CN103985818B - 一种有机电致发光器件 - Google Patents
一种有机电致发光器件 Download PDFInfo
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- CN103985818B CN103985818B CN201410128378.XA CN201410128378A CN103985818B CN 103985818 B CN103985818 B CN 103985818B CN 201410128378 A CN201410128378 A CN 201410128378A CN 103985818 B CN103985818 B CN 103985818B
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- 238000005401 electroluminescence Methods 0.000 title abstract 2
- 239000010410 layer Substances 0.000 claims abstract description 110
- 150000001875 compounds Chemical class 0.000 claims abstract description 47
- 238000002347 injection Methods 0.000 claims abstract description 22
- 239000007924 injection Substances 0.000 claims abstract description 22
- 239000012044 organic layer Substances 0.000 claims abstract description 22
- 230000004888 barrier function Effects 0.000 claims abstract description 5
- 230000005525 hole transport Effects 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 230000005540 biological transmission Effects 0.000 abstract 1
- 230000027756 respiratory electron transport chain Effects 0.000 abstract 1
- 239000000463 material Substances 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
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- 238000006243 chemical reaction Methods 0.000 description 10
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- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 8
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
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- RKBWIDHPFRZHOU-UHFFFAOYSA-N 1-bromophenazine Chemical compound C1=CC=C2N=C3C(Br)=CC=CC3=NC2=C1 RKBWIDHPFRZHOU-UHFFFAOYSA-N 0.000 description 5
- 229910052783 alkali metal Inorganic materials 0.000 description 5
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- 150000001342 alkaline earth metals Chemical class 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 5
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- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- YSUIQYOGTINQIN-UZFYAQMZSA-N 2-amino-9-[(1S,6R,8R,9S,10R,15R,17R,18R)-8-(6-aminopurin-9-yl)-9,18-difluoro-3,12-dihydroxy-3,12-bis(sulfanylidene)-2,4,7,11,13,16-hexaoxa-3lambda5,12lambda5-diphosphatricyclo[13.2.1.06,10]octadecan-17-yl]-1H-purin-6-one Chemical compound NC1=NC2=C(N=CN2[C@@H]2O[C@@H]3COP(S)(=O)O[C@@H]4[C@@H](COP(S)(=O)O[C@@H]2[C@@H]3F)O[C@H]([C@H]4F)N2C=NC3=C2N=CN=C3N)C(=O)N1 YSUIQYOGTINQIN-UZFYAQMZSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 3
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- ITOFPJRDSCGOSA-KZLRUDJFSA-N (2s)-2-[[(4r)-4-[(3r,5r,8r,9s,10s,13r,14s,17r)-3-hydroxy-10,13-dimethyl-2,3,4,5,6,7,8,9,11,12,14,15,16,17-tetradecahydro-1h-cyclopenta[a]phenanthren-17-yl]pentanoyl]amino]-3-(1h-indol-3-yl)propanoic acid Chemical compound C([C@H]1CC2)[C@H](O)CC[C@]1(C)[C@@H](CC[C@]13C)[C@@H]2[C@@H]3CC[C@@H]1[C@H](C)CCC(=O)N[C@H](C(O)=O)CC1=CNC2=CC=CC=C12 ITOFPJRDSCGOSA-KZLRUDJFSA-N 0.000 description 2
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 description 2
- UCCUXODGPMAHRL-UHFFFAOYSA-N 1-bromo-4-iodobenzene Chemical compound BrC1=CC=C(I)C=C1 UCCUXODGPMAHRL-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229910004039 HBF4 Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- XQVWYOYUZDUNRW-UHFFFAOYSA-N N-Phenyl-1-naphthylamine Chemical compound C=1C=CC2=CC=CC=C2C=1NC1=CC=CC=C1 XQVWYOYUZDUNRW-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 125000004946 alkenylalkyl group Chemical group 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000005038 alkynylalkyl group Chemical group 0.000 description 2
- 229940125810 compound 20 Drugs 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 125000004988 dibenzothienyl group Chemical group C1(=CC=CC=2SC3=C(C21)C=CC=C3)* 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
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- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 125000001072 heteroaryl group Chemical group 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 2
- 238000009832 plasma treatment Methods 0.000 description 2
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 2
- 229920000123 polythiophene Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 125000005259 triarylamine group Chemical group 0.000 description 2
- WWTBZEKOSBFBEM-SPWPXUSOSA-N (2s)-2-[[2-benzyl-3-[hydroxy-[(1r)-2-phenyl-1-(phenylmethoxycarbonylamino)ethyl]phosphoryl]propanoyl]amino]-3-(1h-indol-3-yl)propanoic acid Chemical compound N([C@@H](CC=1C2=CC=CC=C2NC=1)C(=O)O)C(=O)C(CP(O)(=O)[C@H](CC=1C=CC=CC=1)NC(=O)OCC=1C=CC=CC=1)CC1=CC=CC=C1 WWTBZEKOSBFBEM-SPWPXUSOSA-N 0.000 description 1
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
- WYSBZCPNRXECEW-UHFFFAOYSA-N 1-diazo-2H-anthracene Chemical class C1=CC=C2C=C3C(=[N+]=[N-])CC=CC3=CC2=C1 WYSBZCPNRXECEW-UHFFFAOYSA-N 0.000 description 1
- IXHWGNYCZPISET-UHFFFAOYSA-N 2-[4-(dicyanomethylidene)-2,3,5,6-tetrafluorocyclohexa-2,5-dien-1-ylidene]propanedinitrile Chemical compound FC1=C(F)C(=C(C#N)C#N)C(F)=C(F)C1=C(C#N)C#N IXHWGNYCZPISET-UHFFFAOYSA-N 0.000 description 1
- VNANLRAWGZHALH-UHFFFAOYSA-N 2h-oxazine;phenol Chemical compound N1OC=CC=C1.OC1=CC=CC=C1 VNANLRAWGZHALH-UHFFFAOYSA-N 0.000 description 1
- YFCSASDLEBELEU-UHFFFAOYSA-N 3,4,5,6,9,10-hexazatetracyclo[12.4.0.02,7.08,13]octadeca-1(18),2(7),3,5,8(13),9,11,14,16-nonaene-11,12,15,16,17,18-hexacarbonitrile Chemical group N#CC1=C(C#N)C(C#N)=C2C3=C(C#N)C(C#N)=NN=C3C3=NN=NN=C3C2=C1C#N YFCSASDLEBELEU-UHFFFAOYSA-N 0.000 description 1
- UDQLIWBWHVOIIF-UHFFFAOYSA-N 3-phenylbenzene-1,2-diamine Chemical class NC1=CC=CC(C=2C=CC=CC=2)=C1N UDQLIWBWHVOIIF-UHFFFAOYSA-N 0.000 description 1
- BWGRDBSNKQABCB-UHFFFAOYSA-N 4,4-difluoro-N-[3-[3-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)-8-azabicyclo[3.2.1]octan-8-yl]-1-thiophen-2-ylpropyl]cyclohexane-1-carboxamide Chemical compound CC(C)C1=NN=C(C)N1C1CC2CCC(C1)N2CCC(NC(=O)C1CCC(F)(F)CC1)C1=CC=CS1 BWGRDBSNKQABCB-UHFFFAOYSA-N 0.000 description 1
- DDBXJDNROBODGD-UHFFFAOYSA-N 9-n,10-n-diphenylphenanthrene-9,10-diamine Chemical compound C=1C=CC=CC=1NC=1C2=CC=CC=C2C2=CC=CC=C2C=1NC1=CC=CC=C1 DDBXJDNROBODGD-UHFFFAOYSA-N 0.000 description 1
- 238000006443 Buchwald-Hartwig cross coupling reaction Methods 0.000 description 1
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- IIRVBNFPODABQL-UHFFFAOYSA-N N,N-diphenylaniline ethene Chemical class C1(=CC=CC=C1)N(C1=CC=CC=C1)C1=CC=CC=C1.C=C IIRVBNFPODABQL-UHFFFAOYSA-N 0.000 description 1
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000006069 Suzuki reaction reaction Methods 0.000 description 1
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
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- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000007611 bar coating method Methods 0.000 description 1
- 125000003785 benzimidazolyl group Chemical class N1=C(NC2=C1C=CC=C2)* 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- RWWUBXBYBPQIJI-UHFFFAOYSA-N cesium;quinolin-8-ol Chemical compound [Cs].C1=CN=C2C(O)=CC=CC2=C1 RWWUBXBYBPQIJI-UHFFFAOYSA-N 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
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- 238000001816 cooling Methods 0.000 description 1
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
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- 125000003914 fluoranthenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC=C4C1=C23)* 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- IDBFBDSKYCUNPW-UHFFFAOYSA-N lithium nitride Chemical compound [Li]N([Li])[Li] IDBFBDSKYCUNPW-UHFFFAOYSA-N 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- SKEDXQSRJSUMRP-UHFFFAOYSA-N lithium;quinolin-8-ol Chemical compound [Li].C1=CN=C2C(O)=CC=CC2=C1 SKEDXQSRJSUMRP-UHFFFAOYSA-N 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 1
- 150000002916 oxazoles Chemical class 0.000 description 1
- 150000002964 pentacenes Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000002987 phenanthrenes Chemical class 0.000 description 1
- 150000005041 phenanthrolines Chemical class 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 150000002988 phenazines Chemical class 0.000 description 1
- 108091008695 photoreceptors Proteins 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical class 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 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 150000003220 pyrenes Chemical class 0.000 description 1
- 125000001725 pyrenyl group Chemical group 0.000 description 1
- 150000003248 quinolines Chemical class 0.000 description 1
- 150000003252 quinoxalines Chemical class 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 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 1
- 150000003918 triazines Chemical class 0.000 description 1
- NHDIQVFFNDKAQU-UHFFFAOYSA-N tripropan-2-yl borate Chemical compound CC(C)OB(OC(C)C)OC(C)C NHDIQVFFNDKAQU-UHFFFAOYSA-N 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
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Abstract
本发明提供了一种有机电致发光器件,其包括阳极、阴极和有机层,有机层包含空穴注入层、空穴传输层、发光层、阻挡层、电子注入层和电子传输层中的一层以上,其特征在于有机层中至少一层包含有如下结构式(I)的化合物
Description
技术领域
本发明涉及有机电致发光材料领域,具体的说涉及一种有机电致发光器件。
背景技术
有机电致发光器件(OLEDs)为在两个金属电极之间通过旋涂或者真空蒸渡沉积一层有机材料制备而成的器件,一个经典的三层有机电致发光器件包含空穴传输层,发光层和电子传输层。由阳极产生的空穴经空穴传输层跟由阴极产生的电子经电子传输层结合在发光层形成激子,而后发光。有机电致发光器件可以根据需要通过改变发光层的材料来调节发射各种需要的光。
有机电致发光器件作为一种新型的显示技术,具有自发光、宽视角、低能耗、效率高、薄、色彩丰富、响应速度快、适用温度范围广、低驱动电压、可制作柔性可弯曲与透明的显示面板以及环境友好等独特优点,可以应用在平板显示器和新一代照明上,也可以作为LCD的背光源。
自从20世纪80年代底发明以来,有机电致发光器件已经在产业上有所应用,比如作为相机和手机等屏幕,但是目前的OLED器件由于效率低,使用寿命短等因素制约其更广泛的应用,特别是大屏幕显示器。而制约其中的一个重要因素就是有机电致发光器件中的有机电致发光材料的性能。另外由于OLED器件在施加电压运行的时候,会产生焦耳热,使得有机材料容易发生结晶,影响了器件的寿命和效率,因此,也需要开发稳定高效的有机电致发光材料。
酚嗪衍生物具有很好的空穴传输性能,在有机电致发光器件上的应用备受关注。以二芳香基邻菲二胺类化合物和卤代芳烃制备而得到的酚嗪类化合物大大地提高了酚嗪的制备,也拓宽了化合物的种类(CN102491950)。在传统的空穴注入材料,如copperphthalocyanine(CuPc),降解慢,制备耗能高,不利于环境保护,而且其会吸收光,影响器件的效率。而就如NPB等原始的空穴传输材料,热稳定性比较差,也很大程度影响器件寿命。因而,需要开发高效稳定的有机电致发光材料。
发明内容
本发明首先提供一种有机电致发光化合物,具有如下结构式(I):
其中,R1-R4分别独立地表示为氢、氘原子、卤素、氰基、硝基、C1-C8烷基、C1-C8烷氧基、C6-C30的取代或者未取代的芳基、C3-C30的取代或者未取代的杂芳基、C2-C8的取代或者未取代的烯烷基、或者C2-C8的取代或者未取代的炔烷基;
其中,Ar1-Ar4分别独立地表示C6-C60的取代或者未取代的芳基、C3-C60的取代或者未取代的带有一个或者多个杂原子的杂芳基、C6-C60的三芳香胺基、或者C6-C30的取代或者未取代的咔唑基;
n为1-4。
进一步优选的为:
R1-R4分别独立地表示为氢、卤素、氰基、硝基、C1-C8烷基、C1-C8烷氧基、C2-C8的取代或者未取代的烯烷基、C2-C8的取代或者未取代的炔烷基、未取代的苯基或者被C1-C4烷基取代的苯基;
Ar1-Ar4分别独立地表示为:
被C1-C4烷基或者C6-C30芳基取代的苯基、
被C1-C4烷基或者C6-C30芳基取代的萘基、
被N-芳基(C6-C30)或者C1-C4烷基取代的咔唑基、蒽基、菲基、芘基、苝基或荧蒽基、
(9,9-二烷基)芴基、
(9,9-二取代或者未取代的芳基)芴基、
9,9-螺芴基、
三芳香(C6-C60)胺基、
取代或者未取代的二苯并噻吩基、
取代或者未取代的二苯并呋喃基;
n优选为1,2。
进一步优选的方式为:
R1-R4分别独立地表示为氢、甲氧基、氟、甲基、乙基、丙基、异丙基、叔丁基、正丁基、苯基或萘基;
Ar4优选为苯基、萘基、芴基、二苯并噻吩基或二苯并呋喃基;
Ar1-Ar3分别独立地优选为下列基团,这些基团可进一步被取代:
进一步优选的,本发明的一种有机电致发光化合物,其为如下1-40的结构式:
本发明的有机电致发光化合物可以通过Suzuki偶联和Buchwald-Hartwig反应制备得到。
本发明的有机电致发光化合物可以应用在有机电致发光器件,有机太阳能电池,有机薄膜晶体管或有机光感受器领域。
本发明还提供了一种有机电致发光器件,该器件包含阳极、阴极和有机层,有机层包含发光层、空穴注入层、空穴传输层、空穴阻挡层和电子传输层中的一层或一层以上,其中所述有机层中至少有一层含有如结构式(I)所述的有机电致发光化合物:
其中R1-R4、Ar1-Ar4以及n的定义如前所述;
其中有机层为发光层;
或者有机层为发光层和空穴注入层;
或者有机层为发光层和空穴传输层;
或者有机层为发光层和电子传输层;
或者有机层为发光层、空穴注入层、空穴传输层和电子传输层;
或者有机层为发光层、空穴注入层、空穴传输层、电子传输层和电子注入层;
或者有机层为发光层、空穴注入层、空穴传输层、电子传输层、电子注入层和阻挡层;
或者有机层为发光层、空穴传输层、电子传输层、电子注入层和阻挡层;
或者有机层为发光层、空穴传输层、电子注入层和阻挡层;
其中如结构式(I)所述的有机电致发光化合物所在的层为发光层、空穴传输层或者空穴注入层;
其中结构式(I)所述的有机电致发光化合物为结构式1-40的化合物;
如结构式I所述的有机电致发光化合物可以单独使用,也可以和其他化合物混合使用;
如结构式I所述的有机电致发光化合物可以单独使用其中的一种化合物,也可以同时使用结构式I中的两种或两种以上的化合物。
本发明的有机电致发光器件,进一步优选的方式为,该有机电致发光器件包含阳极、空穴传输层、发光层、电子传输层、电子注入层和阴极,其中空穴传输层中含有结构式(I)的化合物;进一步优选的,空穴传输层中的化合物为结构式1-40的化合物。
结构式I化合物作为发光层时,可以作为无掺杂发光层或掺杂发光层。
所述掺杂发光层包括主体材料和客体材料,结构式(I)化合物作为主体材料时,其浓度为整个发光层重量的20-99.9%,优选80-99%,更优选为90-99%。结构式(I)化合物作为客体材料时,其浓度为这个发光层重量的0.01-80%,优选1-20%,更优选为1-10%。
可以同时使用结构式I的两个化合物分别作主体材料和客体材料。
本发明的有机电致发光器件有机层的总厚度为1-1000nm,优选50-500nm。
本发明有机电致发光器件的空穴传输层和空穴注入层,所需材料具有很好的空穴传输性能,能够有效地把空穴从阳极传输到发光层上。除了上述具有结构式(I)所述化合物外,还可以包括其他小分子和高分子有机化合物,包括但不限于三芳香胺化合物、联苯二胺化合物、芴类化合物、酞菁类化合物、六氰基六杂三苯(hexanitrilehexaazatriphenylene)、2,3,5,6-四氟-7,7′,8,8′-四氰二甲基对苯醌(F4-TCNQ)、聚乙烯基咔唑、聚噻吩、聚乙烯或聚苯磺酸。
本发明的有机电致发光器件的发光层,具有很好的发光特性,可以根据需要调节可见光的范围。除含有本发明的酚嗪类化合物外,还可以含有如下化合物,包括但是不限于萘类化合物、芘类化合物、芴类化合物、菲类化合物、屈类化合物、荧蒽类化合物、蒽类化合物、并五苯类化合物、苝类化合物、二芳乙烯类化合物、三苯胺乙烯类化合物、胺类化合物、咔唑类化合物、苯并咪唑类化合物、呋喃类化合物、金属有机荧光络合物、金属有机磷光络合物(如Ir,Pt,Os,Cu)、聚乙烯咔唑、聚有机硅化合物、聚噻吩等有机高分子发光材料,它们可以单独使用,也可以多种混合物使用。发光层的膜厚优选为10-50nm。
本发明有机电致发光器件的有机电子传输材料要求具有很好的电子传输性能,能够有效地把电子从阴极传输到发光层中,具有很大的电子迁移率。可以选择如下化合物,但是不限于此,氧杂恶唑,噻唑类化合物,三氮唑类化合物,三氮嗪类化合物,三氮杂苯类化合物,喔啉类化合物,二氮蒽类化合物,含硅杂环类化合物,喹啉类化合物,菲啰啉类化合物,金属螯合物(如Alq3),氟取代苯类化合物。
本发明有机电致发光器件的电子注入层,可以有效的把电子从阴极注入到有机层中,主要选自碱金属或者碱金属的化合物,或选自碱土金属或者碱土金属的化合物或者碱金属络合物,可以选择如下化合物,但是不限于此,碱金属、碱土金属、稀土金属、碱金刷的氧化物或者卤化物、碱土金属的氧化物或者卤化物、稀土金属的氧化物或者卤化物、碱金属或者碱土金属的有机络合物;优选为锂、氟化锂、氧化锂、氮化锂、8-羟基喹啉锂、铯、碳酸铯、8-羟基喹啉铯、钙、氟化钙、氧化钙、镁、氟化镁、碳酸镁、氧化镁,这些化合物可以单独使用也可以混合物使用,也可以跟其他有机电致发光材料配合使用。
本发明的有机电致发光器件中有机层的每一层,可以通过真空蒸渡法、分子束蒸镀法、溶于溶剂的浸涂法、旋涂法、棒涂法或者喷墨打印等方式制备。对于金属电机可以使用蒸镀法或者溅射法进行制备。
器件实验表明,本发明如结构式(I)所述的有机电致发光化合物,具有较好热稳定性,高发光效率,高发光纯度。采用该有机电致发光化合物制作的有机电致发光器件具有电致发光效率良好和色纯度优异以及寿命长的优点。
附图说明
图1为化合物1的核磁谱图。
图2为化合物3的核磁谱图。
图3为化合物20的核磁谱图。
图4为化合物26的核磁谱图。
图5为实施例5、实施例6和对比例1中构建的电致发光器件的结构示意图,110代表为玻璃基板,120代表为阳极,130代表为空穴传输层,140代表为发光层,150代表为电子传输层,160代表为电子注入层,170代表为阴极。
具体实施方式
为了更详细叙述本发明,特举以下例子,但是不限于此。
实施例1
化合物1的合成
中间体溴代酚嗪的合成
在烧瓶中分别加入N9,N10-二苯基菲-9,10-二胺(15g)和对溴碘苯(11.77g),和Cu(OTf)2(2.52g),K2CO3(7.68g,55.6mol),随后加入三氯苯(50g),在机械搅拌下加热至210℃左右回流过夜,反应完全后停止加热,减压蒸馏除去溶剂。通过硅胶柱层析得到4.02g的淡黄色固体,产率18.74%。
化合物1的合成
在烧瓶中,将4.5mgPd(OAc)2和5.8mgP(t-Bu)3HBF4溶于20ml甲苯中,N2保护下依次加入0.5g4-溴吩嗪,二苯胺(0.3g)和0.224g叔丁醇钾,在甲苯中加热回流过夜。反应完全后,停止加热。过滤,水洗,滤液旋蒸除去溶剂,采用硅胶柱层析分离得到410mg白色固体,产率68%。
1HNMR(400MHz,CDCl3)δ8.76(d,2H),8.30(d,1H),8.20(d,1H),7.82-7.56(m,6H),7.37(m,2H),7.16(m,4H),7.07(m,2H),6.96-6.85(m,11H),6.76(d,2H).核磁见图1.
ESI,m/z:[M+H]+calcdforC44H31N3,理论值:602.2596;实测值:602.2596。
实施例2
化合物3的合成
在烧瓶中,将4.5mgPd(OAc)2和5.8mgP(t-Bu)3HBF4溶于20ml甲苯,N2保护下依次加入4-溴吩嗪(0.5g),N-苯基-1-萘胺(0.4g)和叔丁醇钾(0.22g),在甲苯中加热回流过夜。反应完全后,停止加热。过滤,水洗,滤液旋蒸除去溶剂,采用硅胶柱层析分离得到210mg白色固体,产率31%。
1HNMR(400MHz,CDCl3)δ8.70(d,2H),8.17(m,2H),7.83-7.77(m,2H),7.74-7.51(m,7H),7.42-7.34(m,2H),7.28(d,2H),7.24(s,1H),7.13(d,1H),7.08-6.99(m,4H),6.92(d,2H),6.78(m,8H).核磁见图2。
ESI,m/z:[M+H]+calcdforC48H34N3,理论值:652.2753;实测值:652.2750。
实施例3
化合物20的合成
向烧瓶中,依次加入4-溴吩嗪(0.5g),4-三苯胺硼酸(0.3g),THF(20ml),四(三苯基膦)钯(100mg),碳酸钾水溶液(2mol/l,5mL);并用氮气保护加热回流反应过夜。停止反应,旋蒸除去THF(四氢呋喃),用二氯甲烷萃取三次,合并有机相,再水洗至中性;分出有机相,加无水硫酸镁干燥,抽滤,旋干;通过硅胶柱层析得白色固体440mg,产率65%。
1HNMR(400MHz,CDCl3)δ8.74(d,2H),8.13(m,2H),7.62(m,6H),7.33(d,2H),7.30(d,2H),7.22(m,6H),7.14-6.94(m,15H),6.78(s,1H).核磁见图3。
ESI,m/z:[M+H]+calcdforC50H36N3,理论值:678.2909;实测值:678.2969。
实施例4
化合物26的合成
中间体1的合成
向烧瓶依次加入40mL二甲苯,对溴碘苯(12.86g),开动搅拌溶解,然后加入N-(1-萘基)苯胺(10g),氢氧化钾(5.1g,),1,10-菲啰啉(1.8g),加入碘化亚铜(1.74g),氮气保护,加热回流反应6h,降至室温,反应液用过滤,减压蒸除溶剂,旋至有大量固体析出时加入50ml石油醚,抽滤,得到色固体8.9g为中间体1。
中间体2的合成
在烧瓶中,将2g中间体1溶于20mL重蒸过的四氢呋喃溶液中,氩气保护下,冷却至-78℃,缓慢滴加3.9mln-BuLi正己烷溶液(2.5M),搅拌1h,然后缓慢注入4.3mL硼酸三异丙酯,维持这个温度继续搅拌1h,然后升至室温,搅拌过夜,把反应液倒入水中,用2mol/L盐酸调节PH至中性,用乙酸乙酯萃取三次,合并有机层,用无水硫酸钠干燥,减压除去溶剂,得到1.2g白色固体。
化合物26的合成
向烧瓶中,依次加入4-溴吩嗪(0.5g),中间体2(0.4g),THF溶液(30ml),开启搅拌,再加入四(三苯基膦)钯(50mg),碳酸钾水溶液(2mol/l,5mL);氮气保护加热回流反应过夜。停止反应,旋蒸除去THF,用二氯甲烷萃取三次,合并有机相,再水洗至中性;分出有机相,加无水硫酸镁干燥,抽滤,旋干;通过硅胶柱层析得白色固体570mg,产率78.4%。
1HNMR(400MHz,CDCl3)δ8.77(d,2H),8.18-8.11(m,2H),7.91(m,2H),7.78(m,3H),7.67(m,2H),7.60-7.54(m,2H),7.50-7.43(m,2H),7.39-7.31(m,4H),7.29(d,2H),7.27(s,2H),7.25-7.17(m,4H),7.09-6.97(m,10H),6.94(m,1H),6.80(m,1H).核磁见图4。
ESI,m/z:[M+H]+calcdforC54H38N3,理论值为:728.3066;实测值:728.3063。
实施例5
有机电致发光器件的制备
使用本发明的有机电致发光化合物制备OLED
首先,将透明导电ITO玻璃基板110(上面带有阳极120)(中国南玻集团股份有限公司)依次经:去离子水,乙醇,丙酮和去离子水洗净,再用氧等离子处理30秒。
然后,蒸镀化合物1,形成60nm厚的空穴传输层130。
然后,在空穴传输层上蒸镀30nm厚的化合物Alq3作为发光层140。
然后,在发光层上蒸镀20nm厚的Alq3作为电子传输层150。
最后,蒸镀1nmLiF为电子注入层160和100nmAl作为器件阴极170。
具体结构示意图见图5。
所制备的器件用PhotoResearchPR650光谱仪测得在10mA/cm2的电流密度下的效率为0.22cd/A,发射绿光。
其中,所用的Alq3的结构式为:
实施例6
首先,将透明导电ITO玻璃基板110(上面带有阳极120(中国南玻集团股份有限公司))依次经:去离子水,乙醇,丙酮和去离子水洗净,再用氧等离子处理30秒。
然后,蒸镀化合物22,形成60nm厚的空穴传输层130。
然后,在空穴传输层上蒸镀30nm厚的化合物Alq3作为发光层140。
然后,在发光层上蒸镀20nm厚的Alq3作为电子传输层150。
最后,蒸镀1nmLiF为电子注入层160和100nmAl作为器件阴极170。
具体结构示意图见图5。
所制备的器件用PhotoResearchPR650光谱仪测得在10mA/cm2的电流密度下的效率为0.21cd/A,发射绿光。
比较例1
首先,将透明导电ITO玻璃基板110(上面带有阳极120)(中国南玻集团股份有限公司)依次经:去离子水,乙醇,丙酮,去离子水洗净,再用氧等离子处理30秒。
然后,蒸镀NPB,形成60nm厚的空穴传输层130。
然后,在空穴传输层上蒸镀30nm厚的Alq3作为发光层140。
然后,在发光层上蒸镀20nm厚的Alq3作为电子传输层150。
最后,蒸镀1nmLiF为电子注入层160和100nmAl作为器件阴极170。
具体结构示意图见图5。
所制备的器件用PhotoResearchPR650光谱仪测得在10mA/cm2的电流密度下的效率为0.16cd/A,发射绿光。
其中比较例1中所用的NPB为如下结构式:
在相同的条件下,实施例5和6制备的有机电致发光器件的效率明显高于比较例1。因此本发明的有机电致发光化合物具有高的稳定性,有机电致发光器件具有高的效率和光纯度。
Claims (7)
1.一种有机电致发光器件,其包括阳极、阴极和有机层,有机层包含空穴注入层、空穴传输层、发光层、阻挡层、电子注入层和电子传输层中的一层以上,其特征在于有机层中至少一层包含有如下结构式(I)的化合物
其中,
R1-R4分别独立地表示为氢、甲基、乙基、丙基、异丙基、叔丁基或正丁基;
Ar4为苯基;
Ar1-Ar3分别独立地为下列基团,这些基团可进一步被C1-C4的烷基取代:
n为1或2。
2.根据权利要求1所述的有机电致发光器件,其特征在于所述的结构式(I)的化合物为
3.根据权利要求1所述的有机电致发光器件,其特征在于如结构式(I)所述的化合物所在的层为发光层、空穴传输层或者空穴注入层。
4.根据权利要求1所述的有机电致发光器件,其特征在于如结构式(I)所述的化合物单独使用,或者和其他化合物混合使用。
5.根据权利要求1所述的有机电致发光器件,其特征在于如结构式(I)所述的化合物单独使用其中的一种化合物,或者同时使用结构式(I)中的两种以上的化合物。
6.根据权利要求1所述的有机电致发光器件,其包含阳极、空穴传输层、发光层、电子传输层、电子注入层和阴极,其特征在于空穴传输层中含有结构式(I)的化合物。
7.根据权利要求6所述的有机电致发光器件,其特征在于空穴传输层中的化合物为下列结构式1、2、3、5、6、20、22、23或26的化合物:
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