TWI675035B - 一種有機金屬配合物發光材料 - Google Patents
一種有機金屬配合物發光材料 Download PDFInfo
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- TWI675035B TWI675035B TW107132330A TW107132330A TWI675035B TW I675035 B TWI675035 B TW I675035B TW 107132330 A TW107132330 A TW 107132330A TW 107132330 A TW107132330 A TW 107132330A TW I675035 B TWI675035 B TW I675035B
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- light
- aromatic
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- 239000000463 material Substances 0.000 title claims abstract description 27
- 150000004696 coordination complex Chemical class 0.000 title 1
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 46
- 125000002524 organometallic group Chemical group 0.000 claims abstract description 17
- 125000004429 atom Chemical group 0.000 claims abstract description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 11
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 8
- 125000004434 sulfur atom Chemical group 0.000 claims abstract description 8
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 6
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 5
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 4
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 4
- 125000003118 aryl group Chemical group 0.000 claims description 39
- 125000000217 alkyl group Chemical group 0.000 claims description 24
- 125000001072 heteroaryl group Chemical group 0.000 claims description 18
- -1 amino, nitro, fluorenylamino Chemical group 0.000 claims description 14
- 229910052736 halogen Inorganic materials 0.000 claims description 14
- 150000002367 halogens Chemical class 0.000 claims description 14
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 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
- 125000001424 substituent group Chemical group 0.000 claims description 8
- 125000000623 heterocyclic group Chemical group 0.000 claims description 7
- 125000001624 naphthyl group Chemical group 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 125000004104 aryloxy group Chemical group 0.000 claims description 4
- 229910052805 deuterium Inorganic materials 0.000 claims description 4
- 125000005504 styryl group Chemical group 0.000 claims description 4
- 239000011593 sulfur Substances 0.000 claims description 4
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 claims description 2
- 125000005577 anthracene group Chemical group 0.000 claims description 2
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 claims description 2
- 125000004417 unsaturated alkyl group Chemical group 0.000 claims description 2
- 239000004065 semiconductor Substances 0.000 claims 3
- 150000002431 hydrogen Chemical class 0.000 claims 2
- 239000010409 thin film Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000010791 quenching Methods 0.000 abstract description 3
- 230000000171 quenching effect Effects 0.000 abstract description 3
- 229910052737 gold Inorganic materials 0.000 abstract description 2
- 229910052721 tungsten Inorganic materials 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 13
- 239000010410 layer Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 10
- 239000003446 ligand Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000001819 mass spectrum Methods 0.000 description 5
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 4
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 239000002019 doping agent Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical compound N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 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 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 229910052741 iridium Inorganic materials 0.000 description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 description 2
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 2
- BAXOFTOLAUCFNW-UHFFFAOYSA-N 1H-indazole Chemical compound C1=CC=C2C=NNC2=C1 BAXOFTOLAUCFNW-UHFFFAOYSA-N 0.000 description 2
- 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 2
- KDCGOANMDULRCW-UHFFFAOYSA-N 7H-purine Chemical compound N1=CNC2=NC=NC2=C1 KDCGOANMDULRCW-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 101000837344 Homo sapiens T-cell leukemia translocation-altered gene protein Proteins 0.000 description 2
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 2
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 102100028692 T-cell leukemia translocation-altered gene protein Human genes 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 125000004062 acenaphthenyl group Chemical group C1(CC2=CC=CC3=CC=CC1=C23)* 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 125000005605 benzo group Chemical group 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229940125782 compound 2 Drugs 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 238000009877 rendering Methods 0.000 description 2
- UGUHFDPGDQDVGX-UHFFFAOYSA-N 1,2,3-thiadiazole Chemical compound C1=CSN=N1 UGUHFDPGDQDVGX-UHFFFAOYSA-N 0.000 description 1
- YGTAZGSLCXNBQL-UHFFFAOYSA-N 1,2,4-thiadiazole Chemical compound C=1N=CSN=1 YGTAZGSLCXNBQL-UHFFFAOYSA-N 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- CINYXYWQPZSTOT-UHFFFAOYSA-N 3-[3-[3,5-bis(3-pyridin-3-ylphenyl)phenyl]phenyl]pyridine Chemical compound C1=CN=CC(C=2C=C(C=CC=2)C=2C=C(C=C(C=2)C=2C=C(C=CC=2)C=2C=NC=CC=2)C=2C=C(C=CC=2)C=2C=NC=CC=2)=C1 CINYXYWQPZSTOT-UHFFFAOYSA-N 0.000 description 1
- WDBQJSCPCGTAFG-QHCPKHFHSA-N 4,4-difluoro-N-[(1S)-3-[4-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)piperidin-1-yl]-1-pyridin-3-ylpropyl]cyclohexane-1-carboxamide Chemical compound FC1(CCC(CC1)C(=O)N[C@@H](CCN1CCC(CC1)N1C(=NN=C1C)C(C)C)C=1C=NC=CC=1)F WDBQJSCPCGTAFG-QHCPKHFHSA-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
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-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
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical class [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000006620 amino-(C1-C6) alkyl group Chemical group 0.000 description 1
- 229940040526 anhydrous sodium acetate Drugs 0.000 description 1
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 1
- 230000002744 anti-aggregatory effect Effects 0.000 description 1
- RFRXIWQYSOIBDI-UHFFFAOYSA-N benzarone Chemical compound CCC=1OC2=CC=CC=C2C=1C(=O)C1=CC=C(O)C=C1 RFRXIWQYSOIBDI-UHFFFAOYSA-N 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 229940125898 compound 5 Drugs 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005274 electronic transitions Effects 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 1
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- ZLTPDFXIESTBQG-UHFFFAOYSA-N isothiazole Chemical compound C=1C=NSC=1 ZLTPDFXIESTBQG-UHFFFAOYSA-N 0.000 description 1
- CTAPFRYPJLPFDF-UHFFFAOYSA-N isoxazole Chemical compound C=1C=NOC=1 CTAPFRYPJLPFDF-UHFFFAOYSA-N 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- HZVGIXIRNANSHU-UHFFFAOYSA-N naphthalene-1,2,3,4-tetrone Chemical compound C1=CC=C2C(=O)C(=O)C(=O)C(=O)C2=C1 HZVGIXIRNANSHU-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 125000001828 phenalenyl group Chemical group C1(C=CC2=CC=CC3=CC=CC1=C23)* 0.000 description 1
- LFSXCDWNBUNEEM-UHFFFAOYSA-N phthalazine Chemical compound C1=NN=CC2=CC=CC=C21 LFSXCDWNBUNEEM-UHFFFAOYSA-N 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- VNFWTIYUKDMAOP-UHFFFAOYSA-N sphos Chemical compound COC1=CC=CC(OC)=C1C1=CC=CC=C1P(C1CCCCC1)C1CCCCC1 VNFWTIYUKDMAOP-UHFFFAOYSA-N 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003536 tetrazoles Chemical class 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
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Abstract
本發明涉及一種有機金屬配合物發光材料,具有式(I)所述的結構式,其中A,B,C獨立的為取代或非取代的C,N,O,S原子;連結A和B原子的虛線環為取代或非取代的共軛的環狀結構;L1,L2,L3,L4獨立的為單鍵或雙鍵,其中L3和L4為所述連結A和B原子的共軛的環狀結構的一部分;X,X1,Y,Y1獨立的為C,N,O,S原子;Ar1和Ar2獨立的為取代或非取代的共軛的環狀結構;M為Pt,W,Au原子。本發明中的有機金屬配合物具有高螢光量子效率,良好的熱穩定性及低淬滅常數,可以製造高效率低效率滾降的紅光OLED。
Description
本發明涉及一種有機金屬配合物發光材料,尤其是用於OLED發光器件中,在發光層中起光子發射作用的摻雜劑。
OLED(Organic Light-Emitting Diode,有機發光二極體)技術自1987年由柯達公司的鄧青雲博士首次發表相關工作(Organic electroluminescent diodes. Applied Physics Letters. 1987,51卷, 12期, 913頁)以來,到現在已經經過了30年的蓬勃發展。近5年OLED技術由於其獨特性吸引了大量工業界的關注和投資。在顯示領域,相比目前主流的LCD(Liquid Crystal Display,液晶顯示)顯示技術,OLED顯示具有高亮度、高對比、高解析度、超薄顯示、柔性顯示的巨大優勢;在照明領域,OLED照明具有高顯色指數(CRI ,Color Rendering Index)、平面光源、柔性光源等巨大優勢。OLED發光技術目前面臨最大的劣勢,就是成本高,壽命短。
OLED器件由很多功能層構成。其中發光層中,發射綠光和紅光的摻雜劑效果最好、應用最廣的是磷光發光材料。目前常用的磷光發光材料有兩種,一種是含有金屬銥(Ir)的有機金屬配合物,另一種是含有金屬(Pt)的有機金屬配合物。 紅光、綠光金屬Ir配合物均有性能非常好的材料。
由於金屬銥具有6個配位點,所以含有Ir的有機金屬配合物具有正八面體的立體結構。用於合成Ir配合物的有機化合物配體大多數只有兩個配位點,故而一個分子裡需要有3個相同或不同的有機配體。 絕大多數配體結構不對稱,所以合成金屬銥(Ir)的有機金屬配合物的時候,會得到分子量完全一致、發光性能完全不同的兩種構型,稱為經式(mer)構型和面式(fac)構型。面式構型相對經式構型,具有更高的發光效率,但是將其分離出來具有很高的成本,尤其是工業生產過程中。為了解決這個問題,可以引入輔助配體(US6830828),也可以通過紫外線照射提高分子經式向面式構型的轉化率。
金屬鉑具有4個配位點,可以通過設計四齒配體形成唯一構型,可以完全避免異構體的形成。Mark等人用卟啉作為配體,可以形成具有唯一構型的Pt有機金屬配合物(US6303238),但是發光效果不好,器件的量子效率只有不到1%;Chi等設計了一系列具有席夫堿結構的四齒配體(US20050233167),其發光覆蓋了綠光到紅光區的波段。但目前仍存在紅光分子的螢光量子效率低(40%左右)的問題。
針對上述領域中的缺陷,本發明提供一種新型四配位元有機金屬配合物發光材料,其具有更加剛性的構型,可以用來製造高效率的紅光OLED。
本發明還提供該發光材料的製備方法。
本發明還提供該發光材料製備的發光器件。
一種有機金屬配合物發光材料,其結構如式(I)所示,(I) 其中A,B,C獨立的為取代或非取代的C,N,O,S原子; 連結A和B原子的虛線環為取代或非取代的共軛的環狀結構; L1,L2,L3,L4獨立的為單鍵或雙鍵,其中L3和L4為上述共軛環狀結構的一部分; X,X1,Y,Y1獨立的為C,N,O,S原子; Ar1和Ar2獨立的為取代或非取代的共軛的環狀結構; M為Pt,W,Au原子; 如前文所述的“取代”,是指被選自但不限於氫、氘、硫、鹵素、羥基、醯基、烷氧基、醯氧基、氨基、硝基、醯基氨基、氰基、羧基、苯乙烯基、氨基羰基、氨基甲醯基、苄基羰基、芳氧基、含1-30個C原子的飽和烷基鏈、含1-30個C原子的不飽和烷基鏈、含5-30個C原子的芳環、含5-30個C原子的雜芳環; 所述X、X1為N原子,Y、Y1為O原子,M為Pt原子。
如式(I)所述分子,其結構可以優選為如式(II)的結構,(II) 其中m,n,p為0-30的整數; R1
,R2
,R3
為D、E、F環上除氫以外的取代基,R1
,R2
,R3
獨立的選自氘、硫、鹵素、羥基、醯基、烷氧基、醯氧基、氨基、硝基、醯基氨基、氰基、羧基、苯乙烯基、氨基羰基、氨基甲醯基、苄基羰基、芳氧基、含1-30個C原子的飽和烷基、含1-30個C原子的不飽和烷基、含5-30個C原子的芳環基、含5-30個C原子的雜芳環基、相鄰的R1
、R2
、R3
之間可以獨立的相互通過共價鍵連接成環; D,E為含有5-30個C原子的芳環或雜芳環;F為含有9-30個C原子的芳環或雜芳環。
所述D為五元或六元芳環或雜環、苯並芳環或苯並雜環,所述E為五元或六元雜環或苯並雜環,所述F為二或三環芳香環,其中R1
,R2
,R3
獨立的選自鹵素、含1-20個C原子的飽和烷基鏈、含6-20個C原子的芳環、含6-20個C原子的雜芳環、相鄰的R1
、R2
、R3
之間可以獨立的相互通過共價鍵連接成環,其中m,n,p為0-10的整數。
所述D為苯環或萘環,所述E為吡啶環或喹啉環,所述F為萘環或蒽環,其中R1
,R2
,R3
獨立的選自鹵素、含1-10個C原子的飽和烷基鏈、含6-10個C原子的芳環、含6-10個C原子的雜芳環、相鄰的R1
、R2
、R3
之間可以獨立的相互通過共價鍵連接成環,其中m,n,p為0-6的整數。
所述D為苯環,所述E為吡啶環,所述F為萘環,其中R1
為氫、鹵素,所述R2
、R3
獨立為氫、含1-10個C原子的飽和烷基鏈、含6-10個C原子的芳環,其中m,n,p為0-3的整數。
為了本申請的目的,除非另有指明,術語鹵素、烷基、環烷基、芳基、醯基、烷氧基和雜環芳族體系或雜環芳族基團可有以下含義:
上述鹵素或鹵代包括氟、氯、溴和碘,優選F,Cl,Br,特別優選F或Cl,最優選F。
上述共軛的環狀結構、芳基、芳基部分或芳族體系包括具有6-30個碳原子,優選6-20個碳原子,更優選6-10個碳原子並且由一個芳環或多個稠和的芳環組成的芳基。適宜的芳基為,例如苯基,萘基,苊基(acenaphthenyl),二氫苊基(acenaphthenyl),蒽基、芴基、菲基(phenalenyl)。該芳基可為未取代的(即所有能夠取代的碳原子帶有氫原子)或在芳基的一個、多於一個或所有可取代的位置上被取代。適宜的取代基為例如鹵素,優選F、Br或Cl;烷基,優選具有1-20個,1-10個或1-8個碳原子的烷基,特別優選甲基、乙基、異丙基或叔丁基;芳基,優選可再次被取代的或是未取代C6
芳基或芴基;雜芳基,優選含至少一個氮原子的雜芳基,特別優選吡啶基;烯基,優選具有一個雙鍵的烯基,特別優選具有雙鍵和1-8個碳原子的烯基。芳基尤其特別優選帶有選自F和叔丁基的取代基,優選可為給定的芳基或任選被至少一個上述取代基取代的為C6
芳基的芳基,C6
芳基特別優選帶有0、1或2個上述取代基,C6
芳基尤其特別優選未取代的苯基或取代的苯基,諸如聯苯基、被兩個叔丁基優選在間位取代的苯基。
上述烷基或烷基部分包括具有1-20個碳原子,優選1-10個碳原子,優選1-6個碳原子的烷基。該烷基可為支鏈或直鏈的,也可以是環形的,並且可被一個或多個雜原子,優選N、O或S間斷。而且,該烷基可被一個或多個鹵素或上述的關於芳基的取代基所取代。同樣,對於烷基而言,帶有一個或多個芳基是可能的,所有上述的芳基均適用於該目的,烷基特別優選自甲基、乙基、異丙基、正丙基、異丁基、正丁基、叔丁基、仲丁基、異戊基、環丙基、環戊基、環己基。
上述醯基是以單鍵連接至CO基團的,如本文所用的烷基。
上述烷氧基是以單鍵與氧直接相連的,如本文所用的烷基。
上述雜芳族體系或雜芳族基團被理解為與芳族、C3
-C8
環基相關,並且還包含一個氧或硫原子或1-4個氮原子或一個氧或硫原子與最多兩個氮原子的組合,和它們的取代的以及苯並吡啶並稠的衍生物,例如,經由其中一個成環碳原子相連,所述雜芳族體系或雜環芳族基團可被一個或多個提到的關於芳基的取代基所取代。
在某些實施方案中,雜芳基可為攜帶以上獨立的含有0、1或2個取代基的五、六元芳族雜環體系。雜芳基的典型實例包括但不限於未取代的呋喃、苯並呋喃、噻吩、苯並噻吩、吡咯、吡啶、吲哚、唑、苯並唑、異唑、苯並異唑、噻唑、苯並噻唑、異噻唑、咪唑、苯並咪唑、吡唑、吲唑、四唑、喹啉、異喹啉、噠嗪、嘧啶、嘌呤和吡嗪、呋喃、1,2,3-二唑、1,2,3-噻二唑、1,2,4-噻二唑、三唑、苯並三唑、喋啶、苯並唑、二唑、苯並吡唑、喹嗪、噌啉、酞嗪、喹唑和喹喔啉及其單-或二-取代的衍生物。在某些實施方案中,取代基為鹵代、羥基、氰基、O-C1~6
烷基、C1~6
烷基、羥基C1~6
烷基和氨基- C1~6
烷基。
具有結構(II)的化學結構的有機金屬配合物,為了實現紅光發射,需要含有席夫堿的基本結構(即式中N原子與相鄰原子形成的結構)。在背景中提到,具有席夫堿結構的Pt有機金屬配合物的紅光發射存在螢光量子效率偏低的問題。為了提高分子的螢光量子效率,有兩個主要方法:1、引入強σ-給體配體;2、增強分子剛性,減少分子激發態下構型的扭曲(Chi, Chem.sci., 2016, 7, 1653)。在不改變分子的電子結構的情況下,擴大式II中D,E,F環的共軛面積,可以有效地提高分子的剛性。如此設計的分子在激發態下的振動便會受限,電子躍遷的模式會減少,這樣可以直接提高分子的螢光量子效率。
在增強了核心的螢光量子效率的前提下,再通過向D、E、F環引入防聚集基團,可以抑制高激子濃度下,三線態激子的淬滅。如此便可以在保證高工作電流下的電流效率不發生明顯變化的情況下,增加摻雜的濃度,進一步提高器件的工作效率。
如式(II)所示的具體實例,包括但不限於以下結構:
採用具有結構(II)的有機金屬配合物,可製造熱沉積和溶液處理的OLED。
包括含有一種或多種如權利要求1中所述的用於發光二極體的發光材料的有機發光器件。
其中通過熱沉積在該器件中以層形式施加該用於發光二極體的發光材料。
其中通過旋塗在該器件中以層形式施加該用於發光二極體的發光材料。
其中通過噴墨列印在該器件中以層形式施加該用於發光二極體的發光材料。
上述有機發光器件,其中在對層施加電流時該器件發射單色-紅色。
本發明中的有機金屬配合物具有高螢光量子效率,良好的熱穩定性及低淬滅常數,可以製造高效率低效率滾降的紅光OLED。
下面結合實施例對本發明做進一步的詳細說明。
實施例1:(S1) 分子的製備:化合物1、2、4及反應過程中所用無機鹽、催化劑、催化劑配體、溶劑均為市售原材料。 化合物3的合成:將18.6g(0.1mol)化合物1、15.2g(0.11mol)化合物2加入圓底燒瓶。再加入0.575g(0.001mol)Pd(dba)2
,0.82g(0.002mol)SPhos,抽真空30分鐘後充入氮氣保護;400ml甲苯氮氣鼓泡30min後,加入燒瓶;將150ml 2M濃度的碳酸鉀水溶液氮氣鼓泡30min後,加入燒瓶中。在氮氣環境下反應12hr後,冷卻,水洗,無水硫酸鎂乾燥,過濾。有機相蒸除甲苯溶劑後,固體用正己烷/二氯甲烷體系重結晶。得到淡黃色固體18.3g,產率92%。質譜(APCI)m/z:199. 化合物5的合成:將10g(0.063mol)化合物4溶解於30ml乙醇中,加入33.3ml飽和亞硫酸氫鈉水溶液,回流24小時。再加入66.7ml 濃度為6M氫氧化鉀水溶液,回流2hr。用稀鹽酸酸化,乙酸乙酯萃取。收集有機相,無水硫酸鎂乾燥,濃縮,得到棕紅色固體8.14g,產率81%。質譜(APCI)m/z:159. 化合物6的合成:將5g(0.025mol)化合物3、4g(0.025mol)化合物5融於甲苯,氮氣保護下回流12h,分水器除去生成的水。冷卻後加入無水硫酸鎂乾燥,濃縮後甲苯重結晶,得到橘紅色針狀晶體8.1g,產率95%。質譜(APCI)m/z:340. 化合物S1的合成:將5g(0.0147mol)化合物6和2.4g無水醋酸鈉(0.0294mol)溶於100ml DMSO中,攪拌,加熱至80攝氏度。投入四氯鉑酸鉀6.10g(0.0147mol),升溫到120攝氏度,反應5h。趁熱加入500ml水,過濾,收集固體,水洗多次,少量甲醇沖洗。甲苯重結晶後,290攝氏度昇華,得到深紅色晶體5.48g,總產率70%。質譜(APCI)m/z:533.
實施例2(S23) 分子的製備: 製備方法與S1分子的合成路線相同,唯一區別是使用化合物7替代化合物2。化合物7的分子式如式(III)所示:(III) 化合物7的合成路線如下:對比例E1結構如式(IV)所示:(IV) 化合物E1的合成參考專利US20050233167中的合成方法。質譜(APCI):510.
下面是本發明化合物的應用實例。
器件結構如圖1。
器件所用材料TCTA(4,4′,4′′-Tri(9-carbazoyl) triphenylamine)、TAPC(1,1-Bis[4-[N,N’-di(p-tolyl)amino]phenyl]cyclohexane)、TmPYPB(1,3,5-tri[(3-pyridyl)-phen-3-yl]benzene)均為市售材料,其具體的結構分別如式(V)所示:(V) 其他材料如ITO、LiF、Al也是市售材料。
器件製備方式: 首先,將透明導電ITO玻璃(帶有陽極20的玻璃基板10)依次經洗滌劑溶液、去離子水、丙酮超聲清洗、異丙醇蒸汽清洗,再用氧氣等離子處理5分鐘。 然後,在ITO上蒸鍍40nm厚的TAPC作為空穴傳輸層30。 然後,蒸鍍20nm厚的發光層40,其中主體材料為TCTA,摻雜1.5%品質濃度的有機金屬配合物(摻雜劑)。 然後,蒸鍍30nm厚的TmPYPB作為電子傳輸層50。 最後,蒸鍍1nm厚的LiF作為電子注入層60和100nm 金屬Al作為陰極70。 器件1、2、3的結構和製作方法完全相同,區別在於依次使用有機金屬配合物S1、S23、E1作為發光層中的摻雜劑。
器件對比結果如表1所示:
表1
本發明所製備的有機電致發光器件的性能相對於基準器件具有不同程度的性能提升。
圖1為本發明實施例的有發光器件結構圖。
Claims (9)
- 一種有機金屬配合物發光材料,其結構如式(I)所示,
- 如申請專利範圍第1項所述的發光材料,所述X、X1為N原子,Y、Y1為O原子,M為Pt原子。
- 如申請專利範圍第2項所述的發光材料,所述式(I)具有如式(II)所示的結構,
- 如申請專利範圍第3項所述的發光材料,所述D為五元或六元芳環或雜環、苯並芳環或苯並雜環,所述E為五元或六元雜環或苯並雜環,所述F為二或三環芳香環,其中R1,R2,R3獨立的選自鹵素、含1-20個C原子的 飽和烷基鏈、含6-20個C原子的芳環、含6-20個C原子的雜芳環、相鄰的R1、R2、R3之間可以獨立的相互通過共價鍵連接成環,其中m,n,p為0-10的整數。
- 如申請專利範圍第4項所述的發光材料,所述D為苯環或萘環,所述E為吡啶環或喹啉環,所述F為萘環或蒽環,其中R1,R2,R3獨立的選自鹵素、含1-10個C原子的飽和烷基鏈、含6-10個C原子的芳環、含6-10個C原子的雜芳環、相鄰的R1、R2、R3之間可以獨立的相互通過共價鍵連接成環,其中m,n,p為0-6的整數。
- 如申請專利範圍第5項所述的發光材料,所述D為苯環,所述E為吡啶環,所述F為萘環,其中R1為氫、鹵素,所述R2、R3獨立為氫、含1-10個C原子的飽和烷基鏈、含6-10個C原子的芳環,其中m,n,p為0-3的整數。
- 如申請專利範圍第1至3項中之任一項所述的發光材料,所述式(I)具有如下結構:
- 如申請專利範圍第7項所述的發光材料,所述式(I)具有如下結構:
- 一種如申請專利範圍第1至8項中之任一項所述的發光材料在有機發光半導體顯示、有機發光半導體照明、太陽能光電池、有機薄膜半導體中的應用。
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