CN104518095A - Organic electroluminescent device and preparation method thereof - Google Patents
Organic electroluminescent device and preparation method thereof Download PDFInfo
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- CN104518095A CN104518095A CN201310449906.7A CN201310449906A CN104518095A CN 104518095 A CN104518095 A CN 104518095A CN 201310449906 A CN201310449906 A CN 201310449906A CN 104518095 A CN104518095 A CN 104518095A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 230000004888 barrier function Effects 0.000 claims abstract description 98
- 239000000463 material Substances 0.000 claims abstract description 54
- 239000000203 mixture Substances 0.000 claims abstract description 22
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 14
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 13
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 12
- 239000010936 titanium Substances 0.000 claims abstract description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 9
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910003437 indium oxide Inorganic materials 0.000 claims abstract description 9
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 9
- 239000011787 zinc oxide Substances 0.000 claims abstract description 9
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 8
- IBHBKWKFFTZAHE-UHFFFAOYSA-N n-[4-[4-(n-naphthalen-1-ylanilino)phenyl]phenyl]-n-phenylnaphthalen-1-amine Chemical compound 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 abstract description 7
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000010410 layer Substances 0.000 claims description 185
- 238000005401 electroluminescence Methods 0.000 claims description 45
- 239000000758 substrate Substances 0.000 claims description 31
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 21
- 238000001704 evaporation Methods 0.000 claims description 21
- 230000008020 evaporation Effects 0.000 claims description 21
- 239000002346 layers by function Substances 0.000 claims description 19
- 238000007738 vacuum evaporation Methods 0.000 claims description 18
- 230000005540 biological transmission Effects 0.000 claims description 13
- 238000002347 injection Methods 0.000 claims description 13
- 239000007924 injection Substances 0.000 claims description 13
- 230000027756 respiratory electron transport chain Effects 0.000 claims description 12
- 239000004411 aluminium Substances 0.000 claims description 9
- 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 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 8
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 5
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 3
- 230000004913 activation Effects 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 12
- 239000001301 oxygen Substances 0.000 abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 11
- 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 abstract description 3
- 238000004806 packaging method and process Methods 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- STTGYIUESPWXOW-UHFFFAOYSA-N 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline Chemical compound C=12C=CC3=C(C=4C=CC=CC=4)C=C(C)N=C3C2=NC(C)=CC=1C1=CC=CC=C1 STTGYIUESPWXOW-UHFFFAOYSA-N 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 abstract description 2
- 239000005725 8-Hydroxyquinoline Substances 0.000 abstract 1
- 239000013543 active substance Substances 0.000 abstract 1
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 abstract 1
- 229960003540 oxyquinoline Drugs 0.000 abstract 1
- 230000002035 prolonged effect Effects 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000005538 encapsulation Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 238000011017 operating method Methods 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910052738 indium Inorganic materials 0.000 description 4
- 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 3
- 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 3
- 101000837344 Homo sapiens T-cell leukemia translocation-altered gene protein Proteins 0.000 description 3
- 102100028692 T-cell leukemia translocation-altered gene protein Human genes 0.000 description 3
- 238000001994 activation Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000003628 erosive effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 description 2
- 150000005360 2-phenylpyridines Chemical class 0.000 description 2
- AYTVLULEEPNWAX-UHFFFAOYSA-N cesium;azide Chemical group [Cs+].[N-]=[N+]=[N-] AYTVLULEEPNWAX-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical group [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000000505 pernicious effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 125000006617 triphenylamine group Chemical class 0.000 description 1
- 238000005406 washing Methods 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
-
- 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
- H10K50/00—Organic light-emitting devices
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention provides an organic electroluminescent device with the structure of a packaging layer. The packaging layer comprises an organic barrier layer and an inorganic barrier layer which are alternatively stacked. The material of the organic barrier layer is one from copper phthalocyanine, N,N'-diphenyl-N,N'-di(1-naphthyl)-1,1'-biphenyl-4,4'-diamine, (8-hydroxyquinoline)aluminum, 4,4',4''-tris(N-3-methylphenyl-N-phenylamino)triphenylamine, and 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline; and the material of the inorganic barrier layer is a mixture formed by mixing one from a titanium simple substance , a zirconium simple substance and a hafnium simple substance with one from zinc oxide, aluminum oxide and indium oxide according to a mass ratio of 1:9 to 3:7. According to the invention, the organic electroluminescent device can be effectively prevented from being corroded by active substances such as external water, oxygen and the like, and the service life of the organic electroluminescent device can be prolonged. The invention further provides a preparation method of an organic electroluminescent device. The preparation method is simple in process and low in raw material price, and can be easily prepared in a large area.
Description
Technical field
The present invention relates to field of organic electroluminescence, particularly relate to a kind of organic electroluminescence device and preparation method thereof.
Background technology
Organic electroluminescence device (OLED) is a kind of is luminescent material with organic material, can be the energy conversion device of luminous energy the electric energy conversion applied.It has the outstanding properties such as ultra-thin, self-luminous, response are fast, low-power consumption, has application prospect very widely in fields such as display, illuminations.
Electroluminescent organic material invades responsive especially to oxygen and steam.On the one hand because oxygen is quencher, luminous quantum efficiency can be made significantly to decline, and oxygen also can make its transmittability decline to the oxidation of hole transmission layer; On the other hand, steam can produce hydrolysis to organic compound, its stability is declined greatly, thus causes component failure, shortens the life-span of OLED.Therefore, usually need to carry out packaging protection process to OLED, luminescent device and external environment isolated, divides to prevent water, the intrusion of pernicious gas etc., and then improve stability and the useful life of OLED.
For flexible OLED product, if use traditional OLED encapsulation technology, add encapsulation cover plate in device back, the problems such as weight is large, cost is high, bad mechanical strength can be produced, limit the performance of flexible OLED product.At present, the water oxygen resistant ability of most flexible OLED is not strong, and useful life is shorter, and complicated process of preparation, cost are high.
Summary of the invention
In order to solve the problem; the present invention aims to provide a kind of organic electroluminescence device with encapsulation layer structure; this encapsulation layer structure can reduce outside water, oxygen isoreactivity material effectively to the erosion of organic electroluminescence device; thus effective protection is formed to device organic functional material and electrode, extend the useful life of organic electroluminescence device.Present invention also offers a kind of preparation method of organic electroluminescence device, this preparation method's technique is simple, cheaper starting materials, is easy to large area preparation.
First aspect, the invention provides a kind of organic electroluminescence device, comprise the anode conducting substrate, light emitting functional layer, negative electrode and the encapsulated layer that stack gradually, described light emitting functional layer comprises the hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and the electron injecting layer that stack gradually, it is characterized in that, described encapsulated layer is alternately laminated inorganic barrier layer and inorganic barrier layer;
The material of described inorganic barrier layer is CuPc, N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines, oxine aluminium, 4,4', 4''-tri-(N-3-methylphenyl-N-phenyl is amino) triphenylamine and 2, one in 9-dimethyl-4,7-diphenyl-1,10-phenanthroline;
The material of described inorganic barrier layer is a kind of and a kind of mixture be mixed to form according to mass ratio 1:9 ~ 3:7 in zinc oxide, aluminium oxide and indium oxide in titanium, zirconium, hafnium simple substance.
Arrange encapsulated layer at cathode outer side, encapsulated layer is alternately laminated inorganic barrier layer and inorganic barrier layer.
Preferably, encapsulated layer is inorganic barrier layer and the inorganic matter barrier layer of alternately laminated 4 ~ 6 times.
The material of inorganic barrier layer is CuPc (CuPc), N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB), oxine aluminium (Alq
3), one in 4,4', 4''-tri-(N-3-methylphenyl-N-phenyl amino) triphenylamines (m-MTDATA) and 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP).The material of inorganic barrier layer belongs to can the material of vacuum evaporation, and do not destroy vacuum degree, evenness is good, and stress is little.
Preferably, the thickness of inorganic barrier layer is 200 ~ 300nm.
The material of inorganic barrier layer is one in titanium (Ti), zirconium (Zr), hafnium (Hf) simple substance and zinc oxide (ZnO), aluminium oxide (Al
2o
3) and indium oxide (In
2o
3) in a kind of mixture be mixed to form according to mass ratio 1:9 ~ 3:7.Wherein, zinc oxide, aluminium oxide or indium oxide are material of main part, and titanium, zirconium or hafnium simple substance are guest materials.Simple substance and oxide form a kind of salt, as Zr and Al in the surface energy of inorganic barrier layer
2o
3can form zircoaluminate, the molecules of salt density of formation increases, and compact structure, enhances water oxygen resistant ability.
In inorganic barrier layer, the mass ratio of guest materials and material of main part is 1:9 ~ 3:7.
Preferably, the thickness of inorganic barrier layer is 100 ~ 150nm.
Inorganic barrier layer surfacing, can absorb and disperse the stress of each interlayer, and inorganic barrier layer has good water oxygen barrier performance, and by mode that is organic and inorganic combination, the moisture separator that energy forming property is good, prevents slight crack.
Preferably, the material of anode conducting substrate is conducting glass substrate or conduction organic film substrate.More preferably, anode conducting substrate is indium tin oxide (ITO).
Preferably, the thickness of anode conducting substrate is 100nm.
Light emitting functional layer is arranged on anode conducting substrate.
Light emitting functional layer comprises the hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and the electron injecting layer that stack gradually.
Preferably, the material of hole injection layer is MoO
3the mixture be mixed to form according to mass ratio 3:7 with NPB.
Preferably, the thickness of hole injection layer is 10nm.
Preferably, the material of hole transmission layer is 4,4', 4''-tri-(carbazole-9-base) triphenylamine (TCTA).
Preferably, the thickness of hole transmission layer is 30nm.
Preferably, the material of luminescent layer is that three (2-phenylpyridines) close iridium (Ir (ppy)
3) mixture that is mixed to form according to mass ratio 5:95 with 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene (TPBi).
Preferably, the thickness of luminescent layer is 20nm.
Preferably, the material of electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (Bphen)
Preferably, the thickness of electron transfer layer is 10nm.
Preferably, the material of electron injecting layer is cesium azide (CsN
3) mixture that is mixed to form according to mass ratio 3:7 with Bphen.
Preferably, the thickness of electron injecting layer is 20nm.
Negative electrode is arranged in light emitting functional layer.
Preferably, the material of negative electrode is aluminium (Al).
Preferably, the thickness of negative electrode is 100nm.
Second aspect, the invention provides a kind of preparation method of organic electroluminescence device, comprises the following steps:
S1, provide clean anode conducting substrate, and activation processing is carried out to described anode conducting substrate;
S2, prepare light emitting functional layer and negative electrode in the vacuum evaporation of described anode conducting substrate surface, described light emitting functional layer comprises the hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and the electron injecting layer that stack gradually;
S3, the mode of vacuum evaporation is adopted to prepare inorganic barrier layer at described cathode surface, the material of described inorganic barrier layer is CuPc, N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines, oxine aluminium, 4,4', 4''-tri-(N-3-methylphenyl-N-phenyl is amino) triphenylamine and 2,9-dimethyl-4, one in 7-diphenyl-1,10-phenanthroline;
S4, magnetically controlled sputter method is adopted to prepare inorganic barrier layer on described inorganic barrier layer surface, the material of described inorganic barrier layer is a kind of and a kind of mixture be mixed to form according to mass ratio 1:9 ~ 3:7 in zinc oxide, aluminium oxide and indium oxide in titanium, zirconium, hafnium simple substance, described magnetron sputtering condition is accelerating voltage 300 ~ 800V, magnetic field 50 ~ 200G, power density 1 ~ 40W/cm
2, background vacuum 1 × 10
-5~ 1 × 10
-3pa;
Finally obtain described organic electroluminescence device.
In step S1, by the cleaning of antianode electrically-conductive backing plate, the organic pollution of removing anode conducting substrate surface.
Particularly, the clean operation of anode conducting substrate is: cleaned in supersonic wave cleaning machine with acetone, ethanol, deionized water, ethanol successively by anode conducting substrate, then dry up with nitrogen, stove-drying, obtains the anode conducting substrate cleaned.
Surface activation process is carried out to the anode conducting substrate after cleaning, to increase the oxygen content of conductive surface layer, improves the work function of conductive layer surface.
Preferably, the material of anode conducting substrate is conducting glass substrate or conduction organic film substrate.More preferably, anode conducting substrate is indium tin oxide (ITO).
Preferably, the thickness of anode conducting substrate is 100nm.
In step S2, light emitting functional layer is arranged on anode conducting substrate by vacuum evaporation.
Preferably, during vacuum evaporation light emitting functional layer, condition is vacuum degree 3 × 10
-5pa, evaporation rate
Light emitting functional layer comprises the hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and the electron injecting layer that stack gradually.
Preferably, the material of hole injection layer is MoO
3the mixture be mixed to form according to mass ratio 3:7 with NPB.
Preferably, the thickness of hole injection layer is 10nm.
Preferably, the material of hole transmission layer is 4,4', 4''-tri-(carbazole-9-base) triphenylamine (TCTA).
Preferably, the thickness of hole transmission layer is 30nm.
Preferably, the material of luminescent layer is that three (2-phenylpyridines) close iridium (Ir (ppy)
3) mixture that is mixed to form according to mass ratio 5:95 with 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene (TPBi).
Preferably, the thickness of luminescent layer is 20nm.
Preferably, the material of electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (Bphen)
Preferably, the thickness of electron transfer layer is 10nm.
Preferably, the material of electron injecting layer is cesium azide (CsN
3) mixture that is mixed to form according to mass ratio 3:7 with Bphen.
Preferably, the thickness of electron injecting layer is 20nm.
Negative electrode is arranged in light emitting functional layer by vacuum evaporation.
Preferably, during vacuum evaporation negative electrode, condition is vacuum degree 3 × 10
-5pa, evaporation rate
Preferably, the material of negative electrode is aluminium (Al).
Preferably, the thickness of negative electrode is 100nm.
In step S3, inorganic barrier layer is arranged on cathode surface by vacuum evaporation.
The mode of vacuum evaporation is adopted to prepare inorganic barrier layer.Preferably, preparation process condition is vacuum degree 1 × 10
-5pa ~ 1 × 10
-3pa, evaporation rate
The material of inorganic barrier layer is CuPc, N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines, oxine aluminium, 4,4', 4''-tri-(N-3-methylphenyl-N-phenyl is amino) triphenylamine and 2, one in 9-dimethyl-4,7-diphenyl-1,10-phenanthroline.
Preferably, the thickness of inorganic barrier layer is 200 ~ 300nm.
In step S4, inorganic barrier layer adopts magnetically controlled sputter method to be arranged on inorganic barrier layer surface.
During magnetron sputtering preparation mixing barrier layer, condition is accelerating voltage 300 ~ 800V, magnetic field 50 ~ 200G, power density 1 ~ 40W/cm
2, background vacuum 1 × 10
-5~ 1 × 10
-3pa.
The material of inorganic barrier layer is a kind of and a kind of mixture be mixed to form according to mass ratio 1:9 ~ 3:7 in zinc oxide, aluminium oxide and indium oxide in titanium, zirconium, hafnium simple substance.Wherein, zinc oxide, aluminium oxide or indium oxide are material of main part, and titanium, zirconium or hafnium simple substance are guest materials.
In inorganic barrier layer, the mass ratio of guest materials and material of main part is 1:9 ~ 3:7.
Preferably, the thickness of inorganic barrier layer is 100 ~ 150nm.
Preferably, encapsulated layer is inorganic barrier layer and the inorganic matter barrier layer of alternately laminated 4 ~ 6 times.
The present invention has following beneficial effect:
(1) a kind of organic electroluminescence device with encapsulation layer structure provided by the invention, effectively can prevent outside water, oxygen isoreactivity material to the erosion of organic electroluminescence device, have good sealing and longer useful life.
(2) the OLED encapsulation layer structure that the present invention proposes is applicable to the flexible OLED devices that the OLED prepared with substrate of glass and plastics or metal are prepared for substrate, and this technology is specially adapted to the application of flexible OLED devices.
(3) inorganic barrier layer surfacing, can absorb and disperse the stress of each interlayer, and inorganic barrier layer has good water oxygen barrier performance, and by mode that is organic and inorganic combination, the moisture separator that energy forming property is good, prevents slight crack.。
(4) preparation method of a kind of organic electroluminescence device provided by the invention, this preparation method's technique is simple, cheaper starting materials, is easy to large area preparation.
Accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, be briefly described to the accompanying drawing used required in embodiment or description of the prior art 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 structure chart of the organic electroluminescence device that the embodiment of the present invention 6 provides.
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 kind of organic electroluminescence device, is obtained by following operating procedure:
(1) clean anode conducting substrate is provided:
Cleaned in supersonic wave cleaning machine with acetone, ethanol, deionized water, ethanol successively by ito glass substrate, individual event washing cleaning 5 minutes, then dry up with nitrogen, stove-drying is stand-by; Surface activation process is carried out to the ito glass after cleaning; ITO thickness is 100nm;
(2) vacuum evaporation light emitting functional layer on ito glass substrate:
Particularly, light emitting functional layer comprises hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer;
The preparation of hole injection layer: by MoO
3the mixture be mixed to get according to mass ratio 3:7 with NPB as the material of hole injection layer, thickness 10nm, vacuum degree 3 × 10
-5pa, evaporation rate
The preparation of hole transmission layer: adopt 4,4', 4''-tri-(carbazole-9-base) triphenylamine (TCTA) as hole mobile material, vacuum degree 3 × 10
-5pa, evaporation rate
evaporation thickness 30nm;
The preparation of luminescent layer: adopt Ir (ppy)
3the mixture be mixed to form according to mass ratio 5:95 with TPBi as the material of luminescent layer, vacuum degree 3 × 10
-5pa, evaporation rate
evaporation thickness 20nm;
The preparation of electron transfer layer: evaporation one deck 4,7-diphenyl-1,10-phenanthroline (Bphen) as electron transport material, vacuum degree 3 × 10
-5pa, evaporation rate
evaporation thickness 10nm;
The preparation of electron injecting layer: by CsN
3the mixture be mixed to form according to mass ratio 3:7 with Bphen as the material of electron injecting layer, vacuum degree 3 × 10
-5pa, evaporation rate
evaporation thickness 20nm;
(3) negative electrode is prepared on light emitting functional layer surface:
Metallic cathode adopts aluminium (Al), and thickness is 100nm, vacuum degree 3 × 10
-5pa, evaporation rate
(4) encapsulated layer is prepared at cathode outer side:
Encapsulated layer is inorganic barrier layer and the inorganic matter barrier layer of alternately laminated 6 times;
The making of inorganic barrier layer: adopt the mode of vacuum evaporation to prepare one deck CuPc on negative electrode, vacuum degree 1 × 10
-5pa, evaporation rate
thickness 300nm;
The making of inorganic barrier layer: the mixture be mixed to form according to mass ratio 1:4 by Ti and ZnO, as the material of inorganic barrier layer, adopts magnetically controlled sputter method to make, accelerating voltage 450V, magnetic field 150G, power density 25W/cm
2, background vacuum 1 × 10
-5pa, thickness 150nm;
Final obtained organic electroluminescence device.
Embodiment 2:
A kind of organic electroluminescence device, is obtained by following operating procedure:
(1), (2), (3) are with embodiment 1;
(4) encapsulated layer is prepared at cathode outer side:
Encapsulated layer is inorganic barrier layer and the inorganic matter barrier layer of alternately laminated 6 times;
The making of inorganic barrier layer: adopt the mode of vacuum evaporation to prepare one deck NPB on negative electrode, vacuum degree 5 × 10
-5pa, evaporation rate
thickness 250nm;
The making of inorganic barrier layer: by Zr and Al
2o
3the mixture be mixed to form according to mass ratio 3:7, as the material of inorganic barrier layer, adopts magnetically controlled sputter method to make, accelerating voltage 300V, magnetic field 200G, power density 1W/cm
2, background vacuum 1 × 10
-5pa, thickness 150nm;
Final obtained organic electroluminescence device.
Embodiment 3:
A kind of organic electroluminescence device, is obtained by following operating procedure:
(1), (2), (3) are with embodiment 1;
(4) encapsulated layer is prepared at cathode outer side:
Encapsulated layer is inorganic barrier layer and the inorganic matter barrier layer of alternately laminated 6 times;
The making of inorganic barrier layer: adopt the mode of vacuum evaporation to prepare one deck Alq on negative electrode
3, vacuum degree 5 × 10
-5pa, evaporation rate
thickness 200nm;
The making of inorganic barrier layer: by Hf and In
2o
3the mixture be mixed to form according to mass ratio 1:9, as the material of inorganic barrier layer, adopts magnetically controlled sputter method to make, accelerating voltage 800V, magnetic field 50G, power density 40W/cm
2, background vacuum 5 × 10
-5pa, thickness 100nm;
Final obtained organic electroluminescence device.
Embodiment 4:
A kind of organic electroluminescence device, is obtained by following operating procedure:
(1), (2), (3) are with embodiment 1;
(4) encapsulated layer is prepared at cathode outer side:
Encapsulated layer is inorganic barrier layer and the inorganic matter barrier layer of alternately laminated 5 times;
The making of inorganic barrier layer: adopt the mode of vacuum evaporation to prepare one deck m-MTDATA on negative electrode, vacuum degree 5 × 10
-5pa, evaporation rate
thickness 250nm;
The making of inorganic barrier layer: by Hf and In
2o
3the mixture be mixed to form according to mass ratio 1:4, as the material of inorganic barrier layer, adopts magnetically controlled sputter method to make, accelerating voltage 600V, magnetic field 120G, power density 15W/cm
2, background vacuum 5 × 10
-5pa, thickness 120nm;
Final obtained organic electroluminescence device.
Embodiment 5:
A kind of organic electroluminescence device, is obtained by following operating procedure:
(1), (2), (3) are with embodiment 1;
(4) encapsulated layer is prepared at cathode outer side:
Encapsulated layer is inorganic barrier layer and the inorganic matter barrier layer of alternately laminated 5 times;
The making of inorganic barrier layer: adopt the mode of vacuum evaporation to prepare one deck BCP on negative electrode, vacuum degree 5 × 10
-5pa, evaporation rate
thickness 250nm;
The making of inorganic barrier layer: by Hf and In
2o
3the mixture be mixed to form according to mass ratio 3:17, as the material of inorganic barrier layer, adopts magnetically controlled sputter method to make, accelerating voltage 450V, magnetic field 150G, power density 25W/cm
2, background vacuum 5 × 10
-5pa, thickness 130nm;
Final obtained organic electroluminescence device.
Embodiment 6
A kind of organic electroluminescence device, is obtained by following operating procedure:
(1), (2), (3) are with embodiment 1;
(4) encapsulated layer is prepared at cathode outer side:
Encapsulated layer is inorganic barrier layer and the inorganic matter barrier layer of alternately laminated 4 times;
The making of inorganic barrier layer: adopt the mode of vacuum evaporation to prepare one deck CuPc on negative electrode, vacuum degree 1 × 10
-3pa, evaporation rate
thickness 250nm;
The making of inorganic barrier layer: by Hf and In
2o
3the mixture be mixed to form according to mass ratio 3:17, as the material of inorganic barrier layer, adopts magnetically controlled sputter method to make, accelerating voltage 450V, magnetic field 150G, power density 25W/cm
2, background vacuum 1 × 10
-3pa, thickness 120nm;
Final obtained organic electroluminescence device.
Fig. 1 is the structural representation of the organic electroluminescence device of the present embodiment.As shown in Figure 1, the structure of this organic electroluminescence device comprises the anode conducting substrate 10, light emitting functional layer 20, negative electrode 30, the encapsulated layer 40(that stack gradually and comprises inorganic barrier layer 401, inorganic barrier layer 402, inorganic barrier layer 403, inorganic barrier layer 404, inorganic barrier layer 405, inorganic barrier layer 406, inorganic barrier layer 407, inorganic barrier layer 408).
Effect example
Adopt the vapor permeability (WVTR) of Ca film electrical testing system testing organic electroluminescence device, and test life-span (the T70@1000cd/m of organic electroluminescence device
2), from original intensity 1000cd/m
2decay to the time needed for 70%.WVTR and the life-span of the organic electroluminescence device of the embodiment of the present invention 1 ~ 6 preparation are as shown in table 1.As can be seen from the table, WVTR all remains on 10
-4g/ (m
2day) order of magnitude, minimumly reaches 5.9 × 10
-4g/ (m
2day), the real requirement of flexible OLED can be met.The life time of organic electroluminescence device is the longest reaches 4220 hours.This illustrates, the organic electroluminescence device of encapsulation layer structure that prepared by the present invention have can prevent outside water, oxygen isoreactivity material to the erosion of organic electroluminescence device effectively, has good sealing and longer useful life.
Table 1
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (9)
1. an organic electroluminescence device, comprise the anode conducting substrate, light emitting functional layer, negative electrode and the encapsulated layer that stack gradually, described light emitting functional layer comprises the hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and the electron injecting layer that stack gradually, it is characterized in that, described encapsulated layer is alternately laminated inorganic barrier layer and inorganic barrier layer;
The material of described inorganic barrier layer is CuPc, N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines, oxine aluminium, 4,4', 4''-tri-(N-3-methylphenyl-N-phenyl is amino) triphenylamine and 2, one in 9-dimethyl-4,7-diphenyl-1,10-phenanthroline;
The material of described inorganic barrier layer is a kind of and a kind of mixture be mixed to form according to mass ratio 1:9 ~ 3:7 in zinc oxide, aluminium oxide and indium oxide in titanium, zirconium, hafnium simple substance.
2. organic electroluminescence device as claimed in claim 1, it is characterized in that, described encapsulated layer is inorganic barrier layer and the inorganic matter barrier layer of alternately laminated 4 ~ 6 times.
3. organic electroluminescence device as claimed in claim 1, it is characterized in that, the thickness of described inorganic barrier layer is 200 ~ 300nm.
4. organic electroluminescence device as claimed in claim 1, it is characterized in that, the thickness of described inorganic barrier layer is 100 ~ 150nm.
5. a preparation method for organic electroluminescence device, is characterized in that, comprises the following steps:
S1, provide clean anode conducting substrate, and activation processing is carried out to described anode conducting substrate;
S2, prepare light emitting functional layer and negative electrode in the vacuum evaporation of described anode conducting substrate surface, described light emitting functional layer comprises the hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and the electron injecting layer that stack gradually;
S3, the mode of vacuum evaporation is adopted to prepare inorganic barrier layer at described cathode surface, the material of described inorganic barrier layer is CuPc, N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines, oxine aluminium, 4,4 ', 4 ' '-three (N-3-methylphenyl-N-phenyl is amino) triphenylamine and 2,9-dimethyl-4, one in 7-diphenyl-1,10-phenanthroline;
S4, magnetically controlled sputter method is adopted to prepare inorganic barrier layer on described inorganic barrier layer surface, the material of described inorganic barrier layer is a kind of and a kind of mixture be mixed to form according to mass ratio 1:9 ~ 3:7 in zinc oxide, aluminium oxide and indium oxide in titanium, zirconium, hafnium simple substance, described magnetron sputtering condition is accelerating voltage 300 ~ 800V, magnetic field 50 ~ 200G, power density 1 ~ 40W/cm
2, background vacuum 1 × 10
-5~ 1 × 10
-3pa;
Finally obtain described organic electroluminescence device.
6. the preparation method of organic electroluminescence device as claimed in claim 5, it is characterized in that, described inorganic barrier layer preparation process condition is vacuum degree 1 × 10
-5pa ~ 1 × 10
-3pa, evaporation rate
7. the preparation method of organic electroluminescence device as claimed in claim 5, it is characterized in that, described encapsulated layer is inorganic barrier layer and the inorganic matter barrier layer of alternately laminated 4 ~ 6 times.
8. the preparation method of organic electroluminescence device as claimed in claim 5, it is characterized in that, the thickness of described inorganic barrier layer is 200 ~ 300nm.
9. the preparation method of organic electroluminescence device as claimed in claim 5, it is characterized in that, the thickness of described inorganic barrier layer is 100 ~ 150nm.
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| CN108448006A (en) * | 2018-03-29 | 2018-08-24 | 京东方科技集团股份有限公司 | Packaging structure, electronic device and packaging method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108448006A (en) * | 2018-03-29 | 2018-08-24 | 京东方科技集团股份有限公司 | Packaging structure, electronic device and packaging method |
| US10879488B2 (en) | 2018-03-29 | 2020-12-29 | Boe Technology Group Co., Ltd. | Encapsulation structure, electronic device and encapsulation method |
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