KR20220099373A - Novel heterocyclic compound and organic light emitting device comprising the same - Google Patents
Novel heterocyclic compound and organic light emitting device comprising the same Download PDFInfo
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- KR20220099373A KR20220099373A KR1020210001532A KR20210001532A KR20220099373A KR 20220099373 A KR20220099373 A KR 20220099373A KR 1020210001532 A KR1020210001532 A KR 1020210001532A KR 20210001532 A KR20210001532 A KR 20210001532A KR 20220099373 A KR20220099373 A KR 20220099373A
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- aryl
- heteroaryl
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- alkyl
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- 150000002391 heterocyclic compounds Chemical class 0.000 title claims abstract description 56
- 239000011368 organic material Substances 0.000 claims abstract description 25
- 125000003118 aryl group Chemical group 0.000 claims description 67
- 125000001072 heteroaryl group Chemical group 0.000 claims description 49
- 125000006736 (C6-C20) aryl group Chemical group 0.000 claims description 32
- 238000002347 injection Methods 0.000 claims description 27
- 239000007924 injection Substances 0.000 claims description 27
- 125000005549 heteroarylene group Chemical group 0.000 claims description 26
- 125000006749 (C6-C60) aryl group Chemical group 0.000 claims description 25
- 230000005525 hole transport Effects 0.000 claims description 25
- 125000000732 arylene group Chemical group 0.000 claims description 23
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 claims description 18
- 125000000623 heterocyclic group Chemical group 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 14
- 125000006743 (C1-C60) alkyl group Chemical group 0.000 claims description 13
- 125000000592 heterocycloalkyl group Chemical group 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 229910052717 sulfur Inorganic materials 0.000 claims description 12
- 150000002431 hydrogen Chemical class 0.000 claims description 11
- 125000006761 (C6-C60) arylene group Chemical group 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 10
- 125000000923 (C1-C30) alkyl group Chemical group 0.000 claims description 6
- 125000006818 (C3-C60) cycloalkyl group Chemical group 0.000 claims description 6
- 125000005842 heteroatom Chemical group 0.000 claims description 6
- 229910052711 selenium Inorganic materials 0.000 claims description 6
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 5
- 125000003342 alkenyl group Chemical group 0.000 claims description 5
- 125000000304 alkynyl group Chemical group 0.000 claims description 5
- 229910052805 deuterium Inorganic materials 0.000 claims description 5
- 125000006835 (C6-C20) arylene group Chemical group 0.000 claims description 4
- 125000006746 (C1-C60) alkoxy group Chemical group 0.000 claims description 3
- 125000006744 (C2-C60) alkenyl group Chemical group 0.000 claims description 3
- 125000006745 (C2-C60) alkynyl group Chemical group 0.000 claims description 3
- 125000006751 (C6-C60) aryloxy group Chemical group 0.000 claims description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 98
- -1 polycyclic heterocyclic compound Chemical class 0.000 abstract description 47
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical compound C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 abstract description 11
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 abstract description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 7
- 150000001875 compounds Chemical class 0.000 description 93
- 239000010410 layer Substances 0.000 description 88
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 78
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 36
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 32
- 238000002360 preparation method Methods 0.000 description 28
- 238000006243 chemical reaction Methods 0.000 description 17
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 16
- 125000004432 carbon atom Chemical group C* 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- 239000002019 doping agent Substances 0.000 description 13
- 125000001424 substituent group Chemical group 0.000 description 13
- 239000007864 aqueous solution Substances 0.000 description 12
- 229910052763 palladium Inorganic materials 0.000 description 10
- 239000000376 reactant Substances 0.000 description 10
- 238000010992 reflux Methods 0.000 description 10
- 238000004440 column chromatography Methods 0.000 description 9
- 238000000605 extraction Methods 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 239000007983 Tris buffer Substances 0.000 description 8
- 229910052741 iridium Inorganic materials 0.000 description 8
- 125000003367 polycyclic group Chemical group 0.000 description 8
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 8
- 235000017557 sodium bicarbonate Nutrition 0.000 description 8
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 8
- 125000005595 acetylacetonate group Chemical group 0.000 description 7
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 7
- MILUBEOXRNEUHS-UHFFFAOYSA-N iridium(3+) Chemical compound [Ir+3] MILUBEOXRNEUHS-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000000746 purification Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 150000001639 boron compounds Chemical class 0.000 description 6
- 150000001642 boronic acid derivatives Chemical class 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 239000012044 organic layer Substances 0.000 description 6
- 229920000767 polyaniline Polymers 0.000 description 6
- 238000001953 recrystallisation Methods 0.000 description 6
- FKHIFSZMMVMEQY-UHFFFAOYSA-N talc Chemical compound [Mg+2].[O-][Si]([O-])=O FKHIFSZMMVMEQY-UHFFFAOYSA-N 0.000 description 6
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 5
- 238000000151 deposition Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 125000002950 monocyclic group Chemical group 0.000 description 4
- 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
- 150000003254 radicals Chemical class 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 description 3
- FSEXLNMNADBYJU-UHFFFAOYSA-N 2-phenylquinoline Chemical compound C1=CC=CC=C1C1=CC=C(C=CC=C2)C2=N1 FSEXLNMNADBYJU-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 3
- 238000006069 Suzuki reaction reaction Methods 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000005576 amination reaction Methods 0.000 description 3
- 239000012300 argon atmosphere Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000004696 coordination complex Chemical class 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- CECAIMUJVYQLKA-UHFFFAOYSA-N iridium 1-phenylisoquinoline Chemical compound [Ir].C1=CC=CC=C1C1=NC=CC2=CC=CC=C12.C1=CC=CC=C1C1=NC=CC2=CC=CC=C12.C1=CC=CC=C1C1=NC=CC2=CC=CC=C12 CECAIMUJVYQLKA-UHFFFAOYSA-N 0.000 description 3
- UEEXRMUCXBPYOV-UHFFFAOYSA-N iridium;2-phenylpyridine Chemical compound [Ir].C1=CC=CC=C1C1=CC=CC=N1.C1=CC=CC=C1C1=CC=CC=N1.C1=CC=CC=C1C1=CC=CC=N1 UEEXRMUCXBPYOV-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 125000005493 quinolyl group Chemical group 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 238000001771 vacuum deposition Methods 0.000 description 3
- TXBFHHYSJNVGBX-UHFFFAOYSA-N (4-diphenylphosphorylphenyl)-triphenylsilane Chemical compound C=1C=CC=CC=1P(C=1C=CC(=CC=1)[Si](C=1C=CC=CC=1)(C=1C=CC=CC=1)C=1C=CC=CC=1)(=O)C1=CC=CC=C1 TXBFHHYSJNVGBX-UHFFFAOYSA-N 0.000 description 2
- AVJBQMXODCVJCJ-UHFFFAOYSA-M 1,3-bis[2,6-di(propan-2-yl)phenyl]imidazol-1-ium;chloride Chemical compound [Cl-].CC(C)C1=CC=CC(C(C)C)=C1N1C=[N+](C=2C(=CC=CC=2C(C)C)C(C)C)C=C1 AVJBQMXODCVJCJ-UHFFFAOYSA-M 0.000 description 2
- OIRHKGBNGGSCGS-UHFFFAOYSA-N 1-bromo-2-iodobenzene Chemical compound BrC1=CC=CC=C1I OIRHKGBNGGSCGS-UHFFFAOYSA-N 0.000 description 2
- LPCWDYWZIWDTCV-UHFFFAOYSA-N 1-phenylisoquinoline Chemical compound C1=CC=CC=C1C1=NC=CC2=CC=CC=C12 LPCWDYWZIWDTCV-UHFFFAOYSA-N 0.000 description 2
- NRSBAUDUBWMTGL-UHFFFAOYSA-N 2-(1-benzothiophen-2-yl)pyridine Chemical compound S1C2=CC=CC=C2C=C1C1=CC=CC=N1 NRSBAUDUBWMTGL-UHFFFAOYSA-N 0.000 description 2
- FQJQNLKWTRGIEB-UHFFFAOYSA-N 2-(4-tert-butylphenyl)-5-[3-[5-(4-tert-butylphenyl)-1,3,4-oxadiazol-2-yl]phenyl]-1,3,4-oxadiazole Chemical compound C1=CC(C(C)(C)C)=CC=C1C1=NN=C(C=2C=C(C=CC=2)C=2OC(=NN=2)C=2C=CC(=CC=2)C(C)(C)C)O1 FQJQNLKWTRGIEB-UHFFFAOYSA-N 0.000 description 2
- 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 2
- VLRSADZEDXVUPG-UHFFFAOYSA-N 2-naphthalen-1-ylpyridine Chemical compound N1=CC=CC=C1C1=CC=CC2=CC=CC=C12 VLRSADZEDXVUPG-UHFFFAOYSA-N 0.000 description 2
- XBHOUXSGHYZCNH-UHFFFAOYSA-N 2-phenyl-1,3-benzothiazole Chemical compound C1=CC=CC=C1C1=NC2=CC=CC=C2S1 XBHOUXSGHYZCNH-UHFFFAOYSA-N 0.000 description 2
- QLPKTAFPRRIFQX-UHFFFAOYSA-N 2-thiophen-2-ylpyridine Chemical compound C1=CSC(C=2N=CC=CC=2)=C1 QLPKTAFPRRIFQX-UHFFFAOYSA-N 0.000 description 2
- 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 2
- QWOYGNOEJFALQR-UHFFFAOYSA-N 4-[6-[(3-ethyloxetan-3-yl)methoxy]hexyl]-n-[4-[4-(n-[4-[6-[(3-ethyloxetan-3-yl)methoxy]hexyl]phenyl]anilino)phenyl]phenyl]-n-phenylaniline Chemical compound C=1C=C(N(C=2C=CC=CC=2)C=2C=CC(=CC=2)C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=CC(CCCCCCOCC3(CC)COC3)=CC=2)C=CC=1CCCCCCOCC1(CC)COC1 QWOYGNOEJFALQR-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
- YXEMZQLJOPWZTE-UHFFFAOYSA-N 6-methoxy-1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole Chemical compound CC1(C)OB(C2=CC=CC(C3=C4)=C2NC3=CC=C4OC)OC1(C)C YXEMZQLJOPWZTE-UHFFFAOYSA-N 0.000 description 2
- 229940126062 Compound A Drugs 0.000 description 2
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 125000001164 benzothiazolyl group Chemical group S1C(=NC2=C1C=CC=C2)* 0.000 description 2
- 125000004541 benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 description 2
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005281 excited state Effects 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 2
- 125000002541 furyl group Chemical group 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 125000002883 imidazolyl group Chemical group 0.000 description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 2
- 125000001041 indolyl group Chemical group 0.000 description 2
- 125000001786 isothiazolyl group Chemical group 0.000 description 2
- 125000000842 isoxazolyl group Chemical group 0.000 description 2
- IMKMFBIYHXBKRX-UHFFFAOYSA-M lithium;quinoline-2-carboxylate Chemical compound [Li+].C1=CC=CC2=NC(C(=O)[O-])=CC=C21 IMKMFBIYHXBKRX-UHFFFAOYSA-M 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
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- WTEWXIOJLNVYBZ-UHFFFAOYSA-N n-[4-[4-(4-ethenyl-n-naphthalen-1-ylanilino)phenyl]phenyl]-n-(4-ethenylphenyl)naphthalen-1-amine Chemical compound C1=CC(C=C)=CC=C1N(C=1C2=CC=CC=C2C=CC=1)C1=CC=C(C=2C=CC(=CC=2)N(C=2C=CC(C=C)=CC=2)C=2C3=CC=CC=C3C=CC=2)C=C1 WTEWXIOJLNVYBZ-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000004866 oxadiazoles Chemical class 0.000 description 2
- 125000002971 oxazolyl group Chemical group 0.000 description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 2
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 2
- 125000003226 pyrazolyl group Chemical group 0.000 description 2
- 125000002098 pyridazinyl group Chemical group 0.000 description 2
- 125000004076 pyridyl group Chemical group 0.000 description 2
- 125000000714 pyrimidinyl group Chemical group 0.000 description 2
- 125000000168 pyrrolyl group Chemical group 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 125000000335 thiazolyl group Chemical group 0.000 description 2
- 125000001544 thienyl group Chemical group 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 125000004306 triazinyl group Chemical group 0.000 description 2
- WJKHJLXJJJATHN-UHFFFAOYSA-N triflic anhydride Chemical compound FC(F)(F)S(=O)(=O)OS(=O)(=O)C(F)(F)F WJKHJLXJJJATHN-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-N 0.000 description 1
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- 125000001977 isobenzofuranyl group Chemical group C=1(OC=C2C=CC=CC12)* 0.000 description 1
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- BSEKBMYVMVYRCW-UHFFFAOYSA-N n-[4-[3,5-bis[4-(n-(3-methylphenyl)anilino)phenyl]phenyl]phenyl]-3-methyl-n-phenylaniline Chemical compound CC1=CC=CC(N(C=2C=CC=CC=2)C=2C=CC(=CC=2)C=2C=C(C=C(C=2)C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=C(C)C=CC=2)C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=C(C)C=CC=2)=C1 BSEKBMYVMVYRCW-UHFFFAOYSA-N 0.000 description 1
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- OXNIZHLAWKMVMX-UHFFFAOYSA-N picric acid Chemical compound OC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-N 0.000 description 1
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- 238000004904 shortening Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
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- 239000002356 single layer Substances 0.000 description 1
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- 239000011734 sodium Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical class C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 125000001935 tetracenyl group Chemical group C1(=CC=CC2=CC3=CC4=CC=CC=C4C=C3C=C12)* 0.000 description 1
- 125000005247 tetrazinyl group Chemical group N1=NN=NC(=C1)* 0.000 description 1
- 125000003831 tetrazolyl group Chemical group 0.000 description 1
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- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- 125000003960 triphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C3=CC=CC=C3C12)* 0.000 description 1
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- 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
-
- 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
- C07D491/12—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 three hetero rings
- C07D491/14—Ortho-condensed systems
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Abstract
Description
본 발명은 신규한 헤테로고리 화합물 및 이를 포함하는 유기 발광 소자에 관한 것이다.The present invention relates to a novel heterocyclic compound and an organic light emitting device comprising the same.
일반적으로 유기 발광 현상이란 유기 물질을 이용하여 전기에너지를 빛 에너지로 전환시켜주는 현상을 말한다. 유기 발광 현상을 이용하는 유기전자소자는 통상 양극과 음극 및 양극 사이에 유기물층을 포함하는 구조를 가진다. 여기서 유기물 층은 유기전기소자의 효율과 안정성을 높이기 위하여 각기 다른 물질로 구성된 다층의 구조로 이루어진 경우가 많으며, 예컨대 정공주입층, 정공수송층, 발광층, 전자수송층 및 전자주입층 등으로 이루어질 수 있다.In general, the organic light emitting phenomenon refers to a phenomenon in which electric energy is converted into light energy using an organic material. An organic electronic device using an organic light emitting phenomenon generally has a structure including an anode, a cathode, and an organic material layer between the anode. Here, the organic layer is often formed of a multi-layered structure composed of different materials in order to increase the efficiency and stability of the organic electric device, and may include, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer.
유기전자소자에서 유기물층으로 사용되는 재료는 기능에 따라, 발광 재료와 전하 수송 재료, 예컨대 정공주입 재료, 정공수송 재료, 전자수송 재료, 전자주입 재료 등으로 분류될 수 있다. 그리고, 상기 발광 재료는 분자량에 따라 고분자형과 저분자형으로 분류될 수 있고, 발광 메커니즘에 따라 전자의 일중항 여기상태로부터 유래되는 형광 재료와 전자의 삼중항 여기상태로부터 유래되는 인광 재료로 분류될 수 있다. 또한, 발광 재료는 발광색에 따라 청색, 녹색, 적색 발광 재료와 보다 나은 천연색을 구현하기 위해 필요한 노란색 및 주황색 발광 재료로 구분될 수 있다.A material used as an organic layer in an organic electronic device may be classified into a light emitting material and a charge transport material, such as a hole injection material, a hole transport material, an electron transport material, an electron injection material, etc. according to their functions. In addition, the light emitting material can be classified into a high molecular type and a low molecular type according to the molecular weight, and can be classified into a fluorescent material derived from a singlet excited state of an electron and a phosphorescent material derived from a triplet excited state of an electron according to the light emission mechanism. can In addition, the light emitting material may be divided into blue, green, and red light emitting materials and yellow and orange light emitting materials necessary for realizing a better natural color according to the emission color.
특히, 유기전자소자의 우수한 수명 특성을 위해 정공 수송층 또는 완충층(buffer layer)으로 삽입되는 유기물질에 관해 여러 연구가 진행되고 있으며, 이를 위해 양극으로부터 유기층으로의 높은 정공 이동 특성을 부여하면서 증착 후 박막 형성시 균일도가 높고 결정화도가 낮은 정공 주입층 재료가 요구되고 있다.In particular, various studies are being conducted on organic materials inserted into a hole transport layer or a buffer layer for excellent lifespan characteristics of organic electronic devices. A hole injection layer material having a high degree of uniformity and low crystallinity during formation is required.
유기전자소자의 수명단축의 원인 중 하나인 양극전극(ITO)으로부터 금속 산화물이 유기층으로 침투 확산되는 것을 지연시키며, 소자 구동시 발생되는 주울열(Joule heating)에 대해서도 안정된 특성, 즉 높은 유리 전이 온도를 갖는 정공 주입층 재료에 대한 개발이 필요하다. 또한 정공 수송층 재료의 낮은 유리전이 온도는 소자 구동시에 박막 표면의 균일도가 무너지는 특성에 따라 소자수명에 큰 영향을 미치는 것으로 보고되고 있다. 또한, OLED 소자의 형성에 있어서 증착방법이 주류를 이루고 있어, 이러한 증착방법에 오랫동안 견딜 수 있는 내열성 특성이 강한 재료가 필요한 실정이다.It delays the penetration and diffusion of metal oxide from the anode electrode (ITO) into the organic layer, which is one of the causes of shortening the lifespan of organic electronic devices, and has stable properties against Joule heating generated during device driving, that is, high glass transition temperature. It is necessary to develop a hole injection layer material having In addition, it is reported that the low glass transition temperature of the hole transport layer material greatly affects the device lifespan according to the characteristic that the uniformity of the thin film surface is collapsed during device driving. In addition, since the deposition method is the mainstream in the formation of OLED devices, there is a need for a material with strong heat resistance properties that can withstand such deposition methods for a long time.
한편, 발광 재료로서 하나의 물질만 사용하는 경우 분자간 상호 작용에 의하여 최대 발광 파장이 장파장으로 이동하고 색순도가 떨어지거나 발광 감쇄 효과로 소자의 효율이 감소되는 문제가 발생하므로, 색순도의 증가와 에너지 전이를 통한 발광 효율을 증가시키기 위하여 발광 재료로서 호스트/도판트계를 사용할 수 있다. 그 원리는 발광층을 형성하는 호스트보다 에너지 대역 간극이 작은 도판트를 발광층에 소량 혼합하면, 발광층에서 발생한 엑시톤이 도판트로 수송되어 효율이 높은 빛을 내는 것이다. 이때 호스트의 파장이 도판트의 파장대로 이동하므로, 이용하는 도판트의 종류에 따라 원하는 파장의 빛을 얻을 수 있다.On the other hand, when only one material is used as a light emitting material, the maximum emission wavelength shifts to a longer wavelength due to intermolecular interaction, and there is a problem in that the color purity is lowered or the efficiency of the device is decreased due to the emission attenuation effect. A host/dopant system may be used as a light emitting material in order to increase the luminous efficiency through the The principle is that when a small amount of a dopant having a smaller energy band gap than that of the host forming the emission layer is mixed in the emission layer, excitons generated in the emission layer are transported to the dopant to emit light with high efficiency. At this time, since the wavelength of the host moves to the wavelength band of the dopant, light having a desired wavelength can be obtained according to the type of dopant used.
전술한 유기전자소자가 갖는 우수한 특징들을 충분히 발휘하기 위해서는 소자 내 유기물층을 이루는 물질, 예컨대 정공주입 물질, 정공수송 물질, 발광 물질, 전자수송 물질, 전자주입 물질 등이 안정하고 효율적인 재료에 의하여 뒷받침되는 것이 선행되어야 하나, 아직까지 안정하고 효율적인 유기전기소자용 유기물층 재료의 개발이 충분히 이루어지지 않은 상태이며, 따라서 새로운 재료의 개발이 계속 요구되고 있다.In order to fully exhibit the excellent characteristics of the above-described organic electronic device, the material constituting the organic material layer in the device, such as a hole injection material, a hole transport material, a light emitting material, an electron transport material, an electron injection material, etc., is supported by a stable and efficient material. However, the development of a stable and efficient organic material layer material for an organic electric device has not yet been sufficiently developed, and thus, the development of a new material is continuously required.
특히 양극으로부터 유기층으로의 높은 정공 이동 특성을 부여하면서 증착 후 박막 형성시 균일도가 높고 결정화도가 낮은 정공주입층 재료가 절실히 요구되고 있다.In particular, there is an urgent need for a hole injection layer material with high uniformity and low crystallinity when forming a thin film after deposition while providing high hole transport properties from the anode to the organic layer.
본 발명은 유기 발광 소자의 유기물층 재료로서 사용할 수 있는 신규 구조의 헤테로고리 화합물을 제공하는데 목적이 있다.An object of the present invention is to provide a heterocyclic compound having a novel structure that can be used as an organic layer material of an organic light emitting device.
또한, 본 발명은 상기 헤테로고리 화합물을 유기물층 재료로서 포함하는 유기 발광 소자를 제공하는데 목적이 있다.Another object of the present invention is to provide an organic light emitting device including the heterocyclic compound as an organic material layer material.
본 발명은 신규한 헤테로고리 화합물 및 이를 포함하는 유기 발광 소자에 관한 것으로서, 본 발명에 따른 헤테로고리 화합물은 다이벤조퓨란, 카바졸 및 벤젠이 축합고리를 이루되 반드시 7원 고리를 중심으로 형성된 축합고리 골격을 모핵으로 하며, 적어도 하나의 아미노 치환체가 도입된 다환 헤테로고리 화합물로, 유기 발광 소자의 유기물층 재료로서 사용할 수 있다.The present invention relates to a novel heterocyclic compound and an organic light emitting device including the same, wherein the heterocyclic compound according to the present invention is a condensed ring in which dibenzofuran, carbazole and benzene form a condensed ring, but must be formed around a 7-membered ring. A polycyclic heterocyclic compound having a ring skeleton as a parent nucleus and introducing at least one amino substituent, and can be used as a material for an organic material layer of an organic light emitting device.
본 발명은 하기 화학식 1로 표시되는 헤테로고리 화합물을 제공한다.The present invention provides a heterocyclic compound represented by the following formula (1).
[화학식 1][Formula 1]
상기 화학식 1에서,In Formula 1,
L1 내지 L5는 각각 독립적으로 단일결합, C6-C60아릴렌 또는 C3-C60헤테로아릴렌이고;L 1 to L 5 are each independently a single bond, C6-C60 arylene, or C3-C60 heteroarylene;
R1 내지 R10은 각각 독립적으로 C1-C60알킬, C2-C60알케닐, C2-C60알키닐, C3-C60시클로알킬, C2-C60헤테로시클로알킬, C6-C60아릴, C3-C60헤테로아릴 또는 -L11-R11이거나, R1와 R2, R3과 R4, R5와 R6, R7와 R8 및 R9와 R10은 각각 독립적으로 서로 연결되어 방향족고리가 융합되거나 융합되지 않은 헤테로고리를 형성할 수 있으며;R 1 to R 10 are each independently C1-C60 alkyl, C2-C60 alkenyl, C2-C60 alkynyl, C3-C60 cycloalkyl, C2-C60 heterocycloalkyl, C6-C60 aryl, C3-C60 heteroaryl or -L 11 -R 11 or R 1 and R 2 , R 3 and R 4 , R 5 and R 6 , R 7 and R 8 , and R 9 and R 10 are each independently connected to each other so that an aromatic ring is fused or fused can form heterocycles that are not;
L11은 C6-C60아릴렌 또는 C3-C60헤테로아릴렌이며; L 11 is C6-C60 arylene or C3-C60 heteroarylene;
R11은 C6-C60아릴, C3-C60헤테로아릴 또는 -NR12R13이며;R 11 is C6-C60 aryl, C3-C60 heteroaryl or —NR 12 R 13 ;
R12 및 R13은 각각 독립적으로 수소, C1-C60알킬, C6-C60아릴 또는 C3-C60헤테로아릴이며;R 12 and R 13 are each independently hydrogen, C1-C60 alkyl, C6-C60 aryl or C3-C60 heteroaryl;
상기 L1 내지 L5의 아릴렌 및 헤테로아릴렌, R1 내지 R10의 알킬, 알케닐, 알키닐, 시클로알킬, 헤테로시클로알킬, 아릴 및 헤테로아릴, L11의 아릴렌 및 헤테로아릴렌, R11의 아릴 및 헤테로아릴, 및 R12 및 R13의 알킬, 아릴 및 헤테로아릴은 C1-C60알킬, 할로C1-C60알킬, 중수소, 할로겐, 시아노, C3-C60시클로알킬, C1-C60알콕시, C6-C60아릴, C6-C60아릴옥시, C6-C60아릴C1-C60알킬, C1-C60알킬C6-C60아릴, C3-C60헤테로아릴, -NR'R'', 나이트로 및 하이드록시로 이루어진 군으로부터 선택되는 하나 이상으로 더 치환될 수 있고;arylene and heteroarylene of L 1 to L 5 , alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl and heteroaryl of L 11 , arylene and heteroarylene of L 11 , Aryl and heteroaryl of R 11 , and alkyl, aryl and heteroaryl of R 12 and R 13 are C1-C60alkyl, haloC1-C60alkyl, deuterium, halogen, cyano, C3-C60cycloalkyl, C1-C60alkoxy , C6-C60 aryl, C6-C60 aryloxy, C6-C60 arylC1-C60 alkyl, C1-C60 alkylC6-C60 aryl, C3-C60 heteroaryl, -NR'R'', nitro and hydroxy may be further substituted with one or more selected from the group;
R' 및 R''는 각각 독립적으로 수소, C1-C60알킬, C6-C60아릴 또는 C3-C60헤테로아릴이고;R' and R'' are each independently hydrogen, C1-C60 alkyl, C6-C60 aryl or C3-C60 heteroaryl;
p, q 및 s는 서로 독립적으로 0 내지 4의 정수이고, r은 0 내지 3의 정수이고, t는 0 내지 2의 정수이며, 단, p, q, r, s 및 t는 동시에 0이 아니며;p, q and s are independently of each other an integer from 0 to 4, r is an integer from 0 to 3, t is an integer from 0 to 2, provided that p, q, r, s and t are not simultaneously non-zero ;
상기 헤테로아릴렌, 헤테로시클로알킬 및 헤테로아릴은 N, O, S 및 Se로부터 선택되는 하나 이상의 헤테로 원자를 포함한다.Said heteroarylene, heterocycloalkyl and heteroaryl include one or more heteroatoms selected from N, O, S and Se.
또한, 본 발명은 양극, 음극 및 상기 양극과 음극 사이에 구비된 1층 이상의 유기물층을 포함하는 유기 발광 소자로서, 상기 유기물층 중 1층 이상이 상기 화학식 1의 헤테로고리 화합물을 포함하는 유기 발광 소자를 제공한다.In addition, the present invention provides an organic light emitting device comprising an anode, a cathode, and at least one organic material layer provided between the anode and the cathode, wherein at least one layer of the organic material layer comprises an organic light emitting device comprising the heterocyclic compound of Formula 1 to provide.
본 발명에 따른 헤테로고리 화합물은 다이벤조퓨란, 카바졸 및 벤젠이 축합고리를 이루되 반드시 7원 고리를 중심으로 형성된 축합고리 골격을 모핵으로 하며, 적어도 하나의 아미노 치환체가 도입된 다환 헤테로고리 화합물로, 높은 발광 효율, 높은 색순도 등의 효과를 가지고 있어, 유기 발광 소자의 유기물층 재료, 특히 발광보조층 형성용 재료로서 사용할 수 있다.The heterocyclic compound according to the present invention is a polycyclic heterocyclic compound in which dibenzofuran, carbazole, and benzene form a condensed ring, but a condensed ring skeleton formed around a 7-membered ring as the mother nucleus, and at least one amino substituent is introduced As a result, it has effects such as high luminous efficiency and high color purity, and can be used as an organic material layer material of an organic light emitting device, particularly a material for forming a light emitting auxiliary layer.
본 발명에 따른 헤테로고리 화합물은 구조적 특이성으로 인하여 발광층에서 전자와 정공이 효과적으로 이동하여 잘 만날 수 있도록 도와주어 결과적으로 소자의 발광 효율을 높이는 역할을 수행하는 발광보조층 형성용 재료로서 채용가능하다.The heterocyclic compound according to the present invention can be employed as a material for forming a light-emitting auxiliary layer that serves to increase the light-emitting efficiency of the device by helping electrons and holes to move effectively and meet well in the light-emitting layer due to structural specificity.
특히, 본 발명에 따른 헤테로고리 화합물은 양극으로부터 유기층으로의 높은 정공 이동 특성을 부여하면서 증착 후 박막 형성시 균일도가 높고 결정화도가 낮은 정공주입층 재료로 매우 적합하기 때문에, 이를 채용한 유기발광소자는 높은 정공 이동도를 가지며, 이로 인해 높은 효율을 가지는 동시에 낮은 구동전압을 가지며, 수명특성 또한 놀랍도록 향상될 수 있다.In particular, the heterocyclic compound according to the present invention is very suitable as a hole injection layer material with high uniformity and low crystallinity when forming a thin film after deposition while imparting high hole transport properties from the anode to the organic layer. It has high hole mobility, and thus has high efficiency and low driving voltage, and lifespan characteristics can also be surprisingly improved.
즉, 본 발명에 따른 헤테로고리 화합물은 구조적 특이성으로 인해 전자이동성이 우수하여 소자의 전류특성을 개선시켜 구동전압을 강화시켜줌으로써 전력효율의 상승을 유도하여 소비전력이 개선된 고효율, 장수명의 유기 발광 소자를 제작할 수 있다.That is, the heterocyclic compound according to the present invention has excellent electron mobility due to its structural specificity, thereby improving the current characteristics of the device and enhancing the driving voltage, thereby inducing an increase in power efficiency and improving power consumption and long-life organic light emitting diodes. Elements can be crafted.
본 발명에 대하여 이하 상술하나, 이때 사용되는 기술 용어 및 과학 용어에 있어서 다른 정의가 없다면, 이 발명이 속하는 기술 분야에서 통상의 지식을 가진 자가 통상적으로 이해하고 있는 의미를 가지며, 하기의 설명에서 본 발명의 요지를 불필요하게 흐릴 수 있는 공지 기능 및 구성에 대한 설명은 생략한다.Hereinafter, the present invention will be described in detail, but unless there is another definition in the technical and scientific terms used at this time, it has the meaning commonly understood by those of ordinary skill in the art to which this invention belongs, and in the following description Descriptions of well-known functions and configurations that may unnecessarily obscure the gist of the present invention will be omitted.
본 명세서를 통해, 문맥에서 달리 필요하지 않으면, "포함하다" 및 "포함하는"이라는 기재는 제시된 단계 또는 구성요소, 또는 단계 또는 구성요소들의 군을 포함하나, 임의의 다른 단계 또는 구성요소, 또는 단계 또는 구성요소들의 군이 배제되지는 않음을 내포하는 것으로 이해하여야 한다.Throughout this specification, unless the context requires otherwise, references to "comprises" and "comprising" include, but are not limited to, a given step or element, or group of steps or elements, but any other step or element, or It is to be understood that a step or group of elements is meant to be implied not to be excluded.
본 명세서에 있어서, "치환체(substituent)", "라디칼(radical)", "기(group)", "모이어티(moiety)", 및 "절편(fragment)"은 서로 바꾸어 사용할 수 있다.In the present specification, "substituent", "radical", "group", "moiety", and "fragment" may be used interchangeably.
본 명세서에 있어서, "CA-CB"는 "탄소수가 A 이상이고 B 이하"인 것을 의미한다.In the present specification, "C A -C B " means "the number of carbon atoms is greater than or equal to A and less than or equal to B".
본 명세서에 있어서, "알킬", "알콕시" 및 그 외 "알킬" 부분을 포함하는 치환체는 직쇄 또는 분쇄 형태를 모두 포함한다.In the present specification, "alkyl", "alkoxy" and other substituents containing an "alkyl" moiety include both straight-chain or comminuted forms.
본 명세서에 있어서, "알킬"은 탄소수 1 내지 60의 직쇄 또는 분지쇄를 포함하며, 다른 치환기에 의하여 추가로 치환될 수 있다. 알킬의 탄소수는 1 내지 60, 구체적으로 1 내지 30, 더욱 구체적으로, 1 내지 20일 수 있으며, 바람직하게 1 내지 10일 수 있다.In the present specification, "alkyl" includes a straight or branched chain having 1 to 60 carbon atoms, and may be further substituted by other substituents. The number of carbon atoms in the alkyl may be 1 to 60, specifically 1 to 30, more specifically, 1 to 20, preferably 1 to 10.
본 명세서에 있어서, "알케닐"은 탄소수 2 내지 60의 직쇄 또는 분지쇄를 포함하며, 다른 치환기에 의하여 추가로 치환될 수 있다. 알케닐의 탄소수는 2 내지 60, 구체적으로 2 내지 30, 더욱 구체적으로, 2 내지 20일 수 있으며, 바람직하게 2 내지 10일 수 있다.In the present specification, "alkenyl" includes a straight or branched chain having 2 to 60 carbon atoms, and may be further substituted by other substituents. The carbon number of the alkenyl may be 2 to 60, specifically 2 to 30, more specifically, 2 to 20, preferably 2 to 10.
본 명세서에 있어서, "알키닐"은 탄소수 2 내지 60의 직쇄 또는 분지쇄를 포함하며, 다른 치환기에 의하여 추가로 치환될 수 있다. 알키닐의 탄소수는 2 내지 60, 구체적으로 2 내지 30, 더욱 구체적으로, 2 내지 20일 수 있으며, 바람직하게 2 내지 10일 수 있다.In the present specification, "alkynyl" includes a straight or branched chain having 2 to 60 carbon atoms, and may be further substituted by other substituents. The carbon number of the alkynyl may be 2 to 60, specifically 2 to 30, more specifically, 2 to 20, preferably 2 to 10.
본 명세서에 있어서, "시클로알킬"은 탄소수 3 내지 60의 단환 또는 다환을 포함하며, 다른 치환기에 의하여 추가로 치환될 수 있다. 여기서, 다환이란 시클로알킬이 다른 고리기와 직접 연결되거나 축합된 기를 의미한다. 여기서, 다른 고리기란 시클로알킬일 수도 있으나, 다른 종류의 고리기, 예컨대 헤테로시클로알킬, 아릴, 헤테로고리 등일 수도 있다. 시클로알킬의 탄소수는 3 내지 60, 구체적으로 3 내지 30, 더욱 구체적으로 5 내지 20일수 있다.In the present specification, "cycloalkyl" includes a monocyclic or polycyclic ring having 3 to 60 carbon atoms, and may be further substituted by other substituents. Here, polycyclic means a group in which cycloalkyl is directly connected or condensed with another ring group. Here, the other cyclic group may be cycloalkyl, but may be another type of cyclic group, such as heterocycloalkyl, aryl, heterocycle, or the like. The cycloalkyl may have 3 to 60 carbon atoms, specifically 3 to 30, and more specifically 5 to 20 carbon atoms.
본 명세서에 있어서, "헤테로시클로알킬"은 헤테로원자로서 N, O, S 및 Se로부터 선택되는 적어도 하나를 포함하고, 탄소수 2 내지 60의 단환 또는 다환을 포함하며, 다른 치환기에 의하여 추가로 치환될 수 있다. 여기서, 다환이란 헤테로시클로알킬이 다른 고리기와 직접 연결되거나 축합된 기를 의미한다. 여기서, 다른 고리기란 헤테로시클로알킬일 수도 있으나, 다른 종류의 고리기, 예컨대 시클로알킬, 아릴, 헤테로고리 등일 수도 있다. 헤테로시클로알킬의 탄소수는 2 내지 60, 구체적으로 2 내지 30, 더욱 구체적으로 3 내지 20일 수 있다.In the present specification, "heterocycloalkyl" includes at least one selected from N, O, S and Se as a heteroatom, and includes a monocyclic or polycyclic ring having 2 to 60 carbon atoms, and may be further substituted by another substituent. can Here, polycyclic refers to a group in which heterocycloalkyl is directly connected or condensed with another ring group. Here, the other ring group may be heterocycloalkyl, but may be another type of ring group, such as cycloalkyl, aryl, heterocycle, or the like. The heterocycloalkyl may have 2 to 60 carbon atoms, specifically 2 to 30, and more specifically 3 to 20 carbon atoms.
본 명세서에 있어서, "아릴"은 하나의 수소 제거에 의해서 방향족 탄화수소로부터 유도된 유기 라디칼로, 탄소수 6 내지 60의 단환 또는 다환을 포함하며, 다른 치환기에 의하여 추가로 치환될 수 있다. 여기서, 다환이란 아릴이 다른 고리기와 직접 연결되거나 축합된 기를 의미한다. 여기서, 다른 고리기란 아릴일 수도 있으나, 다른 종류의 고리기, 예컨대 시클로알킬, 헤테로시클로알킬, 헤테로고리 등일 수도 있다. 아릴의 탄소수는 6 내지 60, 구체적으로 6 내지 30, 더욱 구체적으로 6 내지 25일 수 있다. 아릴의 구체적인 예로는 페닐, 바이페닐, 트리페닐, 나프틸, 안트릴, 크라이세닐, 페난트레닐, 페릴레닐, 플루오란테닐, 트리페닐레닐, 페날레닐, 파이레닐, 테트라세닐, 펜타세닐, 플루오레닐, 인데닐, 아세나프틸레닐, 플루오레닐 등이나 이들의 축합고리가 있으나, 이에만 한정되는 것은 아니다.In the present specification, "aryl" is an organic radical derived from an aromatic hydrocarbon by removal of one hydrogen, and includes a monocyclic or polycyclic ring having 6 to 60 carbon atoms, and may be further substituted by another substituent. Here, polycyclic means a group in which aryl is directly connected or condensed with another ring group. Here, the other ring group may be aryl, but may be another type of ring group, such as cycloalkyl, heterocycloalkyl, heterocycle, or the like. The carbon number of the aryl may be 6 to 60, specifically 6 to 30, more specifically 6 to 25. Specific examples of aryl include phenyl, biphenyl, triphenyl, naphthyl, anthryl, chrysenyl, phenanthrenyl, perylenyl, fluoranthenyl, triphenylenyl, phenalenyl, pyrenyl, tetracenyl, pentacenyl, fluorenyl, indenyl, acenaphthylenyl, fluorenyl, or the like, or a condensed ring thereof, but is not limited thereto.
본 명세서에 있어서, "아릴렌"은 상기 아릴에서 하나의 수소 제거에 의해 유도된 2가 유기 라디칼을 의미하며, 상기 아릴의 정의를 따른다.In the present specification, "arylene" means a divalent organic radical derived by the removal of one hydrogen from the aryl, and follows the definition of the aryl.
본 명세서에 있어서, "헤테로고리기"는 헤테로원자로서 N, O, S 및 Se로부터 선택되는 적어도 하나를 포함하고, 탄소수 2 내지 60인 단환 또는 다환을 포함하며, 다른 치환기에 의하여 추가로 치환될 수 있다. 헤테로아릴은 헤테로고리기의 범위에 포함되는 것으로서, 헤테로방향족고리기이다. 여기서, 다환이란 헤테로고리기가 다른 고리기와 직접 연결되거나 축합된 기를 의미한다. 여기서, 다른 고리기란 헤테로고리기일 수도 있으나, 다른 종류의 고리기, 예컨대 시클로알킬, 헤테로시클로알킬, 아릴 등일 수도 있다. 헤테로고리기의 탄소수는 2 내지 60, 구체적으로 2 내지 30, 더욱 구체적으로 3 내지 25일 수 있다. 헤테로고리기의 구체적인 예로는 피리딜, 피롤릴, 피리미딜, 피리다지닐, 퓨라닐, 티에닐, 이미다졸릴, 피라졸릴, 옥사졸릴, 이속사졸릴, 티아졸릴, 이소티아졸릴, 트리아졸릴, 푸라자닐, 옥사디아졸릴, 티아디아졸릴, 디티아졸릴, 테트라졸릴, 파이라닐, 티오파이라닐, 디아지닐, 옥사지닐, 티아지닐, 디옥시닐, 트리아지닐, 테트라지닐, 퀴놀릴, 이소퀴놀릴, 퀴나졸리닐, 이소퀴나졸리닐, 나프티리딜, 아크리디닐, 페난트리디닐, 이미다조피리디닐, 디아자나프탈레닐, 트리아자인덴, 인돌릴, 인돌리지닐, 벤조티아졸릴, 벤즈옥사졸릴, 벤조이미다졸릴, 벤조티오펜기, 벤조퓨란기, 디벤조티오펜기, 디벤조퓨란기, 카바졸릴, 벤조카바졸릴, 페나지닐 등이나 이들의 축합고리가 있으나, 이에만 한정되는 것은 아니다.In the present specification, the "heterocyclic group" includes at least one selected from N, O, S and Se as a hetero atom, and includes a monocyclic or polycyclic ring having 2 to 60 carbon atoms, which may be further substituted by another substituent. can Heteroaryl is included in the scope of the heterocyclic group, and is a heteroaromatic ring group. Here, polycyclic refers to a group in which a heterocyclic group is directly connected or condensed with another ring group. Here, the other ring group may be a heterocyclic group, but may be a different type of ring group, for example, cycloalkyl, heterocycloalkyl, aryl, or the like. The heterocyclic group may have 2 to 60 carbon atoms, specifically 2 to 30, and more specifically 3 to 25 carbon atoms. Specific examples of the heterocyclic group include pyridyl, pyrrolyl, pyrimidyl, pyridazinyl, furanyl, thienyl, imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, triazolyl, Furazanyl, oxadiazolyl, thiadiazolyl, dithiazolyl, tetrazolyl, pyranyl, thiopyranyl, diazinyl, oxazinyl, thiazinyl, dioxynyl, triazinyl, tetrazinyl, quinolyl, iso Quinolyl, quinazolinyl, isoquinazolinyl, naphthyridyl, acridinyl, phenanthridinyl, imidazopyridinyl, diazanaphthalenyl, triazaindene, indolyl, indolizinyl, benzothiazolyl, benzoxazolyl, benzoimidazolyl, benzothiophene group, benzofuran group, dibenzothiophene group, dibenzofuran group, carbazolyl, benzocarbazolyl, phenazinyl, etc. it's not going to be
본 명세서에 있어서, "헤테로아릴"은 방향족 고리 골격 원자로서 N, O, S 및 Se로부터 선택되는 적어도 하나의 헤테로원자를 포함하고, 나머지 방향족 고리 골격 원자가 탄소인 아릴 그룹을 의미하는 것으로, 5 내지 6원 단환 헤테로아릴, 및 하나 이상의 벤젠환과 축합된 다환식 헤테로아릴이며, 부분적으로 포화될 수도 있다. 또한, 본 발명에서의 헤테로아릴은 하나 이상의 헤테로아릴이 단일결합으로 연결된 형태도 포함한다. 구체적인 예로서 퓨릴, 티오펜일, 피롤릴, 이미다졸릴, 피라졸릴, 티아졸릴, 이소티아졸릴, 이속사졸릴, 옥사졸릴, 트리아진일, 피리딜, 피라진일, 피리미딘일, 피리다진일 등의 단환 헤테로아릴; 벤조퓨란일, 벤조티오펜일, 이소벤조퓨란일, 벤조이미다졸릴, 벤조티아졸릴, 벤조이소티아졸릴, 벤조이속사졸릴, 벤조옥사졸릴, 이소인돌릴, 인돌릴, 인다졸릴, 퀴놀릴, 이소퀴놀릴, 디벤조퓨란일, 디벤조티오펜일, 카바졸일, 벤조카바졸일 등의 다환식 헤테로아릴; 등을 포함하지만, 이에 한정되지 않는다.As used herein, "heteroaryl" refers to an aryl group including at least one heteroatom selected from N, O, S and Se as an aromatic ring skeleton atom, and the remaining aromatic ring skeleton atoms are carbon, 5 to 6-membered monocyclic heteroaryl, and polycyclic heteroaryl condensed with one or more benzene rings, which may be partially saturated. In addition, heteroaryl in the present invention includes a form in which one or more heteroaryl is connected by a single bond. Specific examples include furyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, isoxazolyl, oxazolyl, triazinyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, etc. monocyclic heteroaryl of; Benzofuranyl, benzothiophenyl, isobenzofuranyl, benzoimidazolyl, benzothiazolyl, benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, quinolyl, iso polycyclic heteroaryls such as quinolyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl and benzocarbazolyl; and the like.
본 명세서에 있어서, "헤테로아릴렌"은 상기 헤테로아릴에서 하나의 수소 제거에 의해 유도된 2가 유기 라디칼을 의미하며, 상기 헤테로아릴의 정의를 따른다.In the present specification, "heteroarylene" refers to a divalent organic radical induced by the removal of one hydrogen from the heteroaryl, and follows the definition of the heteroaryl.
본 발명은 신규한 헤테로고리 화합물 및 이를 포함하는 유기 발광 소자에 관한 것으로, 보다 상세하게는, 본 발명에 따른 헤테로고리 화합물은 하기 화학식 1로 표시될 수 있다:The present invention relates to a novel heterocyclic compound and an organic light emitting device including the same, and more particularly, the heterocyclic compound according to the present invention may be represented by the following Chemical Formula 1:
[화학식 1][Formula 1]
상기 화학식 1에서,In Formula 1,
L1 내지 L5는 각각 독립적으로 단일결합, C6-C60아릴렌 또는 C3-C60헤테로아릴렌이고;L 1 to L 5 are each independently a single bond, C6-C60 arylene, or C3-C60 heteroarylene;
R1 내지 R10은 각각 독립적으로 C1-C60알킬, C2-C60알케닐, C2-C60알키닐, C3-C60시클로알킬, C2-C60헤테로시클로알킬, C6-C60아릴, C3-C60헤테로아릴 또는 -L11-R11이거나, R1와 R2, R3과 R4, R5와 R6, R7와 R8 및 R9와 R10은 각각 독립적으로 서로 연결되어 방향족고리가 융합되거나 융합되지 않은 헤테로고리를 형성할 수 있으며;R 1 to R 10 are each independently C1-C60 alkyl, C2-C60 alkenyl, C2-C60 alkynyl, C3-C60 cycloalkyl, C2-C60 heterocycloalkyl, C6-C60 aryl, C3-C60 heteroaryl or -L 11 -R 11 or R 1 and R 2 , R 3 and R 4 , R 5 and R 6 , R 7 and R 8 , and R 9 and R 10 are each independently connected to each other so that an aromatic ring is fused or fused can form heterocycles that are not;
L11은 C6-C60아릴렌 또는 C3-C60헤테로아릴렌이며; L 11 is C6-C60 arylene or C3-C60 heteroarylene;
R11은 C6-C60아릴, C3-C60헤테로아릴 또는 -NR12R13이며;R 11 is C6-C60 aryl, C3-C60 heteroaryl or —NR 12 R 13 ;
R12 및 R13은 각각 독립적으로 수소, C1-C60알킬, C6-C60아릴 또는 C3-C60헤테로아릴이며;R 12 and R 13 are each independently hydrogen, C1-C60 alkyl, C6-C60 aryl or C3-C60 heteroaryl;
상기 L1 내지 L5의 아릴렌 및 헤테로아릴렌, R1 내지 R10의 알킬, 알케닐, 알키닐, 시클로알킬, 헤테로시클로알킬, 아릴 및 헤테로아릴, L11의 아릴렌 및 헤테로아릴렌, R11의 아릴 및 헤테로아릴, 및 R12 및 R13의 알킬, 아릴 및 헤테로아릴은 C1-C60알킬, 할로C1-C60알킬, 중수소, 할로겐, 시아노, C3-C60시클로알킬, C1-C60알콕시, C6-C60아릴, C6-C60아릴옥시, C6-C60아릴C1-C60알킬, C1-C60알킬C6-C60아릴, C3-C60헤테로아릴, -NR'R'', 나이트로 및 하이드록시로 이루어진 군으로부터 선택되는 하나 이상으로 더 치환될 수 있고;arylene and heteroarylene of L 1 to L 5 , alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl and heteroaryl of L 11 , arylene and heteroarylene of L 11 , Aryl and heteroaryl of R 11 , and alkyl, aryl and heteroaryl of R 12 and R 13 are C1-C60alkyl, haloC1-C60alkyl, deuterium, halogen, cyano, C3-C60cycloalkyl, C1-C60alkoxy , C6-C60 aryl, C6-C60 aryloxy, C6-C60 arylC1-C60 alkyl, C1-C60 alkylC6-C60 aryl, C3-C60 heteroaryl, -NR'R'', nitro and hydroxy may be further substituted with one or more selected from the group;
R' 및 R''는 각각 독립적으로 수소, C1-C60알킬, C6-C60아릴 또는 C3-C60헤테로아릴이고;R' and R'' are each independently hydrogen, C1-C60 alkyl, C6-C60 aryl or C3-C60 heteroaryl;
p, q 및 s는 서로 독립적으로 0 내지 4의 정수이고, r은 0 내지 3의 정수이고, t는 0 내지 2의 정수이며, 단, p, q, r, s 및 t는 동시에 0이 아니며;p, q and s are independently of each other an integer from 0 to 4, r is an integer from 0 to 3, t is an integer from 0 to 2, provided that p, q, r, s and t are not simultaneously non-zero ;
상기 헤테로아릴렌, 헤테로시클로알킬 및 헤테로아릴은 N, O, S 및 Se로부터 선택되는 하나 이상의 헤테로 원자를 포함한다.Said heteroarylene, heterocycloalkyl and heteroaryl include one or more heteroatoms selected from N, O, S and Se.
구체적으로, 상기 화학식 1의 헤테로고리 화합물은 다이벤조퓨란, 카바졸 및 벤젠이 축합고리를 이루되 반드시 7원 고리를 중심으로 형성된 축합고리 골격을 모핵으로 하며, 적어도 하나의 아미노 치환체가 도입된 다환 헤테로고리 화합물로, 유기 발광 소자의 유기물층 재료, 특히 발광보조층 형성용 재료로서 유용하게 사용할 수 있다.Specifically, in the heterocyclic compound of Formula 1, dibenzofuran, carbazole and benzene form a condensed ring, but a condensed ring skeleton formed around a 7-membered ring must be the mother nucleus, and at least one amino substituent is introduced. As a heterocyclic compound, it can be usefully used as a material for an organic material layer of an organic light emitting device, particularly a material for forming a light emitting auxiliary layer.
상기 화학식 1의 헤테로고리 화합물은 상기 구조적 특징에 의하여 유기 발광 소자의 유기물층 특히 유기 발광 소자의 발광보조층 형성용 재료로 채용할 시 구동전압을 낮추고, 발광효율 및 색순도를 향상시키고, 놀랍도록 향상된 수명특성을 나타낼 수 있다. 즉, 상기 화학식 1의 헤테로고리 화합물은 향상된 정공 이동 특성을 부여함과 동시에 높은 균일도 및 낮은 결정화도를 가지는 정공주입층 재료로서 매우 적합할 수 있다.The heterocyclic compound of Formula 1 lowers the driving voltage, improves luminous efficiency and color purity, and surprisingly improves lifespan when employed as a material for forming an organic material layer of an organic light emitting device, particularly a light emitting auxiliary layer of an organic light emitting device, due to the structural features characteristics can be shown. That is, the heterocyclic compound of Formula 1 may be very suitable as a material for a hole injection layer having high uniformity and low crystallinity while imparting improved hole transport properties.
일 실시에에 따른 화학식 1에서, 상기 L1 내지 L5는 각각 독립적으로 단일결합, C6-C60아릴렌 또는 C3-C60헤테로아릴렌이고, 상기 L1 내지 L5의 아릴렌 및 헤테로아릴렌은 C1-C60알킬, C6-C30아릴 및 -NR'R''로 이루어진 군으로부터 선택되는 하나 이상으로 더 치환될 수 있고; R' 및 R''는 각각 독립적으로 C6-C60아릴 또는 C3-C60헤테로아릴이고; R1 내지 R10은 각각 독립적으로 C6-C60아릴, C3-C60헤테로아릴 또는 -L11-R11이거나, R1와 R2, R3과 R4, R5와 R6, R7와 R8 및 R9와 R10은 각각 독립적으로 서로 연결되어 방향족고리가 융합된 헤테로고리를 형성할 수 있으며; L11은 C6-C60아릴렌 또는 C3-C60헤테로아릴렌이며; R11은 C6-C60아릴, C3-C60헤테로아릴 또는 -NR12R13이며; R12 및 R13은 각각 독립적으로 C6-C60아릴 또는 C3-C60헤테로아릴이며; 상기 R1 내지 R10의 아릴 및 헤테로아릴, L11의 아릴렌 및 헤테로아릴렌, R11의 아릴 및 헤테로아릴, 및 R12 및 R13의 아릴 및 헤테로아릴은 C1-C60알킬, 중수소, C6-C60아릴, C6-C60아릴C1-C60알킬, C1-C60알킬C6-C60아릴 및 C3-C60헤테로아릴로 이루어진 군으로부터 선택되는 하나 이상으로 더 치환될 수 있고; p, q, r, s 및 t는 서로 독립적으로 0 내지 2의 정수이며, 단, 1≤p+q+r+s+t≤10를 만족할 수 있다.In Formula 1 according to an exemplary embodiment, L 1 to L 5 are each independently a single bond, C6-C60 arylene, or C3-C60 heteroarylene, and L 1 to L 5 arylene and heteroarylene are may be further substituted with one or more selected from the group consisting of C1-C60 alkyl, C6-C30 aryl and -NR'R'';R' and R'' are each independently C6-C60 aryl or C3-C60 heteroaryl; R 1 to R 10 are each independently C6-C60 aryl, C3-C60 heteroaryl or -L 11 -R 11 , or R 1 and R 2 , R 3 and R 4 , R 5 and R 6 , R 7 and R 8 and R 9 and R 10 may be each independently connected to each other to form a heterocycle in which an aromatic ring is fused; L 11 is C6-C60 arylene or C3-C60 heteroarylene; R 11 is C6-C60 aryl, C3-C60 heteroaryl or —NR 12 R 13 ; R 12 and R 13 are each independently C6-C60 aryl or C3-C60 heteroaryl; The aryl and heteroaryl of R 1 to R 10 , arylene and heteroarylene of L 11 , aryl and heteroaryl of R 11 , and aryl and heteroaryl of R 12 and R 13 are C1-C60alkyl, deuterium, C6 -C60 aryl, C6-C60 aryl, C1-C60 alkyl, C1-C60 alkylC6-C60 aryl and C3-C60 heteroaryl may be further substituted with one or more selected from the group consisting of; p, q, r, s and t are each independently an integer of 0 to 2, provided that 1≤p+q+r+s+t≤10 may be satisfied.
상기 헤테로고리 화합물은 보다 향상된 소자 특성을 구현하기 위하여, 상기 p+q+r+s+t 는 1 또는 2의 정수일 수 있다.In the heterocyclic compound, in order to implement more improved device characteristics, p+q+r+s+t may be an integer of 1 or 2.
일 실시예에 있어서, 상기 헤테로고리 화합물은 하기 화학식 2 내지 4 중 어느 하나로 표시될 수 있다:In one embodiment, the heterocyclic compound may be represented by any one of the following Chemical Formulas 2 to 4:
[화학식 2][Formula 2]
[화학식 3][Formula 3]
[화학식 4][Formula 4]
상기 화학식 2 내지 4에서,In Formulas 2 to 4,
L1, L2 및 L4는 각각 독립적으로 단일결합, C6-C30아릴렌 또는 C3-C30헤테로아릴렌이고, 상기 L1, L2 및 L4의 아릴렌 및 헤테로아릴렌은 C1-C30알킬, C6-C30아릴 및 -NR'R''로 이루어진 군으로부터 선택되는 하나 이상으로 더 치환될 수 있고;L 1 , L 2 and L 4 are each independently a single bond, C6-C30 arylene, or C3-C30 heteroarylene, and the arylene and heteroarylene of L 1 , L 2 and L 4 are C1-C30 alkyl , may be further substituted with one or more selected from the group consisting of C6-C30 aryl and -NR'R'';
R' 및 R''는 각각 독립적으로 C6-C30아릴 또는 C3-C30헤테로아릴이고;R' and R'' are each independently C6-C30 aryl or C3-C30 heteroaryl;
R1, R2, R3, R4, R7 및 R8은 각각 독립적으로 C6-C30아릴, C3-C30헤테로아릴 또는 -L11-R11이거나, R1와 R2, R3과 R4 및 R7와 R8은 각각 독립적으로 서로 연결되어 방향족고리가 융합된 헤테로고리를 형성할 수 있으며;R 1 , R 2 , R 3 , R 4 , R 7 and R 8 are each independently C6-C30 aryl, C3-C30 heteroaryl or -L 11 -R 11 , or R 1 and R 2 , R 3 and R 4 and R 7 and R 8 may be each independently connected to each other to form a heterocycle in which an aromatic ring is fused;
L11은 C6-C30아릴렌 또는 C3-C30헤테로아릴렌이며;L 11 is C6-C30 arylene or C3-C30 heteroarylene;
R11은 C6-C30아릴, C3-C30헤테로아릴 또는 -NR12R13이며;R 11 is C6-C30 aryl, C3-C30 heteroaryl or —NR 12 R 13 ;
R12 및 R13은 각각 독립적으로 C6-C30아릴 또는 C3-C30헤테로아릴이며;R 12 and R 13 are each independently C6-C30 aryl or C3-C30 heteroaryl;
상기 R1, R2, R3, R4, R7 및 R8의 아릴 및 헤테로아릴, L11의 아릴렌 및 헤테로아릴렌, R11의 아릴 및 헤테로아릴, 및 R12 및 R13의 아릴 및 헤테로아릴은 C1-C30알킬, C6-C30아릴, C6-C30아릴C1-C30알킬, C1-C30알킬C6-C30아릴 및 C3-C30헤테로아릴로 이루어진 군으로부터 선택되는 하나 이상으로 더 치환될 수 있고;aryl and heteroaryl of R 1 , R 2 , R 3 , R 4 , R 7 and R 8 , arylene and heteroarylene of L 11 , aryl and heteroaryl of R 11 , and aryl of R 12 and R 13 and heteroaryl may be further substituted with one or more selected from the group consisting of C1-C30 alkyl, C6-C30 aryl, C6-C30 aryl, C1-C30 alkyl, C1-C30 alkylC6-C30 aryl and C3-C30 heteroaryl. there is;
p, q 및 s는 서로 독립적으로 1 또는 2의 정수이다.p, q and s are each independently an integer of 1 or 2.
일 실시예에 있어서, 상기 헤테로고리 화합물은 화학식 5 내지 7 중 어느 하나로 표시될 수 있다:In one embodiment, the heterocyclic compound may be represented by any one of Formulas 5 to 7:
[화학식 5][Formula 5]
[화학식 6][Formula 6]
[화학식 7][Formula 7]
상기 화학식 5 내지 7에서,In Formulas 5 to 7,
L1, L2 및 L4는 각각 독립적으로 단일결합, C6-C20아릴렌 또는 C3-C20헤테로아릴렌이고, 상기 L1, L2 및 L4의 아릴렌 및 헤테로아릴렌은 C1-C20알킬, C6-C20아릴 및 -NR'R''로 이루어진 군으로부터 선택되는 하나 이상으로 더 치환될 수 있고;L 1 , L 2 and L 4 are each independently a single bond, C6-C20 arylene or C3-C20 heteroarylene, and the arylene and heteroarylene of L 1 , L 2 and L 4 are C1-C20 alkyl , may be further substituted with one or more selected from the group consisting of C6-C20 aryl and -NR'R'';
R' 및 R''는 각각 독립적으로 C6-C20아릴 또는 C3-C20헤테로아릴이고;R' and R'' are each independently C6-C20 aryl or C3-C20 heteroaryl;
R1, R2, R3, R4, R7 및 R8은 각각 독립적으로 C6-C20아릴, C3-C20헤테로아릴 또는 -L11-R11이며;R 1 , R 2 , R 3 , R 4 , R 7 and R 8 are each independently C6-C20 aryl, C3-C20 heteroaryl or -L 11 -R 11 ;
L11은 C6-C20아릴렌 또는 C3-C20헤테로아릴렌이며;L 11 is C6-C20 arylene or C3-C20 heteroarylene;
R11은 C6-C20아릴, C3-C20헤테로아릴 또는 -NR12R13이며;R 11 is C6-C20 aryl, C3-C20 heteroaryl or —NR 12 R 13 ;
R12 및 R13은 각각 독립적으로 C6-C20아릴 또는 C3-C20헤테로아릴이며;R 12 and R 13 are each independently C6-C20 aryl or C3-C20 heteroaryl;
상기 R1, R2, R3, R4, R7 및 R8의 아릴 및 헤테로아릴, L11의 아릴렌 및 헤테로아릴렌, R11의 아릴 및 헤테로아릴, 및 R12 및 R13의 아릴 및 헤테로아릴은 C1-C20알킬, C6-C20아릴, C6-C20아릴C1-C20알킬, C1-C20알킬C6-C20아릴 및 C3-C20헤테로아릴로 이루어진 군으로부터 선택되는 하나 이상으로 더 치환될 수 있다.aryl and heteroaryl of R 1 , R 2 , R 3 , R 4 , R 7 and R 8 , arylene and heteroarylene of L 11 , aryl and heteroaryl of R 11 , and aryl of R 12 and R 13 and heteroaryl may be further substituted with one or more selected from the group consisting of C1-C20 alkyl, C6-C20 aryl, C6-C20 arylC1-C20 alkyl, C1-C20 alkylC6-C20 aryl and C3-C20 heteroaryl. have.
일 실시예에 있어서, 상기 L1 내지 L5은 각각 독립적으로 단일결합이거나, 하기 구조에서 선택될 수 있으나, 이에 한정되지는 않는다:In one embodiment, the L 1 to L 5 are each independently a single bond, or may be selected from the following structure, but is not limited thereto:
상기에서,above,
RL1, RL2, RL3 및 RL4는 각각 독립적으로 수소, C6-C20아릴 또는 NR'R''이고; R L1 , R L2 , R L3 and R L4 are each independently hydrogen, C6-C20 aryl or NR'R'';
R' 및 R''는 각각 독립적으로 C6-C20아릴 또는 C3-C20헤테로아릴이고;R' and R'' are each independently C6-C20 aryl or C3-C20 heteroaryl;
Z는 CRZ1RZ2, NRZ3, O 또는 S이고;Z is CR Z1 R Z2 , NR Z3 , O or S;
RZ1 및 RZ2은 각각 독립적으로 C1-C20알킬 또는 C6-C20아릴이고;R Z1 and R Z2 are each independently C1-C20 alkyl or C6-C20 aryl;
RZ3은 C6-C20아릴이다.R Z3 is C6-C20 aryl.
일 실시예에 있어서, 상기 R1 내지 R10은 각각 독립적으로 하기 구조에서 선택될 수 있으나, 이에 한정되지는 않는다:In one embodiment, the R 1 to R 10 may be each independently selected from the following structures, but are not limited thereto:
상기에서,above,
X1은 NR31, O 또는 S이고; X 1 is NR 31 , O or S;
Y1은 CR32R33, O 또는 S이고; Y 1 is CR 32 R 33 , O or S;
R31은 C6-C20아릴 또는 C3-C20헤테로아릴이고;R 31 is C6-C20 aryl or C3-C20 heteroaryl;
R32 및 R33은 각각 독립적으로 C1-C20알킬, C6-C20아릴 또는 C3-C20헤테로아릴이고;R 32 and R 33 are each independently C1-C20 alkyl, C6-C20 aryl or C3-C20 heteroaryl;
R21, R22 및 R23은 서로 독립적으로 수소, C6-C20아릴, C3-C20헤테로아릴 또는 -NR12R13이고;R 21 , R 22 and R 23 are each independently hydrogen, C6-C20 aryl, C3-C20 heteroaryl or —NR 12 R 13 ;
R12 및 R13은 각각 독립적으로 C6-C20아릴 또는 C3-C20헤테로아릴이며;R 12 and R 13 are each independently C6-C20 aryl or C3-C20 heteroaryl;
R24 및 R25는 각각 독립적으로 C1-C20알킬 또는 C6-C20아릴이고;R 24 and R 25 are each independently C1-C20 alkyl or C6-C20 aryl;
상기 R21, R22 및 R23의 아릴 및 헤테로아릴은 C1-C20알킬 및 C6-C20아릴로 이루어진 군으로부터 선택되는 하나 이상으로 더 치환될 수 있다.The aryl and heteroaryl of R 21 , R 22 and R 23 may be further substituted with one or more selected from the group consisting of C1-C20 alkyl and C6-C20 aryl.
일 실시예에 있어서, 상기 헤테로고리 화합물은 하기에서 선택될 수 있으나, 이에 한정되는 것은 아니다.In one embodiment, the heterocyclic compound may be selected from the following, but is not limited thereto.
본 발명의 일 실시예에 따른 헤테로고리 화합물은 그 구조적 특이성으로 인하여 유기발광소자에 적용시 전극으로부터 정공주입이 용이한 HOMO를 가지고 있어 정공수송이 용이하여 소자의 효율 및 수명을 증대시킬 수 있다. 즉, 본 발명의 일 실시예에 따른 헤테로고리 화합물은 유기 발광 소자의 유기물층에 사용될 수 있고, 구체적으로 상기 유기물층 내의 발광보조층 형성용 재료로 사용될 수 있다.The heterocyclic compound according to an embodiment of the present invention has a HOMO that facilitates hole injection from an electrode when applied to an organic light emitting device due to its structural specificity, thereby facilitating hole transport, thereby increasing the efficiency and lifespan of the device. That is, the heterocyclic compound according to an embodiment of the present invention may be used in an organic material layer of an organic light emitting device, and specifically may be used as a material for forming a light emitting auxiliary layer in the organic material layer.
전술한 화합물들은 후술하는 제조예/실시예를 기초로 제조될 수 있다. 후술하는 제조예/실시예들에서는 대표적인 예시들을 기재하지만, 필요에 따라, 치환기를 추가하거나 제외할 수 있으며, 치환기의 위치를 변경할 수 있다. 또한, 당 기술분야에 알려져 있는 기술을 기초로, 출발물질, 반응물질, 반응 조건 등을 변경할 수 있다. 필요에 따라 나머지 위치의 치환기의 종류 또는 위치를 변경하는 것은 당업자가 당 기술분야에 알려져 있는 기술을 이용하여 수행할 수 있다.The above-mentioned compounds may be prepared based on Preparation Examples/Examples to be described later. Although representative examples are described in Preparation Examples/Examples to be described later, if necessary, a substituent may be added or excluded, and the position of the substituent may be changed. In addition, based on techniques known in the art, starting materials, reactants, reaction conditions, and the like can be changed. Changing the type or position of the substituents at the remaining positions as needed can be performed by those skilled in the art using techniques known in the art.
또한, 본 발명은 상기 화학식 1의 헤테로고리 화합물을 포함하는 유기 발광 소자를 제공한다.In addition, the present invention provides an organic light emitting device including the heterocyclic compound of Formula 1 above.
구체적으로, 본 발명에 따른 유기발광소자는 양극, 음극 및 양극과 음극 사이에 구비된 1층 이상의 유기물층을 포함하고, 상기 유기물층 중 1층 이상은 상기 화학식 1의 헤테로고리 화합물을 포함한다.Specifically, the organic light emitting device according to the present invention includes an anode, a cathode, and at least one organic material layer provided between the anode and the cathode, and at least one of the organic material layers includes the heterocyclic compound of Formula 1 above.
상기 유기물층은 빛을 발광하는 발광층과 발광을 돕는 보조층으로 구성되며, 본 발명의 헤테로고리 화합물은 발광을 돕는 보조층 형성 재료로 사용될 수 있다. The organic material layer is composed of a light-emitting layer that emits light and an auxiliary layer that helps light emission, and the heterocyclic compound of the present invention can be used as a material for forming an auxiliary layer that helps light emission.
상기 보조층은 정공주입층, 정공수송층, 전자수송층, 전자주입층 또는 발광보조층일 수 있다.The auxiliary layer may be a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, or a light emitting auxiliary layer.
일 예로, 상기 발광보조층은 정공수송층과 발광층 사이에 형성될 수 있으며, 이는 제2정공수송층으로 작용하여 상기 정공수송층(제1정공수송층)으로부터 상기 발광층으로 정공이 보다 빠르게 전달되어 우수한 발광효율을 가지는 유기발광소자를 구현할 수 있다.As an example, the light emitting auxiliary layer may be formed between the hole transport layer and the light emitting layer, which acts as a second hole transport layer, so that holes are transferred from the hole transport layer (first hole transport layer) to the light emitting layer more quickly, resulting in excellent luminous efficiency. It is possible to implement an organic light emitting device.
그러나, 당 기술분야에 알려져 있는 유기 발광 소자의 구조가 본 발명에도 적용될 수 있다. 이와 같은 적층구조에 의하여 본 발명의 범위가 한정되는 것은 아니다.However, the structure of the organic light emitting device known in the art may also be applied to the present invention. The scope of the present invention is not limited by such a laminated structure.
본 발명에 따른 유기 발광 소자는 유기물층 중 1층 이상에 상기 화학식 1의 헤테로고리 화합물을 포함하는 것을 제외하고는 당기술분야에 알려져 있는 재료와 방법으로 제조될 수 있다.The organic light-emitting device according to the present invention may be manufactured using materials and methods known in the art, except for including the heterocyclic compound of Formula 1 in at least one layer of the organic material layer.
상기 화학식 1의 헤테로고리 화합물은 단독으로 유기발광소자의 유기물층 중 1층 이상을 구성할 수 있다. 그러나, 필요에 따라 다른 물질과 혼합하여 유기물층을 구성할 수도 있다.The heterocyclic compound of Formula 1 may constitute one or more layers of the organic material layer of the organic light emitting device alone. However, if necessary, the organic material layer may be formed by mixing with other materials.
상기 화학식 1의 헤테로고리 화합물은 유기발광소자에서 발광보조층 형성용 재료, 일예로 정공주입재료, 정공수송재료, 전자수송재료, 전자주입재료 등으로 사용될 수 있다. 상기 헤테로고리 화합물은 정공주입층, 정공수송층, 전자수송층, 전자주입층 중 한층 이상의 재료로 사용될 수 있다. 한 예로서, 상기 헤테로고리 화합물은 유기발광소자의 정공 주입 및 수송층 재료로서 사용될 수 있다. 한 예로서, 상기 헤테로고리 화합물은 유기발광소자의 전자 주입 및 수송층 재료로서 사용될 수 있다. 바람직하게 상기 헤테로고리 화합물은 유기발광소자의 정공수송층 재료로서 사용될 수 있다.The heterocyclic compound of Formula 1 may be used as a material for forming a light emitting auxiliary layer in an organic light emitting device, for example, a hole injection material, a hole transport material, an electron transport material, an electron injection material, and the like. The heterocyclic compound may be used as a material of one or more of a hole injection layer, a hole transport layer, an electron transport layer, and an electron injection layer. As an example, the heterocyclic compound may be used as a material for a hole injection and transport layer of an organic light emitting device. As an example, the heterocyclic compound may be used as a material for an electron injection and transport layer of an organic light emitting device. Preferably, the heterocyclic compound may be used as a material for a hole transport layer of an organic light emitting device.
본 발명에 따른 유기 발광 소자에 있어서, 상기 헤테로고리 화합물 이외의 재료를 하기에 예시하지만, 이들은 예시를 위한 것일 뿐 본 발명의 범위를 한정하기 위한 것은 아니며, 당 기술분야에 공지된 재료들로 대체될 수 있다.In the organic light emitting device according to the present invention, materials other than the heterocyclic compound are exemplified below, but these are only for illustration and not for limiting the scope of the present invention, and substitute materials known in the art can be
양극 재료로는 비교적 일함수가 큰 재료들을 이용할 수 있으며, 구체적인 일예로 바나듐, 크롬, 구리, 아연, 금과 같은 금속 또는 이들의 합금, 아연 산화물, 인듐 산화물, 인듐 주석 산화물(ITO), 인듐 아연 산화물(IZO)과 같은 금속 산화물, ZnO:Al 또는 SnO2:Sb와 같은 금속과 산화물의 조합, 폴리(3-메틸티오펜), 폴리[3,4-(에틸렌-1,2-디옥시)티오펜](PEDT), 폴리피롤 및 폴리아닐린과 같은 전도성 고분자 등을 사용할 수 있으나, 이들에만 한정되는 것은 아니다. 또한 상기 양극층은 전술한 재료들 중 한 가지 타입으로만 형성되거나 또는 복수개의 재료의 혼합물로도 형성될 수 있으며, 동일한 조성 또는 상이한 조성의 복수개의 층으로 구성되는 다층 구조가 형성될 수 있다.Materials having a relatively large work function may be used as the anode material, and specific examples thereof include metals such as vanadium, chromium, copper, zinc, and gold or alloys thereof, zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc. Metal oxides such as oxides (IZO), combinations of metals and oxides such as ZnO:Al or SnO2:Sb, poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thi Offene] (PEDT), a conductive polymer such as polypyrrole and polyaniline may be used, but the present invention is not limited thereto. In addition, the anode layer may be formed of only one type of the above-mentioned materials or a mixture of a plurality of materials, and a multilayer structure composed of a plurality of layers having the same composition or different compositions may be formed.
음극 재료로는 비교적 일함수가 낮은 재료들을 이용할 수 있으며, 구체적인 일 예로 마그네슘, 칼슘, 나트륨, 칼륨, 타이타늄, 인듐, 이트륨, 리튬, 가돌리늄, 알루미늄, 은, 주석 및 납과 같은 금속 또는 이들의 합금, LiF/Al 또는 LiO2/Al과 같은 다층 구조 물질 등을 사용할 수 있다.Materials having a relatively low work function may be used as the anode material, and specific examples thereof include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof. , a multi-layered material such as LiF/Al or LiO2/Al may be used.
정공주입재료로는 공지된 정공주입재료를 이용할 수도 있는데, 예를 들면, 미국특허 제 4,356,429호에 개시된 CuPc (copper phthalocyanine) 등의 프탈로시아닌 화합물 또는 문헌 [Advanced Material, 6, p.677 (1994)]에 기재되어 있는 스타버스트형 아민 유도체류, 예컨대 TCTA (tris(4-carbazoyl-9-ylphenyl)amine), m-MTDATA (4,4',4"-tris(3-Methylphenylphenylamino)triphenylamine), m-MTDAPB (1,3,5-tris[4-(3-metylphenylphenylamino)phenyl]benzene), 용해성이 있는 전도성 고분자인 Pani/DBSA (Polyaniline/Dodecylbenzenesulfonic acid) 또는 PEDOT:PSS (poly(3,4-ethylenedioxythiophene)-poly(styrnesulfonate)), Pani/CSA (Polyaniline/Camphor sulfonic acid) 또는 PANI/PSS (Polyaniline/Poly(4-styrene-sulfonate)) 등을 사용할 수 있으며, 이로 한정되지는 않는다.As the hole injection material, a known hole injection material may be used, for example, a phthalocyanine compound such as CuPc (copper phthalocyanine) disclosed in U.S. Patent No. 4,356,429 or Advanced Material, 6, p.677 (1994)] Starburst-type amine derivatives described in, such as TCTA (tris(4-carbazoyl-9-ylphenyl)amine), m-MTDATA (4,4',4"-tris(3-Methylphenylphenylamino)triphenylamine), m- MTDAPB (1,3,5-tris[4-(3-metylphenylphenylamino)phenyl]benzene), soluble conductive polymer Pani/DBSA (Polyaniline/Dodecylbenzenesulfonic acid) or PEDOT:PSS (poly(3,4-ethylenedioxythiophene) -poly(styrnesulfonate)), Pani/CSA (Polyaniline/Camphor sulfonic acid), or PANI/PSS (Polyaniline/Poly(4-styrene-sulfonate)) may be used, but is not limited thereto.
정공수송재료로는 본 발명의 일 실시예에 따른 헤테로고리 화합물을 단독으로 포함하거나, 알려진 정공수송재료와 혼합하여 사용할 수 있다. 정공수송층은 단일층 이거나 멀티층일 수 있다.As the hole transport material, the heterocyclic compound according to an embodiment of the present invention may be included alone or may be used in combination with a known hole transport material. The hole transport layer may be a single layer or a multilayer.
구체적으로 정공수송재료는 본 발명의 일 실시예에 따른 헤테로고리 화합물을 포함하되, 피라졸린 유도체, 아릴아민계 유도체, 스틸벤 유도체, 트리페닐디아민 유도체 등과 함께 사용될 수 있으며, 저분자 또는 고분자 재료가 함께 또는 독립적으로 사용될 수도 있다. 구체적인 일 예로 NPB (N,N'-bis(naphthalen-1-yl)-N,N'-bis(phenyl)-benzidine), NPD (N,N'-bis(naphthalen-1-yl)-N,N'-bis(phenyl)-2,2'-dimethylbenzidine), mCP (1,3-Bis(N-carbazolyl)benzene), TPD (N,N'-Bis(3-methylphenyl)-N,N'-diphenylbenzidine), TTB (N,N,N',N'-tetrakis(4-methylphenyl)-(1,1'-biphenyl)-4,4-diamine), TTP (N1,N4-diphenyl-N1,N4-dim-tolylbenzene-1,4-diamine), ETPD (N,N'-bis(4-methylphenyl)-N,N'-bis(4-ethylphenyl)-[1,1'-(3,3'-dimethyl)biphenyl]-4,4'-diamine), VNPB (N4,N4'-di(naphthalen-1-yl)-N4,N4'-bis(4-vinylphenyl)biphenyl-4,4'-diamine), ONPB (N4,N4'-bis(4-(6-((3-ethyloxetan-3-yl)methoxy)hexyl)phenyl)-N4,N4'-diphenylbiphenyl-4,4'-diamine), OTPD (N4,N4'-bis(4-(6-((3-ethyloxetan-3-yl)methoxy)hexyl)phenyl)-N4,N4'-diphenylbiphenyl-4,4'-diamine), HATCN (1,4,5,8,9,11-Hexaazatriphenylenehexacarbonitrile) 등의 저분자 정공 전달 물질과; PVK (poly-N-vinylcarbazole), 폴리아닐린, (페닐메닐)폴리실란 등의 고분자 정공수송물질이 있다.Specifically, the hole transport material includes the heterocyclic compound according to an embodiment of the present invention, and may be used together with a pyrazoline derivative, an arylamine derivative, a stilbene derivative, a triphenyldiamine derivative, etc. Or it may be used independently. As a specific example, NPB (N,N'-bis(naphthalen-1-yl)-N,N'-bis(phenyl)-benzidine), NPD (N,N'-bis(naphthalen-1-yl)-N, N'-bis(phenyl)-2,2'-dimethylbenzidine), mCP (1,3-Bis(N-carbazolyl)benzene), TPD (N,N'-Bis(3-methylphenyl)-N,N'- diphenylbenzidine), TTB (N,N,N',N'-tetrakis(4-methylphenyl)-(1,1'-biphenyl)-4,4-diamine), TTP (N1,N4-diphenyl-N1,N4- dim-tolylbenzene-1,4-diamine), ETPD (N,N'-bis(4-methylphenyl)-N,N'-bis(4-ethylphenyl)-[1,1'-(3,3'-dimethyl) )biphenyl]-4,4'-diamine), VNPB (N4,N4'-di(naphthalen-1-yl)-N4,N4'-bis(4-vinylphenyl)biphenyl-4,4'-diamine), ONPB (N4,N4'-bis(4-(6-((3-ethyloxetan-3-yl)methoxy)hexyl)phenyl)-N4,N4'-diphenylbiphenyl-4,4'-diamine), OTPD (N4,N4 '-bis(4-(6-((3-ethyloxetan-3-yl)methoxy)hexyl)phenyl)-N4,N4'-diphenylbiphenyl-4,4'-diamine), HATCN (1,4,5,8 ,9,11-Hexaazatriphenylenehexacarbonitrile) and other low molecular weight hole transport materials; There are polymer hole transport materials such as PVK (poly-N-vinylcarbazole), polyaniline, and (phenylmenyl)polysilane.
전자수송재료로는 옥사디아졸 유도체, 안트라퀴노디메탄 및 이의 유도체, 벤조퀴논 및 이의 유도체, 나프토퀴논 및 이의 유도체, 안트라퀴논 및 이의 유도체, 테트라시아노안트라퀴노디메탄 및 이의 유도체, 플루오레논 유도체, 디페닐디시아노에틸렌 및 이의 유도체, 디페노퀴논 유도체, 8-히드록시퀴놀린 및 이의 유도체의 금속 착체등이 사용될 수 있으며, 저분자 물질 뿐만 아니라 고분자 물질이 사용될 수도 있다. 구체적인 일 예로 TSPO1 (diphenyl[4-(triphenylsilyl)phenyl]phosphine oxide), TPBI (1,3,5-tris(N-phenylbenzimidazol-2-yl)benzene); Alq3 (tris(8-hydroxyquinolinato)aluminum); BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline); PBD (2-(4-biphenyl)-5-(4-tert-butyl-phenyl)-1,3,4-oxadizole), TAZ (3-(4-biphenyl)-4-phenyl-5-(4-tert-butyl-phenyl)-1,2,4-triazole), OXD-7 (1,3-bis[2-(4-tert-butylphenyl)-1,3,4-oxadiazo-5-yl]benzene)과 같은 아졸 화합물; tris(phenylquinoxaline) (TPQ); TmPyPB (3,3'-[5'-[3-(3-Pyridinyl)phenyl][1,1':3',1''-terphenyl]-3,3''-diyl]bispyridine) 등을 사용할 수 있으나, 이에 한정되지 않는다.Examples of the electron transport material include oxadiazole derivatives, anthraquinodimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, tetracyanoanthraquinodimethane and its derivatives, and fluorenone. Derivatives, diphenyldicyanoethylene and derivatives thereof, diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline and derivatives thereof, etc. may be used, and polymer materials as well as low molecular weight materials may be used. Specific examples include TSPO1 (diphenyl[4-(triphenylsilyl)phenyl]phosphine oxide), TPBI (1,3,5-tris(N-phenylbenzimidazol-2-yl)benzene); Alq 3 (tris(8-hydroxyquinolinato)aluminum); BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline); PBD (2-(4-biphenyl)-5-(4-tert-butyl-phenyl)-1,3,4-oxadizole), TAZ (3-(4-biphenyl)-4-phenyl-5-(4- tert-butyl-phenyl)-1,2,4-triazole), OXD-7 (1,3-bis[2-(4-tert-butylphenyl)-1,3,4-oxadiazo-5-yl]benzene) azole compounds such as; tris(phenylquinoxaline) (TPQ); TmPyPB (3,3'-[5'-[3-(3-Pyridinyl)phenyl][1,1':3',1''-terphenyl]-3,3''-diyl]bispyridine) However, the present invention is not limited thereto.
전자주입재료로는 예를 들어, LIF 또는 Liq(lithium quinolate)가 당업계에서 대표적으로 사용되나, 이에 한정되는 것은 아니다.As the electron injection material, for example, LIF or lithium quinolate (Liq) is typically used in the art, but is not limited thereto.
발광재료로는 적색, 녹색 또는 청색 발광재료가 사용될 수 있으며, 필요한 경우 2 이상의 발광재료를 혼합하여 사용할 수 있다. 또한, 발광재료로서 형광 재료를 사용할 수도 있으나, 인광 재료로서 사용할 수도 있다. 발광 재료로는 단독으로서 양극과 음극으로부터 각각 주입된 정공과 전자를 결합하여 발광시키는 재료가 사용될 수도 있으나, 호스트 재료와 도펀트 재료가 함께 발광에 관여하는 재료들이 사용될 수도 있다.A red, green or blue light emitting material may be used as the light emitting material, and if necessary, two or more light emitting materials may be mixed and used. In addition, although a fluorescent material can be used as a light emitting material, it can also be used as a phosphorescent material. As the light emitting material, a material that emits light by combining holes and electrons respectively injected from the anode and the cathode may be used, but materials in which the host material and the dopant material together participate in light emission may be used.
발광층은 발광재료를 진공증착법, 스핀코팅법, 캐스트법, LB법 등과 같은 방법에 의해 형성할 수 있고, 더욱 구체적으로 진공층착법에 의해 발광층을 형성하는 경우 그 증착조건은 사용하는 화합물에 따라 다르지만 일반적으로 정공주입층의 형성과 거의 동일한 조건 범위에서 선택할 수 있다. 또한 발광층 재로는 공지의 화합물을 호스트 또는 도펀트로 사용할 수 있다.The light emitting layer can be formed by a method such as vacuum deposition, spin coating, casting, LB method, etc. on the light emitting material. More specifically, when the light emitting layer is formed by vacuum deposition, the deposition conditions vary depending on the compound used. In general, it can be selected within the range of conditions almost identical to that of the formation of the hole injection layer. In addition, as the light emitting layer material, a known compound may be used as a host or a dopant.
또한 일례로 발광층 재료로 형광 도펀트로는 이데미츠사(Idemitsu사)의 IDE102 또는 IDE105, BD-331 또는 BD-142(N6,N12-비스(3,4-디메틸페닐)-N6,N12-디메시틸트리센-6,12-디아민)을 사용할 수 있으며, 인광 도펀트로는 녹색 인광 도펀트 Ir(ppy)3(트리스(2-페닐피리딘)이리듐), 청색 도트 F2Irpic(이리듐(Ⅲ) 비스[4,6-다이플루오로페닐)-피리디나토-N,C2']피콜린산염), UDC사의 적색 인광 도펀트 RD61 등이 공동 진공증착(도핑)될 수 있다.In addition, for example, as a fluorescent dopant as a light emitting layer material, IDE102 or IDE105, BD-331 or BD-142 (N 6 ,N 12 -bis(3,4-dimethylphenyl)-N 6 ,N 12 manufactured by Idemitsu Corporation) -Dimesityltricene-6,12-diamine) can be used, and the phosphorescent dopant is a green phosphorescent dopant Ir(ppy) 3 (tris(2-phenylpyridine)iridium), and a blue dot F2Irpic (iridium(III) bis[ 4,6-difluorophenyl)-pyridinato-N,C2']picolinic acid salt), UDC's red phosphorescent dopant RD61, etc. may be co-evacuated (doped).
인광 도판트는 삼중항 여기자로부터 발광할 수 있는 화합물로, 삼중항 여기자로부터 발광하는 한 특별히 한정되지 않는다. 구체적인 일 예로는 Ir, Ru, Pd, Pt, Os 및 Re 등으로 이루어지는 군에서 선택되는 하나 이상의 금속을 포함하는 금속 착체일 수 있고, 포르피린 금속 착체 또는 오르토 금속화 금속 착체일 수 있다.The phosphorescent dopant is a compound capable of emitting light from triplet excitons, and is not particularly limited as long as it emits light from triplet excitons. A specific example may be a metal complex including one or more metals selected from the group consisting of Ir, Ru, Pd, Pt, Os and Re, and may be a porphyrin metal complex or an ortho metalized metal complex.
상기 포르피린 금속 착체는 구체적으로 포르피린 백금 착체일 수 있다.The porphyrin metal complex may be specifically a porphyrin platinum complex.
상기 오르토 금속화 금속 착체는 2-페닐피리딘(2-phenylpyridine, ppy) 유도체, 7,8-벤조퀴놀린 유도체, 2-(2-티에닐)피리딘(2-(2-thienyl)pyridine, tp) 유도체, 2-(1-나프틸)피리딘(2-(1-naphthyl)pyridine, npy) 유도체, 2-페닐퀴놀린(2-phenylquinoline, pq) 유도체 등을 배위자로 포함하는 것일 수 있다. 이때, 이들 유도체는 필요에 따라서 치환기를 가질 수도 있다. 보조 배위자로서 아세틸아세토네이토(acetylacetonato, acac), 피크르산(picric acid) 등의 상기 배위자 이외의 배위자를 더 가질 수도 있다. 구체적 예로는, 비스티에닐피리딘 아세틸아세토네이트 이리듐(bisthienylpyridine acetylacetonate Iridium), 비스(2-벤조[b]티오펜-2-일-피리딘)(아세틸아세토네이토)이리듐(III) (bis(2-benzo[b]thiophen-2-yl-pyridine)(acetylacetonato)iridium(III), Ir(btp)2(acac)), 비스(2-페닐벤조티아졸)(아세틸아세토네이토)이리듐(III) (bis(2-phenylbenzothiazole)(acetylacetonato)iridium(III), Ir(bt)2(acac)), 비스(1-페닐이소퀴놀린)(아세틸아세토네이토)이리듐(III) (bis(1-phenylisoquinoline)(acetylacetonato)Iridium(III), Ir(piq)2(acac)), 트리스(1-페닐이소퀴놀린)이리듐(III) (tris(1-phenylisoquinoline)iridium(III), Ir(piq)3), 트리스(2-페닐피리딘)이리듐(III) (tris(2-phenylpyridine)iridium(III), Ir(ppy)3), 트리스(2-비페닐피리딘)이리듐(tris(2-biphenylpyridine)iridium), 트리스(3-비페닐피리딘)이리듐(tris(3-biphenylpyridine)iridium), 트리스(4-비페닐피리딘)이리듐(tris(4-biphenylpyridine)iridium) 등을 들 수 있으나 이에 한정되는 것은 아니다.The ortho metallized metal complex is a 2-phenylpyridine (ppy) derivative, a 7,8-benzoquinoline derivative, and a 2-(2-thienyl)pyridine (2-(2-thienyl)pyridine, tp) derivative. , 2-(1-naphthyl)pyridine (2-(1-naphthyl)pyridine, npy) derivative, 2-phenylquinoline (pq) derivative, etc. may be included as a ligand. In this case, these derivatives may have a substituent if necessary. As an auxiliary ligand, it may further have a ligand other than the above ligands such as acetylacetonato (acac) and picric acid. Specific examples include bisthienylpyridine acetylacetonate Iridium, bis(2-benzo[b]thiophen-2-yl-pyridine)(acetylacetonato)iridium(III) (bis(2- benzo[b]thiophen-2-yl-pyridine)(acetylacetonato)iridium(III), Ir(btp) 2 (acac)), bis(2-phenylbenzothiazole)(acetylacetonato)iridium(III) ( bis(2-phenylbenzothiazole)(acetylacetonato)iridium(III), Ir(bt) 2 (acac)), bis(1-phenylisoquinoline)(acetylacetonato)iridium(III) (bis(1-phenylisoquinoline)( acetylacetonato)Iridium(III), Ir(piq) 2 (acac)), tris(1-phenylisoquinoline)iridium(III) (tris(1-phenylisoquinoline)iridium(III), Ir(piq) 3 ), tris( 2-phenylpyridine) iridium (III) (tris (2-phenylpyridine) iridium (III), Ir (ppy) 3 ), tris (2-biphenylpyridine) iridium (tris (2-biphenylpyridine) iridium), tris (3) -biphenylpyridine) iridium (tris (3-biphenylpyridine) iridium), tris (4-biphenylpyridine) iridium (tris (4-biphenylpyridine) iridium), etc., but are not limited thereto.
또한, 발광층에 인광 도펀트와 함께 사용할 경우에는 삼중항 여기자 또는 정공이 전자수송층으로 확산되는 현상을 방지하기 위하여 정공억제재료(HBL)를 추가로 진공증착법 또는 스핀코팅법에 의해 적층시킬 수 있다. 이때 사용할 수 있는 정공억제물질은 특별히 제한되지는 않으나, 정공억제재료로 사용되고 있는 공지의 것에서 임의의 것을 선택해서 이용할 수 있다. 예를 들면 옥사디아졸 유도체나 트리아졸 유도체 페난트롤린 유도체일 수 있으며 구체적으로 Balq(비스(8-하이드록시-2-메틸퀴놀리놀나토)-알루미늄 비페녹사이드), 페난트롤린(phenanthrolines)계 화합물(: UDC사 BCP(바쏘쿠프로인)) 등을 사용할 수 있다.In addition, when used together with a phosphorescent dopant in the light emitting layer, a hole blocking material (HBL) may be additionally laminated by vacuum deposition or spin coating to prevent triplet excitons or holes from diffusing into the electron transport layer. In this case, the hole-blocking material that can be used is not particularly limited, and any one can be used by selecting from known materials used as the hole-blocking material. For example, it may be an oxadiazole derivative or a triazole derivative phenanthroline derivative, and specifically, Balq (bis(8-hydroxy-2-methylquinolinolnato)-aluminum biphenoxide), phenanthrolines system compounds (: UDC BCP (vasocuproin)) and the like can be used.
이하에서, 실시예를 통하여 본 발명을 더욱 상세하게 설명하지만, 이들은 본 발명을 예시하기 위한 것일 뿐, 본 발명의 범위를 한정하기 위한 것은 아니다.Hereinafter, the present invention will be described in more detail by way of Examples, but these are only for illustrating the present invention and not for limiting the scope of the present invention.
[실시예 1] 화합물 P1 및 P2의 제조[Example 1] Preparation of compounds P1 and P2
화합물 A-5의 제조Preparation of compound A-5
DME(dimethylglycol)/H2O (부피비 1:1, 170mL)에 4-아이오도다이벤조퓨란(4-iodo-dibenzo[b,d]furan) 10g(34.00mmol)을 녹이고, 여기에 6-메톡시-1-(4,4,5,5-테트라메틸-1,3,2-다이옥사보로란-2-일)-9H-카바졸(6-methoxy-1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2yl)-9H-carbazole) 13.19g(40.8mmol), 포타슘 카보네이트 (potassium carbonate, K2CO3) 9.40g(68.00mmol)을 넣고 온도를 30℃까지 가온시켰다. 여기에 테트라키스(트리페닐포스핀)팔라듐(0) (Tetrakis(triphenylphosphine)palladium(0), Pd(PPh3)4) 1.97g(1.7mmol)을 넣고, 24시간 환류 교반 시켰다. 반응이 완결되면 MC와 소듐 바이카보네이트(NaHCO₃) 수용액으로 추출한 후, 용매를 제거하고, MC(methylene chloride)와 Hex(hexane)을 사용하여 컬럼크로마토그래피 정제하여 목적화합물 A-5 7.8g(63%)를 얻었다.Dissolve 10g (34.00mmol) of 4-iodo-dibenzofuran (4-iodo-dibenzo[b,d]furan) in DME (dimethylglycol)/H 2 O (volume ratio 1:1, 170 mL), and therein 6-methyl Toxy-1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole (6-methoxy-1-(4,4,5, 5-tetramethyl-1,3,2-dioxaborolan-2yl)-9H-carbazole) 13.19 g (40.8 mmol) and potassium carbonate (K 2 CO 3 ) 9.40 g (68.00 mmol) were added and the temperature was raised to 30°C. warmed up Here, 1.97 g (1.7 mmol) of tetrakis (triphenylphosphine) palladium (0) (Tetrakis (triphenylphosphine) palladium (0), Pd (PPh 3 ) 4 ) was added, and the mixture was stirred under reflux for 24 hours. When the reaction is complete, extraction is performed with MC and sodium bicarbonate (NaHCO₃) aqueous solution, the solvent is removed, and column chromatography is purified using MC (methylene chloride) and Hex (hexane) to purify the target compound A-5 7.8 g (63%). ) was obtained.
화합물 A-4의 제조Preparation of compound A-4
톨루엔 100mL에 화합물 A-5 5g (13.76mmol)을 녹인 후, 1-브로모-2-아이오도벤젠(1-bromo-2-iodobenzene) 2.12mL(16.51mmol), 트리스(디벤질리덴아세톤)디팔라듐(0) (tris(dibenzylideneacetone)dipalladium(0), Pd2(dba)3) 0.76g(0.83mmol), 트리(터셔리-부틸)포스핀(tri(tert-butyl)phosphine, P(t-Bu)3, 1.0M solution in Toluene) 2.1mL(2.07mmol), 소듐 터셔리-부톡사이드(sodium tert-butoxide, NaOt-Bu) 2.65g(27.52mmol) 넣고 80℃에서 24시간 교반시켰다. 1N HCl 수용액을 가하여 반응을 종결시키고, MC와 NaHCO₃ 수용액으로 추출한 후, 용매를 제거하고, MC와 Hex을 사용하여 컬럼크로마토그래피 정제하여 목적화합물 A-4 5.6g(51%)를 얻었다.After dissolving 5 g (13.76 mmol) of Compound A-5 in 100 mL of toluene, 2.12 mL (16.51 mmol) of 1-bromo-2-iodobenzene, and tris (dibenzylideneacetone) di Palladium(0) (tris(dibenzylideneacetone)dipalladium(0), Pd 2 (dba) 3 ) 0.76 g (0.83 mmol), tri(tert-butyl)phosphine, P(t- Bu) 3 , 1.0M solution in Toluene) 2.1mL (2.07mmol), sodium tert-butoxide (NaOt-Bu) 2.65g (27.52mmol), and stirred at 80 ℃ for 24 hours. 1N HCl aqueous solution was added to terminate the reaction, and after extraction with MC and NaHCO₃ aqueous solution, the solvent was removed and purified by column chromatography using MC and Hex to obtain 5.6 g (51%) of the target compound A-4.
화합물 A-3의 제조Preparation of compound A-3
DMA(dimethylacetamide) 100mL에 화합물 A-4 5g (9.65mmol)을 녹인 후, 팔라듐 아세테이트(palladium(II) acetate, Pd(OAc)2) 0.43g(1.93mmol), K2CO3 2.67g(19.3mmol), 1,3-비스(2,6-다이아이소프로필페닐)이미다졸리움 클로라이드(1,3-bis(2,6-diisopropylphenyl)imidazolium chloride) 2.88g(6.74mmol)을 가하고 24시간동안 환류 교반시켰다. 1N HCl 수용액을 가하여 반응을 종결시키고, MC와 NaHCO₃ 수용액으로 추출한 후, 용매를 제거하고, MC와 Hex을 사용하여 컬럼크로마토그래피 정제하여 목적화합물 A-3 2.2g(51%)를 얻었다.After dissolving 5 g (9.65 mmol) of Compound A-4 in 100 mL of DMA (dimethylacetamide), palladium acetate (palladium(II) acetate, Pd(OAc) 2 ) 0.43 g (1.93 mmol), K 2 CO 3 2.67 g (19.3 mmol) ), 1,3-bis (2,6-diisopropylphenyl) imidazolium chloride (1,3-bis (2,6-diisopropylphenyl) imidazolium chloride) was added 2.88 g (6.74 mmol) and stirred under reflux for 24 hours. made it 1N HCl aqueous solution was added to terminate the reaction, extraction was performed with MC and NaHCO₃ aqueous solution, the solvent was removed, and column chromatography was purified using MC and Hex to obtain 2.2 g (51%) of the target compound A-3.
화합물 A-2의 제조Preparation of compound A-2
MC 90mL에 화합물 A-3 10g(22.86mmol)을 녹인 후, 온도를 0℃까지 낮추었다. 그 후 보론 트리브로마이드(boron tribromide) 2.7mL(27.43mmol)를 천천히 적가하였다. 그 후 서서히 상온으로 온도를 올리면서 교반시켰다. 반응이 종결되면 MC와 H2O를 사용하여 추출한 후 용매를 제거하고, MC와 Hex을 사용하여 컬럼크로마토그래피 정제하여 목적화합물 A-2 8.23g (85%)를 얻었다.After dissolving 10 g (22.86 mmol) of Compound A-3 in 90 mL of MC, the temperature was lowered to 0°C. Then, 2.7 mL (27.43 mmol) of boron tribromide was slowly added dropwise. Thereafter, the mixture was stirred while gradually raising the temperature to room temperature. When the reaction was completed, extraction was performed using MC and H 2 O, the solvent was removed, and column chromatography was purified using MC and Hex to obtain 8.23 g (85%) of the target compound A-2.
화합물 A-1의 제조Preparation of compound A-1
THF 95mL에 화합물 A-2 10g(23.61mmol)을 녹인 후, 피리딘 5mL(59.04mmol), 4-디메틸아미노피리딘(4-(dimethylamino)pyridine, DMAP) 0.29g(2.36mmol)을 넣고 온도를 0℃까지 낮추었다. 그후 트리플루오르메탄술폰닉 언하이드라이드(trifluoromethanesulfonic anhydride, Tf2O) 4.8mL(28.33mmol)를 천천히 적가하였다. 그 후 서서히 상온으로 온도를 올리면서 교반시켰다. 반응이 종결되면 MC와 H2O를 사용하여 추출한 후 제거하고, MC와 Hex을 사용하여 컬럼크로마토그래피 정제하여 목적화합물 A-1 10.4g (79%)를 얻었다.After dissolving 10 g (23.61 mmol) of Compound A-2 in 95 mL of THF, 5 mL (59.04 mmol) of pyridine and 0.29 g (2.36 mmol) of 4-dimethylaminopyridine (4-(dimethylamino)pyridine, DMAP) were added and the temperature was adjusted to 0°C. lowered to Then, 4.8 mL (28.33 mmol) of trifluoromethanesulfonic anhydride (Tf 2 O) was slowly added dropwise. Thereafter, the mixture was stirred while gradually raising the temperature to room temperature. Upon completion of the reaction, extraction was performed using MC and H 2 O, followed by removal, and column chromatography purification was performed using MC and Hex to obtain 10.4 g (79%) of the target compound A-1.
화합물 P1의 제조Preparation of compound P1
화합물 A-1과 보론 화합물 및 팔라듐 촉매를 이용하여 스즈키 커플링(Suzuki coupling) 반응을 통해 목적화합물 P1을 얻었다.A target compound P1 was obtained through a Suzuki coupling reaction using compound A-1, a boron compound, and a palladium catalyst.
톨루엔/에탄올/물 (부피비 4:1:1, 100mL)에 화합물 A-1 (1eq.), 치환된 보론산 또는 보로닉 에스테르 화합물 (1,2eq.), Pd(PPh3)4 (0.05eq.), 및 K2CO3 (2eq.)을 넣은 후, 질소 분위기 하 120℃에서 환류 교반시켰다. 반응이 종결되면 셀라이트(celite)와 플로리실(florisil)을 사용하여 필터한 후 MC로 씻어주었다. EA와 Hex을 사용하여 재결정 정제하여 목적화합물 P1을 얻었다.Compound A-1 (1eq.), substituted boronic acid or boronic ester compound (1,2eq.), Pd(PPh 3 ) 4 (0.05eq.) in toluene/ethanol/water (volume ratio 4:1:1, 100mL) .), and K 2 CO 3 (2eq.) was added, and then stirred under reflux at 120° C. under a nitrogen atmosphere. When the reaction was completed, it was filtered using celite and florisil and washed with MC. The target compound P1 was obtained by recrystallization and purification using EA and Hex.
화합물 P2의 제조Preparation of compound P2
화합물 A-1과 이차아민(secondary amine) 화합물 및 팔라듐 촉매를 이용하여 팔라듐 아미네이션(palladium amination)을 통해 목적화합물 P2를 얻었다.A target compound P2 was obtained through palladium amination using compound A-1, a secondary amine compound, and a palladium catalyst.
톨루엔에 화합물 A-1 (1eq.), 이차아민(secondary amine) 화합물 (1,2eq.), Pd2(dba)3 (0.05eq.), P(t-Bu)3 (0.15eq.), 및 NaOt-Bu (2eq.)을 넣은 후 아르곤 분위기 하 120℃에서 환류 교반시켰다. 반응이 종결되면 셀라이트와 플로리실을 사용하여 필터한 후 MC로 씻어주었다. EA와 Hex을 사용하여 재결정 정제하여 목적화합물 P2를 얻었다.Compound A-1 (1eq.), secondary amine compound (1,2eq.), Pd 2 (dba) 3 (0.05eq.), P(t-Bu) 3 (0.15eq.), in toluene And NaOt-Bu (2eq.) was added, followed by reflux stirring at 120 °C under an argon atmosphere. When the reaction was completed, it was filtered using Celite and Florisil and washed with MC. The target compound P2 was obtained by recrystallization and purification using EA and Hex.
반응물인 치환된 보론산, 보로닉 에스테르 및 이차아민 화합물의 구조, 및 제조된 화합물 P1 및 P2의 구조와 수율은 하기 표 1에 기재하였다. 그러나, 반응물인 보론 화합물과 이차아민 화합물의 구조가 하기에 한정되는 것은 아니다.The structures of the reactants of the substituted boronic acid, boronic ester and secondary amine compound, and the structures and yields of the prepared compounds P1 and P2 are shown in Table 1 below. However, the structures of the boron compound and the secondary amine compound as reactants are not limited to the following.
[실시예 2] 화합물 P3 및 P4의 제조[Example 2] Preparation of compounds P3 and P4
화합물 B-3의 제조Preparation of compound B-3
DME/H2O (부피비 1:1, 170mL)에 4-아이오도-8-클로로-다이벤조[b,d]퓨란(4-iodo-8-chlorodibenzo[b,d]furan) 10g(30.44mmol)을 녹이고, 여기에 1-(4,4,5,5-테트라메틸-1,3,2-다이옥사보로란-2-일)-9H-카바졸(1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2yl)9H-carbazole) 8.41g(36.53mmol), K2CO3 9.40g(60.88mmol)을 넣고 온도를 30℃까지 가온시켰다. 여기에 Pd(PPh3)4 1.76g(1.52mmol)을 넣고, 24시간 환류 교반 시켰다. 반응이 완결 되면 MC와 NaHCO₃ 수용액으로 추출한 후, 용매를 제거하고, MC와 Hex을 사용하여 컬럼크로마토그래피 정제하여 목적화합물 B-3 9.63g(86%)를 얻었다.DME / H 2 O (volume ratio 1:1, 170 mL) in 4-iodo-8-chloro-dibenzo [b, d] furan (4-iodo-8-chlorodibenzo [b, d] furan) 10 g (30.44 mmol) ), and 1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole (1-(4,4,5, 5-tetramethyl-1,3,2-dioxaborolan-2yl)9H-carbazole) 8.41g (36.53mmol), K 2 CO 3 9.40g (60.88mmol) were added, and the temperature was heated to 30°C. Pd(PPh 3 ) 4 1.76 g (1.52 mmol) was added thereto, and the mixture was stirred under reflux for 24 hours. When the reaction was completed, extraction was performed with MC and NaHCO₃ aqueous solution, the solvent was removed, and column chromatography was purified using MC and Hex to obtain 9.63 g (86%) of the target compound B-3.
화합물 B-2의 제조Preparation of compound B-2
톨루엔 100mL에 화합물 B-3 5g (13.59mmol)을 녹인 후, 1-브로모-2-아이오도벤젠 2.1mL(16.31mmol), Pd2(dba)3 0.75g (0.82mmol), P(t-Bu)3 (1.0M solution in Toluene) 2.5mL(2.45mmol), NaOt-Bu 2.61g(27.18mmol) 넣고 120℃에서 24시간 교반시켰다. 1N HCl 수용액을 가하여 반응을 종결시키고, MC와 NaHCO₃ 수용액으로 추출한 후, 용매를 제거하고, MC와 Hex을 사용하여 컬럼크로마토그래피 정제하여 목적화합물 B-2 5.8g(82%)를 얻었다.After dissolving 5 g (13.59 mmol) of compound B-3 in 100 mL of toluene, 2.1 mL (16.31 mmol) of 1-bromo-2-iodobenzene, 0.75 g (0.82 mmol) of Pd 2 (dba) 3 , P(t- Bu) 3 (1.0M solution in Toluene) 2.5mL (2.45mmol), NaOt-Bu 2.61g (27.18mmol) was added and stirred at 120°C for 24 hours. 1N HCl aqueous solution was added to terminate the reaction, and after extraction with MC and NaHCO₃ aqueous solution, the solvent was removed, and column chromatography was purified using MC and Hex to obtain 5.8 g (82%) of the target compound B-2.
화합물 B-1의 제조Preparation of compound B-1
DMA 100mL에 화합물 B-2 5g (9.56mmol)을 녹인 후, Pd(OAc)2 0.43g(1.91mmol), K2CO3 2.64g(19.12mmol), 1,3-비스(2,6-다이아이소프로필페닐)이미다졸리움 클로라이드 2.86g(6.69mmol) 24시간동안 환류 교반시켰다. 1N HCl 수용액을 가하여 반응을 종결시키고, MC와 NaHCO₃ 수용액으로 추출한 후, 용매를 제거하고, MC와 Hex을 사용하여 컬럼크로마토그래피 정제하여 목적화합물 B-1 2.7g(63%)를 얻었다.After dissolving 5 g (9.56 mmol) of Compound B-2 in 100 mL of DMA, Pd(OAc) 2 0.43 g (1.91 mmol), K 2 CO 3 2.64 g (19.12 mmol), 1,3-bis (2,6-dia) 2.86 g (6.69 mmol) of isopropylphenyl)imidazolium chloride was stirred under reflux for 24 hours. 1N HCl aqueous solution was added to terminate the reaction, extraction was performed with MC and NaHCO₃ aqueous solution, the solvent was removed, and column chromatography was purified using MC and Hex to obtain 2.7 g (63%) of the target compound B-1.
화합물 P3의 제조Preparation of compound P3
화합물 B-1과 보론 화합물 및 팔라듐 촉매를 이용하여 스즈키 커플링 반응을 통해 목적화합물 P3을 얻었다.A target compound P3 was obtained through a Suzuki coupling reaction using compound B-1, a boron compound, and a palladium catalyst.
톨루엔/에탄올/물 (부피비 4:1:1, 100mL)에 화합물 B-1 (1eq.), 치환된 보론산 또는 보로닉 에스테르 화합물 (1,2eq.), Pd(PPh3)4 (0.05eq.), 및 K2CO3 (2eq.)을 넣은 후, 질소 분위기 하 120℃에서 환류 교반시켰다. 반응이 종결되면 셀라이트와 플로리실을 사용하여 필터한 후 MC로 씻어주었다. EA와 Hex을 사용하여 재결정 정제하여 목적화합물 P3을 얻었다.Compound B-1 (1eq.), substituted boronic acid or boronic ester compound (1,2eq.), Pd(PPh 3 ) 4 (0.05eq.) in toluene/ethanol/water (volume ratio 4:1:1, 100mL) .), and K 2 CO 3 (2eq.) was added, and then stirred under reflux at 120° C. under a nitrogen atmosphere. When the reaction was completed, it was filtered using Celite and Florisil and washed with MC. The target compound P3 was obtained by recrystallization and purification using EA and Hex.
화합물 P4의 제조Preparation of compound P4
화합물 B-1과 이차아민 화합물 및 팔라듐 촉매를 이용하여 팔라듐 아미네이션을 통해 목적화합물 P4를 얻었다.A target compound P4 was obtained through palladium amination using compound B-1, a secondary amine compound, and a palladium catalyst.
톨루엔에 화합물 B-1 (1eq.), 이차아민 화합물 (1,2eq.), Pd2(dba)3 (0.05eq.), P(t-Bu)3 (0.15eq.), 및 NaOt-Bu (2eq.)을 넣은 후 아르곤 분위기 하 120℃에서 환류 교반시켰다. 반응이 종결되면 셀라이트와 플로리실을 사용하여 필터한 후 MC로 씻어주었다. EA와 Hex을 사용하여 재결정 정제하여 목적화합물 P4를 얻었다.Compound B-1 (1eq.), secondary amine compound (1,2eq.), Pd 2 (dba) 3 (0.05eq.), P(t-Bu) 3 (0.15eq.), and NaOt-Bu in toluene (2eq.) was added, followed by reflux stirring at 120° C. under an argon atmosphere. When the reaction was completed, it was filtered using Celite and Florisil and washed with MC. The target compound P4 was obtained by recrystallization and purification using EA and Hex.
반응물인 치환된 보론산, 보로닉 에스테르 및 이차아민 화합물의 구조, 및 제조된 화합물 P3 및 P4의 구조와 수율은 하기 표 2에 기재하였다. 그러나, 반응물인 보론 화합물과 이차아민 화합물의 구조가 하기에 한정되는 것은 아니다.The structures of the reactants of the substituted boronic acid, boronic ester, and secondary amine compound, and the structures and yields of the prepared compounds P3 and P4 are shown in Table 2 below. However, the structures of the boron compound and the secondary amine compound as reactants are not limited to the following.
[실시예 3] 화합물 P5 및 P6의 제조[Example 3] Preparation of compounds P5 and P6
화합물 C-5의 제조Preparation of compound C-5
6-메톡시-1-(4,4,5,5-테트라메틸-1,3,2-다이옥사보로란-2-일)-9H-카바졸 대신에 1-(4,4,5,5-테트라메틸-1,3,2-다이옥사보로란-2-일)-9H-카바졸 11.96g(40.8mmol)을 사용하는 것을 제외하고는 실시예 1의 화합물 A-5의 제조방법과 동일하게 반응시켜 목적화합물 8.8g(78%)를 얻었다.1-(4,4,5, instead of 6-methoxy-1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole 5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole 11.96g (40.8mmol) of the preparation method of the compound A-5 of Example 1, except that The same reaction was performed to obtain 8.8 g (78%) of the target compound.
화합물 C-4의 제조Preparation of compound C-4
톨루엔 100mL에 화합물 C-5 5g (15.00mmol)을 녹인 후, 2-브로모-1-아이오도-4-메톡시벤젠(2-bromo-1-iodo-4-methoxybenzene) 5.63g(18.00mmol), Pd2(dba)3 0.69g(0.75mmol), P(t-Bu)3 (1.0M solution in Toluene) 2.3mL(2.25mmol), NaOt-Bu 2.88g(30.00.mmol) 넣고 80℃에서 24시간 교반시켰다. 1N HCl 수용액을 가하여 반응을 종결시키고, MC와 NaHCO₃ 수용액으로 추출한 후, 용매를 제거하고, MC와 Hex을 사용하여 컬럼크로마토그래피 정제하여 목적화합물 C-4 5.75g(74%)를 얻었다.After dissolving 5 g (15.00 mmol) of compound C-5 in 100 mL of toluene, 5.63 g (18.00 mmol) of 2-bromo-1-iodo-4-methoxybenzene , Pd 2 (dba) 3 0.69g(0.75mmol), P(t-Bu) 3 (1.0M solution in Toluene) 2.3mL(2.25mmol), NaOt-Bu 2.88g(30.00.mmol) at 80℃ 24 time was stirred. 1N HCl aqueous solution was added to terminate the reaction, and after extraction with MC and NaHCO₃ aqueous solution, the solvent was removed and purified by column chromatography using MC and Hex to obtain 5.75 g (74%) of the target compound C-4.
화합물 C-3의 제조Preparation of compound C-3
화합물 A-4 대신에 화합물 C-4 5g (9.65mmol)을 사용하는 것을 제외하고는 실시예 1의 화합물 A-3의 제조방법과 동일하게 반응시켜 목적화합물 C-3 2.11g(50%)를 얻었다.In the same manner as in the preparation method of Example 1, except for using 5 g (9.65 mmol) of Compound C-4 instead of Compound A-4, 2.11 g (50%) of the target compound C-3 was obtained. got it
화합물 C-2의 제조Preparation of compound C-2
화합물 A-3 대신에 화합물 C-3 10g(22.86mmol)을 사용하는 것을 제외하고는 실시예 1의 화합물 A-2의 제조방법과 동일하게 반응시켜 목적화합물 C-2 7.55g (78%)를 얻었다.7.55 g (78%) of the target compound C-2 was prepared in the same manner as in the preparation method of Example 1, except that 10 g (22.86 mmol) of Compound C-3 was used instead of Compound A-3. got it
화합물 C-1의 제조Preparation of compound C-1
화합물 A-2 대신에 화합물 C-2 10g(23.61mmol)을 사용하는 것을 제외하고는 실시예 1의 화합물 A-1의 제조방법과 동일하게 반응시켜 목적화합물 C-1 9.45g (72%)를 얻었다.9.45 g (72%) of the target compound C-1 was prepared in the same manner as in the preparation method of Example 1, except that 10 g (23.61 mmol) of Compound C-2 was used instead of Compound A-2. got it
화합물 P5의 제조Preparation of compound P5
화합물 C-1과 보론 화합물 및 팔라듐 촉매를 이용하여 스즈키 커플링 반응을 통해 목적화합물 P5을 얻었다.A target compound P5 was obtained through a Suzuki coupling reaction using compound C-1, a boron compound, and a palladium catalyst.
톨루엔/에탄올/물 (부피비 4:1:1, 100mL)에 화합물 C-1 (1eq.), 치환된 보론산 또는 보로닉 에스테르 화합물 (1,2eq.), Pd(PPh3)4 (0.05eq.), 및 K2CO3 (2eq.)을 넣은 후, 질소 분위기 하 120℃에서 환류 교반시켰다. 반응이 종결되면 셀라이트와 플로리실을 사용하여 필터한 후 MC로 씻어주었다. EA와 Hex을 사용하여 재결정 정제하여 목적화합물 P5을 얻었다.Compound C-1 (leq.), substituted boronic acid or boronic ester compound (1,2eq.), Pd(PPh 3 ) 4 (0.05eq.) in toluene/ethanol/water (volume ratio 4:1:1, 100mL) .), and K 2 CO 3 (2eq.) was added, and then stirred under reflux at 120° C. under a nitrogen atmosphere. When the reaction was completed, it was filtered using Celite and Florisil and washed with MC. The target compound P5 was obtained by recrystallization and purification using EA and Hex.
화합물 P6의 제조Preparation of compound P6
화합물 C-1과 이차아민 화합물 및 팔라듐 촉매를 이용하여 팔라듐 아미네이션을 통해 목적화합물 P6를 얻었다.A target compound P6 was obtained through palladium amination using compound C-1, a secondary amine compound, and a palladium catalyst.
톨루엔에 화합물 C-1 (1eq.), 이차아민 화합물 (1,2eq.), Pd2(dba)3 (0.05eq.), P(t-Bu)3 (0.15eq.), 및 NaOt-Bu (2eq.)을 넣은 후 아르곤 분위기 하 120℃에서 환류 교반시켰다. 반응이 종결되면 셀라이트와 플로리실을 사용하여 필터한 후 MC로 씻어주었다. EA와 Hex을 사용하여 재결정 정제하여 목적화합물 P6를 얻었다.Compound C-1 (1eq.), secondary amine compound (1,2eq.), Pd 2 (dba) 3 (0.05eq.), P(t-Bu) 3 (0.15eq.), and NaOt-Bu in toluene (2eq.) was added, followed by reflux stirring at 120° C. under an argon atmosphere. When the reaction was completed, it was filtered using Celite and Florisil and washed with MC. The target compound P6 was obtained by recrystallization and purification using EA and Hex.
반응물인 치환된 보론산, 보로닉 에스테르 및 이차아민 화합물의 구조, 및 제조된 화합물 P5 및 P6의 구조와 수율은 하기 표 3에 기재하였다. 그러나, 반응물인 보론 화합물과 이차아민 화합물의 구조가 하기에 한정되는 것은 아니다.The structures of the reactants of the substituted boronic acid, boronic ester and secondary amine compound, and the structures and yields of the prepared compounds P5 and P6 are shown in Table 3 below. However, the structures of the boron compound and the secondary amine compound as reactants are not limited to the following.
상기 실시예들에서 제조된 화합물들의 1H NMR 및 MS 값을 하기 표 4에 나타내었다. 1 H NMR and MS values of the compounds prepared in the Examples are shown in Table 4 below.
[실시예 4] 유기 발광 소자의 제조 및 평가[Example 4] Manufacturing and evaluation of organic light emitting device
실시예에서 얻은 화합물들을 각각 발광보조층 형성용 재료로 사용하여 통상적인 방법에 따라 유기발광소자를 제작하였다.An organic light emitting diode was manufactured according to a conventional method by using the compounds obtained in Examples as materials for forming the light emitting auxiliary layer, respectively.
인듐틴옥사이드(ITO)가 1500Å두께로 박막 코팅된 유리 기판을 증류수 초음파로 세척하였다. 증류수 세척이 끝나면 이소프로필 알코올, 아세톤, 메탄올의 용제로 초음파 세척을 하고, 건조시켰다. 플라즈마 세정기로 이송시킨 다음, 산소 플라즈마를 이용하여 상기 기판을 5분간 세정하고, ITO 기판 상부에 열 진공 증착기(thermal evaporator)를 이용하여 정공주입층 HI01 600Å, HATCN 50Å; 정공수송층 HT01 250Å; 발광보조층으로 본 발명의 실시예에서 제조된 헤테로고리 화합물 100Å을 순차적으로 제막한 다음, 발광층으로 BH01:BD01 3%로 도핑하여 250Å 제막하였다. 다음으로 전자수송층으로 ET01:Liq (1:1) 300Å 제막한 후, LiF 10Å, 알루미늄(Al)을 1000Å 제막한 다음, 이 소자를 글로브 박스에서 밀봉(encapsulation)함으로써 유기발광소자를 제작하였다.A glass substrate coated with indium tin oxide (ITO) to a thickness of 1500 Å was washed with distilled water and ultrasonic waves. After washing with distilled water, ultrasonic washing was performed with a solvent of isopropyl alcohol, acetone, and methanol, followed by drying. After transferring to a plasma cleaner, the substrate was cleaned for 5 minutes using oxygen plasma, and the hole injection layer HI01 600 Å, HATCN 50 Å; hole transport layer HT01 250Å; 100 Å of the heterocyclic compound prepared in Examples of the present invention was sequentially formed as a light emitting auxiliary layer, and then 250 Å was formed as a light emitting layer by doping with BH01:BD01 3%. Next, ET01:Liq (1:1) 300 Å was formed as an electron transport layer, LiF 10 Å, and aluminum (Al) 1000 Å were formed into a film, and then the device was encapsulated in a glove box to manufacture an organic light emitting device.
[비교예 1 내지 4][Comparative Examples 1 to 4]
발광보조층 형성용 재료로 본 발명의 헤테로고리 화합물 대신 하기 비교화합물 A, 비교화합물 B, 비교화합물 C 또는 비교화합물 D를 사용한 점을 제외하고는 상기 실시예 4와 동일한 방법으로 유기발광소자를 제조하였다.An organic light emitting device was manufactured in the same manner as in Example 4, except that the following comparative compound A, comparative compound B, comparative compound C, or comparative compound D was used as a material for forming the light emitting auxiliary layer instead of the heterocyclic compound of the present invention. did.
본 발명의 실시예 4 및 비교예 1 내지 4에 의해 제조된 각각의 유기발광소자에 키슬리의 표준 시리즈 2400 소스 측정 장치(Kiethley 2400 source measurement unit)로 전압을 인가하여 전자 및 정공을 주입하고, 코니카 미놀타(Konica Minolta) 분광복사계(CS-2000)를 이용하여 빛이 방출될 때의 휘도를 측정함으로써, 유기발광소자의 성능을 인가전압에 대한 전류 밀도 및 휘도를 대기압 조건 하에 측정하여 평가하였으며, 수명 측정 장비를 통해 T95 수명을 측정하였다. 측정 결과를 하기 표 5에 기재하였다. T95는 발광 소자의 효울이 초기 효율 대비 95%가 되기까지 걸린 시간을 의미한다.Electrons and holes are injected by applying a voltage to each of the organic light-emitting devices manufactured by Example 4 and Comparative Examples 1 to 4 of the present invention with a standard series 2400 source measurement unit of Keithley, By measuring the luminance when light is emitted using a Konica Minolta spectroradiometer (CS-2000), the performance of the organic light emitting device was evaluated by measuring the current density and luminance with respect to the applied voltage under atmospheric pressure conditions, T95 lifetime was measured using a lifetime measuring device. The measurement results are shown in Table 5 below. T95 means the time it takes for the efficiency of the light emitting device to reach 95% of the initial efficiency.
(V)drive voltage
(V)
(mA/cm2)electric current
(mA/cm 2 )
(Cd/A)efficiency
(Cd/A)
(%)QE
(%)
상기 표 5로부터 본 발명에서 개발한 헤테로고리 화합물들은 발광보조층 형성용 재료로서 공지 화합물 대비 보다 우수한 발광특성 및 효율을 보임과 동시에 구동전압을 강하시켜 전력효율상승을 유도하여 소비전력을 향상시킬 수 있음을 알 수 있으며, 또한 수명 특성에 있어서도 현저한 증가를 보임을 알 수 있다.From Table 5 above, the heterocyclic compounds developed in the present invention as a material for forming a light-emitting auxiliary layer show superior light-emitting characteristics and efficiency compared to known compounds, and at the same time lower the driving voltage to induce an increase in power efficiency, thereby improving power consumption. It can be seen that there is a significant increase in the lifespan characteristics.
따라서, 본 발명의 헤테로고리 화합물은 유기물층 형성 재료, 특히 발광보조층 형성용 재료로 사용되어 낮은 구동전압, 우수한 색순도, 높은 발광효율 및 장수명 특성을 나타내는 유기전계발광소자를 제조할 수 있다. 이는 본 발명의 헤테로고리 화합물의 구조적 특징에 기인되는 빠른 정공 이동도(hole mobility)에 의한 것으로, 다이벤조퓨란, 카바졸 및 벤젠이 축합고리를 이루되 반드시 7원 고리를 중심으로 형성된 축합고리 형태의 모핵 및 적어도 하나의 아미노 치환체의 도입으로 인하여 극대화된 정공이동도를 나타내면서 상기 발광층 내에 엑시톤이 가두어 우수한 발광 효율을 갖는 유기 전계 발광 소자를 구현할 수 있다. Therefore, the heterocyclic compound of the present invention can be used as an organic material layer-forming material, particularly a material for forming a light-emitting auxiliary layer, to produce an organic electroluminescent device exhibiting low driving voltage, excellent color purity, high luminous efficiency and long lifespan characteristics. This is due to the fast hole mobility due to the structural characteristics of the heterocyclic compound of the present invention, and dibenzofuran, carbazole and benzene form a condensed ring, but must be formed around a 7-membered ring. An organic electroluminescent device having excellent luminous efficiency can be realized by trapping excitons in the light emitting layer while exhibiting maximized hole mobility due to the introduction of the parent nucleus and at least one amino substituent.
이상에서 살펴본 바와 같이 본 발명의 실시예에 대해 상세히 기술되었지만, 본 발명이 속하는 기술분야에 있어서 통상의 지식을 가진 사람이라면, 첨부된 청구범위에 정의된 본 발명의 정신 및 범위를 벗어나지 않으면서 본 발명을 여러 가지로 변형하여 실시할 수 있을 것이다. 따라서 본 발명의 앞으로의 실시예들의 변경은 본 발명의 기술을 벗어날 수 없을 것이다.Although the embodiments of the present invention have been described in detail as described above, those of ordinary skill in the art to which the present invention pertains, without departing from the spirit and scope of the present invention as defined in the appended claims The invention may be practiced with various modifications. Accordingly, modifications of future embodiments of the present invention will not depart from the technology of the present invention.
Claims (9)
[화학식 1]
상기 화학식 1에서,
L1 내지 L5는 각각 독립적으로 단일결합, C6-C60아릴렌 또는 C3-C60헤테로아릴렌이고;
R1 내지 R10은 각각 독립적으로 C1-C60알킬, C2-C60알케닐, C2-C60알키닐, C3-C60시클로알킬, C2-C60헤테로시클로알킬, C6-C60아릴, C3-C60헤테로아릴 또는 -L11-R11이거나, R1와 R2, R3과 R4, R5와 R6, R7와 R8 및 R9와 R10은 각각 독립적으로 서로 연결되어 방향족고리가 융합되거나 융합되지 않은 헤테로고리를 형성할 수 있으며;
L11은 C6-C60아릴렌 또는 C3-C60헤테로아릴렌이며;
R11은 C6-C60아릴, C3-C60헤테로아릴 또는 -NR12R13이며;
R12 및 R13은 각각 독립적으로 수소, C1-C60알킬, C6-C60아릴 또는 C3-C60헤테로아릴이며;
상기 L1 내지 L5의 아릴렌 및 헤테로아릴렌, R1 내지 R10의 알킬, 알케닐, 알키닐, 시클로알킬, 헤테로시클로알킬, 아릴 및 헤테로아릴, L11의 아릴렌 및 헤테로아릴렌, R11의 아릴 및 헤테로아릴, 및 R12 및 R13의 알킬, 아릴 및 헤테로아릴은 C1-C60알킬, 할로C1-C60알킬, 중수소, 할로겐, 시아노, C3-C60시클로알킬, C1-C60알콕시, C6-C60아릴, C6-C60아릴옥시, C6-C60아릴C1-C60알킬, C1-C60알킬C6-C60아릴, C3-C60헤테로아릴, -NR'R'', 나이트로 및 하이드록시로 이루어진 군으로부터 선택되는 하나 이상으로 더 치환될 수 있고;
R' 및 R''는 각각 독립적으로 수소, C1-C60알킬, C6-C60아릴 또는 C3-C60헤테로아릴이고;
p, q 및 s는 서로 독립적으로 0 내지 4의 정수이고, r은 0 내지 3의 정수이고, t는 0 내지 2의 정수이며, 단, p, q, r, s 및 t는 동시에 0이 아니며;
상기 헤테로아릴렌, 헤테로시클로알킬 및 헤테로아릴은 N, O, S 및 Se로부터 선택되는 하나 이상의 헤테로 원자를 포함한다.A heterocyclic compound represented by the following formula (1):
[Formula 1]
In Formula 1,
L 1 to L 5 are each independently a single bond, C6-C60 arylene, or C3-C60 heteroarylene;
R 1 to R 10 are each independently C1-C60 alkyl, C2-C60 alkenyl, C2-C60 alkynyl, C3-C60 cycloalkyl, C2-C60 heterocycloalkyl, C6-C60 aryl, C3-C60 heteroaryl or -L 11 -R 11 or R 1 and R 2 , R 3 and R 4 , R 5 and R 6 , R 7 and R 8 , and R 9 and R 10 are each independently connected to each other so that an aromatic ring is fused or fused can form heterocycles that are not;
L 11 is C6-C60 arylene or C3-C60 heteroarylene;
R 11 is C6-C60 aryl, C3-C60 heteroaryl or —NR 12 R 13 ;
R 12 and R 13 are each independently hydrogen, C1-C60 alkyl, C6-C60 aryl or C3-C60 heteroaryl;
arylene and heteroarylene of L 1 to L 5 , alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl and heteroaryl of L 11 , arylene and heteroarylene of L 11 , Aryl and heteroaryl of R 11 , and alkyl, aryl and heteroaryl of R 12 and R 13 are C1-C60alkyl, haloC1-C60alkyl, deuterium, halogen, cyano, C3-C60cycloalkyl, C1-C60alkoxy , C6-C60 aryl, C6-C60 aryloxy, C6-C60 arylC1-C60 alkyl, C1-C60 alkylC6-C60 aryl, C3-C60 heteroaryl, -NR'R'', nitro and hydroxy may be further substituted with one or more selected from the group;
R' and R'' are each independently hydrogen, C1-C60 alkyl, C6-C60 aryl or C3-C60 heteroaryl;
p, q and s are independently of each other an integer from 0 to 4, r is an integer from 0 to 3, t is an integer from 0 to 2, provided that p, q, r, s and t are not simultaneously non-zero ;
Said heteroarylene, heterocycloalkyl and heteroaryl include one or more heteroatoms selected from N, O, S and Se.
상기 L1 내지 L5는 각각 독립적으로 단일결합, C6-C60아릴렌 또는 C3-C60헤테로아릴렌이고, 상기 L1 내지 L5의 아릴렌 및 헤테로아릴렌은 C1-C60알킬, C6-C30아릴 및 -NR'R''로 이루어진 군으로부터 선택되는 하나 이상으로 더 치환될 수 있고;
R' 및 R''는 각각 독립적으로 C6-C60아릴 또는 C3-C60헤테로아릴이고;
R1 내지 R10은 각각 독립적으로 C6-C60아릴, C3-C60헤테로아릴 또는 -L11-R11이거나, R1와 R2, R3과 R4, R5와 R6, R7와 R8 및 R9와 R10은 각각 독립적으로 서로 연결되어 방향족고리가 융합된 헤테로고리를 형성할 수 있으며;
L11은 C6-C60아릴렌 또는 C3-C60헤테로아릴렌이며;
R11은 C6-C60아릴, C3-C60헤테로아릴 또는 -NR12R13이며;
R12 및 R13은 각각 독립적으로 C6-C60아릴 또는 C3-C60헤테로아릴이며;
상기 R1 내지 R10의 아릴 및 헤테로아릴, L11의 아릴렌 및 헤테로아릴렌, R11의 아릴 및 헤테로아릴, 및 R12 및 R13의 아릴 및 헤테로아릴은 C1-C60알킬, 중수소, C6-C60아릴, C6-C60아릴C1-C60알킬, C1-C60알킬C6-C60아릴 및 C3-C60헤테로아릴로 이루어진 군으로부터 선택되는 하나 이상으로 더 치환될 수 있고;
p, q, r, s 및 t는 서로 독립적으로 0 내지 2의 정수이며, 단, 1≤p+q+r+s+t≤10를 만족하는, 헤테로고리 화합물.The method of claim 1,
Wherein L 1 To L 5 are each independently a single bond, C6-C60 arylene or C3-C60 heteroarylene, and the arylene and heteroarylene of L 1 To L 5 are C1-C60 alkyl, C6-C30 aryl and -NR'R'' may be further substituted with one or more selected from the group consisting of;
R' and R'' are each independently C6-C60 aryl or C3-C60 heteroaryl;
R 1 to R 10 are each independently C6-C60 aryl, C3-C60 heteroaryl or -L 11 -R 11 , or R 1 and R 2 , R 3 and R 4 , R 5 and R 6 , R 7 and R 8 and R 9 and R 10 may be each independently connected to each other to form a heterocycle in which an aromatic ring is fused;
L 11 is C6-C60 arylene or C3-C60 heteroarylene;
R 11 is C6-C60 aryl, C3-C60 heteroaryl or —NR 12 R 13 ;
R 12 and R 13 are each independently C6-C60 aryl or C3-C60 heteroaryl;
The aryl and heteroaryl of R 1 to R 10 , arylene and heteroarylene of L 11 , aryl and heteroaryl of R 11 , and aryl and heteroaryl of R 12 and R 13 are C1-C60alkyl, deuterium, C6 -C60 aryl, C6-C60 aryl, C1-C60 alkyl, C1-C60 alkylC6-C60 aryl and C3-C60 heteroaryl may be further substituted with one or more selected from the group consisting of;
p, q, r, s and t are each independently an integer of 0 to 2, provided that 1≤p+q+r+s+t≤10 is satisfied, a heterocyclic compound.
상기 헤테로고리 화합물은 하기 화학식 2 내지 4 중 어느 하나로 표시되는 것인, 헤테로고리 화합물:
[화학식 2]
[화학식 3]
[화학식 4]
상기 화학식 2 내지 4에서,
L1, L2 및 L4는 각각 독립적으로 단일결합, C6-C30아릴렌 또는 C3-C30헤테로아릴렌이고, 상기 L1, L2 및 L4의 아릴렌 및 헤테로아릴렌은 C1-C30알킬, C6-C30아릴 및 -NR'R''로 이루어진 군으로부터 선택되는 하나 이상으로 더 치환될 수 있고;
R' 및 R''는 각각 독립적으로 C6-C30아릴 또는 C3-C30헤테로아릴이고;
R1, R2, R3, R4, R7 및 R8은 각각 독립적으로 C6-C30아릴, C3-C30헤테로아릴 또는 -L11-R11이거나, R1와 R2, R3과 R4 및 R7와 R8은 각각 독립적으로 서로 연결되어 방향족고리가 융합된 헤테로고리를 형성할 수 있으며;
L11은 C6-C30아릴렌 또는 C3-C30헤테로아릴렌이며;
R11은 C6-C30아릴, C3-C30헤테로아릴 또는 -NR12R13이며;
R12 및 R13은 각각 독립적으로 C6-C30아릴 또는 C3-C30헤테로아릴이며;
상기 R1, R2, R3, R4, R7 및 R8의 아릴 및 헤테로아릴, L11의 아릴렌 및 헤테로아릴렌, R11의 아릴 및 헤테로아릴, 및 R12 및 R13의 아릴 및 헤테로아릴은 C1-C30알킬, C6-C30아릴, C6-C30아릴C1-C30알킬, C1-C30알킬C6-C30아릴 및 C3-C30헤테로아릴로 이루어진 군으로부터 선택되는 하나 이상으로 더 치환될 수 있고;
p, q 및 s는 서로 독립적으로 1 또는 2의 정수이다.3. The method of claim 2,
The heterocyclic compound is represented by any one of the following formulas 2 to 4, a heterocyclic compound:
[Formula 2]
[Formula 3]
[Formula 4]
In Formulas 2 to 4,
L 1 , L 2 and L 4 are each independently a single bond, C6-C30 arylene, or C3-C30 heteroarylene, and the arylene and heteroarylene of L 1 , L 2 and L 4 are C1-C30 alkyl , C6-C30 aryl and -NR'R'' may be further substituted with one or more selected from the group consisting of;
R' and R'' are each independently C6-C30 aryl or C3-C30 heteroaryl;
R 1 , R 2 , R 3 , R 4 , R 7 and R 8 are each independently C6-C30 aryl, C3-C30 heteroaryl or -L 11 -R 11 , or R 1 and R 2 , R 3 and R 4 and R 7 and R 8 may be each independently connected to each other to form a heterocycle in which an aromatic ring is fused;
L 11 is C6-C30 arylene or C3-C30 heteroarylene;
R 11 is C6-C30 aryl, C3-C30 heteroaryl or —NR 12 R 13 ;
R 12 and R 13 are each independently C6-C30 aryl or C3-C30 heteroaryl;
aryl and heteroaryl of R 1 , R 2 , R 3 , R 4 , R 7 and R 8 , arylene and heteroarylene of L 11 , aryl and heteroaryl of R 11 , and aryl of R 12 and R 13 and heteroaryl may be further substituted with one or more selected from the group consisting of C1-C30 alkyl, C6-C30 aryl, C6-C30 aryl, C1-C30 alkyl, C1-C30 alkylC6-C30 aryl and C3-C30 heteroaryl. there is;
p, q and s are each independently an integer of 1 or 2.
상기 헤테로고리 화합물은 하기 화학식 5 내지 7 중 어느 하나로 표시되는 것인, 헤테로고리 화합물:
[화학식 5]
[화학식 6]
[화학식 7]
상기 화학식 5 내지 7에서,
L1, L2 및 L4는 각각 독립적으로 단일결합, C6-C20아릴렌 또는 C3-C20헤테로아릴렌이고, 상기 L1, L2 및 L4의 아릴렌 및 헤테로아릴렌은 C1-C20알킬, C6-C20아릴 및 -NR'R''로 이루어진 군으로부터 선택되는 하나 이상으로 더 치환될 수 있고;
R' 및 R''는 각각 독립적으로 C6-C20아릴 또는 C3-C20헤테로아릴이고;
R1, R2, R3, R4, R7 및 R8은 각각 독립적으로 C6-C20아릴, C3-C20헤테로아릴 또는 -L11-R11이며;
L11은 C6-C20아릴렌 또는 C3-C20헤테로아릴렌이며;
R11은 C6-C20아릴, C3-C20헤테로아릴 또는 -NR12R13이며;
R12 및 R13은 각각 독립적으로 C6-C20아릴 또는 C3-C20헤테로아릴이며;
상기 R1, R2, R3, R4, R7 및 R8의 아릴 및 헤테로아릴, L11의 아릴렌 및 헤테로아릴렌, R11의 아릴 및 헤테로아릴, 및 R12 및 R13의 아릴 및 헤테로아릴은 C1-C20알킬, C6-C20아릴, C6-C20아릴C1-C20알킬, C1-C20알킬C6-C20아릴 및 C3-C20헤테로아릴로 이루어진 군으로부터 선택되는 하나 이상으로 더 치환될 수 있다.4. The method of claim 3,
The heterocyclic compound is represented by any one of the following formulas 5 to 7, a heterocyclic compound:
[Formula 5]
[Formula 6]
[Formula 7]
In Formulas 5 to 7,
L 1 , L 2 and L 4 are each independently a single bond, C6-C20 arylene or C3-C20 heteroarylene, and the arylene and heteroarylene of L 1 , L 2 and L 4 are C1-C20 alkyl , may be further substituted with one or more selected from the group consisting of C6-C20 aryl and -NR'R'';
R' and R'' are each independently C6-C20 aryl or C3-C20 heteroaryl;
R 1 , R 2 , R 3 , R 4 , R 7 and R 8 are each independently C6-C20 aryl, C3-C20 heteroaryl or -L 11 -R 11 ;
L 11 is C6-C20 arylene or C3-C20 heteroarylene;
R 11 is C6-C20 aryl, C3-C20 heteroaryl or —NR 12 R 13 ;
R 12 and R 13 are each independently C6-C20 aryl or C3-C20 heteroaryl;
aryl and heteroaryl of R 1 , R 2 , R 3 , R 4 , R 7 and R 8 , arylene and heteroarylene of L 11 , aryl and heteroaryl of R 11 , and aryl of R 12 and R 13 and heteroaryl may be further substituted with one or more selected from the group consisting of C1-C20 alkyl, C6-C20 aryl, C6-C20 arylC1-C20 alkyl, C1-C20 alkylC6-C20 aryl and C3-C20 heteroaryl. have.
상기 L1 내지 L5은 각각 독립적으로 단일결합이거나, 하기 구조에서 선택되는 것인, 헤테로고리 화합물:
상기에서,
RL1, RL2, RL3 및 RL4는 각각 독립적으로 수소, C6-C20아릴 또는 NR'R''이고;
R' 및 R''는 각각 독립적으로 C6-C20아릴 또는 C3-C20헤테로아릴이고;
Z는 CRZ1RZ2, NRZ3, O 또는 S이고;
RZ1 및 RZ2은 각각 독립적으로 C1-C20알킬 또는 C6-C20아릴이고;
RZ3은 C6-C20아릴이다.3. The method of claim 2,
The L 1 To L 5 Are each independently a single bond, or a heterocyclic compound selected from the following structure:
above,
R L1 , R L2 , R L3 and R L4 are each independently hydrogen, C6-C20 aryl or NR'R'';
R' and R'' are each independently C6-C20 aryl or C3-C20 heteroaryl;
Z is CR Z1 R Z2 , NR Z3 , O or S;
R Z1 and R Z2 are each independently C1-C20 alkyl or C6-C20 aryl;
R Z3 is C6-C20 aryl.
상기 R1 내지 R10은 각각 독립적으로 하기 구조에서 선택되는 것인, 헤테로고리 화합물:
상기에서,
X1은 NR31, O 또는 S이고;
Y1은 CR32R33, O 또는 S이고;
R31은 C6-C20아릴 또는 C3-C20헤테로아릴이고;
R32 및 R33은 각각 독립적으로 C1-C20알킬, C6-C20아릴 또는 C3-C20헤테로아릴이고;
R21, R22 및 R23은 서로 독립적으로 수소, C6-C20아릴, C3-C20헤테로아릴 또는 -NR12R13이고;
R12 및 R13은 각각 독립적으로 C6-C20아릴 또는 C3-C20헤테로아릴이며;
R24 및 R25는 각각 독립적으로 C1-C20알킬 또는 C6-C20아릴이고;
상기 R21, R22 및 R23의 아릴 및 헤테로아릴은 C1-C20알킬 및 C6-C20아릴로 이루어진 군으로부터 선택되는 하나 이상으로 더 치환될 수 있다.3. The method of claim 2,
Wherein R 1 To R 10 Are each independently selected from the following structure, a heterocyclic compound:
above,
X 1 is NR 31 , O or S;
Y 1 is CR 32 R 33 , O or S;
R 31 is C6-C20 aryl or C3-C20 heteroaryl;
R 32 and R 33 are each independently C1-C20 alkyl, C6-C20 aryl or C3-C20 heteroaryl;
R 21 , R 22 and R 23 are each independently hydrogen, C6-C20 aryl, C3-C20 heteroaryl or —NR 12 R 13 ;
R 12 and R 13 are each independently C6-C20 aryl or C3-C20 heteroaryl;
R 24 and R 25 are each independently C1-C20 alkyl or C6-C20 aryl;
The aryl and heteroaryl of R 21 , R 22 and R 23 may be further substituted with one or more selected from the group consisting of C1-C20 alkyl and C6-C20 aryl.
상기 헤테로고리 화합물은 하기에서 선택되는 것인, 헤테로고리 화합물:
The heterocyclic compound is a heterocyclic compound selected from:
상기 유기물층은 정공주입층, 정공수송층, 전자수송층, 전자주입층 및 발광보조층 중에서 선택되는 적어도 하나의 층인, 유기 발광 소자.9. The method of claim 8,
The organic material layer is at least one layer selected from a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, and a light emitting auxiliary layer, an organic light emitting device.
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