is as inorganic barrier layer, and background vacuum is 5 × 10
-4pa;
Adopt magnetron sputtering method at Bi again
2te layer surface preparation a layer thickness be the BaO layer of 200nm as moisture absorption layer, background vacuum is 5 × 10
-4pa;
(4) BaO layer surface evaporation prepare a layer thickness be the metallic silver layer of 500nm as heat dissipating layer, vacuum degree control is 5 × 10
-5pa, evaporation rate is
(5) in metallic silver layer, cover a tinsel as cap, at tinsel edge-coating UV glue, UV glue is epoxy resin, and coating thickness is 10 μm, is cured, light intensity 25mW/cm with UV light (λ=365nm)
2, time for exposure 400s, sealing forms enclosure space, is contained in this enclosure space by hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer, aluminium negative electrode, protective layer and heat dissipating layer, is formed and is sealed with organic electroluminescence devices.
The structure of organic electroluminescence device prepared by the present embodiment is:
Ito glass substrate/(MoO
3-NPB)/TCTA/ (TPBI-Ir (ppy)
3)/Bphen/ (Bphen-CsN
3)/Al/NPB/Bi
2te/BaO/Ag/ tinsel.
Water vapour permeability (WVTR, the g/m of organic electroluminescence device prepared by the present embodiment
2day) be 1.9 × 10
-4, at T701000cd/m
2luminescent condition under life-span of testing be 9112 hours.
Embodiment 3
A preparation method for organic electroluminescence device, comprises the following steps:
(1) ito glass substrate is got, carry out acetone cleaning → ethanol purge → washed with de-ionized water → ethanol purge successively, all clean with supersonic wave cleaning machine, individual event washing cleaning 5 minutes, then dry up with nitrogen, stove-drying is stand-by, then carries out surface activation process to the ito glass substrate after cleaning, to increase the oxygen content of ito glass substrate superficial layer, improve the work function on ito glass substrate surface; ITO thickness 100nm;
(2) adopt the mode of vacuum evaporation in clean drying and ito glass 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, specifically prepare with embodiment 1;
(3) prepare protective layer on the cathode, obtain organic electroluminescence device, wherein, described protective layer comprises inorganic barrier layer, inorganic barrier layer and moisture absorption layer, and concrete preparation method is as follows:
Prepare at cathode surface the Alq that a layer thickness is 200nm by the mode of vacuum evaporation
3film is as inorganic barrier layer, and vacuum degree control is 5 × 10
-5pa, evaporation rate is
At Alq
3film adopt on the surface magnetron sputtering method prepare a layer thickness be the CdTe layer of 200nm as inorganic barrier layer, background vacuum is 5 × 10
-4pa;
Adopt again magnetron sputtering method CdTe layer surface preparation a layer thickness be the SrO layer of 150nm as moisture absorption layer, background vacuum is 5 × 10
-4pa;
(3) SrO layer surface evaporation prepare a layer thickness be the metal copper layer of 300nm as heat dissipating layer, vacuum degree control is 5 × 10
-5pa, evaporation rate is
(5) in metal copper layer, cover a tinsel as cap, at tinsel edge-coating UV glue, UV glue is epoxy resin, and coating thickness is 10 μm, is cured, light intensity 15mW/cm with UV light (λ=365nm)
2, time for exposure 300s, sealing forms enclosure space, is contained in this enclosure space by hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer, aluminium negative electrode, protective layer and heat dissipating layer, is formed and is sealed with organic electroluminescence devices.
The structure of organic electroluminescence device prepared by the present embodiment is:
Ito glass substrate/(MoO
3-NPB)/TCTA/ (TPBI-Ir (ppy)
3)/Bphen/ (Bphen-CsN
3)/Al/Alq
3/ CdTe/SrO/Cu tinsel.
Water vapour permeability (WVTR, the g/m of organic electroluminescence device prepared by the present embodiment
2day) be 1.2 × 10
-4, at T701000cd/m
2luminescent condition under life-span of testing be 9338 hours.
Embodiment 4
A preparation method for organic electroluminescence device, comprises the following steps:
(1) ito glass substrate is got, carry out acetone cleaning → ethanol purge → washed with de-ionized water → ethanol purge successively, all clean with supersonic wave cleaning machine, individual event washing cleaning 5 minutes, then dry up with nitrogen, stove-drying is stand-by, then carries out surface activation process to the ito glass substrate after cleaning, to increase the oxygen content of ito glass substrate superficial layer, improve the work function on ito glass substrate surface; ITO thickness 100nm;
(2) adopt the mode of vacuum evaporation in clean drying and ito glass 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, specifically prepare with embodiment 1;
(3) prepare protective layer on the cathode, obtain organic electroluminescence device, wherein, described protective layer comprises inorganic barrier layer, inorganic barrier layer and moisture absorption layer, and concrete preparation method is as follows:
By the mode of vacuum evaporation cathode surface prepare a layer thickness be the m-MTDATA film of 250nm as inorganic barrier layer, vacuum degree control is 5 × 10
-5pa, evaporation rate is
At m-MTDATA film adopt magnetron sputtering method to prepare on the surface In that a layer thickness is 100nm
2te
3layer is as inorganic barrier layer, and background vacuum is 2 × 10
-4pa;
Adopt magnetron sputtering method at In again
2te
3layer surface preparation a layer thickness be the MgO layer of 100nm as moisture absorption layer, background vacuum is 5 × 10
-4pa;
(4) prepare metallic copper that a layer thickness is 500nm, aluminium alloy layer as heat dissipating layer at MgO layer surface evaporation, the mass ratio of copper and aluminium is 3:1, and vacuum degree control is 5 × 10
-5pa, evaporation rate is
(5) on metallic copper, aluminium alloy layer, cover a tinsel as cap, at tinsel edge-coating UV glue, UV glue is epoxy resin, and coating thickness is 10 μm, is cured, light intensity 20mW/cm with UV light (λ=365nm)
2, time for exposure 350s, sealing forms enclosure space, is contained in this enclosure space by hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer, aluminium negative electrode, protective layer and heat dissipating layer, is formed and is sealed with organic electroluminescence devices.
The structure of organic electroluminescence device prepared by the present embodiment is:
Ito glass substrate/(MoO
3-NPB)/TCTA/ (TPBI-Ir (ppy)
3)/Bphen/ (Bphen-CsN
3)/Al/m-MTDATA/In
2te
3/ MgO/Cu-Al/ tinsel.
Water vapour permeability (WVTR, the g/m of organic electroluminescence device prepared by the present embodiment
2day) be 2.2 × 10
-4, at T701000cd/m
2luminescent condition under life-span of testing be 9093 hours.
Embodiment 5
A preparation method for organic electroluminescence device, comprises the following steps:
(1) ito glass substrate is got, carry out acetone cleaning → ethanol purge → washed with de-ionized water → ethanol purge successively, all clean with supersonic wave cleaning machine, individual event washing cleaning 5 minutes, then dry up with nitrogen, stove-drying is stand-by, then carries out surface activation process to the ito glass substrate after cleaning, to increase the oxygen content of ito glass substrate superficial layer, improve the work function on ito glass substrate surface; ITO thickness 100nm;
(2) adopt the mode of vacuum evaporation in clean drying and ito glass 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, specifically prepare with embodiment 1;
(3) prepare protective layer on the cathode, obtain organic electroluminescence device, wherein, described protective layer comprises inorganic barrier layer, inorganic barrier layer and moisture absorption layer, and concrete preparation method is as follows:
By the mode of vacuum evaporation cathode surface prepare a layer thickness be the BCP film of 250nm as inorganic barrier layer, vacuum degree control is 5 × 10
-5pa, evaporation rate is
BCP film adopt on the surface magnetron sputtering method prepare a layer thickness be the SnTe layer of 150nm as inorganic barrier layer, background vacuum is 2 × 10
-4pa;
Adopt again magnetron sputtering method SnTe layer surface preparation a layer thickness be the CaO layer of 200nm as moisture absorption layer, background vacuum is 5 × 10
-4pa;
(4) CaO layer surface evaporation prepare a layer thickness be the metallic aluminum of 300nm as heat dissipating layer, vacuum degree control is 5 × 10
-5pa, evaporation rate is
(5) on metallic aluminum, cover a tinsel as cap, at tinsel edge-coating UV glue, UV glue is epoxy resin, and coating thickness is 10 μm, is cured, light intensity 20mW/cm with UV light (λ=365nm)
2, time for exposure 340s, sealing forms enclosure space, is contained in this enclosure space by hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer, aluminium negative electrode, protective layer and heat dissipating layer, is formed and is sealed with organic electroluminescence devices.
The structure of organic electroluminescence device prepared by the present embodiment is:
Ito glass substrate/(MoO
3-NPB)/TCTA/ (TPBI-Ir (ppy)
3)/Bphen/ (Bphen-CsN
3)/Al/BCP/SnTe/CaO/Al/ tinsel.
Water vapour permeability (WVTR, the g/m of organic electroluminescence device prepared by the present embodiment
2day) be 3.1 × 10
-4, at T701000cd/m
2luminescent condition under life-span of testing be 9022 hours.
Embodiment 6
A preparation method for organic electroluminescence device, comprises the following steps:
(1) ito glass substrate is got, carry out acetone cleaning → ethanol purge → washed with de-ionized water → ethanol purge successively, all clean with supersonic wave cleaning machine, individual event washing cleaning 5 minutes, then dry up with nitrogen, stove-drying is stand-by, then carries out surface activation process to the ito glass substrate after cleaning, to increase the oxygen content of ito glass substrate superficial layer, improve the work function on ito glass substrate surface; ITO thickness 100nm;
(2) adopt the mode of vacuum evaporation in clean drying and ito glass 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, specifically prepare with embodiment 1;
(3) prepare protective layer on the cathode, obtain organic electroluminescence device, wherein, described protective layer comprises inorganic barrier layer, inorganic barrier layer and moisture absorption layer, and concrete preparation method is as follows:
By the mode of vacuum evaporation cathode surface prepare a layer thickness be the CuPc film of 250nm as inorganic barrier layer, vacuum degree control is 1 × 10
-3pa, evaporation rate is
CuPc film adopt on the surface magnetron sputtering method prepare a layer thickness be the PbTe layer of 120nm as inorganic barrier layer, background vacuum is 1 × 10
-3pa;
Adopt again magnetron sputtering method PbTe layer surface preparation a layer thickness be the BaO layer of 150nm as moisture absorption layer, background vacuum is 1 × 10
-3pa;
(4) BaO layer surface evaporation prepare a layer thickness be the metallic silver layer of 300nm as heat dissipating layer, vacuum degree control is 5 × 10
-5pa, evaporation rate is
(5) in metallic silver layer, cover a tinsel as cap, at tinsel edge-coating UV glue, UV glue is epoxy resin, and coating thickness is 10 μm, is cured, light intensity 18mW/cm with UV light (λ=365nm)
2, time for exposure 360s, sealing forms enclosure space, is contained in this enclosure space by hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer, aluminium negative electrode, protective layer and heat dissipating layer, is formed and is sealed with organic electroluminescence devices.
The structure of organic electroluminescence device prepared by the present embodiment is:
Ito glass substrate/(MoO
3-NPB)/TCTA/ (TPBI-Ir (ppy)
3)/Bphen/ (Bphen-CsN
3)/Al/CuPc/PbTe/BaO/Ag/ tinsel.
Water vapour permeability (WVTR, the g/m of organic electroluminescence device prepared by the present embodiment
2day) be 1.5 × 10
-4, at T701000cd/m
2luminescent condition under life-span of testing be 9203 hours.
Embodiment 7
A preparation method for organic electroluminescence device, comprises the following steps:
(1) ito glass substrate is got, carry out acetone cleaning → ethanol purge → washed with de-ionized water → ethanol purge successively, all clean with supersonic wave cleaning machine, individual event washing cleaning 5 minutes, then dry up with nitrogen, stove-drying is stand-by, then carries out surface activation process to the ito glass substrate after cleaning, to increase the oxygen content of ito glass substrate superficial layer, improve the work function on ito glass substrate surface; ITO thickness 100nm;
(2) adopt the mode of vacuum evaporation in clean drying and ito glass 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, specifically prepare with embodiment 1;
(3) prepare protective layer on the cathode, obtain organic electroluminescence device, wherein, described protective layer comprises inorganic barrier layer, inorganic barrier layer and moisture absorption layer, and concrete preparation method is as follows:
By the mode of vacuum evaporation cathode surface prepare a layer thickness be the CuPc film of 250nm as inorganic barrier layer, vacuum degree control is 1 × 10
-3pa, evaporation rate is
CuPc film adopt on the surface magnetron sputtering method prepare a layer thickness be the PbTe layer of 120nm as inorganic barrier layer, background vacuum is 1 × 10
-3pa;
Adopt again magnetron sputtering method PbTe layer surface preparation a layer thickness be the BaO layer of 150nm as moisture absorption layer, background vacuum is 1 × 10
-3pa;
The structure of organic electroluminescence device prepared by the present embodiment is:
Ito glass substrate/(MoO
3-NPB)/TCTA/ (TPBI-Ir (ppy)
3)/Bphen/ (Bphen-CsN
3)/Al/CuPc/PbTe/BaO.
Water vapour permeability (WVTR, the g/m of organic electroluminescence device prepared by the present embodiment
2day) be 2.1 × 10
-1, at T701000cd/m
2luminescent condition under life-span of testing be 1546 hours.
To sum up; the preparation method of the organic electroluminescence device that the embodiment of the present invention provides, can reduce steam and oxygen effectively to the erosion of organic electroluminescence device, can evacuate heat by heat transfer in time; improve the life-span of organic electroluminescence device significantly, and negative electrode can be protected to exempt from destruction.
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 stacked gradually, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode, it is characterized in that, also comprise the protective layer being arranged on described cathode surface, described protective layer comprises inorganic barrier layer successively, inorganic barrier layer and moisture absorption layer, the material of described inorganic barrier layer is CuPc, N, N '-(1-naphthyl)-N, N '-diphenyl-4, 4 '-benzidine, 8-hydroxyquinoline aluminum, 4, 4', 4 "-three (N-3-methylphenyl-N-phenyl is amino) triphenylamine or 4, 7-diphenyl-1, 10-Phen, the material of described inorganic barrier layer is metal telluride, and described metal telluride is Sb
2te
3, Bi
2te, CdTe, In
2te
3, one or more in SnTe and PbTe, the material of described moisture absorption layer is calcium oxide, barium monoxide, strontium oxide strontia or magnesium oxide.
2. organic electroluminescence device as claimed in claim 1; it is characterized in that; also comprise and be arranged on heat dissipating layer on described protective layer and 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 heat dissipating layer are contained in described enclosure space.
3. organic electroluminescence device as claimed in claim 1, it is characterized in that, the thickness of described inorganic barrier layer is 200 ~ 300nm; The thickness of described inorganic barrier layer is 100 ~ 200nm; The thickness of described moisture absorption layer is 100 ~ 200nm.
4. organic electroluminescence device as claimed in claim 2, is characterized in that, the material of described heat dissipating layer is one or more combinations in metallic aluminium, silver and copper, and the thickness of described heat dissipating layer is 200 ~ 500nm.
5. organic electroluminescence device as claimed in claim 1 or 2, it is characterized in that, the material of described hole injection layer is MoO
3adulterate the N of 30% mass fraction, the composite material that N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines is formed; The material of described hole transmission layer is 4,4', 4 " and-three (carbazole-9-base) triphenylamine; The material of described luminescent layer is that adulterate three (2-phenylpyridines) of 5% mass fraction of 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene close the composite material that iridium formed; The material of described electron transfer layer is 4,7-diphenyl-1,10-phenanthroline; The material of described electron injecting layer is that 4,7-diphenyl-1,10-phenanthroline (Bphen) adulterates the CsN of 30% mass fraction
3the composite material formed.
6. a preparation method for organic electroluminescence device, is characterized in that, comprises the following steps:
(1) provide clean anode electrically-conductive backing plate, on anode substrate, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode are prepared in vacuum evaporation successively;
(2) prepare protective layer on the cathode, obtain organic electroluminescence device; Wherein, described protective layer comprises inorganic barrier layer, inorganic barrier layer and moisture absorption layer, concrete preparation method is as follows: prepare inorganic barrier layer by the mode of vacuum evaporation at described cathode surface evaporation, then adopts magnetron sputtering method to stack gradually on described inorganic barrier layer surface to prepare inorganic barrier layer and moisture absorption layer;
The material of described inorganic barrier layer is CuPc, N, N '-(1-naphthyl)-N, N '-diphenyl-4,4 '-benzidine, 8-hydroxyquinoline aluminum, 4,4', 4 "-three (N-3-methylphenyl-N-phenyl is amino) triphenylamine or 4; 7-diphenyl-1,10-Phen; The material of described inorganic barrier layer is metal telluride, and described metal telluride is Sb
2te
3, Bi
2te, CdTe, In
2te
3, one or more in SnTe and PbTe; The material of described moisture absorption layer is calcium oxide, barium monoxide, strontium oxide strontia or magnesium oxide.
7. the preparation method of organic electroluminescence device as claimed in claim 6, it is characterized in that, described preparation method comprises further: prepare heat dissipating layer at described moisture absorption layer surface vacuum evaporation; At described heat dissipating layer surface coverage cap; at described cap edge-coating UV glue; by the described UV glue of mode drying sclerosis of ultraviolet curing; sealing forms enclosure space; described hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer, negative electrode, protective layer and heat dissipating 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, the thickness of described inorganic barrier layer is 200 ~ 300nm; The thickness of described inorganic barrier layer is 100 ~ 200nm; The thickness of described moisture absorption layer is 100 ~ 200nm.
9. the preparation method of organic electroluminescence device as claimed in claim 7, is characterized in that, the material of described heat dissipating layer is one or more combinations in metallic aluminium, silver and copper, and the thickness of described heat dissipating layer is 200 ~ 500nm.
10. the preparation method of organic electroluminescence device as claimed in claims 6 or 7, it is characterized in that, the material of described hole injection layer is MoO
3adulterate the N of 30% mass fraction, the composite material that N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines is formed; The material of described hole transmission layer is 4,4', 4 " and-three (carbazole-9-base) triphenylamine; The material of described luminescent layer is that adulterate three (2-phenylpyridines) of 5% mass fraction of 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene close the composite material that iridium formed; The material of described electron transfer layer is 4,7-diphenyl-1,10-phenanthroline; The material of described electron injecting layer is that 4,7-diphenyl-1,10-phenanthroline (Bphen) adulterates the CsN of 30% mass fraction
3the composite material formed.
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