CN104037348A - Stacked organic light emitting device and preparation method thereof - Google Patents
Stacked organic light emitting device and preparation method thereof Download PDFInfo
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- CN104037348A CN104037348A CN201310071516.0A CN201310071516A CN104037348A CN 104037348 A CN104037348 A CN 104037348A CN 201310071516 A CN201310071516 A CN 201310071516A CN 104037348 A CN104037348 A CN 104037348A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 161
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 142
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 142
- 229910052751 metal Inorganic materials 0.000 claims abstract description 61
- 239000002184 metal Substances 0.000 claims abstract description 61
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical class [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims abstract description 34
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000001704 evaporation Methods 0.000 claims description 180
- 230000008020 evaporation Effects 0.000 claims description 180
- 230000027756 respiratory electron transport chain Effects 0.000 claims description 81
- 230000005540 biological transmission Effects 0.000 claims description 80
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 claims description 50
- 238000002347 injection Methods 0.000 claims description 41
- 239000007924 injection Substances 0.000 claims description 41
- 239000002131 composite material Substances 0.000 claims description 32
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 32
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical group O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 26
- 229910052782 aluminium Inorganic materials 0.000 claims description 24
- 239000004411 aluminium Substances 0.000 claims description 24
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 24
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [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 23
- 239000000203 mixture Substances 0.000 claims description 22
- 239000010931 gold Substances 0.000 claims description 21
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 20
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims description 20
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 16
- 229910052709 silver Inorganic materials 0.000 claims description 16
- 239000004332 silver Substances 0.000 claims description 16
- 229910052792 caesium Inorganic materials 0.000 claims description 15
- 229920002554 vinyl polymer Polymers 0.000 claims description 15
- 229910021541 Vanadium(III) oxide Inorganic materials 0.000 claims description 13
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical group [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 13
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 13
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 12
- 229910052737 gold Inorganic materials 0.000 claims description 12
- 229910052697 platinum Inorganic materials 0.000 claims description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 10
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 10
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims description 10
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 claims description 10
- 229910052725 zinc Inorganic materials 0.000 claims description 10
- 239000011701 zinc Substances 0.000 claims description 10
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Natural products C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims description 9
- 229910021542 Vanadium(IV) oxide Inorganic materials 0.000 claims description 8
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 8
- 238000007738 vacuum evaporation Methods 0.000 claims description 8
- GRUMUEUJTSXQOI-UHFFFAOYSA-N vanadium dioxide Chemical compound O=[V]=O GRUMUEUJTSXQOI-UHFFFAOYSA-N 0.000 claims description 8
- 239000004305 biphenyl Substances 0.000 claims description 7
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 claims description 6
- 238000000605 extraction Methods 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 414
- ZVFQEOPUXVPSLB-UHFFFAOYSA-N 3-(4-tert-butylphenyl)-4-phenyl-5-(4-phenylphenyl)-1,2,4-triazole Chemical compound C1=CC(C(C)(C)C)=CC=C1C(N1C=2C=CC=CC=2)=NN=C1C1=CC=C(C=2C=CC=CC=2)C=C1 ZVFQEOPUXVPSLB-UHFFFAOYSA-N 0.000 description 18
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 18
- 239000011521 glass Substances 0.000 description 17
- 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 13
- 101000837344 Homo sapiens T-cell leukemia translocation-altered gene protein Proteins 0.000 description 13
- 102100028692 T-cell leukemia translocation-altered gene protein Human genes 0.000 description 13
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- DHDHJYNTEFLIHY-UHFFFAOYSA-N 4,7-diphenyl-1,10-phenanthroline Chemical compound C1=CC=CC=C1C1=CC=NC2=C1C=CC1=C(C=3C=CC=CC=3)C=CN=C21 DHDHJYNTEFLIHY-UHFFFAOYSA-N 0.000 description 11
- 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 10
- 238000005401 electroluminescence Methods 0.000 description 10
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical group [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 9
- 239000000075 oxide glass Substances 0.000 description 9
- HXWWMGJBPGRWRS-CMDGGOBGSA-N 4- -2-tert-butyl-6- -4h-pyran Chemical compound O1C(C(C)(C)C)=CC(=C(C#N)C#N)C=C1\C=C\C1=CC(C(CCN2CCC3(C)C)(C)C)=C2C3=C1 HXWWMGJBPGRWRS-CMDGGOBGSA-N 0.000 description 8
- ZOKIJILZFXPFTO-UHFFFAOYSA-N 4-methyl-n-[4-[1-[4-(4-methyl-n-(4-methylphenyl)anilino)phenyl]cyclohexyl]phenyl]-n-(4-methylphenyl)aniline Chemical compound C1=CC(C)=CC=C1N(C=1C=CC(=CC=1)C1(CCCCC1)C=1C=CC(=CC=1)N(C=1C=CC(C)=CC=1)C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 ZOKIJILZFXPFTO-UHFFFAOYSA-N 0.000 description 8
- 239000010955 niobium Substances 0.000 description 8
- MQCHTHJRANYSEJ-UHFFFAOYSA-N n-[(2-chlorophenyl)methyl]-1-(3-methylphenyl)benzimidazole-5-carboxamide Chemical compound CC1=CC=CC(N2C3=CC=C(C=C3N=C2)C(=O)NCC=2C(=CC=CC=2)Cl)=C1 MQCHTHJRANYSEJ-UHFFFAOYSA-N 0.000 description 7
- RAPHUPWIHDYTKU-WXUKJITCSA-N 9-ethyl-3-[(e)-2-[4-[4-[(e)-2-(9-ethylcarbazol-3-yl)ethenyl]phenyl]phenyl]ethenyl]carbazole Chemical compound C1=CC=C2C3=CC(/C=C/C4=CC=C(C=C4)C4=CC=C(C=C4)/C=C/C=4C=C5C6=CC=CC=C6N(C5=CC=4)CC)=CC=C3N(CC)C2=C1 RAPHUPWIHDYTKU-WXUKJITCSA-N 0.000 description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000003599 detergent Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 150000004880 oxines Chemical group 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- 238000001259 photo etching Methods 0.000 description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 6
- TZRXHJWUDPFEEY-UHFFFAOYSA-N Pentaerythritol Tetranitrate Chemical compound [O-][N+](=O)OCC(CO[N+]([O-])=O)(CO[N+]([O-])=O)CO[N+]([O-])=O TZRXHJWUDPFEEY-UHFFFAOYSA-N 0.000 description 5
- JYMITAMFTJDTAE-UHFFFAOYSA-N aluminum zinc oxygen(2-) Chemical compound [O-2].[Al+3].[Zn+2] JYMITAMFTJDTAE-UHFFFAOYSA-N 0.000 description 5
- SNTWKPAKVQFCCF-UHFFFAOYSA-N 2,3-dihydro-1h-triazole Chemical compound N1NC=CN1 SNTWKPAKVQFCCF-UHFFFAOYSA-N 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 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 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 239000002346 layers by function Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
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- 238000010276 construction Methods 0.000 description 2
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- 238000010168 coupling process Methods 0.000 description 2
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- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 238000004770 highest occupied molecular orbital Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
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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
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2101/00—Properties of the organic materials covered by group H10K85/00
- H10K2101/40—Interrelation of parameters between multiple constituent active layers or sublayers, e.g. HOMO values in adjacent layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/16—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering
- H10K71/166—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering using selective deposition, e.g. using a mask
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Manufacturing & Machinery (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention discloses a stacked organic light emitting device and a preparation method thereof. The stacked organic light emitting device comprises a charge generating layer. The charge generating layer comprises a first metal oxide layer, a metal layer and a second metal oxide layer which are sequentially stacked. The first metal oxide layer is made of a mixed material formed by doping metal cesium salt in a bipolar metal oxide according to the mass ratio of 1-3:5. The second metal oxide layer is made of a mixed material formed by doping a phthalocyanine material in a metal oxide with the refractive index being 1.9-2.2 according to the mass ratio of 1-4:20. The stacked organic light emitting device of the invention has strong electron transport capability, good conductive performance and high light extraction efficiency. The preparation method is simple to operate, is easily automated, and is suitable for large-scale industrialized production.
Description
Technical field
The present invention relates to organic electroluminescent field, particularly a kind of laminated organic electroluminescent device and preparation method thereof.
Background technology
Organic electroluminescence device (Organic light-emitting Devices, be called for short OLEDs) be a kind of multilayer luminescent device that uses luminous organic material, comprise the anode layer, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and the negative electrode that stack gradually.The principle of luminosity of OLED is based under the effect of extra electric field, electronics is injected into organic lowest unocccupied molecular orbital (LUMO) from negative electrode, and hole is injected into organic highest occupied molecular orbital (HOMO) from anode, meet at luminescent layer in electronics and hole, compound, formation exciton, and exciton moves under electric field action, and energy is passed to luminescent material, excitation electron is from ground state transition to excitation state, excited energy, by Radiation-induced deactivation, produces photon, discharges luminous energy.Luminous efficiency is high, driving voltage is low, visual angle is wide, glow color range of choice is wide, manufacture craft is simple because it has for OLED, and easily realize the features such as panchromatic and flexible demonstration, cause increasing concern in illumination and flat panel display field, and be considered to be most likely at the device of new generation that occupies dominance on following illumination and display device market.
1987, Eastman Kodak company of the U.S. utilized ultrathin film technology to prepare high brightness, and OLED has been advanced a new epoch by high efficiency double-deck organic electroluminescence device.In order to improve luminosity and luminous efficiency, increasing research is taking laminated device as main, this structure is normally together in series several luminescence units as articulamentum with charge generation layer, compared with unit component, multilayer devices often has current efficiency and luminosity at double, is one of leading developing direction of high brightness OLED.The laminated organic electroluminescent device of prior art be generally utilize two or more to have that hole is injected or material of electronic injection as charge generating layers (as Cs:BCP/V
2o
5), or N-shaped and p-type doped layer as charge generation layer (as N-shaped (Alq
3: Li) and p-type (NPB:FeCl
3)) or Al-WO
3-Au etc. are linked in sequence multiple luminescence units and form, but this device light transmission rate and luminous efficiency are all lower.
Summary of the invention
The object of the invention is to overcome above-mentioned technological deficiency, a kind of laminated organic electroluminescent device and preparation method thereof is provided.The charge generation layer of this laminated organic electroluminescent device comprises the metal oxide layer of the bipolarity metal oxide layer of mixing cesium salt, metal level and the doping phthalocyanine material that stack gradually, and electron transport ability is strong, good conductivity, and light extraction efficiency is high.
First aspect, the invention provides a kind of laminated organic electroluminescent device, comprise the anode, hole injection layer, the first hole transmission layer, the first luminescent layer, the first electron transfer layer, charge generation layer, the second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer and the negative electrode that stack gradually; Described charge generation layer comprises the first metal oxide layer, metal level and the second metal oxide layer that stack gradually, wherein,
The material of described the first metal oxide layer is that metal cesium salt mixes the composite material forming in bipolarity metal oxide according to the ratio of mass ratio 1～3:5;
The material of described metal level is silver, aluminium, platinum or gold;
To be phthalocyanine material mix refractive index according to the ratio of mass ratio 1～4:20 to the material of described the second metal oxide layer is the composite material forming in 1.9～2.2 metal oxide.
Preferably, in described the first metal oxide layer, described metal cesium salt is cesium carbonate (Cs
2cO
3), phosphoric acid caesium (Cs
3pO
4) or cesium fluoride (CsF), described bipolarity metal oxide is molybdenum trioxide (MoO
3), tungstic acid (WO
3) or vanadic oxide (V
2o
5).
Preferably, in described the second metal oxide layer, described phthalocyanine material is CuPc (CuPc) or Phthalocyanine Zinc (ZnPc), and the metal oxide that described refractive index is 1.9～2.2 is tantalum pentoxide (Ta
2o
5), niobium pentaoxide (Nb
2o
5) or vanadium dioxide (VO
2).
Preferably, the thickness of described the first metal oxide layer is 5～30nm, and the thickness of described metal level is 1～10nm, and the thickness of described the second metal oxide layer is 5～20nm.
Preferably, described anode is indium tin oxide glass (ITO), aluminium zinc oxide glass (AZO) or indium-zinc oxide glass (IZO).More preferably, described anode is indium tin oxide glass (ITO).
Preferably, the material of described hole injection layer is molybdenum trioxide (MoO
3), tungstic acid (WO
3) or vanadic oxide (V
2o
5).More preferably, the material of described hole injection layer is tungstic acid (WO
3).
Preferably, the thickness of described hole injection layer is 20～80nm.More preferably, the thickness of described hole injection layer is 30nm.
Preferably, the material of described the first hole transmission layer and the second hole transmission layer is all selected from 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane (TAPC), 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA) and N, N '-(1-naphthyl)-N, N '-diphenyl-4, any one in 4 '-benzidine (NPB).
More preferably, the material of described the first hole transmission layer is 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA), the material of described the second hole transmission layer is N, N '-(1-naphthyl)-N, N '-diphenyl-4,4 '-benzidine (NPB).
Preferably, the thickness of described the first hole transmission layer and the second hole transmission layer is 20～60nm.More preferably, the thickness of described the first hole transmission layer and the second hole transmission layer is 25nm.
Preferably, the material of described the first luminescent layer and the second luminescent layer is all selected from 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans (DCJTB), 9,10-bis--β-naphthylene anthracene (ADN), 4, two (the 9-ethyl-3-carbazole vinyl)-1 of 4'-, 1'-biphenyl (BCzVBi) and oxine aluminium (Alq
3) in any one.
More preferably, the material of described the first luminescent layer and the second luminescent layer is oxine aluminium (Alq
3).
Preferably, the thickness of described the first luminescent layer and the second luminescent layer is 5～40nm.More preferably, the thickness of described the first luminescent layer and the second luminescent layer is 10nm.
Preferably, the material of described the first electron transfer layer and the second electron transfer layer is all selected from 4,7-diphenyl-1,10-phenanthroline (Bphen), 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1, any one in 2,4-triazole (TAZ) and N-aryl benzimidazole (TPBI).
More preferably, described the first electron transfer layer material be 4,7-diphenyl-1,10-phenanthroline (Bphen), the material of described the second electron transfer layer is 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole (TAZ).
Preferably, the thickness of described the first electron transfer layer and the second electron transfer layer is 40～200nm.More preferably, the thickness of described the first electron transfer layer and the second electron transfer layer is 100nm.
Preferably, the material of described electron injecting layer is cesium carbonate (Cs
2cO
3), cesium fluoride (CsF), nitrine caesium (CsN
3) or lithium fluoride (LiF).More preferably, the material of described electron injecting layer is lithium fluoride (LiF).
Preferably, the thickness of described electron injecting layer is 0.5～10nm.More preferably, the thickness of described electron injecting layer is 0.7nm.
Preferably, the material of described negative electrode is silver (Ag), aluminium (Al), platinum (Pt) or gold (Au).More preferably, the material of described negative electrode is silver (Ag).
Preferably, the thickness of described negative electrode is 60～300nm.More preferably, the thickness of described negative electrode is 150nm.
Laminated organic electroluminescent device of the present invention, comprise charge generation layer, described charge generation layer comprises the first metal oxide layer stacking gradually, metal level and the second metal oxide layer, wherein the material of the first metal oxide layer is that metal cesium salt mixes the composite material forming in bipolarity metal oxide, bipolarity metal oxide can provide electronics on the one hand, improve the regeneration of electronics, on the other hand owing to being metal oxide, therefore it and metal level compatibility are better, more coupling, can reduce defect between interface, and the existence of metal cesium salt can improve the transmission rate of electronics, be conducive to the compound of electronics and hole, wherein the existence of metal level can strengthen the conductivity of charge generation layer, wherein the material of the second metal oxide layer is that to mix refractive index be the composite material forming in 1.9～2.2 metal oxide to phthalocyanine material, refractive index is that 1.9～2.2 metal oxide and other functional layers can form refringence, the effectively total reflection phenomenon between preventing layer, thereby raising light extraction efficiency, and the existence of phthalocyanine, be about-the 5.3eV of energy level of phthalocyanine on the one hand, can mate with hole mobile material well, after doping, can make the work content of metal oxide be improved, be conducive to injection and the transmission in hole, the easy crystallization of phthalocyanine micromolecular on the other hand, after crystallization, can carry out scattering to light, improve light extraction efficiency, this laminated device can effectively improve luminous efficiency.Therefore, laminated organic electroluminescent device electron transport ability using such structure as charge generation layer is strong, good conductivity, and light extraction efficiency is high.
Second aspect, the present invention also provides a kind of preparation method of laminated organic electroluminescent device, comprises the steps:
Required size anode is provided, clean rear dry;
At described anode surface successively evaporation hole injection layer, the first hole transmission layer, the first luminescent layer, the first electron transfer layer;
Evaporation the first metal oxide layer, metal level and the second metal oxide layer successively on described the first electron transfer layer, form charge generation layer, the material of described the first metal oxide layer is that metal cesium salt mixes the composite material forming in bipolarity metal oxide according to the ratio of mass ratio 1～3:5; The material of described metal level is silver, aluminium, platinum or gold; To be phthalocyanine material mix refractive index according to the ratio of mass ratio 1～4:20 to the material of described the second metal oxide layer is the composite material forming in 1.9～2.2 metal oxide; The evaporation of described the first metal oxide layer, metal level and the second metal oxide layer is vacuum evaporation, and condition is that evaporation pressure is 2 × 10
-4～5 × 10
-3pa, evaporation speed is 0.1～10nm/s;
Evaporation the second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer and negative electrode successively on described charge generation layer, obtain laminated organic electroluminescent device.
Preferably, the evaporation of described hole injection layer, the first hole transmission layer, the first luminescent layer, the first electron transfer layer, the second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer and negative electrode all adopts vacuum evaporation, and evaporation pressure is 2 × 10
-4～5 × 10
-3pa, evaporation speed is 0.1～10nm/s.
Preferably, in described the first metal oxide layer, described metal cesium salt is cesium carbonate (Cs
2cO
3), phosphoric acid caesium (Cs
3pO
4) or cesium fluoride (CsF), described bipolarity metal oxide is molybdenum trioxide (MoO
3), tungstic acid (WO
3) or vanadic oxide (V
2o
5).
Preferably, in described the second metal oxide layer, described phthalocyanine material is CuPc (CuPc) or Phthalocyanine Zinc (ZnPc), and the metal oxide that described refractive index is 1.9～2.2 is tantalum pentoxide (Ta
2o
5), niobium pentaoxide (Nb
2o
5) or vanadium dioxide (VO
2).
Preferably, the thickness of described the first metal oxide layer is 5～30nm, and the thickness of described metal level is 1～10nm, and the thickness of described the second metal oxide layer is 5～20nm.
Preferably, described anode is indium tin oxide glass (ITO), aluminium zinc oxide glass (AZO) or indium-zinc oxide glass (IZO).More preferably, described anode is indium tin oxide glass (ITO).
Preferably, described in the anode of required size is provided, concrete operations are: anode substrate is carried out to photoetching treatment, be then cut into needed size.
Preferably, anode is used successively liquid detergent by being operating as that described cleaning is dried afterwards, deionized water, and acetone, ethanol, the each ultrasonic 15min of isopropyl alcohol, the organic pollution of removal glass surface, cleans up rear air-dry.
Preferably, the material of described hole injection layer is molybdenum trioxide (MoO
3), tungstic acid (WO
3) or vanadic oxide (V
2o
5).More preferably, the material of described hole injection layer is tungstic acid (WO
3).
Preferably, the thickness of described hole injection layer is 20～80nm.More preferably, the thickness of described hole injection layer is 30nm.
Preferably, the material of described the first hole transmission layer and the second hole transmission layer is all selected from 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane (TAPC), 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA) and N, N '-(1-naphthyl)-N, N '-diphenyl-4, any one in 4 '-benzidine (NPB).
More preferably, the material of described the first hole transmission layer is 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA), the material of described the second hole transmission layer is N, N '-(1-naphthyl)-N, N '-diphenyl-4,4 '-benzidine (NPB).
Preferably, the thickness of described the first hole transmission layer and the second hole transmission layer is 20～60nm.More preferably, the thickness of described the first hole transmission layer and the second hole transmission layer is 25nm.
Preferably, the material of described the first luminescent layer and the second luminescent layer is all selected from 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans (DCJTB), 9,10-bis--β-naphthylene anthracene (ADN), 4, two (the 9-ethyl-3-carbazole vinyl)-1 of 4'-, 1'-biphenyl (BCzVBi) and oxine aluminium (Alq
3) in any one.
More preferably, the material of described the first luminescent layer and the second luminescent layer is oxine aluminium (Alq
3).
Preferably, the thickness of described the first luminescent layer and the second luminescent layer is 5～40nm.More preferably, the thickness of described the first luminescent layer and the second luminescent layer is 10nm.
Preferably, the material of described the first electron transfer layer and the second electron transfer layer is all selected from 4,7-diphenyl-1,10-phenanthroline (Bphen), 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1, any one in 2,4-triazole (TAZ) and N-aryl benzimidazole (TPBI).
More preferably, described the first electron transfer layer material be 4,7-diphenyl-1,10-phenanthroline (Bphen), the material of described the second electron transfer layer is 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole (TAZ).
Preferably, the thickness of described the first electron transfer layer and the second electron transfer layer is 40～200nm.More preferably, the thickness of described the first electron transfer layer and the second electron transfer layer is 100nm.
Preferably, the material of described electron injecting layer is cesium carbonate (Cs
2cO
3), cesium fluoride (CsF), nitrine caesium (CsN
3) or lithium fluoride (LiF).More preferably, the material of described electron injecting layer is lithium fluoride (LiF).
Preferably, the thickness of described electron injecting layer is 0.5～10nm.More preferably, the thickness of described electron injecting layer is 0.7nm.
Preferably, the material of described negative electrode is silver (Ag), aluminium (Al), platinum (Pt) or gold (Au).More preferably, the material of described negative electrode is silver (Ag).
Preferably, the thickness of described negative electrode is 60～300nm.More preferably, the thickness of described negative electrode is 150nm.
The preparation of preparation method's all functions structure of the present invention only adopts vacuum evaporation to complete, simple to operate, easily is automated, and is applicable to large-scale industrial production.
Than prior art, laminated organic electroluminescent device of the present invention and preparation method thereof has following beneficial effect:
(1) charge generation layer of laminated organic electroluminescent device of the present invention comprises the metal oxide layer of the bipolarity metal oxide layer of mixing cesium salt, metal level and the doping phthalocyanine material that stack gradually, electron transport ability is strong, good conductivity, and light extraction efficiency is high;
(2) preparation of all functions structure only adopts vacuum evaporation to complete, and preparation method is simple to operate, easily is automated, and is applicable to large-scale industrial production.
Brief description of the drawings
In order to be illustrated more clearly in technical scheme of the present invention, to the accompanying drawing of required use in execution mode be briefly described below, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skill in the art, do not paying under the prerequisite of creative work, can also obtain according to these accompanying drawings other accompanying drawing.
Fig. 1 is the structural representation of embodiment of the present invention laminated organic electroluminescent device;
Fig. 2 is the graph of a relation of organic electroluminescence device current efficiency and brightness described in laminated organic electroluminescent device and comparative example described in the embodiment of the present invention one.
Embodiment
Below in conjunction with the accompanying drawing in embodiment of the present invention, the technical scheme in embodiment of the present invention is clearly and completely described.
Please refer to Fig. 1, Fig. 1 is the structural representation of embodiment of the present invention laminated organic electroluminescent device, as shown in Figure 1, laminated organic electroluminescent device of the present invention, comprises the anode 1, hole injection layer 2, the first hole transmission layer 3, the first luminescent layer 4, the first electron transfer layer 5, charge generation layer 6, the second hole transmission layer 7, the second luminescent layer 8, the second electron transfer layer 9, electron injecting layer 10 and the negative electrode 11 that stack gradually; Described charge generation layer 6 comprises the first metal oxide layer 61, metal level 62 and the second metal oxide layer 63 that stack gradually, wherein,
The material of described the first metal oxide layer is that metal cesium salt mixes the composite material forming in bipolarity metal oxide according to the ratio of mass ratio 1～3:5;
The material of described metal level is silver, aluminium, platinum or gold;
To be phthalocyanine material mix refractive index according to the ratio of mass ratio 1～4:20 to the material of described the second metal oxide layer is the composite material forming in 1.9～2.2 metal oxide.
In described the first metal oxide layer, described metal cesium salt is cesium carbonate (Cs
2cO
3), phosphoric acid caesium (Cs
3pO
4) or cesium fluoride (CsF), described bipolarity metal oxide is molybdenum trioxide (MoO
3), tungstic acid (WO
3) or vanadic oxide (V
2o
5).
In described the second metal oxide layer, described phthalocyanine material is CuPc (CuPc) or Phthalocyanine Zinc (ZnPc), and the metal oxide that described refractive index is 1.9～2.2 is tantalum pentoxide (Ta
2o
5), niobium pentaoxide (Nb
2o
5) or vanadium dioxide (VO
2).
The thickness of described the first metal oxide layer is 5～30nm, and the thickness of described metal level is 1～10nm, and the thickness of described the second metal oxide layer is 5～20nm.
Described anode is indium tin oxide glass (ITO), aluminium zinc oxide glass (AZO) or indium-zinc oxide glass (IZO).
Described anode is indium tin oxide glass (ITO).
The material of described hole injection layer is molybdenum trioxide (MoO
3), tungstic acid (WO
3) or vanadic oxide (V
2o
5).
The material of described hole injection layer is tungstic acid (WO
3).
The thickness of described hole injection layer is 20～80nm.More preferably, the thickness of described hole injection layer is 30nm.
The material of described the first hole transmission layer and the second hole transmission layer is all selected from 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane (TAPC), 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA) and N, N '-(1-naphthyl)-N, N '-diphenyl-4, any one in 4 '-benzidine (NPB).
The material of described the first hole transmission layer is 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA), and the material of described the second hole transmission layer is N,, N '-(1-naphthyl)-N, N '-diphenyl-4,4 '-benzidine (NPB).
The thickness of described the first hole transmission layer and the second hole transmission layer is 20～60nm.
The thickness of described the first hole transmission layer and the second hole transmission layer is 25nm.
The material of described the first luminescent layer and the second luminescent layer is all selected from 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans (DCJTB), 9,10-bis--β-naphthylene anthracene (ADN), 4, two (the 9-ethyl-3-carbazole vinyl)-1 of 4'-, 1'-biphenyl (BCzVBi) and oxine aluminium (Alq
3) in any one.
The material of described the first luminescent layer and the second luminescent layer is oxine aluminium (Alq
3).
The thickness of described the first luminescent layer and the second luminescent layer is 5～40nm.More preferably, the thickness of described the first luminescent layer and the second luminescent layer is 10nm.
The material of described the first electron transfer layer and the second electron transfer layer is all selected from 4,7-diphenyl-1,10-phenanthroline (Bphen), 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1, any one in 2,4-triazole (TAZ) and N-aryl benzimidazole (TPBI).
Described the first electron transfer layer material be 4,7-diphenyl-1,10-phenanthroline (Bphen), the material of described the second electron transfer layer is 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole (TAZ).
The thickness of described the first electron transfer layer and the second electron transfer layer is 40～200nm.
The thickness of described the first electron transfer layer and the second electron transfer layer is 100nm.
The material of described electron injecting layer is cesium carbonate (Cs
2cO
3), cesium fluoride (CsF), nitrine caesium (CsN
3) or lithium fluoride (LiF).
The material of described electron injecting layer is lithium fluoride (LiF).
The thickness of described electron injecting layer is 0.5～10nm.
The thickness of described electron injecting layer is 0.7nm.
The material of described negative electrode is silver (Ag), aluminium (Al), platinum (Pt) or gold (Au).
The material of described negative electrode is silver (Ag).
The thickness of described negative electrode is 60～300nm.
The thickness of described negative electrode is 150nm.
Laminated organic electroluminescent device of the present invention, comprise charge generation layer, described charge generation layer comprises the first metal oxide layer stacking gradually, metal level and the second metal oxide layer, wherein the material of the first metal oxide layer is that metal cesium salt mixes the composite material forming in bipolarity metal oxide, bipolarity metal oxide can provide electronics on the one hand, improve the regeneration of electronics, on the other hand owing to being metal oxide, therefore it and metal level compatibility are better, more coupling, can reduce defect between interface, and the existence of metal cesium salt can improve the transmission rate of electronics, be conducive to the compound of electronics and hole, wherein the existence of metal level can strengthen the conductivity of charge generation layer, wherein the material of the second metal oxide layer is that to mix refractive index be the composite material forming in 1.9～2.2 metal oxide to phthalocyanine material, refractive index is that 1.9～2.2 metal oxide and other functional layers can form refringence, the effectively total reflection phenomenon between preventing layer, thereby raising light extraction efficiency, and the existence of phthalocyanine, be about-the 5.3eV of energy level of phthalocyanine on the one hand, can mate with hole mobile material well, after doping, can make the work content of metal oxide be improved, be conducive to injection and the transmission in hole, the easy crystallization of phthalocyanine micromolecular on the other hand, after crystallization, can carry out scattering to light, improve light extraction efficiency, this laminated device can effectively improve luminous efficiency.Therefore, laminated organic electroluminescent device electron transport ability using such structure as charge generation layer is strong, good conductivity, and light extraction efficiency is high.
In addition, the present invention also provides a kind of preparation method of laminated organic electroluminescent device, comprises the steps:
Required size anode is provided, clean rear dry;
At described anode surface successively evaporation hole injection layer, the first hole transmission layer, the first luminescent layer, the first electron transfer layer;
Evaporation the first metal oxide layer, metal level and the second metal oxide layer successively on described the first electron transfer layer, form charge generation layer, the material of described the first metal oxide layer is that metal cesium salt mixes the composite material forming in bipolarity metal oxide according to the ratio of mass ratio 1～3:5; The material of described metal level is silver, aluminium, platinum or gold; To be phthalocyanine material mix refractive index according to the ratio of mass ratio 1～4:20 to the material of described the second metal oxide layer is the composite material forming in 1.9～2.2 metal oxide; The evaporation of described the first metal oxide layer, metal level and the second metal oxide layer is vacuum evaporation, and condition is that evaporation pressure is 2 × 10
-4～5 × 10
-3pa, evaporation speed is 0.1～10nm/s;
Evaporation the second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer and negative electrode successively on described charge generation layer, obtain laminated organic electroluminescent device.
The evaporation of described hole injection layer, the first hole transmission layer, the first luminescent layer, the first electron transfer layer, the second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer and negative electrode all adopts vacuum evaporation, and evaporation pressure is 2 × 10
-4～5 × 10
-3pa, evaporation speed is 0.1～10nm/s.
In described the first metal oxide layer, described metal cesium salt is cesium carbonate (Cs
2cO
3), phosphoric acid caesium (Cs
3pO
4) or cesium fluoride (CsF), described bipolarity metal oxide is molybdenum trioxide (MoO
3), tungstic acid (WO
3) or vanadic oxide (V
2o
5).
In described the second metal oxide layer, described phthalocyanine material is CuPc (CuPc) or Phthalocyanine Zinc (ZnPc), and the metal oxide that described refractive index is 1.9～2.2 is tantalum pentoxide (Ta
2o
5), niobium pentaoxide (Nb
2o
5) or vanadium dioxide (VO
2).
The thickness of described the first metal oxide layer is 5～30nm, and the thickness of described metal level is 1～10nm, and the thickness of described the second metal oxide layer is 5～20nm.
Described anode is indium tin oxide glass (ITO), aluminium zinc oxide glass (AZO) or indium-zinc oxide glass (IZO).
Described anode is indium tin oxide glass (ITO).
The described anode that required size is provided, concrete operations are: anode substrate is carried out to photoetching treatment, be then cut into needed size.
Anode is used successively liquid detergent by being operating as that described cleaning is dried afterwards, deionized water, and acetone, ethanol, the each ultrasonic 15min of isopropyl alcohol, the organic pollution of removal glass surface, cleans up rear air-dry.
The material of described hole injection layer is molybdenum trioxide (MoO
3), tungstic acid (WO
3) or vanadic oxide (V
2o
5).
The material of described hole injection layer is tungstic acid (WO
3).
The thickness of described hole injection layer is 20～80nm.
The thickness of described hole injection layer is 30nm.
The material of described the first hole transmission layer and the second hole transmission layer is all selected from 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane (TAPC), 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA) and N, N '-(1-naphthyl)-N, N '-diphenyl-4, any one in 4 '-benzidine (NPB).
The material of described the first hole transmission layer is 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA), and the material of described the second hole transmission layer is N,, N '-(1-naphthyl)-N, N '-diphenyl-4,4 '-benzidine (NPB).
The thickness of described the first hole transmission layer and the second hole transmission layer is 20～60nm.
The thickness of described the first hole transmission layer and the second hole transmission layer is 25nm.
The material of described the first luminescent layer and the second luminescent layer is all selected from 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans (DCJTB), 9,10-bis--β-naphthylene anthracene (ADN), 4, two (the 9-ethyl-3-carbazole vinyl)-1 of 4'-, 1'-biphenyl (BCzVBi) and oxine aluminium (Alq
3) in any one.
The material of described the first luminescent layer and the second luminescent layer is oxine aluminium (Alq
3).
The thickness of described the first luminescent layer and the second luminescent layer is 5～40nm.More preferably, the thickness of described the first luminescent layer and the second luminescent layer is 10nm.
The material of described the first electron transfer layer and the second electron transfer layer is all selected from 4,7-diphenyl-1,10-phenanthroline (Bphen), 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1, any one in 2,4-triazole (TAZ) and N-aryl benzimidazole (TPBI).
Described the first electron transfer layer material be 4,7-diphenyl-1,10-phenanthroline (Bphen), the material of described the second electron transfer layer is 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole (TAZ).
The thickness of described the first electron transfer layer and the second electron transfer layer is 40～200nm.
The thickness of described the first electron transfer layer and the second electron transfer layer is 100nm.
The material of described electron injecting layer is cesium carbonate (Cs
2cO
3), cesium fluoride (CsF), nitrine caesium (CsN
3) or lithium fluoride (LiF).
The material of described electron injecting layer is lithium fluoride (LiF).
The thickness of described electron injecting layer is 0.5～10nm.
The thickness of described electron injecting layer is 0.7nm.
The material of described negative electrode is silver (Ag), aluminium (Al), platinum (Pt) or gold (Au).
The material of described negative electrode is silver (Ag).
The thickness of described negative electrode is 60～300nm.
The thickness of described negative electrode is 150nm.
The preparation of preparation method's all functions structure of the present invention only adopts vacuum evaporation to complete, simple to operate, easily is automated, and is applicable to large-scale industrial production.
Embodiment mono-
A preparation method for laminated organic electroluminescent device, comprises the steps:
(1) anode is selected indium tin oxide glass (ITO), first anode is carried out to photoetching treatment, is cut into the square that the length of side is 2mm, then uses successively liquid detergent, deionized water, acetone, ethanol, the each ultrasonic 15min of isopropyl alcohol, the organic pollution of removal glass surface, cleans up rear air-dry; Then at anode surface successively evaporation hole injection layer, the first hole transmission layer, the first luminescent layer, the first electron transfer layer, wherein:
The material of hole injection layer is tungstic acid (WO
3), evaporation pressure is 5 × 10
-3pa, evaporation speed is 0.1nm/s, evaporation thickness is 30nm;
The material of the first hole transmission layer is 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA), and evaporation pressure is 5 × 10
-3pa, evaporation speed is 0.1nm/s, evaporation thickness is 25nm;
The material of the first luminescent layer is oxine aluminium (Alq
3), evaporation pressure is 5 × 10
-3pa, evaporation speed is 0.1nm/s, evaporation thickness is 10nm;
The material of the first electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (Bphen), and evaporation pressure is 5 × 10
-3pa, evaporation speed is 0.1nm/s, evaporation thickness is 100nm.
(2) evaporation the first metal oxide layer, metal level and the second metal oxide layer successively on described the first electron transfer layer, forms charge generation layer, wherein:
The material of the first metal oxide layer is phosphoric acid caesium (Cs
3pO
4) mix molybdenum trioxide (MoO according to the ratio of mass ratio 3:10
3) the middle composite material forming, evaporation pressure is 5 × 10
-3pa, evaporation speed is 0.1nm/s, evaporation thickness is 20nm;
The material of metal level is silver (Ag), and evaporation pressure is 5 × 10
-3pa, evaporation speed is 0.1nm/s, evaporation thickness is 2nm;
The material of the second metal oxide layer is that CuPc (CuPc) mixes tantalum pentoxide (Ta according to the ratio of mass ratio 3:50
2o
5) the middle composite material forming, evaporation pressure is 5 × 10
-3pa, evaporation speed is 0.1nm/s, evaporation thickness is 10nm.
(3) evaporation the second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer and negative electrode successively on described charge generation layer, obtain laminated organic electroluminescent device, wherein:
The material of the second hole transmission layer is N, N '-(1-naphthyl)-N, and N '-diphenyl-4,4 '-benzidine (NPB), evaporation pressure is 5 × 10
-3pa, evaporation speed is 0.1nm/s, evaporation thickness is 25nm;
The material of the second luminescent layer is oxine aluminium (Alq
3), evaporation pressure is 5 × 10
-3pa, evaporation speed is 0.1nm/s, evaporation thickness is 10nm;
The material of the second electron transfer layer is 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole (TAZ), and evaporation pressure is 5 × 10
-3pa, evaporation speed is 0.1nm/s, evaporation thickness is 100nm;
The material of electron injecting layer is lithium fluoride (LiF), and evaporation pressure is 5 × 10
-3pa, evaporation speed is 0.1nm/s, evaporation thickness is 0.7nm;
The material silver (Ag) of negative electrode, evaporation pressure is 5 × 10
-3pa, evaporation speed is 0.1nm/s, evaporation thickness is 150nm.
Laminated organic electroluminescent device prepared by the present embodiment, comprises the anode, hole injection layer, the first hole transmission layer, the first luminescent layer, the first electron transfer layer, charge generation layer, the second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer and the negative electrode that stack gradually; Described charge generation layer comprises the first metal oxide layer, metal level and the second metal oxide layer that stack gradually, wherein,
The material of the first metal oxide layer is phosphoric acid caesium (Cs
3pO
4) mix molybdenum trioxide (MoO according to the ratio of mass ratio 3:10
3) in composition composite material (be expressed as Cs
3pO
4-MoO
3);
The material of the second metal oxide layer is that CuPc (CuPc) mixes tantalum pentoxide (Ta according to the ratio of mass ratio 3:50
2o
5) in composition composite material (be expressed as CuPc:Ta
2o
5).
The concrete structure of laminated organic electroluminescent device prepared by the present embodiment is:
ITO/WO
3/ TCTA/Alq
3/ Bphen/(Cs
3pO
4-MoO
3)/Ag/(CuPc:Ta
2o
5)/NPB/Alq
3/ TAZ/LiF/Ag, wherein, brace "/" represents layer structure, CuPc:Ta
2o
5in colon ": " represent mix, lower with.
Embodiment bis-
A preparation method for laminated organic electroluminescent device, comprises the steps:
(1) anode aluminium zinc oxide glass (AZO), first carries out photoetching treatment by anode, is cut into the circle of diameter 1.2mm, then uses successively liquid detergent, deionized water, acetone, ethanol, the each ultrasonic 15min of isopropyl alcohol, the organic pollution of removal glass surface, cleans up rear air-dry; Then at anode surface successively evaporation hole injection layer, the first hole transmission layer, the first luminescent layer, the first electron transfer layer, wherein:
The material of hole injection layer is vanadic oxide (V
2o
5), evaporation pressure is 2 × 10
-4pa, evaporation speed is 10nm/s, evaporation thickness is 80nm;
The material of the first hole transmission layer is 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA), and evaporation pressure is 2 × 10
-4pa, evaporation speed is 10nm/s, evaporation thickness is 60nm;
The material of the first luminescent layer is 9,10-, bis--β-naphthylene anthracene (ADN), and evaporation pressure is 2 × 10
-4pa, evaporation speed is 10nm/s, evaporation thickness is 5nm;
The material of the first electron transfer layer is N-aryl benzimidazole (TPBI), and evaporation pressure is 2 × 10
-4pa, evaporation speed is 10nm/s, evaporation thickness is 40nm.
(2) evaporation the first metal oxide layer, metal level and the second metal oxide layer successively on described the first electron transfer layer, forms charge generation layer, wherein:
The material of the first metal oxide layer is cesium carbonate (Cs
2cO
3) mix tungstic acid (WO according to the ratio of mass ratio 1:5
3) the middle composite material forming, evaporation pressure is 2 × 10
-4pa, evaporation speed is 10nm/s, evaporation thickness is 5nm;
The material of metal level is platinum (Pt), and evaporation pressure is 2 × 10
-4pa, evaporation speed is 10nm/s, evaporation thickness is 1nm;
The material of the second metal oxide layer is that Phthalocyanine Zinc (ZnPc) is mixed niobium pentaoxide (Nb according to the ratio of mass ratio 1:5
2o
5) the middle composite material forming, evaporation pressure is 2 × 10
-4pa, evaporation speed is 10nm/s, evaporation thickness is 5nm.
(3) evaporation the second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer and negative electrode successively on described charge generation layer, obtain laminated organic electroluminescent device, wherein:
The material of the second hole transmission layer is N, N '-(1-naphthyl)-N, and N '-diphenyl-4,4 '-benzidine (NPB), evaporation pressure is 2 × 10
-4pa, evaporation speed is 10nm/s, evaporation thickness is 20nm;
The material of the second luminescent layer is two (the 9-ethyl-3-carbazole vinyl)-1 of 4,4'-, 1'-biphenyl (BCzVBi), and evaporation pressure is 2 × 10
-4pa, evaporation speed is 10nm/s, evaporation thickness is 40nm;
The material of the second electron transfer layer is N-aryl benzimidazole (TPBI), and evaporation pressure is 2 × 10
-4pa, evaporation speed is 10nm/s, evaporation thickness is 200nm;
The material of electron injecting layer is nitrine caesium (CsN
3), evaporation pressure is 2 × 10
-4pa, evaporation speed is 10nm/s, evaporation thickness is 0.5nm;
The material platinum (Pt) of negative electrode, evaporation pressure is 2 × 10
-4pa, evaporation speed is 10nm/s, evaporation thickness is 60nm.
Laminated organic electroluminescent device prepared by the present embodiment, comprises the anode, hole injection layer, the first hole transmission layer, the first luminescent layer, the first electron transfer layer, charge generation layer, the second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer and the negative electrode that stack gradually; Described charge generation layer comprises the first metal oxide layer, metal level and the second metal oxide layer that stack gradually, wherein,
The material of the first metal oxide layer is cesium carbonate (Cs
2cO
3) mix tungstic acid (WO according to the ratio of mass ratio 1:5
3) in composition composite material (be expressed as Cs
2cO
3-WO
3);
The material of the second metal oxide layer is that Phthalocyanine Zinc (ZnPc) is mixed niobium pentaoxide (Nb according to the ratio of mass ratio 1:5
2o
5) in composition composite material (be expressed as ZnPc:Nb
2o
5).
The concrete structure of laminated organic electroluminescent device prepared by the present embodiment is:
AZO/V
2O
5/TCTA/ADN/TPBI/（Cs
2CO
3-WO
3）/Pt/（ZnPc:Nb
2O
5）/NPB/BCzVBi/TPBI/CsN
3/Pt。
Embodiment tri-
A preparation method for laminated organic electroluminescent device, comprises the steps:
(1) anode is selected indium-zinc oxide glass (IZO), first anode is carried out to photoetching treatment, is cut into the rectangle of 2mm × 3mm, then uses successively liquid detergent, deionized water, acetone, ethanol, the each ultrasonic 15min of isopropyl alcohol, the organic pollution of removal glass surface, cleans up rear air-dry; Then at anode surface successively evaporation hole injection layer, the first hole transmission layer, the first luminescent layer, the first electron transfer layer, wherein:
The material of hole injection layer is tungstic acid (WO
3), evaporation pressure is 5 × 10
-4pa, evaporation speed is 1nm/s, evaporation thickness is 20nm;
The material of the first hole transmission layer is 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane (TAPC), evaporation pressure is 5 × 10
-4pa, evaporation speed is 0.5nm/s, evaporation thickness is 30nm;
The material of the first luminescent layer is 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans (DCJTB), evaporation pressure is 5 × 10
-4pa, evaporation speed is 0.5nm/s, evaporation thickness is 10nm;
The material of the first electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (Bphen), and evaporation pressure is 5 × 10
-4pa, evaporation speed is 0.5nm/s, evaporation thickness is 200nm.
(2) evaporation the first metal oxide layer, metal level and the second metal oxide layer successively on described the first electron transfer layer, forms charge generation layer, wherein:
The material of the first metal oxide layer is that cesium fluoride (CsF) mixes vanadic oxide (V according to the ratio of mass ratio 3:5
2o
5) the middle composite material forming, evaporation pressure is 5 × 10
-4pa, evaporation speed is 0.5nm/s, evaporation thickness is 30nm;
The material of metal level is aluminium (Al), and evaporation pressure is 5 × 10
-4pa, evaporation speed is 0.1nm/s, evaporation thickness is 10nm;
The material of the second metal oxide layer is that CuPc (CuPc) mixes vanadium dioxide (VO according to the ratio of mass ratio 3:20
2) the middle composite material forming, evaporation pressure is 5 × 10
-4pa, evaporation speed is 0.5nm/s, evaporation thickness is 20nm.
(3) evaporation the second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer and negative electrode successively on described charge generation layer, obtain laminated organic electroluminescent device, wherein:
The material of the second hole transmission layer is 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane (TAPC), evaporation pressure is 5 × 10
-4pa, evaporation speed is 0.5nm/s, evaporation thickness is 60nm;
The material of the second luminescent layer is 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans (DCJTB), evaporation pressure is 5 × 10
-4pa, evaporation speed is 0.5nm/s, evaporation thickness is 5nm;
The material of the second electron transfer layer is N-aryl benzimidazole (TPBI), and evaporation pressure is 5 × 10
-4pa, evaporation speed is 0.5nm/s, evaporation thickness is 40nm;
The material of electron injecting layer is cesium fluoride (CsF), and evaporation pressure is 5 × 10
-4pa, evaporation speed is 0.5nm/s, evaporation thickness is 10nm;
The material aluminium (Al) of negative electrode, evaporation pressure is 5 × 10
-4pa, evaporation speed is 0.5nm/s, evaporation thickness is 300nm.
Laminated organic electroluminescent device prepared by the present embodiment, comprises the anode, hole injection layer, the first hole transmission layer, the first luminescent layer, the first electron transfer layer, charge generation layer, the second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer and the negative electrode that stack gradually; Described charge generation layer comprises the first metal oxide layer, metal level and the second metal oxide layer that stack gradually, wherein,
The material of the first metal oxide layer is that cesium fluoride (CsF) mixes vanadic oxide (V according to the ratio of mass ratio 3:5
2o
5) in composition composite material (be expressed as CsF-V
2o
5);
The material of the second metal oxide layer is that CuPc (CuPc) mixes vanadium dioxide (VO according to the ratio of mass ratio 3:20
2) in composition composite material (be expressed as CuPc:VO
2).
The concrete structure of laminated organic electroluminescent device prepared by the present embodiment is:
IZO/WO
3/TAPC/DCJTB/Bphen/（CsF-V
2O
5）/Al/（CuPc:VO
2）/TAPC/DCJTB/TPBI/CsF/Al。
Embodiment tetra-
A preparation method for laminated organic electroluminescent device, comprises the steps:
(1) anode is selected indium-zinc oxide glass (IZO), first anode is carried out to photoetching treatment, is cut into the circle of diameter 2mm, then uses successively liquid detergent, deionized water, acetone, ethanol, the each ultrasonic 15min of isopropyl alcohol, the organic pollution of removal glass surface, cleans up rear air-dry; Then at anode surface successively evaporation hole injection layer, the first hole transmission layer, the first luminescent layer, the first electron transfer layer, wherein:
The material of hole injection layer is molybdenum trioxide (MoO
3), evaporation pressure is 2 × 10
-4pa, evaporation speed is 1nm/s, evaporation thickness is 30nm;
The material of the first hole transmission layer is N, N '-(1-naphthyl)-N, and N '-diphenyl-4,4 '-benzidine (NPB), evaporation pressure is 2 × 10
-4pa, evaporation speed is 0.5nm/s, evaporation thickness is 50nm;
The material of the first luminescent layer is 9,10-, bis--β-naphthylene anthracene (ADN), and evaporation pressure is 1 × 10
-4pa, evaporation speed is 0.5nm/s, evaporation thickness is 8nm;
The material of the first electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (Bphen), and evaporation pressure is 2 × 10
-4pa, evaporation speed is 0.5nm/s, evaporation thickness is 400nm.
(2) evaporation the first metal oxide layer, metal level and the second metal oxide layer successively on described the first electron transfer layer, forms charge generation layer, wherein:
The material of the first metal oxide layer is phosphoric acid caesium (Cs
3pO
4) mix tungstic acid (WO according to the ratio of mass ratio 9:20
3) the middle composite material forming, evaporation pressure is 2 × 10
-4pa, evaporation speed is 0.5nm/s, evaporation thickness is 25nm;
The material of metal level is gold (Au), and evaporation pressure is 2 × 10
-4pa, evaporation speed is 0.1nm/s, evaporation thickness is 3nm;
The material of the second metal oxide layer is that Phthalocyanine Zinc (ZnPc) is mixed tantalum pentoxide (Ta according to the ratio of mass ratio 3:25
2o
5) the middle composite material forming, evaporation pressure is 1 × 10
-4pa, evaporation speed is 0.5nm/s, evaporation thickness is 8nm.
(3) evaporation the second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer and negative electrode successively on described charge generation layer, obtain laminated organic electroluminescent device, wherein:
The material of the second hole transmission layer is N, N '-(1-naphthyl)-N, and N '-diphenyl-4,4 '-benzidine (NPB), evaporation pressure is 2 × 10
-4pa, evaporation speed is 0.5nm/s, evaporation thickness is 50nm;
The material of the second luminescent layer is 9,10-, bis--β-naphthylene anthracene (ADN), and evaporation pressure is 2 × 10
-4pa, evaporation speed is 0.5nm/s, evaporation thickness is 7nm;
The material of the second electron transfer layer is 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole (TAZ), and evaporation pressure is 2 × 10
-4pa, evaporation speed is 0.5nm/s, evaporation thickness is 100nm;
The material of electron injecting layer is cesium carbonate (Cs
2cO
3), evaporation pressure is 2 × 10
-4pa, evaporation speed is 0.5nm/s, evaporation thickness is 2nm;
The material of negative electrode is gold (Au), and evaporation pressure is 1 × 10
-4pa, evaporation speed is 0.5nm/s, evaporation thickness is 180nm.
Laminated organic electroluminescent device prepared by the present embodiment, comprises the anode, hole injection layer, the first hole transmission layer, the first luminescent layer, the first electron transfer layer, charge generation layer, the second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer and the negative electrode that stack gradually; Described charge generation layer comprises the first metal oxide layer, metal level and the second metal oxide layer that stack gradually, wherein,
The material of the first metal oxide layer is phosphoric acid caesium (Cs
3pO
4) mix tungstic acid (WO according to the ratio of mass ratio 9:20
3) in composition composite material (be expressed as Cs
3pO
4-WO
3);
The material of the second metal oxide layer is that Phthalocyanine Zinc (ZnPc) is mixed tantalum pentoxide (Ta according to the ratio of mass ratio 3:25
2o
5) in composition composite material (be expressed as ZnPc:Ta
2o
5).
The concrete structure of laminated organic electroluminescent device prepared by the present embodiment is:
IZO/MoO
3/NPB/ADN/Bphen/（Cs
3PO
4-WO
3）/Au/（ZnPc:Ta
2O
5）/NPB/ADN/TAZ/Cs
2CO
3/Au。
Comparative example
For being presented as beneficial effect of the present invention, the present invention is also provided with comparative example, comparative example is the organic electroluminescence device of existing non-lamination, the material of its functional layer is similar to embodiment mono-, comprise the anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the negative electrode that stack gradually, the structure of this organic electroluminescence device is: ITO/WO
3/ TCTA/Alq
3/ Bphen/LiF/Ag.
Effect embodiment
Adopt the USB4000 fiber spectrometer testing electroluminescent spectrum of U.S. marine optics Ocean Optics, current-voltage tester (Keithly company of the U.S., model: 2400), colorimeter (Japanese Konica Minolta company, model: CS-100A) laminated organic electroluminescent device and curve that described in comparative example, organic electroluminescence device current efficiency changes with brightness described in test implementation example one, to investigate the luminous efficiency of device, test result as shown in Figure 2, Fig. 2 is the graph of a relation of organic electroluminescence device current efficiency and brightness described in laminated organic electroluminescent device and comparative example described in the embodiment of the present invention one, in figure, curve 1 is the graph of a relation of laminated organic electroluminescent device current efficiency and brightness described in embodiment mono-, curve 2 is the graph of a relation of organic electroluminescence device current efficiency and brightness described in comparative example.
As can be seen from Figure 2, under each brightness, all large than the described organic electroluminescence device of comparative example example of the current efficiency of laminated organic electroluminescent device described in embodiment mono-, described in embodiment mono-, the maximum current efficiency of laminated organic electroluminescent device is 11.3lm/W, and that comparative example is only 5.9lm/W, prompting adopts laminated construction, and with the bipolarity metal oxide layer of doping metals cesium salt, the stepped construction of the metal oxide layer composition that the refractive index of metal level and doping phthalocyanine material is 1.9～2.2 is as charge generation layer, can improve the transmission of electronics, strengthen the conductivity of charge generation layer, effectively improve the luminous efficiency of organic electroluminescence device.
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. a laminated organic electroluminescent device, it is characterized in that, comprise the anode, hole injection layer, the first hole transmission layer, the first luminescent layer, the first electron transfer layer, charge generation layer, the second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer and the negative electrode that stack gradually, described charge generation layer comprises the first metal oxide layer, metal level and the second metal oxide layer that stack gradually, wherein
The material of described the first metal oxide layer is that metal cesium salt mixes the composite material forming in bipolarity metal oxide according to the ratio of mass ratio 1～3:5;
The material of described metal level is silver, aluminium, platinum or gold;
To be phthalocyanine material mix refractive index according to the ratio of mass ratio 1～4:20 to the material of described the second metal oxide layer is the composite material forming in 1.9～2.2 metal oxide.
2. laminated organic electroluminescent device as claimed in claim 1, it is characterized in that, in described the first metal oxide layer, described metal cesium salt is cesium carbonate, phosphoric acid caesium or cesium fluoride, and described bipolarity metal oxide is molybdenum trioxide, tungstic acid or vanadic oxide.
3. laminated organic electroluminescent device as claimed in claim 1, it is characterized in that, in described the second metal oxide layer, described phthalocyanine material is CuPc or Phthalocyanine Zinc, and the metal oxide that described refractive index is 1.9～2.2 is tantalum pentoxide, niobium pentaoxide or vanadium dioxide.
4. laminated organic electroluminescent device as claimed in claim 1, is characterized in that, the thickness of described the first metal oxide layer is 5～30nm, and the thickness of described metal level is 1～10nm, and the thickness of described the second metal oxide layer is 5～20nm.
5. laminated organic electroluminescent device as claimed in claim 1, it is characterized in that, the material of described the first luminescent layer and the second luminescent layer is all selected from 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans, 9,10-bis--β-naphthylene anthracene, 4, two (the 9-ethyl-3-carbazole vinyl)-1 of 4'-, any one in 1'-biphenyl and oxine aluminium.
6. a preparation method for laminated organic electroluminescent device, is characterized in that, comprises the steps:
Required size anode is provided, clean rear dry;
At described anode surface successively evaporation hole injection layer, the first hole transmission layer, the first luminescent layer, the first electron transfer layer;
Evaporation the first metal oxide layer, metal level and the second metal oxide layer successively on described the first electron transfer layer, form charge generation layer, the material of described the first metal oxide layer is that metal cesium salt mixes the composite material forming in bipolarity metal oxide according to the ratio of mass ratio 1～3:5; The material of described metal level is silver, aluminium, platinum or gold; To be phthalocyanine material mix refractive index according to the ratio of mass ratio 1～4:20 to the material of described the second metal oxide layer is the composite material forming in 1.9～2.2 metal oxide; The evaporation of described the first metal oxide layer, metal level and the second metal oxide layer is vacuum evaporation, and condition is that evaporation pressure is 2 × 10
-4～5 × 10
-3pa, evaporation speed is 0.1～10nm/s;
Evaporation the second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer and negative electrode successively on described charge generation layer, obtain laminated organic electroluminescent device.
7. the preparation method of laminated organic electroluminescent device as claimed in claim 6, it is characterized in that, in described the first metal oxide layer, described metal cesium salt is cesium carbonate, phosphoric acid caesium or cesium fluoride, and described bipolarity metal oxide is molybdenum trioxide, tungstic acid or vanadic oxide.
8. the preparation method of laminated organic electroluminescent device as claimed in claim 6, it is characterized in that, in described the second metal oxide layer, described phthalocyanine material is CuPc or Phthalocyanine Zinc, and the metal oxide that described refractive index is 1.9～2.2 is tantalum pentoxide, niobium pentaoxide or vanadium dioxide.
9. the preparation method of laminated organic electroluminescent device as claimed in claim 6, is characterized in that, the thickness of described the first metal oxide layer is 5～30nm, and the thickness of described metal level is 1～10nm, and the thickness of described the second metal oxide layer is 5～20nm.
10. the preparation method of laminated organic electroluminescent device as claimed in claim 6, it is characterized in that, the material of described the first luminescent layer and the second luminescent layer is all selected from 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans, 9,10-bis--β-naphthylene anthracene, 4, two (the 9-ethyl-3-carbazole vinyl)-1 of 4'-, any one in 1'-biphenyl and oxine aluminium.
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