CN104253243A - Organic electroluminescent device and preparation method thereof - Google Patents
Organic electroluminescent device and preparation method thereof Download PDFInfo
- Publication number
- CN104253243A CN104253243A CN201310261059.1A CN201310261059A CN104253243A CN 104253243 A CN104253243 A CN 104253243A CN 201310261059 A CN201310261059 A CN 201310261059A CN 104253243 A CN104253243 A CN 104253243A
- Authority
- CN
- China
- Prior art keywords
- layer
- phthalocyanine
- oxide
- evaporation
- thickness
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 52
- 230000027756 respiratory electron transport chain Effects 0.000 claims abstract description 48
- 239000002184 metal Substances 0.000 claims abstract description 36
- 229910052751 metal Inorganic materials 0.000 claims abstract description 35
- 238000002347 injection Methods 0.000 claims abstract description 33
- 239000007924 injection Substances 0.000 claims abstract description 33
- 229910000311 lanthanide oxide Inorganic materials 0.000 claims abstract description 32
- 230000008020 evaporation Effects 0.000 claims description 97
- 238000001704 evaporation Methods 0.000 claims description 97
- 239000000463 material Substances 0.000 claims description 97
- 230000005540 biological transmission Effects 0.000 claims description 48
- 150000004706 metal oxides Chemical class 0.000 claims description 48
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical group [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 46
- 238000005401 electroluminescence Methods 0.000 claims description 43
- 150000001875 compounds Chemical class 0.000 claims description 40
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 25
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 23
- 239000011787 zinc oxide Substances 0.000 claims description 22
- 239000010931 gold Substances 0.000 claims description 17
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 16
- 229920002554 vinyl polymer Polymers 0.000 claims description 16
- 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 13
- 239000004411 aluminium Substances 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 12
- LBAIJNRSTQHDMR-UHFFFAOYSA-N magnesium phthalocyanine Chemical compound [Mg].C12=CC=CC=C2C(N=C2NC(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2N1 LBAIJNRSTQHDMR-UHFFFAOYSA-N 0.000 claims description 12
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000005566 electron beam evaporation Methods 0.000 claims description 11
- 238000007747 plating Methods 0.000 claims description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Natural products C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims description 8
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052737 gold Inorganic materials 0.000 claims description 8
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- 229910052697 platinum Inorganic materials 0.000 claims description 8
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 8
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 8
- 239000004332 silver Substances 0.000 claims description 8
- 229910052709 silver Inorganic materials 0.000 claims description 8
- 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
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000003599 detergent Substances 0.000 claims description 7
- 229910000765 intermetallic Inorganic materials 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 239000011368 organic material Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical class C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- CIEHQLJGGPHJPU-UHFFFAOYSA-N [Pr+3].[O-2].[O-2].[Ti+4] Chemical group [Pr+3].[O-2].[O-2].[Ti+4] CIEHQLJGGPHJPU-UHFFFAOYSA-N 0.000 claims description 6
- 239000004305 biphenyl Substances 0.000 claims description 6
- 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 claims description 6
- UZLYXNNZYFBAQO-UHFFFAOYSA-N oxygen(2-);ytterbium(3+) Chemical class [O-2].[O-2].[O-2].[Yb+3].[Yb+3] UZLYXNNZYFBAQO-UHFFFAOYSA-N 0.000 claims description 6
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 6
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 6
- 238000002203 pretreatment Methods 0.000 claims description 6
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 claims description 6
- FEONEKOZSGPOFN-UHFFFAOYSA-K tribromoiron Chemical compound Br[Fe](Br)Br FEONEKOZSGPOFN-UHFFFAOYSA-K 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 claims description 4
- 229910000449 hafnium oxide Inorganic materials 0.000 claims description 4
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 claims description 4
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical group [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 4
- 238000001259 photo etching Methods 0.000 claims description 4
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 claims description 4
- 229910001954 samarium oxide Inorganic materials 0.000 claims description 4
- 229940075630 samarium oxide Drugs 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 4
- 229910003454 ytterbium oxide Inorganic materials 0.000 claims description 4
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 3
- 238000010894 electron beam technology Methods 0.000 claims description 3
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 3
- QWODREODAXFISP-UHFFFAOYSA-N n-[4-(4-anilinophenyl)phenyl]-n-phenylnaphthalen-1-amine Chemical compound C=1C=C(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C3=CC=CC=C3C=CC=2)C=CC=1NC1=CC=CC=C1 QWODREODAXFISP-UHFFFAOYSA-N 0.000 claims 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims 2
- 230000005525 hole transport Effects 0.000 abstract 2
- -1 phthalocyanine compound Chemical class 0.000 abstract 2
- 150000003839 salts Chemical class 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 254
- 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 15
- 101000837344 Homo sapiens T-cell leukemia translocation-altered gene protein Proteins 0.000 description 15
- 102100028692 T-cell leukemia translocation-altered gene protein Human genes 0.000 description 15
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 14
- 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 12
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 12
- 239000011521 glass Substances 0.000 description 12
- 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
- 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 8
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 6
- 239000002800 charge carrier Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000010944 silver (metal) Substances 0.000 description 6
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 6
- 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 5
- 229910010413 TiO 2 Inorganic materials 0.000 description 5
- 238000004770 highest occupied molecular orbital Methods 0.000 description 5
- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical compound [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 description 5
- 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 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 239000003574 free electron Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 230000006798 recombination Effects 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 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 2
- 229910021541 Vanadium(III) oxide Inorganic materials 0.000 description 2
- JYMITAMFTJDTAE-UHFFFAOYSA-N aluminum zinc oxygen(2-) Chemical compound [O-2].[Al+3].[Zn+2] JYMITAMFTJDTAE-UHFFFAOYSA-N 0.000 description 2
- 229910052792 caesium Inorganic materials 0.000 description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(iv) oxide Chemical compound O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 2
- KAEAMHPPLLJBKF-UHFFFAOYSA-N iron(3+) sulfide Chemical compound [S-2].[S-2].[S-2].[Fe+3].[Fe+3] KAEAMHPPLLJBKF-UHFFFAOYSA-N 0.000 description 2
- 239000000075 oxide glass Substances 0.000 description 2
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 2
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000004776 molecular orbital Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000001771 vacuum deposition 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
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/80—Constructional details
- H10K30/865—Intermediate layers comprising a mixture of materials of the adjoining active layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
- H10K50/125—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers specially adapted for multicolour light emission, e.g. for emitting white light
- H10K50/13—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers specially adapted for multicolour light emission, e.g. for emitting white light comprising stacked EL layers within one EL unit
- H10K50/131—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers specially adapted for multicolour light emission, e.g. for emitting white light comprising stacked EL layers within one EL unit with spacer layers between the electroluminescent 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
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/311—Phthalocyanine
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
Landscapes
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Electromagnetism (AREA)
- Manufacturing & Machinery (AREA)
- Optics & Photonics (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention relates to an organic electroluminescent device comprising an anode, a hole injection layer, a first hole transport layer, a first luminous layer, a first electron transfer layer, a charge generating layer, a second hole transport layer, a second luminous layer, a second electron transport layer, an electron injection layer and a cathode. The components are successively laminated. The charge generating layer includes an n type layer, an intermediate layer, and a p type layer; and the n type layer is made of metal and metallic oxide doped in the metal, the intermediate layer is made of a phthalocyanine compound and ferric salt and metallic oxide that are doped in the phthalocyanine compound, and the p type layer is made of lanthanide oxide and metallic oxide doped in the lanthanide oxide. The luminous efficiency of the organic electroluminescent device is high. In addition, the invention also provides a preparation method of the organic electroluminescent device.
Description
Technical field
The present invention relates to a kind of organic electroluminescence device and preparation method thereof.
Background technology
Under the principle of luminosity of organic electroluminescence device is based on the effect of extra electric field, electronics is injected into organic lowest unocccupied molecular orbital (LUMO) from negative electrode, and hole is injected into organic highest occupied molecular orbital (HOMO) from anode.Meet at luminescent layer in electronics and hole, compound, formation exciton, and exciton moves under electric field action, and by energy transferring to luminescent material, and excitation electron is from ground state transition to excitation state, and excited energy, by Radiation-induced deactivation, produces photon, release luminous energy.But the luminous efficiency of current organic electroluminescence device is lower.
Summary of the invention
Based on this, be necessary to provide organic electroluminescence device that a kind of luminous efficiency is higher and preparation method thereof.
A kind of organic electroluminescence device, comprises the anode stacked gradually, hole injection layer, first hole transmission layer, first luminescent layer, first electron transfer layer, charge generation layer, second hole transmission layer, second luminescent layer, second electron transfer layer, electron injecting layer and negative electrode, described charge generation layer comprises n-layer, intermediate layer and p-type layer, the metal oxide that described n-layer material is metal and is entrained in described metal, intermediate layer material is phthalocyanine-like compound and the molysite be entrained in described phthalocyanine-like compound and metal oxide, the metal oxide that p-type layer is lanthanide oxide and is entrained in described lanthanide oxide, wherein, described metal is selected from silver, aluminium, at least one in platinum or gold, described phthalocyanine-like compound is selected from CuPc, Phthalocyanine Zinc, at least one in phthalocyanine vanadium or magnesium phthalocyanine, described molysite is selected from iron chloride, at least one in ferric bromide or iron sulfide, described lanthanide oxide is selected from titanium dioxide praseodymium, praseodymium sesquioxide, at least one in three ytterbium oxides or samarium oxide, described metal oxide is selected from zinc oxide, at least one in titanium dioxide or hafnium oxide or zirconium dioxide, wherein, the mass ratio of described metal and described metal oxide is 1:100 ~ 1:10, the mass ratio of described molysite and described phthalocyanine-like compound is 1:100 ~ 1:10, the mass ratio of described metal oxide and described phthalocyanine-like compound is 1:1000 ~ 1:100, and the mass ratio of described metal oxide and described lanthanide oxide is 1:100 ~ 1:10.
In a preferred embodiment, the thickness of described n-layer is 10nm ~ 40nm, and described intermediate layer thickness is 10nm ~ 40nm, and the thickness of described p-type layer is 5nm ~ 30nm.
In a preferred embodiment, the material of described first luminescent layer and described second luminescent layer is selected from 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river pyridine of a specified duration-9-vinyl)-4H-pyrans, 9, at least one in 10-bis--β-naphthylene anthracene, 4,4'-two (9-ethyl-3-carbazole vinyl)-1,1'-biphenyl and oxine aluminium.
In a preferred embodiment, the material of described first hole transmission layer and described second hole transmission layer is selected from 1,1-bis-[4-[N, N '-two (p-tolyl) is amino] phenyl] cyclohexane, 4,4', 4''-tri-(carbazole-9-base) triphenylamine and N, N '-(1-naphthyl)-N, at least one in N '-diphenyl-4,4 '-benzidine.
In a preferred embodiment, the material of described first electron transfer layer and described second electron transfer layer is selected from least one in 4,7-diphenyl-1,10-phenanthroline, 1,2,4-triazole derivative and N-aryl benzimidazole.
A preparation method for organic electroluminescence device, comprises the following steps:
Hole injection layer, the first hole transmission layer, the first luminescent layer and the first electron transfer layer is prepared at anode surface successively evaporation;
Charge generation layer is prepared on described first electron transfer layer surface, described charge generation layer comprises n-layer, intermediate layer and p-type layer, n-layer and p-type layer adopt evaporation mode to prepare, intermediate layer adopts the preparation of electron beam mode evaporation, the metal oxide that described n-layer material is metal and is entrained in described metal, intermediate layer material is phthalocyanine-like compound and the molysite be entrained in described phthalocyanine-like compound and metal oxide, the metal oxide that p-type layer is lanthanide oxide and is entrained in described lanthanide oxide, wherein, described metal is selected from silver, aluminium, at least one in platinum or gold, described phthalocyanine-like compound is selected from CuPc, Phthalocyanine Zinc, at least one in phthalocyanine vanadium or magnesium phthalocyanine, described molysite is selected from iron chloride, at least one in ferric bromide or iron sulfide, described lanthanide oxide is selected from titanium dioxide praseodymium, praseodymium sesquioxide, at least one in three ytterbium oxides or samarium oxide, described metal oxide is selected from zinc oxide, at least one in titanium dioxide or hafnium oxide or zirconium dioxide, wherein, the mass ratio of described metal and described metal oxide is 1:100 ~ 1:10, the mass ratio of described molysite and described phthalocyanine-like compound is 1:100 ~ 1:10, the mass ratio of described metal oxide and described phthalocyanine-like compound is 1:1000 ~ 1:100, the mass ratio of described metal oxide and described lanthanide oxide is 1:100 ~ 1:10, evaporation is 2 × 10 at vacuum pressure
-3~ 5 × 10
-5carry out under Pa, the evaporation rate of organic material is 0.1 ~ 1nm/s, and the evaporation rate of metal and metallic compound is 1 ~ 10nm/s, and the energy density of electron beam evaporation plating is 10-l00W/cm
2, and
In a preferred embodiment, the second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer and negative electrode is formed on described charge generation layer surface successively evaporation.
In a preferred embodiment, the material of described first luminescent layer and described second luminescent layer is selected from 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river pyridine of a specified duration-9-vinyl)-4H-pyrans, 9, at least one in 10-bis--β-naphthylene anthracene, 4,4'-two (9-ethyl-3-carbazole vinyl)-1,1'-biphenyl and oxine aluminium.
In a preferred embodiment, the material of described first hole transmission layer and described second hole transmission layer is selected from 1,1-bis-[4-[N, N '-two (p-tolyl) is amino] phenyl] cyclohexane, 4,4', 4''-tri-(carbazole-9-base) triphenylamine and N, N '-(1-naphthyl)-N, at least one in N '-diphenyl-4,4 '-benzidine.
In a preferred embodiment, the thickness of described n-layer is 10nm ~ 40nm, and described intermediate layer thickness is 10nm ~ 40nm, and the thickness of described p-type layer is 5nm ~ 30nm.
Before described anode surface forms hole injection layer, first antianode carries out pre-treatment, pre-treatment comprises: anode is carried out photoetching treatment, be cut into required size, adopt liquid detergent, deionized water, acetone, ethanol, each Ultrasonic Cleaning 15min of isopropyl acetone, to remove the organic pollution of anode surface.
Above-mentioned organic electroluminescence device and preparation method thereof, charge generation layer is by comprising n-layer, intermediate layer and p-type layer are formed, wherein, n-layer material is that metal carrying supplies free electron thus improves the concentration of charge carrier, improve electron transfer rate, , the molysite that intermediate layer is phthalocyanine-like compound and is entrained in phthalocyanine-like compound, the conductivity that carrier concentration improves intermediate layer can be improved by this doping, phthalocyanine-like compound can improve the injection efficiency in hole and the easy crystallization of this material can improve the scattering of light, p-type layer material is lanthanide oxide, the work function of lanthanide oxide is higher (about-6.7eV ~-7.5eV), with the HOMO energy level comparison match of hole mobile material, hole injection barrier can be reduced, improve the injectability in hole, be conducive to the injection in hole, be conducive to the transmission of charge carrier, improve exciton recombination probability, a small amount of metal oxide is added in these three layers, utilize the nanometer Large stone of metal oxide and larger specific area to improve the scattering of light, this charge generation layer effectively can improve the luminous efficiency of organic electroluminescence device.
Accompanying drawing explanation
Fig. 1 is the structural representation of the organic electroluminescence device of an execution mode;
Fig. 2 is the flow chart of the preparation method of the organic electroluminescence device of an execution mode;
Fig. 3 is current density and the current efficiency graph of a relation of organic electroluminescence device prepared by embodiment 1.
Embodiment
Below in conjunction with the drawings and specific embodiments, organic electroluminescence device and preparation method thereof is illustrated further.
Refer to Fig. 1, the organic electroluminescence device 100 of one execution mode comprises the anode 10, hole injection layer 20, first hole transmission layer 32, first luminescent layer 34, first electron transfer layer 36, charge generation layer 40, second hole transmission layer 52, second luminescent layer 54, second electron transfer layer 56, electron injecting layer 60 and the negative electrode 70 that stack gradually, charge generation layer 40 comprises n-layer 401, intermediate layer 402 and p-type layer 403.
Anode 10 is indium tin oxide glass (ITO), aluminium zinc oxide glass (AZO) or indium-zinc oxide glass (IZO), is preferably ITO.
Hole injection layer 20 is formed at anode 10 surface.The material of hole injection layer 20 is selected from molybdenum trioxide (MoO
3), tungstic acid (WO
3) and vanadic oxide (V
2o
5) at least one, be preferably WO
3.The thickness of hole injection layer 20 is 20nm ~ 80nm, is preferably 40nm.
First hole transmission layer 32 is formed at the surface of hole injection layer 20.The material of the first hole transmission layer 32 is selected from 1,1-bis-[4-[N, N '-two (p-tolyl) is amino] phenyl] cyclohexane (TAPC), 4,4', 4''-tri-(carbazole-9-base) triphenylamine (TCTA) and N, N '-(1-naphthyl)-N, N '-diphenyl-4, at least one in 4 '-benzidine (NPB), is preferably TAPC.The thickness of the first hole transmission layer 32 is 20nm ~ 60nm, is preferably 55nm.
First luminescent layer 34 is formed at the surface of the first hole transmission layer 32.The material of the first luminescent layer 34 is selected from 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river pyridine of a specified duration-9-vinyl)-4H-pyrans (DCJTB), 9,10-bis--β-naphthylene anthracene (ADN), 4, two (9-ethyl-3-carbazole vinyl)-1, the 1'-biphenyl (BCzVBi) of 4'-and 8-hydroxyquinoline aluminum (Alq
3) at least one, be preferably Alq
3.The thickness of luminescent layer 40 is 5nm ~ 40nm, is preferably 20nm.
First electron transfer layer 36 is formed at the surface of the first luminescent layer 32.The material of the first electron transfer layer 36 is selected from least one in 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2,4-triazole derivative (as TAZ) and N-aryl benzimidazole (TPBI), is preferably TAZ.The thickness of the first electron transfer layer 36 is 40nm ~ 300nm, is preferably 60nm.
Charge generation layer 40 is formed at the surface of the first electron transfer layer 36.Charge generation layer 40, charge generation layer 40 comprises n-layer 401, intermediate layer 402 and p-type layer 403, the metal oxide that described N-shaped 401 material is metal and is entrained in described metal, intermediate layer 402 material is phthalocyanine-like compound and the molysite be entrained in described phthalocyanine-like compound and metal oxide, the metal oxide that p-type layer 403 is lanthanide oxide and is entrained in described lanthanide oxide, wherein, described metal is selected from silver (Ag), aluminium (Al), platinum (Pt) or the middle at least one of gold (Au), described phthalocyanine-like compound is selected from CuPc (CuPc), Phthalocyanine Zinc (ZnPc), phthalocyanine vanadium (VPc) or the middle at least one of magnesium phthalocyanine (MgPc), described molysite is selected from iron chloride (FeCl
3), ferric bromide (FeBr
3) or iron sulfide (Fe
2s
3) middle at least one, described lanthanide oxide is selected from titanium dioxide praseodymium (PrO
2), praseodymium sesquioxide (Pr
2o
3), three ytterbium oxide (Yb
2o
3) or samarium oxide (Sm
2o
3) middle at least one, described metal oxide is selected from zinc oxide (ZnO), titanium dioxide (TiO
2) or hafnium oxide (HfO
2) or zirconium dioxide (ZrO
2) middle at least one, wherein, the mass ratio of described metal and described metal oxide is 1:100 ~ 1:10, the mass ratio of described molysite and described phthalocyanine-like compound is 1:100 ~ 1:10, the mass ratio of described metal oxide and described phthalocyanine-like compound is 1:1000 ~ 1:100, and the mass ratio of described metal oxide and described lanthanide oxide is 1:100 ~ 1:10.The thickness of n-layer 401 is 10nm ~ 40nm, and intermediate layer 402 thickness is 10nm ~ 40nm, and the thickness of p-type layer 403 is 5nm ~ 30nm.
Second hole transmission layer 52 is formed at the surface of charge generation layer 40.The material of the second hole transmission layer 52 is selected from 1,1-bis-[4-[N, N '-two (p-tolyl) is amino] phenyl] cyclohexane (TAPC), 4,4', 4''-tri-(carbazole-9-base) triphenylamine (TCTA) and N, N '-(1-naphthyl)-N, N '-diphenyl-4, at least one in 4 '-benzidine (NPB), is preferably TCTA.The thickness of the second hole transmission layer 52 is 20nm ~ 60nm, is preferably 40nm.
Second luminescent layer 54 is formed at the surface of the second hole transmission layer 52.The material of the second luminescent layer 54 is selected from 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river pyridine of a specified duration-9-vinyl)-4H-pyrans (DCJTB), 9,10-bis--β-naphthylene anthracene (ADN), 4, two (9-ethyl-3-carbazole vinyl)-1, the 1'-biphenyl (BCzVBi) of 4'-and 8-hydroxyquinoline aluminum (Alq
3) at least one, be preferably Alq
3.The thickness of luminescent layer 40 is 5nm ~ 40nm, is preferably 25nm.
Second electron transfer layer 56 is formed at the surface of the second luminescent layer 52.The material of the second electron transfer layer 56 is selected from least one in 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2,4-triazole derivative (as TAZ) and N-aryl benzimidazole (TPBI), is preferably TAZ.The thickness of the second electron transfer layer 56 is 40nm ~ 300nm, is preferably 60nm.
Electron injecting layer 60 is formed at the second electron transfer layer 56 surface.The material of electron injecting layer 60 is selected from cesium carbonate (Cs
2cO
3), cesium fluoride (CsF), nitrine caesium (CsN
3) and lithium fluoride (LiF) at least one, be preferably LiF.The thickness of electron injecting layer 60 is 0.5nm ~ 10nm, is preferably 0.7nm.
Negative electrode 70 is formed at electron injecting layer 60 surface.The material of negative electrode 70 is selected from least one in silver (Ag), aluminium (Al), platinum (Pt) and gold (Au), is preferably Al.The thickness of negative electrode 70 is 60nm ~ 300nm, is preferably 150nm.
Above-mentioned organic electroluminescence device 100, charge generation layer 40 is by comprising n-layer 401, intermediate layer 402 and p-type layer 403 are formed, wherein, n-layer material is that metal carrying supplies free electron thus improves the concentration of charge carrier, improve electron transfer rate, the molysite that intermediate layer is phthalocyanine-like compound and is entrained in phthalocyanine-like compound, the conductivity that carrier concentration improves intermediate layer can be improved by this doping, phthalocyanine-like compound can improve the injection efficiency in hole and the easy crystallization of this material can improve the scattering of light, p-type layer material is lanthanide oxide, the work function of lanthanide oxide is higher (about-6.7eV ~-7.5eV), with the HOMO energy level comparison match of hole mobile material, hole injection barrier can be reduced, improve the injectability in hole, be conducive to the injection in hole, be conducive to the transmission of charge carrier, improve exciton recombination probability, a small amount of metal oxide is added in these three layers, utilize the nanometer Large stone of metal oxide and larger specific area to improve the scattering of light, this charge generation layer effectively can improve the luminous efficiency of organic electroluminescence device.
Be appreciated that in this organic electroluminescence device 100 and also can other functional layers be set as required.
Please refer to Fig. 2, the preparation method of the organic electroluminescence device 100 of an embodiment, it comprises the following steps:
Step S110, prepare hole injection layer 20, first hole transmission layer 32, first luminescent layer 34 and the first electron transfer layer 36 at anode surface successively evaporation.
Anode 10 is indium tin oxide glass (ITO), aluminium zinc oxide glass (AZO) or indium-zinc oxide glass (IZO), is preferably ITO.
In present embodiment, before anode 10 surface forms hole injection layer 20, first antianode 10 carries out pre-treatment, pre-treatment comprises: anode 10 is carried out photoetching treatment, be cut into required size, adopt liquid detergent, deionized water, acetone, ethanol, each Ultrasonic Cleaning 15min of isopropyl acetone, to remove the organic pollution on anode 10 surface.
Hole injection layer 20 is formed at the surface of anode 10.Hole injection layer 20 is prepared by evaporation.The material of hole injection layer 20 is selected from molybdenum trioxide (MoO
3), tungstic acid (WO
3) and vanadic oxide (V
2o
5) at least one, be preferably WO
3.The thickness of hole injection layer 20 is 20nm ~ 80nm, is preferably 40nm.Evaporation is 2 × 10 at vacuum pressure
-3pa ~ 5 × 10
-5carry out under Pa, evaporation rate is 0.1nm/s ~ 1nm/s.
First hole transmission layer 32 is formed at the surface of hole injection layer 20.First hole transmission layer 32 is prepared by evaporation.The material of the first hole transmission layer 32 is selected from 1,1-bis-[4-[N, N '-two (p-tolyl) is amino] phenyl] cyclohexane (TAPC), 4,4', 4''-tri-(carbazole-9-base) triphenylamine (TCTA) and N, N '-(1-naphthyl)-N, N '-diphenyl-4, at least one in 4 '-benzidine (NPB), is preferably TAPC.The thickness of the first hole transmission layer 32 is 20nm ~ 60nm, is preferably 55nm.Evaporation is 2 × 10 at vacuum pressure
-3pa ~ 5 × 10
-5carry out under Pa, evaporation rate is 0.1nm/s ~ 1nm/s.
First luminescent layer 34 is formed at the surface of the first hole transmission layer 32.First luminescent layer 34 is prepared by evaporation.The material of the first luminescent layer 34 is selected from 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river pyridine of a specified duration-9-vinyl)-4H-pyrans (DCJTB), 9,10-bis--β-naphthylene anthracene (ADN), 4, two (9-ethyl-3-carbazole vinyl)-1, the 1'-biphenyl (BCzVBi) of 4'-and 8-hydroxyquinoline aluminum (Alq
3) at least one, be preferably Alq
3.The thickness of luminescent layer 40 is 5nm ~ 40nm, is preferably 20nm.Evaporation is 2 × 10 at vacuum pressure
-3pa ~ 5 × 10
-5carry out under Pa, evaporation rate is 0.1nm/s ~ 1nm/s.
First electron transfer layer 36 is formed at the surface of the first luminescent layer 32.First electron transfer layer 36 is prepared by evaporation.The material of the first electron transfer layer 36 is selected from least one in 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2,4-triazole derivative (as TAZ) and N-aryl benzimidazole (TPBI), is preferably TAZ.The thickness of the first electron transfer layer 36 is 40nm ~ 300nm, is preferably 60nm.Evaporation is 2 × 10 at vacuum pressure
-3pa ~ 5 × 10
-5carry out under Pa, evaporation rate is 0.1nm/s ~ 1nm/s.
Step S120, prepare charge generation layer 40 on the first electron transfer layer 36 surface.
Charge generation layer 40 is formed at the surface of the first electron transfer layer 36, charge generation layer 40 comprises n-layer 401, intermediate layer 402 and p-type layer 403, n-layer 401 and p-type layer 403 adopt evaporation mode to prepare, intermediate layer 402 adopts electron beam mode evaporation to prepare, the metal oxide that described N-shaped 401 material is metal and is entrained in described metal, intermediate layer 402 material is phthalocyanine-like compound and the molysite be entrained in described phthalocyanine-like compound and metal oxide, the metal oxide that p-type layer 403 is lanthanide oxide and is entrained in described lanthanide oxide, wherein, described metal is selected from silver (Ag), aluminium (Al), platinum (Pt) or the middle at least one of gold (Au), described phthalocyanine-like compound is selected from CuPc (CuPc), Phthalocyanine Zinc (ZnPc), phthalocyanine vanadium (VPc) or the middle at least one of magnesium phthalocyanine (MgPc), described molysite is selected from iron chloride (FeCl
3), ferric bromide (FeBr
3) or iron sulfide (Fe
2s
3) middle at least one, described lanthanide oxide is selected from titanium dioxide praseodymium (PrO
2), praseodymium sesquioxide (Pr
2o
3), three ytterbium oxide (Yb
2o
3) or samarium oxide (Sm
2o
3) middle at least one, described metal oxide is selected from zinc oxide (ZnO), titanium dioxide (TiO
2) or hafnium oxide (HfO
2) or zirconium dioxide (ZrO
2) middle at least one, wherein, the mass ratio of described metal and described metal oxide is 1:100 ~ 1:10, the mass ratio of described molysite and described phthalocyanine-like compound is 1:100 ~ 1:10, the mass ratio of described metal oxide and described phthalocyanine-like compound is 1:1000 ~ 1:100, and the mass ratio of described metal oxide and described lanthanide oxide is 1:100 ~ 1:10.The thickness of n-layer 401 is 10nm ~ 40nm, and intermediate layer 402 thickness is 10nm ~ 40nm, and the thickness of p-type layer 403 is 5nm ~ 30nm.Evaporation is 2 × 10 at vacuum pressure
-3~ 5 × 10
-5carry out under Pa, the evaporation rate of organic material is 0.1 ~ 1nm/s, and the evaporation rate of metal and metallic compound is 1 ~ 10nm/s, and the energy density of electron beam evaporation plating is 10-l00W/cm
2.
Step S130, prepare the second hole transmission layer 52, second luminescent layer 54, second electron transfer layer 56, electron injecting layer 60 and negative electrode 70 on charge generation layer surface successively evaporation.
Second hole transmission layer 52 is formed at the surface of doped zinc oxide diamicton 403.The material of the second hole transmission layer 52 is selected from 1,1-bis-[4-[N, N '-two (p-tolyl) is amino] phenyl] cyclohexane (TAPC), 4,4', 4''-tri-(carbazole-9-base) triphenylamine (TCTA) and N, N '-(1-naphthyl)-N, N '-diphenyl-4, at least one in 4 '-benzidine (NPB), is preferably TCTA.The thickness of the second hole transmission layer 52 is 20nm ~ 60nm, is preferably 40nm.Evaporation is 2 × 10 at vacuum pressure
-3~ 5 × 10
-5carry out under Pa, evaporation rate is 0.1nm/s ~ 1nm/s.
Second luminescent layer 54 is formed at the surface of the second hole transmission layer 52.The material of the second luminescent layer 54 is selected from 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river pyridine of a specified duration-9-vinyl)-4H-pyrans (DCJTB), 9,10-bis--β-naphthylene anthracene (ADN), 4, two (9-ethyl-3-carbazole vinyl)-1, the 1'-biphenyl (BCzVBi) of 4'-and 8-hydroxyquinoline aluminum (Alq
3) at least one, be preferably Alq3.The thickness of luminescent layer 40 is 5nm ~ 40nm, is preferably 25nm.Evaporation is 2 × 10 at vacuum pressure
-3~ 5 × 10
-5carry out under Pa, evaporation rate is 0.1nm/s ~ 1nm/s.
Second electron transfer layer 56 is formed at the surface of the second luminescent layer 52.The material of the second electron transfer layer 56 is selected from least one in 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2,4-triazole derivative (as TAZ) and N-aryl benzimidazole (TPBI), is preferably TAZ.The thickness of the second electron transfer layer 56 is 40nm ~ 300nm, is preferably 60nm.Evaporation is 2 × 10 at vacuum pressure
-3~ 5 × 10
-5carry out under Pa, evaporation rate is 0.1nm/s ~ 1nm/s.
Electron injecting layer 60 is formed at the second electron transfer layer 56 surface.The material of electron injecting layer 60 is selected from cesium carbonate (Cs
2cO
3), cesium fluoride (CsF), nitrine caesium (CsN
3) and lithium fluoride (LiF) at least one, be preferably LiF.The thickness of electron injecting layer 60 is 0.5nm ~ 10nm, is preferably 1nm.Evaporation is 2 × 10 at vacuum pressure
-3~ 5 × 10
-5carry out under Pa, evaporation rate is 0.1nm/s ~ 1nm/s.
Negative electrode 70 is formed at electron injecting layer 60 surface.The material of negative electrode 70 is selected from least one in silver (Ag), aluminium (Al), platinum (Pt) and gold (Au), is preferably Al.The thickness of negative electrode 70 is 60nm ~ 300nm, is preferably 150nm.Evaporation is 2 × 10 at vacuum pressure
-3~ 5 × 10
-5carry out under Pa, evaporation rate is 1nm/s ~ 10nm/s.
Above-mentioned organic electroluminescence device preparation method, technique is simple, and the luminous efficiency of the organic electroluminescence device of preparation is higher.
Below in conjunction with specific embodiment, the preparation method to organic electroluminescence device provided by the invention is described in detail.
The embodiment of the present invention and the preparation used by comparative example and tester are: high vacuum coating system (scientific instrument development center, Shenyang Co., Ltd), the USB4000 fiber spectrometer testing electroluminescent spectrum of U.S. marine optics Ocean Optics, the Keithley2400 of Keithley company of the U.S. tests electric property, the CS-100A colorimeter test brightness of Japanese Konica Minolta company and colourity.
Embodiment 1
Structure prepared by the present embodiment is ITO/WO
3/ TAPC/Alq
3/ TAZ/FeCl
3: CuPc:ZnO/PrO
2: ZnO/TCTA/Alq
3the organic electroluminescence device of/TAZ/LiF/Al.Wherein, "/" presentation layer stack structure, ": " represents doping or mixing, and following examples are identical.
First ITO is carried out photoetching treatment, be cut into required size, use liquid detergent successively, deionized water, acetone, ethanol, each ultrasonic 15min of isopropyl alcohol, remove the organic pollution of glass surface; Evaporation hole injection layer, material is WO
3, thickness is 40nm; Evaporation first hole transmission layer, material is TAPC, and thickness is 55nm; Evaporation first luminescent layer, material is Alq
3, thickness is 20nm; Evaporation first electron transfer layer, material is TAZ, and thickness is 60nm; Prepare charge generation layer, it be the mass ratio of Ag:ZnO, Ag and ZnO is 1:20 that evaporation prepares n-layer, and thickness is 20nm, and it is FeCl that electron beam evaporation plating prepares intermediate layer material
3: CuPc:ZnO, FeCl
3the mass ratio being 1:50, ZnO and CuPc with the mass ratio of CuPc is 3:10, and intermediate layer thickness is 30nm, and it is PrO that evaporation prepares p-type layer material
2: ZnO, PrO
2be 1:50 with the mass ratio of ZnO, thickness is 15nm; Evaporation second hole transmission layer, material is TCTA, and thickness is 40nm; Evaporation second luminescent layer, material is Alq
3, thickness is 25nm; Evaporation second electron transfer layer, material is TAZ, and thickness is 60nm; Evaporation electron injecting layer, material is LiF, and thickness is 0.7nm; Evaporation negative electrode, material is Al, and thickness is 150nm.Finally obtain required electroluminescent device.Evaporation is 8 × 10 at vacuum pressure
-5carry out under Pa, the evaporation rate of organic material is 0.2nm/s, and the evaporation rate of metal and metallic compound is 3nm/s, and the energy density of electron beam evaporation plating is 50W/cm
2.
Refer to Fig. 3, the structure being depicted as preparation in embodiment 1 is ITO/WO
3/ TAPC/Alq
3/ TAZ/FeCl
3: CuPc:ZnO/PrO
2: ZnO/TCTA/Alq
3structure prepared by organic electroluminescence device (curve 1) and the comparative example of/TAZ/LiF/Al is ito glass/WO
3/ TAPC/Alq
3/ TAZ/LiF/Al(curve 2) current density and the relation of current efficiency.In organic electroluminescence device prepared by comparative example, each layer thickness is identical with each layer thickness in organic electroluminescence device prepared by embodiment 1.
Can see from figure, under different current densities, the current efficiency of embodiment 1 is all larger than comparative example, the maximum current efficiency of organic electroluminescence device prepared by embodiment 1 is 6.4cd/A, and the current efficiency of organic electroluminescence device prepared by comparative example is 4.6cd/A, and the current efficiency of comparative example declines fast along with the increase of brightness, this explanation, n-layer material is that metal carrying supplies free electron thus improves the concentration of charge carrier, improve electron transfer rate, the molysite that intermediate layer is phthalocyanine-like compound and is entrained in phthalocyanine-like compound, the conductivity that carrier concentration improves intermediate layer can be improved by this doping, phthalocyanine-like compound can improve the injection efficiency in hole and the easy crystallization of this material can improve the scattering of light, p-type layer material is lanthanide oxide, the work function of lanthanide oxide is higher (about-6.7eV ~-7.5eV), with the HOMO energy level comparison match of hole mobile material, hole injection barrier can be reduced, improve the injectability in hole, be conducive to the injection in hole, be conducive to the transmission of charge carrier, improve exciton recombination probability, a small amount of metal oxide is added in these three layers, utilize the nanometer Large stone of metal oxide and larger specific area to improve the scattering of light, this charge generation layer effectively can improve the luminous efficiency of organic electroluminescence device.
The current efficiency of organic electroluminescence device prepared of each embodiment is all similar with embodiment 1 below, and each organic electroluminescence device also has similar current efficiency, repeats no more below.
Embodiment 2
Structure prepared by the present embodiment is AZO/WO
3/ TCTA/ADN/TPBi/Al:TiO
2/ FeBr
3: ZnPc:HfO
2/ Pr
2o
3: ZnO/NPB/ADN/TAZ/CsN
3the organic electroluminescence device of/Pt.
First AZO substrate of glass is used liquid detergent successively, deionized water, ultrasonic 15min, remove the organic pollution of glass surface; Evaporation prepares hole injection layer, and material is WO
3, thickness is 80nm; Evaporation prepares the first hole transmission layer, and material is TCTA, and thickness is 60nm; Evaporation prepares the first luminescent layer, and material is ADN, and thickness is 5nm; Evaporation prepares the first electron transfer layer, and material is TPBi, and thickness is 200nm; Prepare charge generation layer, it is Al:TiO that evaporation prepares n-layer
2, Al and TiO
2mass ratio be 1:100, thickness is 40nm, and it is FeBr that electron beam evaporation plating prepares intermediate layer material
3: ZnPc:HfO
2, FeBr
3with ZnPc mass ratio be 1:100, HfO
2be 1:100 with the mass ratio of ZnPc, intermediate layer thickness is 10nm, and it is Pr that evaporation prepares p-type layer material
2o
3: ZnO, Pr
2o
3be 1:10 with the mass ratio of ZnO, thickness is 5nm; Evaporation prepares the second hole transmission layer, and material is NPB, and thickness is 20nm, the second luminescent layer, and material is ADN, and thickness is 7nm; Evaporation prepares the second electron transfer layer, and material is TAZ, and thickness is 40nm; Evaporation prepares electron injecting layer, and material is CsN
3, thickness is 10nm; Evaporation prepares negative electrode, and material is Pt, and thickness is 60nm, finally obtains required electroluminescent device.Evaporation is 2 × 10 at vacuum pressure
-3carry out under Pa, the evaporation rate of organic material is 0.1nm/s, and the evaporation rate of metal and metallic compound is 10nm/s, and the energy density of electron beam evaporation plating is 10W/cm
2.
Embodiment 3
Structure prepared by the present embodiment is IZO/V
2o
5/ NPB/BCzVBi/TAZ/Pt:ZnO/Fe
2s
3: VPc:TiO
2/ Yb
2o
3: ZrO
2the organic electroluminescence device of/TCTA/BCzVBi/Bphen/CsF/Al.
First IZO substrate of glass is used liquid detergent successively, deionized water, ultrasonic 15min, remove the organic pollution of glass surface; Evaporation prepares hole injection layer, and material is V
2o
5, thickness is 20nm; Evaporation prepares the first hole transmission layer, and material is NPB, and thickness is 30nm; Evaporation prepares the first luminescent layer, and material is BCzVBi, and thickness is 40nm; Evaporation prepares the first electron transfer layer, and material is TAZ, and thickness is 60nm; Prepare charge generation layer, it be the mass ratio of Pt:ZnO, Pt and ZnO is 1:10 that evaporation prepares n-layer, and thickness is 10nm, and it is Fe that electron beam evaporation plating prepares intermediate layer material
2s
3: VPc:TiO
2, Fe
2s
3with VPc mass ratio be 1:10, TiO
2be 1:1000 with the mass ratio of VPc, intermediate layer thickness is 40nm, and it is Yb that evaporation prepares p-type layer material
2o
3: ZrO
2, Yb
2o
3with ZrO
2mass ratio be 1:100, thickness is 30nm; Evaporation prepares the second hole transmission layer, and material is TCTA, and thickness is 200nm; Evaporation prepares the second luminescent layer, and material is BCzVBi, and thickness is 30nm; Evaporation prepares the second electron transfer layer, and material is Bphen, and thickness is 40nm; Evaporation prepares electron injecting layer, and material is CsF, and thickness is 0.5nm; Evaporation prepares negative electrode, and material is Al, and thickness is 300nm, finally obtains required electroluminescent device.Evaporation is 5 × 10 at vacuum pressure
-5carry out under Pa, the evaporation rate of organic material is 1nm/s, and the evaporation rate of metal and metallic compound is 1nm/s, and the energy density of electron beam evaporation plating is 100W/cm
2.
Embodiment 4
Structure prepared by the present embodiment is IZO/MoO
3/ TAPC/DCJTB/Bphen/Au:ZrO
2/ FeCl
3: MgPc:ZrO
2/ Sm
2o
3: ZrO
2/ TCTA/DCJTB/TPBi/Cs
2cO
3the organic electroluminescence device of/Au.
First IZO substrate of glass is used liquid detergent successively, deionized water, ultrasonic 15min, remove the organic pollution of glass surface; Evaporation prepares hole injection layer, and material is MoO
3, thickness is 30nm; Evaporation prepares the first hole transmission layer, and material is TAPC, and thickness is 50nm; Evaporation prepares the first luminescent layer, and material is DCJTB, and thickness is 5nm; Evaporation prepares the first electron transfer layer, and material is Bphen, and thickness is 40nm; Prepare charge generation layer, it is Au:ZrO that evaporation prepares n-layer
2, the mass ratio of Au and ZnO is 1:50, and thickness is 15nm, and it is FeCl that electron beam evaporation plating prepares intermediate layer material
3: MgPc:ZrO
2, FeCl
3with MgPc mass ratio be 3:100, ZrO
2be 1:125 with the mass ratio of MgPc, intermediate layer thickness is 30nm, and it is Sm that evaporation prepares p-type layer material
2o
3: ZrO
2, Sm
2o
3with ZrO
2mass ratio be 3:100, thickness is 20nm; Evaporation prepares the second hole transmission layer, and material is TCTA, and thickness is 50nm, the second luminescent layer, and material is DCJTB, and thickness is 5nm; Evaporation prepares the second electron transfer layer, and material is TPBi, and thickness is 80nm; Evaporation prepares electron injecting layer, and material is Cs
2cO
3, thickness is 2nm; Evaporation prepares negative electrode, and material is Au, and thickness is 100nm, finally obtains required electroluminescent device.Evaporation is 5 × 10 at vacuum pressure
-4carry out under Pa, the evaporation rate of organic material is 0.2nm/s, and the evaporation rate of metal and metallic compound is 5nm/s, and the energy density of electron beam evaporation plating is 20W/cm
2.
The above embodiment only have expressed several execution mode of the present invention, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection range of patent of the present invention should be as the criterion with claims.
Claims (10)
1. an organic electroluminescence device, is characterized in that, comprises the anode stacked gradually, hole injection layer, first hole transmission layer, first luminescent layer, first electron transfer layer, charge generation layer, second hole transmission layer, second luminescent layer, second electron transfer layer, electron injecting layer and negative electrode, described charge generation layer comprises n-layer, intermediate layer and p-type layer, the metal oxide that described n-layer material is metal and is entrained in described metal, intermediate layer material is phthalocyanine-like compound and the molysite be entrained in described phthalocyanine-like compound and metal oxide, the metal oxide that p-type layer is lanthanide oxide and is entrained in described lanthanide oxide, wherein, described metal is selected from silver, aluminium, at least one in platinum or gold, described phthalocyanine-like compound is selected from CuPc, Phthalocyanine Zinc, at least one in phthalocyanine vanadium or magnesium phthalocyanine, described molysite is selected from iron chloride, at least one in ferric bromide or iron sulfide, described lanthanide oxide is selected from titanium dioxide praseodymium, praseodymium sesquioxide, at least one in three ytterbium oxides or samarium oxide, described metal oxide is selected from zinc oxide, at least one in titanium dioxide or hafnium oxide or zirconium dioxide, wherein, the mass ratio of described metal and described metal oxide is 1:100 ~ 1:10, the mass ratio of described molysite and described phthalocyanine-like compound is 1:100 ~ 1:10, the mass ratio of described metal oxide and described phthalocyanine-like compound is 1:1000 ~ 1:100, and the mass ratio of described metal oxide and described lanthanide oxide is 1:100 ~ 1:10.
2. organic electroluminescence device according to claim 1, is characterized in that, the thickness of described n-layer is 10nm ~ 40nm, and described intermediate layer thickness is 10nm ~ 40nm, and the thickness of described p-type layer is 5nm ~ 30nm.
3. organic electroluminescence device according to claim 1, it is characterized in that, the material of described first luminescent layer and described second luminescent layer is selected from 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river pyridine of a specified duration-9-vinyl)-4H-pyrans, 9,10-bis--β-naphthylene anthracene, 4, at least one in two (9-ethyl-3-carbazole vinyl)-1, the 1'-biphenyl of 4'-and oxine aluminium.
4. organic electroluminescence device according to claim 1, it is characterized in that, the material of described first hole transmission layer and described second hole transmission layer is selected from 1,1-bis-[4-[N, N '-two (p-tolyl) are amino] phenyl] cyclohexane, 4,4', 4''-tri-(carbazole-9-base) triphenylamine and N, at least one in N '-(1-naphthyl)-N, N '-diphenyl-4,4 '-benzidine.
5. organic electroluminescence device according to claim 1, is characterized in that, the material of described first electron transfer layer and described second electron transfer layer is selected from 4,7-diphenyl-1, at least one in 10-phenanthroline, 1,2,4-triazole derivative and N-aryl benzimidazole.
6. a preparation method for organic electroluminescence device, is characterized in that, comprises the following steps:
Hole injection layer, the first hole transmission layer, the first luminescent layer and the first electron transfer layer is prepared at anode surface successively evaporation;
Charge generation layer is prepared on described first electron transfer layer surface, described charge generation layer comprises n-layer, intermediate layer and p-type layer, n-layer and p-type layer adopt evaporation mode to prepare, intermediate layer adopts the preparation of electron beam mode evaporation, the metal oxide that described n-layer material is metal and is entrained in described metal, intermediate layer material is phthalocyanine-like compound and the molysite be entrained in described phthalocyanine-like compound and metal oxide, the metal oxide that p-type layer is lanthanide oxide and is entrained in described lanthanide oxide, wherein, described metal is selected from silver, aluminium, at least one in platinum or gold, described phthalocyanine-like compound is selected from CuPc, Phthalocyanine Zinc, at least one in phthalocyanine vanadium or magnesium phthalocyanine, described molysite is selected from iron chloride, at least one in ferric bromide or iron sulfide, described lanthanide oxide is selected from titanium dioxide praseodymium, praseodymium sesquioxide, at least one in three ytterbium oxides or samarium oxide, described metal oxide is selected from zinc oxide, at least one in titanium dioxide or hafnium oxide or zirconium dioxide, wherein, the mass ratio of described metal and described metal oxide is 1:100 ~ 1:10, the mass ratio of described molysite and described phthalocyanine-like compound is 1:100 ~ 1:10, the mass ratio of described metal oxide and described phthalocyanine-like compound is 1:1000 ~ 1:100, the mass ratio of described metal oxide and described lanthanide oxide is 1:100 ~ 1:10, evaporation is 2 × 10 at vacuum pressure
-3~ 5 × 10
-5carry out under Pa, the evaporation rate of organic material is 0.1 ~ 1nm/s, and the evaporation rate of metal and metallic compound is 1 ~ 10nm/s, and the energy density of electron beam evaporation plating is 10-l00W/cm
2, and
The second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer and negative electrode is formed on described charge generation layer surface successively evaporation.
7. the preparation method of organic electroluminescence device according to claim 6, it is characterized in that, the material of described first luminescent layer and described second luminescent layer is selected from 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river pyridine of a specified duration-9-vinyl)-4H-pyrans, 9,10-bis--β-naphthylene anthracene, 4, at least one in two (9-ethyl-3-carbazole vinyl)-1, the 1'-biphenyl of 4'-and oxine aluminium.
8. the preparation method of organic electroluminescence device according to claim 6, it is characterized in that, the material of described first hole transmission layer and described second hole transmission layer is selected from 1,1-bis-[4-[N, N '-two (p-tolyl) are amino] phenyl] cyclohexane, 4,4', 4''-tri-(carbazole-9-base) triphenylamine and N, at least one in N '-(1-naphthyl)-N, N '-diphenyl-4,4 '-benzidine.
9. the preparation method of organic electroluminescence device according to claim 6, is characterized in that, the thickness of described n-layer is 10nm ~ 40nm, and described intermediate layer thickness is 10nm ~ 40nm, and the thickness of described p-type layer is 5nm ~ 30nm.
10. the preparation method of organic electroluminescence device according to claim 6, it is characterized in that, before described anode surface forms hole injection layer, first antianode carries out pre-treatment, pre-treatment comprises: anode is carried out photoetching treatment, be cut into required size, adopt liquid detergent, deionized water, acetone, ethanol, each Ultrasonic Cleaning 15min of isopropyl acetone, to remove the organic pollution of anode surface.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310261059.1A CN104253243A (en) | 2013-06-26 | 2013-06-26 | Organic electroluminescent device and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310261059.1A CN104253243A (en) | 2013-06-26 | 2013-06-26 | Organic electroluminescent device and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104253243A true CN104253243A (en) | 2014-12-31 |
Family
ID=52187950
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310261059.1A Pending CN104253243A (en) | 2013-06-26 | 2013-06-26 | Organic electroluminescent device and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104253243A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017032802A1 (en) * | 2015-08-25 | 2017-03-02 | Osram Oled Gmbh | Organic light-emitting component and lamp |
| CN113421984A (en) * | 2021-06-23 | 2021-09-21 | 上海晶合光电科技有限公司 | OLED device and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1738502A (en) * | 2001-12-05 | 2006-02-22 | 株式会社半导体能源研究所 | organic semiconductor device |
| CN101006594A (en) * | 2004-08-20 | 2007-07-25 | 伊斯曼柯达公司 | White OLED having multiple white electroluminescent units |
| CN101444142A (en) * | 2006-05-11 | 2009-05-27 | 出光兴产株式会社 | organic electroluminescent element |
| CN102097598A (en) * | 2010-12-06 | 2011-06-15 | 电子科技大学 | Organic light-emitting device and production method thereof |
-
2013
- 2013-06-26 CN CN201310261059.1A patent/CN104253243A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1738502A (en) * | 2001-12-05 | 2006-02-22 | 株式会社半导体能源研究所 | organic semiconductor device |
| CN101006594A (en) * | 2004-08-20 | 2007-07-25 | 伊斯曼柯达公司 | White OLED having multiple white electroluminescent units |
| CN101444142A (en) * | 2006-05-11 | 2009-05-27 | 出光兴产株式会社 | organic electroluminescent element |
| CN102097598A (en) * | 2010-12-06 | 2011-06-15 | 电子科技大学 | Organic light-emitting device and production method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017032802A1 (en) * | 2015-08-25 | 2017-03-02 | Osram Oled Gmbh | Organic light-emitting component and lamp |
| US10608197B2 (en) | 2015-08-25 | 2020-03-31 | Osram Oled Gmbh | Organic light-emitting component and lamp |
| CN113421984A (en) * | 2021-06-23 | 2021-09-21 | 上海晶合光电科技有限公司 | OLED device and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103972413A (en) | Organic light-emitting device and production method thereof | |
| CN104183738A (en) | Organic electroluminescent device and preparation method thereof | |
| CN104183778A (en) | Organic electroluminescent device and preparation method thereof | |
| CN104253243A (en) | Organic electroluminescent device and preparation method thereof | |
| CN103972420A (en) | Organic light-emitting device and method for manufacturing same | |
| CN104253228A (en) | Organic light emitting diode and preparation method thereof | |
| CN103972408A (en) | Organic light-emitting device and method for manufacturing same | |
| CN103972421A (en) | Organic light-emitting device and production method thereof | |
| CN104183732A (en) | Organic light emitting device and manufacturing method thereof | |
| CN104253229A (en) | Organic light-emitting device and manufacturing method thereof | |
| CN104253227A (en) | Organic light emitting diode and preparation method thereof | |
| CN104078568A (en) | Organic light-emitting diode and preparation method thereof | |
| CN104183731A (en) | Organic light emitting device and manufacturing method thereof | |
| CN104183729A (en) | Organic light emitting device and manufacturing method thereof | |
| CN104078575A (en) | Organic light-emitting diode and preparation method thereof | |
| CN103972400A (en) | Organic light-emitting device and method for manufacturing same | |
| CN104183777A (en) | Organic light emitting device and manufacturing method thereof | |
| CN103972411A (en) | Organic light-emitting device and production method thereof | |
| CN103824956A (en) | Organic electroluminescent device and preparation method thereof | |
| CN104183740A (en) | Organic electroluminescent device and preparation method thereof | |
| CN103972409A (en) | Organic light-emitting device and method for manufacturing same | |
| CN104425745A (en) | Organic electroluminescent device and preparation method thereof | |
| CN104253230A (en) | Organic electroluminescent device and preparation method thereof | |
| CN104183739A (en) | Organic electroluminescent device and preparation method thereof | |
| CN104253233A (en) | Organic electroluminescent device and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20141231 |