CN106749050B - It is a kind of using cyclic diketones as the hot activation delayed fluorescence OLED material of core and its application - Google Patents
It is a kind of using cyclic diketones as the hot activation delayed fluorescence OLED material of core and its application Download PDFInfo
- Publication number
- CN106749050B CN106749050B CN201611159423.3A CN201611159423A CN106749050B CN 106749050 B CN106749050 B CN 106749050B CN 201611159423 A CN201611159423 A CN 201611159423A CN 106749050 B CN106749050 B CN 106749050B
- Authority
- CN
- China
- Prior art keywords
- layer
- compound
- thickness
- preparation
- delayed fluorescence
- 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.)
- Active
Links
- 239000000463 material Substances 0.000 title claims abstract description 59
- 230000004913 activation Effects 0.000 title claims abstract description 13
- 230000003111 delayed effect Effects 0.000 title claims abstract description 13
- 239000010410 layer Substances 0.000 claims abstract description 126
- 238000005401 electroluminescence Methods 0.000 claims abstract description 10
- 239000002346 layers by function Substances 0.000 claims abstract description 5
- -1 hexamethylene, pentamethylene Chemical group 0.000 claims description 10
- 125000004836 hexamethylene group Chemical class [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 abstract description 73
- 125000003118 aryl group Chemical group 0.000 abstract description 5
- 230000009477 glass transition Effects 0.000 abstract description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 48
- 238000002360 preparation method Methods 0.000 description 40
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 23
- 238000000921 elemental analysis Methods 0.000 description 20
- 150000002500 ions Chemical class 0.000 description 20
- 238000001819 mass spectrum Methods 0.000 description 20
- 239000007787 solid Substances 0.000 description 20
- 239000002994 raw material Substances 0.000 description 19
- 230000005540 biological transmission Effects 0.000 description 13
- 238000002347 injection Methods 0.000 description 13
- 239000007924 injection Substances 0.000 description 13
- 239000000758 substrate Substances 0.000 description 13
- 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 12
- 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
- 238000002156 mixing Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 230000027756 respiratory electron transport chain Effects 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- JGGSOWGJMBNDHS-UHFFFAOYSA-N 10-phenyl-5h-phenazine Chemical compound C12=CC=CC=C2NC2=CC=CC=C2N1C1=CC=CC=C1 JGGSOWGJMBNDHS-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 125000001118 alkylidene group Chemical group 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 3
- 238000001771 vacuum deposition Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- KTADSLDAUJLZGL-UHFFFAOYSA-N 1-bromo-2-phenylbenzene Chemical group BrC1=CC=CC=C1C1=CC=CC=C1 KTADSLDAUJLZGL-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 230000003760 hair shine Effects 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N phenyl bromide Natural products BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 150000003512 tertiary amines Chemical group 0.000 description 2
- 238000007738 vacuum evaporation Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- CXNIUSPIQKWYAI-UHFFFAOYSA-N xantphos Chemical compound C=12OC3=C(P(C=4C=CC=CC=4)C=4C=CC=CC=4)C=CC=C3C(C)(C)C2=CC=CC=1P(C=1C=CC=CC=1)C1=CC=CC=C1 CXNIUSPIQKWYAI-UHFFFAOYSA-N 0.000 description 2
- ZQRANPMEQCFOBX-UHFFFAOYSA-N 1-phenyl-5,10-dihydrophenazine Chemical compound N1C2=CC=CC=C2NC2=C1C=CC=C2C1=CC=CC=C1 ZQRANPMEQCFOBX-UHFFFAOYSA-N 0.000 description 1
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 description 1
- WJNDBVIYUQZIAS-UHFFFAOYSA-N C(C1=CC=CC=C1)#N.C1=CC=CC=2C3=CC=CC=C3NC12 Chemical class C(C1=CC=CC=C1)#N.C1=CC=CC=2C3=CC=CC=C3NC12 WJNDBVIYUQZIAS-UHFFFAOYSA-N 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical group [Se] BUGBHKTXTAQXES-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
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010351 charge transfer process Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- QEGNUYASOUJEHD-UHFFFAOYSA-N gem-dimethylcyclohexane Natural products CC1(C)CCCCC1 QEGNUYASOUJEHD-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 230000005428 wave function Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
- C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
- C07D241/38—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems with only hydrogen or carbon atoms directly attached to the ring nitrogen atoms
- C07D241/46—Phenazines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
- C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
- C07D221/04—Ortho- or peri-condensed ring systems
- C07D221/18—Ring systems of four or more rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
- C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
- C07D221/20—Spiro-condensed ring systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/04—Ortho-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/06—Peri-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/12—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains three hetero rings
- C07D471/20—Spiro-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
- C07D487/06—Peri-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
- C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
- C07D491/04—Ortho-condensed systems
- C07D491/044—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring
- C07D491/048—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring the oxygen-containing ring being five-membered
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
- C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
- C07D491/10—Spiro-condensed systems
- C07D491/107—Spiro-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D498/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
- C07D498/06—Peri-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D513/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00
- C07D513/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 in which the condensed system contains two hetero rings
- C07D513/06—Peri-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- 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
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
-
- 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
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
- C09K2211/1033—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with oxygen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
- C09K2211/1037—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with sulfur
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention discloses a kind of using cyclic diketones as the hot activation delayed fluorescence OLED material of core and its application, belongs to organic photoelectrical material technical field.It is with structure shown in formula I:The invention also discloses the applications of above-mentioned OLED material.OLED material of the invention is one kind using cyclic diketones as notable feature, and the organic micromolecule compound that nitrogen-containing heterocycle is constituted is connected by aromatic group, with suitable molecular entergy level, higher glass transition temperature, and there is apparent hot activation delayed fluorescence (TADF) characteristic, can be used as TADF material, be used to prepare the functional layer of organic electroluminescence device, especially luminescent layer is applied in field of organic electroluminescence.
Description
Technical field
The present invention relates to a kind of using cyclic diketones as the hot activation delayed fluorescence OLED material of core and its application, and belonging to has
Machine optoelectronic materials technology.
Background technique
Currently, the commodity based on OLED display technology, have been carried out industrialization.Compared with liquid crystal type display technology, OLED
Display technology has thin self-luminous, radiationless, light weight, thickness, wide viewing angle, wide colour gamut, colour stable, fast response time, ring
Border adapts to many advantages, such as strong, achievable Flexible Displays, and therefore, OLED display technology is obtaining people and more and more paying close attention to
With corresponding Technical investment.
The infrastructure element that OLED is shown is OLED device, and OLED device can be divided into glimmering according to the difference of luminous mechanism
Optical device and two kinds of phosphorescent devices.Fluorescence 0LED based on singlet emitter its theoretic interior amount as first generation luminescent material
Sub- efficiency only has 25%, can not further increase its efficiency；Phosphorescence 0LED is referred to as the second generation, and internal quantum efficiency can reach
100%.Although phosphor material passes through between being since the strong SO coupling in heavy atom center enhances, can efficiently use
It is electrically excited the singlet exciton to be formed and Triplet exciton, makes the internal quantum efficiency of device up to 100%.But phosphor material is deposited
It is limited in the problems such as expensive, stability of material is poor, and service life is short, and device efficiency tumbles seriously, and blue emitting phosphor is weak
Its application in OLED.
2009, the Adachi professor of Kyushu University designed and synthesized a kind of carbazole Benzonitrile derivatives, then
Have found that, based on triplet state-singlet transition hot activation delayed fluorescence (TADF) new material, internal quantum efficiency is close
100%, this kind of material is the third generation luminous organic material developed after organic fluorescence materials and organic phosphorescent material.Such
Material generally has small singlet-triplet poor (△ EST), and triplet excitons can be transformed by anti-intersystem crossing
Singlet exciton shines.This can make full use of the singlet exciton and triplet excitons that are electrically excited lower formation, the interior amount of device
Sub- efficiency can achieve 100%.Meanwhile material structure is controllable, and property is stablized, and it is cheap to be not necessarily to precious metal, it is led in OLED
Domain has a extensive future.But not clear, the limitation of material structure and the correlation of its photophysical property and device efficiency
The exploitation of efficient delayed fluorescence material, causes existing TADF material category single, and the efficiency of device is lower, is unable to satisfy efficiently
The requirement of Organic Light Emitting Diode.
During high efficiency electroluminous process usually requires that electronics returns ground state through excitation state radiation transistion, molecule frontier orbit
Wave function have and be utmostly overlapped, overlapping degree is too small to accelerate intersystem crossing process, reduce luminous efficiency.It is partly led organic
In body material, charge transfer process corresponds to the redox reaction between neutral molecule and corresponding zwitterion, electron donor list
Member and electron acceptor unit are respectively provided with the property of transporting holes and electronics.In recent years, bipolar materials are because having the sky of balance
Cave and electronic carrier stream are attract attention in electroluminescent device field, and the life that gradually moves towards the industrialization
It produces.
It has been reported that the organic compound with TADF performance, be that there is apparent electron-donating group and inhale in structure
Bipolarity organic micromolecule compound made of electron group direct or indirect connection.Novel TADF material undoubtedly has wide hair
Exhibition prospect.
Summary of the invention
An object of the present invention is to provide a kind of using cyclic diketones as the hot activation delayed fluorescence OLED material of core.
The compound of the present invention is applied to Organic Light Emitting Diode, the present invention using cyclic diketones as core, as luminescent layer material of main part
The device of production has good photoelectric properties, can satisfy the requirement of panel manufacturing enterprise.
The technical scheme to solve the above technical problems is that a kind of postpone by the hot activation of core of cyclic diketones
Fluorescence OLED material has structure shown in formula I:
Wherein, L is expressed as hexamethylene, pentamethylene or C1-C10Alkyl-substituted hexamethylene；Ar1Indicate C5-C30Aryl；
Ar2Structure shown in selection formula II, formula III, formula IV or formula V:
Wherein, X is expressed as oxygen atom, sulphur atom, selenium atom, C1-C10The alkylidene or C that straight chained alkyl replaces1-C10Branch
One of the tertiary amine groups that alkylidene, alkyl-substituted tertiary amine groups or the aryl that alkyl-substituted alkylidene, aryl replace replace.
Based on the above technical solution, the present invention can also be improved as follows.
Further, the Ar2Are as follows:
In appoint
It is a kind of.Further, the concrete structure formula of the OLED material are as follows:
Any one of.
The second object of the present invention is to provide a kind of organic electroluminescence device.With common commercialization material of main part CBP
It compares, the organic electroluminescence device made using material of the present invention, there is better current efficiency and longer device
Service life.
The technical scheme to solve the above technical problems is that a kind of organic electroluminescence device, at least one layer of function
Ergosphere contains above-mentioned using cyclic diketones as the hot activation delayed fluorescence OLED material of core.
Based on the above technical solution, the present invention can also be improved as follows.
Further, the functional layer is luminescent layer.
The beneficial effects of the present invention are:
1. the material is using cyclic diketones as notable feature, Ke Yizuo the present invention provides a kind of electroluminescent organic material
For the material of main part with TADF property, apply in field of organic electroluminescence.
2. using material provided by the invention as functional layer, the organic electroluminescence device of production has preferable performance,
It is characterized in that:
(1) present invention has been synthesized a kind of using cyclic diketones as the hot activation delayed fluorescence of core by the reaction such as coupling
OLED material, and " D- π-A type " organic micromolecule compound that nitrogen-containing heterocycle is constituted, this kind of molecule tool are connected by aromatic group
There are suitable molecular weight (400~900), wider energy gap (being in 2.5-3.5eV), with small singlet --- triplet state
Energy level difference (i.e. △ EST, 0-0.2eV), higher glass transition temperature Tg (120 DEG C or more) are suitable as the layer main body that shines
Material.
(2) molecular structure according to the present invention, electron donating group pass through suitable aryl with drawing electron group and connect,
The configuration of this distortion increases the stereoeffect of entire molecule, the biography of the electronics and hole that are more advantageous in luminescent layer
It leads and combines, be of great significance to current efficiency is improved.
(3) light emitting host material is made with such material, adulterates existing luminescent material GD-19, Ir (PPy) respectively3、GD-
PACTZ has preferable performance as luminescent layer, prepared organic electroluminescence device, and maximum current efficiency is up to 33cd/
A, the LT95 service life are 13.0Hr.
3. compared with common commercialization material of main part CBP, the organic electroluminescent that is made using material of the present invention
Device has better current efficiency and longer device lifetime.
4. compound-material of the present invention has good application effect in OLED luminescent device, there is good production
Industry prospect.
Detailed description of the invention
Fig. 1 is the device architecture schematic diagram using the compounds of this invention.
Wherein, 1, transparent substrate layer, 2, ito anode layer, 3, hole injection layer, 4, hole transmission layer, 5, luminescent layer, 6, electricity
Sub- transport layer, 7, electron injecting layer, 8, cathode reflection electrode layer.
Specific embodiment
Principles and features of the present invention are described below in conjunction with specific attached drawing, example is served only for explaining this hair
It is bright, it is not intended to limit the scope of the present invention.
Embodiment 1: the preparation of compound C1
In 500mL there-necked flask, 2- (4- bromophenyl) hexamethylene -1,3- diketone (2.67g, 0.01mol), 5- benzene is added
Base -5,10- dihydrophenazine (2.58g, 0.01mol), sodium tert-butoxide (2.88g, 0.03mol), dimethylbenzene (300mL), palladium acetate
(0.074g) is warming up to reflux, insulation reaction 12h is down to room temperature, into reaction flask under Xantphos (0.348g), N2 protection
150mL deionized water is added, stirs 5min, liquid separation, 200mL deionized water is washed organic phase 2 times, and organic phase is collected, anhydrous
Na2SO4 is dried, filtered, and sloughs solvent, and crude product crosses silica gel column chromatography purifying, and eluant, eluent is toluene: petroleum ether=1:2 is changed
Close object C1, faint yellow solid 2.85g, yield 64.2%.
High resolution mass spectrum, the source ESI, positive ion mode, molecular formula C30H24N2O2, theoretical value 444.1838, test value
444.1667.Elemental analysis (C30H24N2O2), theoretical value C:81.06, H:5.44, N:6.30, O:7.20, measured value C:81.04,
H:5.44, N:6.31, O:7.21.
Embodiment 2: the preparation of compound C4
The preparation method is the same as that of Example 1 by compound C4, the difference is that using the 5- benzene in 1 alternative embodiment 1 of raw material A
Base -5,10- dihydrophenazine obtains compound C4, faint yellow solid 3.23g, yield 66.7%.
High resolution mass spectrum, the source ESI, positive ion mode, molecular formula C33H28N2O2, theoretical value 484.2151, test value
484.2331.Elemental analysis (C33H28N2O2), theoretical value C:81.79, H:5.83, N:5.78, O:6.60, measured value C:81.78,
H:5.84, N:5.77, O:6.61.
Embodiment 3: the preparation of compound C7
The preparation method is the same as that of Example 1 by compound C7, the difference is that using the 5- benzene in 2 alternative embodiment 1 of raw material A
Base -5,10- dihydrophenazine obtains compound C7, faint yellow solid 3.06g, yield 57.3%.
High resolution mass spectrum, the source ESI, positive ion mode, molecular formula C37H27NO3, theoretical value 533.1991, test value
533.1860.Elemental analysis (C37H27NO3), theoretical value C:83.28, H:5.10, N:2.62, O:8.99, measured value C:83.30,
H:5.12, N:2.61, O:8.97.
Embodiment 4: the preparation of compound C18
The preparation method is the same as that of Example 1 by compound C18, the difference is that using raw material 2- (the bromo- 2' of 4'-, 5'- diformazan
Base biphenyl -4- base) 2- (4- bromophenyl) hexamethylene -1,3- diketone in hexamethylene -1,3- diketone alternative embodiment 1, changed
Close object C18, faint yellow solid 3.69g, yield 67.2%.
High resolution mass spectrum, the source ESI, positive ion mode, molecular formula C38H32N2O2, theoretical value 548.2464, test value
548.2410.Elemental analysis (C38H32N2O2), theoretical value C:83.18, H:5.88, N:5.11, O:5.83, measured value C:83.15,
H:5.89, N:5.12, O:5.84.
Embodiment 5: the preparation of compound C27
The preparation method is the same as that of Example 1 by compound C27, the difference is that using raw material 2- (the bromo- 1- naphthalene of 4-) hexamethylene
2- (4- bromophenyl) hexamethylene -1,3- diketone in alkane -1,3- diketone alternative embodiment 1, obtains compound C27, pale yellow colored solid
Body 3.79g, yield 76.6%.
High resolution mass spectrum, the source ESI, positive ion mode, molecular formula C34H26N2O2, theoretical value 494.1994, test value
494.1871.Elemental analysis (C34H26N2O2), theoretical value C:82.57, H:5.30, N:5.66, O:6.47, measured value C:82.55,
H:5.30, N:5.67, O:6.48.
Embodiment 6: the preparation of compound C31
The preparation method is the same as that of Example 1 by compound C31, the difference is that using raw material 2- (4- bromophenyl) pentamethylene-
2- (4- bromophenyl) hexamethylene -1,3- diketone in 1,3- diketone alternative embodiment 1, obtains compound C31, faint yellow solid
3.09g, yield 71.7%.
High resolution mass spectrum, the source ESI, positive ion mode, molecular formula C29H22N2O2, theoretical value 430.1681, test value
430.1770.Elemental analysis (C29H22N2O2), theoretical value C:80.91, H:5.15, N:6.51, O:7.43, measured value C:80.93,
H:5.14, N:6.51, O:7.42.
Embodiment 7: the preparation of compound C37
The preparation method of compound C37 is with embodiment 3, the difference is that using raw material 2- (4- bromophenyl) pentamethylene-
2- (4- bromophenyl) hexamethylene -1,3- diketone in 1,3- diketone alternative embodiment 1, obtains compound C37, faint yellow solid
3.31g, yield 63.8%.
High resolution mass spectrum, the source ESI, positive ion mode, molecular formula C36H25NO3, theoretical value 519.1834, test value
519.1760.Elemental analysis (C36H25NO3), theoretical value C:83.22, H:4.84, N:2.70, O:9.24, measured value C:83.20,
H:4.85, N:2.70, O:9.25.
Embodiment 8: the preparation of compound C40
The preparation method of compound C40 is with embodiment 6, the difference is that using the 5- in 3 alternative embodiment 1 of raw material A
Phenyl -5,10- dihydrophenazine obtains compound C40, faint yellow solid 3.73g, yield 79.2%.
High resolution mass spectrum, the source ESI, positive ion mode, molecular formula C32H25NO3, theoretical value 471.1834, test value
471.1622.Elemental analysis (C32H25NO3), theoretical value C:81.51, H:5.34, N:2.97, O:10.18, measured value C:81.52,
H:5.33, N:2.98, O:10.17.
Embodiment 9: the preparation of compound C57
The preparation method is the same as that of Example 1 by compound C57, the difference is that using raw material 2- (the bromo- 1- naphthalene of 4-) ring penta
2- (4- bromophenyl) hexamethylene -1,3- diketone in alkane -1,3- diketone alternative embodiment 1, obtains compound C57, pale yellow colored solid
Body 3.29g, yield 68.5%.
High resolution mass spectrum, the source ESI, positive ion mode, molecular formula C33H24N2O2, theoretical value 480.1838, test value
480.1668.Elemental analysis (C33H24N2O2), theoretical value C:82.48, H:5.03, N:5.83, O:6.66, measured value C:82.46,
H:5.04, N:5.82, O:6.68.
Embodiment 10: the preparation of compound C67
The preparation method is the same as that of Example 1 by compound C67, the difference is that using raw material 2- (4- bromophenyl) -5,5- bis-
2- (4- bromophenyl) hexamethylene -1,3- diketone in hexahydrotoluene -1,3- diketone alternative embodiment 1, obtains compound C67,
Faint yellow solid 3.33g, yield 70.4%.
High resolution mass spectrum, the source ESI, positive ion mode, molecular formula C32H28N2O2, theoretical value 472.2151, test value
472.2251.Elemental analysis (C32H28N2O2), theoretical value C:81.33, H:5.97, N:5.93, O:6.77, measured value C:81.32,
H:5.98, N:5.92, O:6.78.
Embodiment 11: the preparation of compound C68
The preparation method is the same as that of Example 10 by compound C68, the difference is that using in 4 alternative embodiment 10 of raw material A
5- phenyl -5,10- dihydrophenazine obtains compound C68, faint yellow solid 3.59g, yield 73.7%.
High resolution mass spectrum, the source ESI, positive ion mode, molecular formula C32H26N2O3, theoretical value 486.1943, test value
486.1825.Elemental analysis (C32H26N2O3), theoretical value C:78.99, H:5.39, N:5.76, O:9.86, measured value C:78.98,
H:5.37, N:5.78, O:9.87.
Embodiment 12: the preparation of compound C70
The preparation method is the same as that of Example 10 by compound C70, the difference is that using in 1 alternative embodiment 10 of raw material A
5- phenyl -5,10- dihydrophenazine obtains compound C70, faint yellow solid 3.74g, yield 72.9%.
High resolution mass spectrum, the source ESI, positive ion mode, molecular formula C35H32N2O2, theoretical value 512.2464, test value
512.2335.Elemental analysis (C35H32N2O2), theoretical value C:82.00, H:6.30, N:5.46, O:6.24, measured value C:82.02,
H:6.31, N:5.45, O:6.22.
Embodiment 13: the preparation of compound C72
The preparation method is the same as that of Example 10 by compound C72, the difference is that using in 5 alternative embodiment 10 of raw material A
5- phenyl -5,10- dihydrophenazine obtains compound C72, faint yellow solid 3.55g, yield 63.2%.
High resolution mass spectrum, the source ESI, positive ion mode, molecular formula C38H31N3O2, theoretical value 561.2416, test value
561.2337.Elemental analysis (C38H31N3O2), theoretical value C:81.26, H:5.56, N:7.48, O:5.70, measured value C:81.24,
H:5.55, N:7.49, O:5.72.
Embodiment 14: the preparation of compound C73
The preparation method is the same as that of Example 10 by compound C73, the difference is that using in 2 alternative embodiment 10 of raw material A
5- phenyl -5,10- dihydrophenazine obtains compound C73, faint yellow solid 3.76g, yield 66.9%.
High resolution mass spectrum, the source ESI, positive ion mode, molecular formula C39H31NO3, theoretical value 561.2304, test value
561.2213.Elemental analysis (C39H31NO3), theoretical value C:83.40, H:5.56, N:2.49, O:8.55, measured value C:83.42,
H:5.56, N:2.49, O:8.53.
Embodiment 15: the preparation of compound C74
The preparation method is the same as that of Example 10 by compound C74, the difference is that using in 6 alternative embodiment 10 of raw material A
5- phenyl -5,10- dihydrophenazine obtains compound C74, faint yellow solid 3.65g, yield 62.1%.
High resolution mass spectrum, the source ESI, positive ion mode, molecular formula C42H37NO2, theoretical value 587.2824, test value
587.2775.Elemental analysis (C42H37NO2), theoretical value C:85.83, H:6.35, N:2.38, O:5.44, measured value C:85.85,
H:6.33, N:2.39, O:5.43.
Embodiment 16: the preparation of compound C92
The preparation method is the same as that of Example 12 by compound C92, the difference is that using raw material 2- (the bromo- 1- naphthalene of 4-) -5,
2- (4- bromophenyl) -5,5- dimethyl cyclohexane -1,3- two in 5- dimethyl cyclohexane -1,3- diketone alternative embodiment 10
Ketone obtains compound C92, faint yellow solid 4.24g, yield 75.3%.
High resolution mass spectrum, the source ESI, positive ion mode, molecular formula C39H34N2O2, theoretical value 562.2620, test value
562.2517.Elemental analysis (C39H34N2O2), theoretical value C:83.24, H:6.09, N:4.98, O:5.69, measured value C:83.26,
H:6.07, N:4.99, O:5.68.
Embodiment 17: the preparation of compound C97
The preparation method of compound C97 is with embodiment 8, the difference is that using the A3 in 7 alternative embodiment 8 of raw material A,
Obtain compound C97, faint yellow solid 3.54g, yield 71.2%.
High resolution mass spectrum, the source ESI, positive ion mode, molecular formula C35H31NO2, theoretical value 497.2355, test value
497.2357.Elemental analysis (C35H31NO2), theoretical value C, 84.48；H,6.28；N,2.81；O, 6.43, measured value C:84.46,
H:6.17, N:2.89, O:6.48.
Embodiment 18: the preparation of compound C98
The preparation method of compound C98 is with embodiment 8, the difference is that using the A3 in 8 alternative embodiment 8 of raw material A,
Obtain compound C98, faint yellow solid 3.85g, yield 70.5%.
High resolution mass spectrum, the source ESI, positive ion mode, molecular formula C38H30N2O2, theoretical value 546.2307, test value
546.2309.Elemental analysis (C38H30N2O2), theoretical value C, 83.49；H, 5.53；N, 5.12；O, 5.85, measured value C:83.46,
H:5.57, N:5.13, O:5.84.
Embodiment 19: the preparation of compound C100
The preparation method is the same as that of Example 17 by compound C100, the difference is that using the raw material 2- (bromo- biphenyl -3- of 4'-
Base) 2- (4'- bromobenzene)-pentamethylene -1,3- diketone in-pentamethylene -1,3- diketone alternative embodiment 17, obtain compound
C100, faint yellow solid 2.63g, yield 45.9%.
High resolution mass spectrum, the source ESI, positive ion mode, molecular formula C41H35NO2, theoretical value 573.2668, test value
573.2672.Elemental analysis (C41H35NO2), theoretical value C, 85.83；H,6.15；N,2.44；O, 5.58, measured value C:85.76,
H:6.15, N:2.38, O:5.71.
Embodiment 20: the preparation of compound C103
The preparation method is the same as that of Example 18 by compound C103, the difference is that using the raw material 2- (bromo- biphenyl -3- of 4'-
Base) 2- (4'- bromobenzene)-pentamethylene -1,3- diketone in-pentamethylene -1,3- diketone alternative embodiment 17, obtain compound
C103, faint yellow solid 4.10g, yield 66.0%.
High resolution mass spectrum, the source ESI, positive ion mode, molecular formula C44H34N2O2, theoretical value 622.2620, test value
622.2623.Elemental analysis (C44H34N2O2), theoretical value C, 84.86；H,5.50；N,4.50；O, 5.14, measured value C, 84.79；
H,5.52；N,4.54；O,5.15.
The 21-28 and comparative example 1-3 compound conduct in the devices that the present invention will be described in detail synthesizes by the following examples
The application effect of luminescent layer material of main part.Embodiment 22-28 of the present invention, comparative example 1-3 device compared with embodiment 21
The manufacture craft of part is identical, and uses identical baseplate material and electrode material, and the film thickness of electrode material is also protected
It holds unanimously, except that being converted to the luminescent layer material of main part in device.The structure composition of device is as shown in table 2；Institute
The test result for obtaining device is shown in Table 3.
Embodiment 21
Transparent substrate layer 1/ITO anode layer 2/ hole injection layer 3 (molybdenum trioxide MoO3, thickness 10nm)/hole transmission layer 4
(weight ratio blending of the compound C7 and GD-19 according to 100:5, thickness the 30nm)/electronics of (TAPC, thickness 80nm)/luminescent layer 5 passes
Defeated 6 (TPBI, thickness 40nm)/electron injecting layer of layer, 7 (LiF, thickness 1nm)/negative electrode layer 8 (Al).The molecule of each compound
Structural formula is as follows:
Specific preparation process is as follows:
Transparent substrate layer 1 uses transparent material, such as glass；Ito anode layer 2 (film thickness 150nm) is washed, i.e., according to
Ultraviolet-ozone washing is carried out after secondary progress neutralizing treatment, pure water, drying again to remove the organic residue on the transparent surface ITO
Object.
On having carried out the ito anode layer 2 after above-mentioned washing, using vacuum deposition apparatus, it is 10nm's that film thickness, which is deposited,
Molybdenum trioxide MoO3 is used as hole injection layer 3.And then the TAPC of 80nm thickness is deposited as hole transmission layer 4.
After above-mentioned hole mobile material vapor deposition, the luminescent layer 5 of OLED luminescent device is made, structure includes OLED hair
The used material compound C7 of photosphere 5 is as material of main part, and for GD-19 as dopant material, dopant material doping ratio is 5% weight
Ratio is measured, luminescent layer film thickness is 30nm.
After above-mentioned luminescent layer 5, continuation vacuum evaporation electron transport layer materials are TPBI, the vacuum evaporation coating of the material
Thickness is 40nm, this layer is electron transfer layer 6.
On electron transfer layer 6, by vacuum deposition apparatus, lithium fluoride (LiF) layer that film thickness is 1nm is made, this layer is
Electron injecting layer 7.
On electron injecting layer 7, by vacuum deposition apparatus, aluminium (Al) layer that film thickness is 80nm is made, this layer is cathode
Reflection electrode layer 8 uses.
After completing OLED luminescent device as described above, anode and cathode is connected with well known driving circuit, is surveyed
The I-E characteristic of the luminous efficiency of metering device, luminescent spectrum and device.
Embodiment 22
Transparent substrate layer 1/ITO anode layer 2/ hole injection layer 3 (molybdenum trioxide MoO3, thickness 10nm)/hole transmission layer 4
(TAPC, thickness 80nm)/luminescent layer 5 (weight ratio blending of the compound C40 and GD-19 according to 100:5, thickness 30nm)/electronics
Transport layer 6 (TPBI, thickness 40nm)/electron injecting layer 7 (LiF, thickness 1nm)/negative electrode layer 8 (Al).
Embodiment 23
Transparent substrate layer 1/ITO anode layer 2/ hole injection layer 3 (molybdenum trioxide MoO3, thickness 10nm)/hole transmission layer 4
(TAPC, thickness 80nm)/luminescent layer 5 (weight ratio blending of the compound C73 and Ir (PPy) 3 according to 100:10, thickness 30nm)/
Electron transfer layer 6 (TPBI, thickness 40nm)/electron injecting layer 7 (LiF, thickness 1nm)/negative electrode layer 8 (Al).
Embodiment 24
Transparent substrate layer 1/ITO anode layer 2/ hole injection layer 3 (molybdenum trioxide MoO3, thickness 10nm)/hole transmission layer 4
(TAPC, thickness 80nm)/luminescent layer 5 (weight ratio blending of the compound C97 and Ir (PPy) 3 according to 100:10, thickness 30nm)/
Electron transfer layer 6 (TPBI, thickness 40nm)/electron injecting layer 7 (LiF, thickness 1nm)/negative electrode layer 8 (Al).
Embodiment 25
Transparent substrate layer 1/ITO anode layer 2/ hole injection layer 3 (molybdenum trioxide MoO3, thickness 10nm)/hole transmission layer 4
(TAPC, thickness 80nm)/luminescent layer 5 (weight ratio blending of the compound C98 and GD-PACTZ according to 100:5, thickness 30nm)/electricity
Sub- 6 (TPBI, thickness 40nm)/electron injecting layer of transport layer, 7 (LiF, thickness 1nm)/negative electrode layer 8 (Al).
Embodiment 26
Transparent substrate layer 1/ITO anode layer 2/ hole injection layer 3 (molybdenum trioxide MoO3, thickness 10nm)/hole transmission layer 4
(TAPC, thickness 80nm)/luminescent layer 5 (weight ratio blending of the compound C100 and GD-PACTZ according to 100:5, thickness 30nm)/
Electron transfer layer 6 (TPBI, thickness 40nm)/electron injecting layer 7 (LiF, thickness 1nm)/negative electrode layer 8 (Al).
Embodiment 27
Transparent substrate layer 1/ITO anode layer 2/ hole injection layer 3 (molybdenum trioxide MoO3, thickness 10nm)/hole transmission layer 4
(TAPC, thickness 80nm)/luminescent layer 5 (compound C103, GH-204 and Ir (PPy) 3 according to 70:30:10 weight ratio blending,
Thickness 30nm)/electron transfer layer 6 (TPBI, thickness 40nm)/electron injecting layer 7 (LiF, thickness 1nm)/negative electrode layer 8
(Al)。
Embodiment 28
Transparent substrate layer 1/ITO anode layer 2/ hole injection layer 3 (molybdenum trioxide MoO3, thickness 10nm)/hole transmission layer 4
(TAPC, thickness 80nm)/luminescent layer 5 (the weight ratio blending of compound C40, GH-204 and GD-PACTZ according to 70:30:5, thickness
Spend 30nm)/electron transfer layer 6 (TPBI, thickness 40nm)/electron injecting layer 7 (LiF, thickness 1nm)/negative electrode layer 8 (Al).
Comparative example 1
Transparent substrate layer 1/ITO anode layer 2/ hole injection layer 3 (molybdenum trioxide MoO3, thickness 10nm)/hole transmission layer 4
(TAPC, thickness 80nm)/luminescent layer 5 (the weight ratio blending of CBP and GD-19 according to 100:5, thickness 30nm)/electron transfer layer 6
(TPBI, thickness 40nm)/electron injecting layer 7 (LiF, thickness 1nm)/negative electrode layer 8 (Al).
Comparative example 2
Transparent substrate layer 1/ITO anode layer 2/ hole injection layer 3 (molybdenum trioxide MoO3, thickness 10nm)/hole transmission layer 4
(the weight ratio blending of CBP and Ir (PPy) 3 according to 100:10, thickness the 30nm)/electronics of (TAPC, thickness 80nm)/luminescent layer 5 passes
Defeated 6 (TPBI, thickness 40nm)/electron injecting layer of layer, 7 (LiF, thickness 1nm)/negative electrode layer 8 (Al).
Comparative example 3
Transparent substrate layer 1/ITO anode layer 2/ hole injection layer 3 (molybdenum trioxide MoO3, thickness 10nm)/hole transmission layer 4
(TAPC, thickness 80nm)/luminescent layer 5 (the weight ratio blending of CBP and GD-PACTZ according to 100:5, thickness 30nm)/electron-transport
Layer 6 (TPBI, thickness 40nm)/electron injecting layer, 7 (LiF, thickness 1nm)/negative electrode layer 8 (Al).
The device architecture of made OLED luminescent device is shown in Table 1, and the test result of made OLED luminescent device is shown in
Table 2.
The device architecture of OLED luminescent device made by table 1
The test result of OLED luminescent device made by table 2
Illustrate: the current efficiency of comparative example 1 is 6.5cd/A (@10mA/cm2)；Starting voltage is 4.3V (@1cd/m2),
LT95 life time decay is 3.8Hr under 5000nit brightness.The current efficiency of comparative example 2 is 24.6cd/A (@10mA/cm2)；
LT95 life time decay is 4.3Hr under 5000nit brightness.The current efficiency of comparative example 3 is 25.1cd/A (@10mA/cm2)；Starting
Voltage is 3.5V (@1cd/m2), and LT95 life time decay is 7.8Hr under 5000nit brightness.
Compound of the present invention can shine as luminescent layer material of main part using with OLED from the results shown in Table 2
Element manufacturing, and compared with comparative example 1-3, either efficiency or service life obtain larger change than known OLED material,
Especially the driving service life of device obtains biggish promotion.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (4)
1. a kind of using cyclic diketones as the hot activation delayed fluorescence OLED material of core, which is characterized in that have and tied shown in formula I
Structure:
Wherein, L is expressed as hexamethylene, pentamethylene or C1-C10Alkyl-substituted hexamethylene；Ar1Indicate C5-C30Aryl；Ar2Are as follows:
Any one of.
2. a kind of using cyclic diketones as the hot activation delayed fluorescence OLED material of core, which is characterized in that the OLED material
Concrete structure formula are as follows:
Any one of.
3. a kind of organic electroluminescence device, which is characterized in that at least one functional layer contains any one of claim 1-2 institute
State using cyclic diketones as the hot activation delayed fluorescence OLED material of core.
4. a kind of organic electroluminescence device according to claim 3, which is characterized in that the functional layer is luminescent layer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611159423.3A CN106749050B (en) | 2016-12-15 | 2016-12-15 | It is a kind of using cyclic diketones as the hot activation delayed fluorescence OLED material of core and its application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611159423.3A CN106749050B (en) | 2016-12-15 | 2016-12-15 | It is a kind of using cyclic diketones as the hot activation delayed fluorescence OLED material of core and its application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106749050A CN106749050A (en) | 2017-05-31 |
| CN106749050B true CN106749050B (en) | 2019-02-26 |
Family
ID=58889104
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611159423.3A Active CN106749050B (en) | 2016-12-15 | 2016-12-15 | It is a kind of using cyclic diketones as the hot activation delayed fluorescence OLED material of core and its application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106749050B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106831773A (en) * | 2017-01-05 | 2017-06-13 | 华南理工大学 | Compound containing 9, 9' -spiroacridine and preparation method and application thereof |
| US10472564B2 (en) * | 2017-09-26 | 2019-11-12 | Feng-wen Yen | Delayed fluorescence compound and organic electroluminescent device using the same |
| US20210210709A1 (en) * | 2017-10-19 | 2021-07-08 | Cynora Gmbh | Lighting device for motor vehicles and increased operating temperatures |
| CN108048076A (en) * | 2017-11-07 | 2018-05-18 | 中节能万润股份有限公司 | A kind of thermal activation delayed fluorescence material and its application |
| CN109942578B (en) * | 2019-04-22 | 2020-10-27 | 吉林奥来德光电材料股份有限公司 | Organic compounds of heteroanthracene class, preparation method and application |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5520560B2 (en) * | 2009-09-29 | 2014-06-11 | 富士フイルム株式会社 | Photoelectric conversion element, photoelectric conversion element material, optical sensor, and imaging element |
| JP2013214730A (en) * | 2012-03-05 | 2013-10-17 | Fujifilm Corp | Photoelectric conversion element and method of using the same, imaging element, optical sensor, and compound |
| JP6887805B2 (en) * | 2013-11-15 | 2021-06-16 | メルク パテント ゲーエムベーハー | Compounds with a novel 6-membered ring structure for use in organic electronic devices |
| JP6777983B2 (en) * | 2014-11-04 | 2020-10-28 | 三星電子株式会社Ｓａｍｓｕｎｇ Ｅｌｅｃｔｒｏｎｉｃｓ Ｃｏ．，Ｌｔｄ． | Compounds for organic photoelectric devices, organic photoelectric devices containing them, image sensors and electronic devices |
| CN105693608B (en) * | 2016-03-24 | 2019-01-04 | 中国科学院理化技术研究所 | 2, 2-dimethyl-1, 3-indene dione derivatives and organic electroluminescent devices based thereon |
-
2016
- 2016-12-15 CN CN201611159423.3A patent/CN106749050B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN106749050A (en) | 2017-05-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106467553B (en) | A kind of boracic organic electroluminescent compounds and its application in OLED device | |
| EP2799515B1 (en) | Compound for organic optoelectric device, organic light-emitting diode including same, and display device including organic light-emitting diode | |
| TWI508343B (en) | Nitrogen-containing aromatic compounds, organic semiconductor materials and organic electronic devices | |
| EP2497811B1 (en) | Compound for an organic photoelectric device, and organic photoelectric device comprising same | |
| KR101412437B1 (en) | New compounds and organic electronic device using the same | |
| JP5774267B2 (en) | Organic electroluminescent compound and light emitting diode using the same | |
| KR101153910B1 (en) | Chemical Comprising Indole Derivatives and Organic Electronic Element using the same, Terminal thereof | |
| TWI454469B (en) | Compound for organic electroluminescent device and organic electroluminescent devices using the same | |
| CN106467554A (en) | A kind of boracic organic electroluminescent compounds and its application | |
| WO2014104515A1 (en) | Compound for organic optoelectric device, organic light emitting diode comprising same, and display apparatus comprising organic light emitting diode | |
| CN106749050B (en) | It is a kind of using cyclic diketones as the hot activation delayed fluorescence OLED material of core and its application | |
| KR101732969B1 (en) | Phosphine oxide derivative compound and organic electroluminescent device using the same | |
| Ku et al. | High-luminescence non-doped green OLEDs based on a 9, 9-diarylfluorene-terminated 2, 1, 3-benzothiadiazole derivative | |
| TW201502122A (en) | Compound for organic optoelectronic device, organic light emitting diode including the same and display including the organic light emitting diode | |
| CN105367603B (en) | Anthracene-based diphosphonic hetero six-membered ring organic electroluminescent compound, synthetic method therefor and application thereof | |
| JP5650654B2 (en) | Novel chrysene derivative and organic electronic device using the same | |
| WO2020124771A1 (en) | Thermally activated delayed fluorescent compound, preparation method therefor and organic electroluminescent diode device thereof | |
| CN106432158A (en) | Organic light emitting compound material and application thereof | |
| CN106749200A (en) | Ketone electroluminescent organic material of a kind of chromene 4 and its preparation method and application | |
| CN106800526B (en) | It is a kind of using cyclic diketones as the electroluminescent organic material of core and its application | |
| KR101219485B1 (en) | Chemical comprising dibenzocarbazole and organic electroric element using the same, terminal thererof | |
| CN106892903B (en) | Organic electroluminescent compound based on phenazine and carbazole and luminescent device thereof | |
| CN105968100A (en) | Imidazole derivative compound and preparation method thereof and luminescent device | |
| CN104762079A (en) | Indole based luminescent compound | |
| CN105348325B (en) | A kind of double phosphine heterocycle organic electroluminescent compounds containing spiro fluorene structure, synthetic method and its application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Thermally activated delayed fluorescent OLED material with cyclic diketone as core and its application Effective date of registration: 20211202 Granted publication date: 20190226 Pledgee: Yantai Branch of China Merchants Bank Co.,Ltd. Pledgor: VALIANT Co.,Ltd. Registration number: Y2021980013807 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20220823 Granted publication date: 20190226 Pledgee: Yantai Branch of China Merchants Bank Co.,Ltd. Pledgor: VALIANT Co.,Ltd. Registration number: Y2021980013807 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right |