KR20150061811A - Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof - Google Patents
Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof Download PDFInfo
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- KR20150061811A KR20150061811A KR1020130145992A KR20130145992A KR20150061811A KR 20150061811 A KR20150061811 A KR 20150061811A KR 1020130145992 A KR1020130145992 A KR 1020130145992A KR 20130145992 A KR20130145992 A KR 20130145992A KR 20150061811 A KR20150061811 A KR 20150061811A
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 70
- 239000011368 organic material Substances 0.000 claims abstract description 40
- 125000004432 carbon atom Chemical group C* 0.000 claims description 43
- 125000003118 aryl group Chemical group 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 31
- 125000000217 alkyl group Chemical group 0.000 claims description 21
- 125000000623 heterocyclic group Chemical group 0.000 claims description 18
- 125000003342 alkenyl group Chemical group 0.000 claims description 15
- 125000003545 alkoxy group Chemical group 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 14
- 125000001931 aliphatic group Chemical group 0.000 claims description 13
- 125000000304 alkynyl group Chemical group 0.000 claims description 12
- 125000005842 heteroatom Chemical group 0.000 claims description 12
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 11
- 125000001424 substituent group Chemical group 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 8
- 125000004104 aryloxy group Chemical group 0.000 claims description 8
- 125000000732 arylene group Chemical group 0.000 claims description 7
- 229910052736 halogen Inorganic materials 0.000 claims description 7
- 150000002367 halogens Chemical class 0.000 claims description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 229910052805 deuterium Inorganic materials 0.000 claims description 5
- 125000005018 aryl alkenyl group Chemical group 0.000 claims description 4
- 125000005567 fluorenylene group Chemical group 0.000 claims description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical group [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 125000006736 (C6-C20) aryl group Chemical group 0.000 claims description 2
- 125000004414 alkyl thio group Chemical group 0.000 claims description 2
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- 238000004528 spin coating Methods 0.000 claims description 2
- 239000010410 layer Substances 0.000 description 190
- 239000000463 material Substances 0.000 description 65
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 39
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- 230000000052 comparative effect Effects 0.000 description 32
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 22
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- 239000000741 silica gel Substances 0.000 description 22
- 229960001866 silicon dioxide Drugs 0.000 description 22
- ABRVLXLNVJHDRQ-UHFFFAOYSA-N [2-pyridin-3-yl-6-(trifluoromethyl)pyridin-4-yl]methanamine Chemical compound FC(C1=CC(=CC(=N1)C=1C=NC=CC=1)CN)(F)F ABRVLXLNVJHDRQ-UHFFFAOYSA-N 0.000 description 20
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
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- 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 8
- 239000000758 substrate Substances 0.000 description 7
- MAYZWDRUFKUGGP-VIFPVBQESA-N (3s)-1-[5-tert-butyl-3-[(1-methyltetrazol-5-yl)methyl]triazolo[4,5-d]pyrimidin-7-yl]pyrrolidin-3-ol Chemical compound CN1N=NN=C1CN1C2=NC(C(C)(C)C)=NC(N3C[C@@H](O)CC3)=C2N=N1 MAYZWDRUFKUGGP-VIFPVBQESA-N 0.000 description 6
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 6
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- 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 6
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- 239000002019 doping agent Substances 0.000 description 5
- 238000004770 highest occupied molecular orbital Methods 0.000 description 5
- -1 oxygen radical Chemical class 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 229910001508 alkali metal halide Inorganic materials 0.000 description 4
- 150000008045 alkali metal halides Chemical class 0.000 description 4
- UFVXQDWNSAGPHN-UHFFFAOYSA-K bis[(2-methylquinolin-8-yl)oxy]-(4-phenylphenoxy)alumane Chemical compound [Al+3].C1=CC=C([O-])C2=NC(C)=CC=C21.C1=CC=C([O-])C2=NC(C)=CC=C21.C1=CC([O-])=CC=C1C1=CC=CC=C1 UFVXQDWNSAGPHN-UHFFFAOYSA-K 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
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- 238000005259 measurement Methods 0.000 description 4
- VFUDMQLBKNMONU-UHFFFAOYSA-N 9-[4-(4-carbazol-9-ylphenyl)phenyl]carbazole Chemical group C12=CC=CC=C2C2=CC=CC=C2N1C1=CC=C(C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=C1 VFUDMQLBKNMONU-UHFFFAOYSA-N 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 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
- 239000001301 oxygen Substances 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 2
- 101100030361 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) pph-3 gene Proteins 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
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- 125000003302 alkenyloxy group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
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- 125000005129 aryl carbonyl group Chemical group 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 239000000872 buffer Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 125000001188 haloalkyl group Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000004404 heteroalkyl group Chemical group 0.000 description 2
- 125000001072 heteroaryl group Chemical group 0.000 description 2
- 150000002431 hydrogen Chemical group 0.000 description 2
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
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- 239000000126 substance Substances 0.000 description 2
- NHDIQVFFNDKAQU-UHFFFAOYSA-N tripropan-2-yl borate Chemical compound CC(C)OB(OC(C)C)OC(C)C NHDIQVFFNDKAQU-UHFFFAOYSA-N 0.000 description 2
- 238000007738 vacuum evaporation Methods 0.000 description 2
- ICPSWZFVWAPUKF-UHFFFAOYSA-N 1,1'-spirobi[fluorene] Chemical group C1=CC=C2C=C3C4(C=5C(C6=CC=CC=C6C=5)=CC=C4)C=CC=C3C2=C1 ICPSWZFVWAPUKF-UHFFFAOYSA-N 0.000 description 1
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 1
- IRPVABHDSJVBNZ-RTHVDDQRSA-N 5-[1-(cyclopropylmethyl)-5-[(1R,5S)-3-(oxetan-3-yl)-3-azabicyclo[3.1.0]hexan-6-yl]pyrazol-3-yl]-3-(trifluoromethyl)pyridin-2-amine Chemical compound C1=C(C(F)(F)F)C(N)=NC=C1C1=NN(CC2CC2)C(C2[C@@H]3CN(C[C@@H]32)C2COC2)=C1 IRPVABHDSJVBNZ-RTHVDDQRSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- VIZUPBYFLORCRA-UHFFFAOYSA-N 9,10-dinaphthalen-2-ylanthracene Chemical compound C12=CC=CC=C2C(C2=CC3=CC=CC=C3C=C2)=C(C=CC=C2)C2=C1C1=CC=C(C=CC=C2)C2=C1 VIZUPBYFLORCRA-UHFFFAOYSA-N 0.000 description 1
- ZDMAXGYBXVYOQC-UHFFFAOYSA-N Brc1cc(-c(cc2)cc3c2c(cccc2)c2[n]3-c2ccccc2)cc(-c(cc2)cc(c3c(cccc4)c4ccc33)c2[n]3-c2ccccc2)c1 Chemical compound Brc1cc(-c(cc2)cc3c2c(cccc2)c2[n]3-c2ccccc2)cc(-c(cc2)cc(c3c(cccc4)c4ccc33)c2[n]3-c2ccccc2)c1 ZDMAXGYBXVYOQC-UHFFFAOYSA-N 0.000 description 1
- LYSOUQSSNDTGMF-UHFFFAOYSA-N Brc1cc(-c(cc2)cc3c2c(cccc2)c2[n]3-c2ccccc2)cc(-c(cc2)cc(c3ccccc33)c2[n]3-c2ccccc2)c1 Chemical compound Brc1cc(-c(cc2)cc3c2c(cccc2)c2[n]3-c2ccccc2)cc(-c(cc2)cc(c3ccccc33)c2[n]3-c2ccccc2)c1 LYSOUQSSNDTGMF-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- MAWIMXZUWQPCJQ-UHFFFAOYSA-N C1(=CC=CC=C1)C1=NC(=CC2=CC=CC=C12)[Ir+]C=1N=C(C2=CC=CC=C2C=1)C1=CC=CC=C1 Chemical compound C1(=CC=CC=C1)C1=NC(=CC2=CC=CC=C12)[Ir+]C=1N=C(C2=CC=CC=C2C=1)C1=CC=CC=C1 MAWIMXZUWQPCJQ-UHFFFAOYSA-N 0.000 description 1
- QRMLAMCEPKEKHS-UHFFFAOYSA-N CC1(C)c2cc(Nc(cc3)ccc3-c3ccccc3)ccc2-c2ccccc12 Chemical compound CC1(C)c2cc(Nc(cc3)ccc3-c3ccccc3)ccc2-c2ccccc12 QRMLAMCEPKEKHS-UHFFFAOYSA-N 0.000 description 1
- LLVYAUKGGUCFKM-UHFFFAOYSA-N CC1C(c(cc2)ccc2N(c(cc2)cc3c2-c2ccccc2C3(C)C)c2cc(-c(cc3)cc4c3c(cccc3)c3[n]4-c3ccccc3)cc(-c(cc3)cc(c4ccccc44)c3[n]4-c3ccccc3)c2)=CC=CC1 Chemical compound CC1C(c(cc2)ccc2N(c(cc2)cc3c2-c2ccccc2C3(C)C)c2cc(-c(cc3)cc4c3c(cccc3)c3[n]4-c3ccccc3)cc(-c(cc3)cc(c4ccccc44)c3[n]4-c3ccccc3)c2)=CC=CC1 LLVYAUKGGUCFKM-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
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- 125000003277 amino group Chemical group 0.000 description 1
- 125000002102 aryl alkyloxo group Chemical group 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- XGRQCVNMASSEKR-UHFFFAOYSA-N c(cc1)ccc1N(c1ccccc1)c1cc(-c(cc2)cc3c2c(cccc2)c2[n]3-c2ccccc2)cc(-c(cc2)cc(c3c(cccc4)c4ccc33)c2[n]3-c2ccccc2)c1 Chemical compound c(cc1)ccc1N(c1ccccc1)c1cc(-c(cc2)cc3c2c(cccc2)c2[n]3-c2ccccc2)cc(-c(cc2)cc(c3c(cccc4)c4ccc33)c2[n]3-c2ccccc2)c1 XGRQCVNMASSEKR-UHFFFAOYSA-N 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
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- 238000000434 field desorption mass spectrometry Methods 0.000 description 1
- RMBPEFMHABBEKP-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2C3=C[CH]C=CC3=CC2=C1 RMBPEFMHABBEKP-UHFFFAOYSA-N 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
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- 125000005549 heteroarylene group Chemical group 0.000 description 1
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- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
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- IBHBKWKFFTZAHE-UHFFFAOYSA-N n-[4-[4-(n-naphthalen-1-ylanilino)phenyl]phenyl]-n-phenylnaphthalen-1-amine Chemical group C1=CC=CC=C1N(C=1C2=CC=CC=C2C=CC=1)C1=CC=C(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C3=CC=CC=C3C=CC=2)C=C1 IBHBKWKFFTZAHE-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
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- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 1
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- 239000002861 polymer material Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
- C07D403/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a carbon chain containing aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
- C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
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Abstract
Description
본 발명은 유기전기소자용 화합물, 이를 이용한 유기전기소자 및 그 전자 장치에 관한 것이다.TECHNICAL FIELD The present invention relates to a compound for an organic electric device, an organic electric device using the same, and an electronic device therefor.
일반적으로 유기 발광 현상이란 유기 물질을 이용하여 전기에너지를 빛 에너지로 전환시켜주는 현상을 말한다. 유기 발광 현상을 이용하는 유기전기소자는 통상 양극과 음극 및 이 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, organic light emission phenomenon refers to a phenomenon in which an organic material is used to convert electric energy into light energy. An organic electric device using an organic light emitting phenomenon generally has a structure including an anode, an anode, and an organic material layer therebetween. Here, in order to increase the efficiency and stability of the organic electronic device, the organic material layer is often formed of a multilayer structure composed of different materials, and may be formed of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer.
유기전기소자에서 유기물층으로 사용되는 재료는 기능에 따라, 발광 재료와 전하수송 재료, 예컨대 정공주입 재료, 정공수송 재료, 전자수송 재료, 전자주입 재료 등으로 분류될 수 있다.A material used as an organic material layer in an organic electric device may be classified into a light emitting material and a charge transporting material such as a hole injecting material, a hole transporting material, an electron transporting material, and an electron injecting material depending on functions.
현재 휴대용 디스플레이 시장은 대면적 디스플레이로 그 크기가 증가하고 있는 추세이며, 이로 인해 기존 휴대용 디스플레이에서 요구하던 소비전력보다 더 큰 소비전력이 요구되고 있다. 따라서 배터리라는 제한적인 전력 공급원을 가지고 있는 휴대용 디스플레이입장에서는 소비전력이 매우 중요한 요소가 되었고, 효율과 수명 문제 또한 반드시 해결되어야 하는 상황이다.Currently, the portable display market is increasing in size as a large-area display, which requires more power than the power consumption required by existing portable displays. Therefore, power consumption is a very important factor for portable displays, which have a limited power source, such as a battery, and efficiency and lifetime issues must be solved.
효율과 수명, 구동전압 등은 서로 연관이 있으며, 효율이 증가되면 상대적으로 구동전압이 떨어지고, 구동전압이 떨어지면서 구동시 발생되는 주울열(Joule heating)에 의한 유기물질의 결정화가 적어져 결과적으로 수명이 높아지는 경향을 나타낸다.The efficiency, lifetime, and driving voltage are related to each other. As the efficiency increases, the driving voltage drops and the driving voltage drops. As a result, crystallization of the organic material due to Joule heating, which occurs during driving, And the lifetime tends to increase.
하지만 상기 유기물층을 단순히 개선한다고 하여 효율을 극대화시킬 수는 없다. 왜냐하면 각 유기물층 간의 에너지 준위 및 T1 값, 물질의 고유특성(이동도, 계면특성 등) 등이 최적의 조합을 이루었을 때 긴 수명과 높은 효율을 동시에 달성할 수 있기 때문이다.However, simply improving the organic material layer can not maximize the efficiency. This is because, when the optimal combination of the energy level and T1 value between each organic material layer and the intrinsic properties (mobility, interface characteristics, etc.) of the material are achieved, long life and high efficiency can be achieved at the same time.
또한, 최근 유기 전기 발광소자에 있어 정공수송층에서의 발광 문제 및 구동전압 문제를 해결하기 위해서는 정공수송층과 발광층 사이에 발광보조층이 존재하여야 하며, 각각의 발광층(R, G, B)에 따른 서로 다른 발광보조층의 개발이 필요한 시점이다.In order to solve the emission problem and the driving voltage problem in the hole transport layer in recent organic electroluminescent devices, a light-emission-assisting layer must be present between the hole transport layer and the light emitting layer, and the light emitting layer (R, G, B) It is necessary to develop another light-emitting auxiliary layer.
일반적으로 전자수송층에서 발광층으로 전자(electron)가 전달되고 정공(hole)이 정공수송층에서 발광층으로 전달되어 재조합(recombination)에 의해 엑시톤(exciton)이 생성된다. Generally, electrons are transferred from the electron transport layer to the light emitting layer, and holes are transferred from the hole transport layer to the light emitting layer to generate excitons by recombination.
하지만 정공수송층에 사용되는 물질의 경우 낮은 HOMO 값을 가져야 하기 때문에 대부분 낮은 T1 값을 가지며, 이로 인해 발광층에서 생성된 엑시톤(exciton)이 정공수송층으로 넘어가게 되어 결과적으로 정공수송층 내 또는 정공수송층 계면에서 발광하게 되어 유기전기소자의 색순도 저하, 효율 및 수명 감소 현상이 나타나게 된다.However, the material used for the hole transport layer has a low HOMO value and therefore has a low T 1 value. As a result, the exciton generated in the light emitting layer is transferred to the hole transport layer. As a result, in the hole transport layer or the hole transport layer interface The organic electroluminescent device is exposed to light, resulting in deterioration of the color purity of the organic electroluminescent device, efficiency and life span.
또한, 정공 이동도(hole mobility)가 빠른 물질을 사용하여 구동전압을 낮출 수 있으나 정공 이동도(hole mobility)가 전자 이동도(electron mobility) 보다 빨라 발광층 내 전하 불균형(charge unbalance)을 초래하여 유기전기소자의 색순도 및 효율이 저하되고 수명이 짧아지는 문제점이 발생하게 된다.In addition, although the driving voltage can be lowered by using a material having a high hole mobility, the hole mobility is faster than the electron mobility, which causes a charge unbalance in the light emitting layer, There arises a problem that the color purity and efficiency of the electric device are lowered and the service life is shortened.
따라서 높은 T1 값을 가지며, 정공수송층 HOMO 에너지 준위와 발광층의 HOMO 에너지 준위 사이의 HOMO 준위를 갖는 발광보조층이 개발이 절실히 요구된다.Therefore, it is urgently required to develop a light emitting auxiliary layer having a high T 1 value and a HOMO level between the HOMO energy level of the hole transport layer and the HOMO energy level of the light emitting layer.
한편, 유기전기소자의 수명단축 원인 중 하나인 양극전극(ITO)으로부터 금속 산화물이 유기층으로 침투확산되는 것을 지연시키면서, 소자 구동시 발생되는 주울열(Joule heating)에 대해서도 안정된 특성, 즉 높은 유리 전이 온도를 갖는 정공주입층 재료에 대한 개발이 필요하다. 정공수송층 재료의 낮은 유리전이 온도는 소자 구동시, 박막 표면의 균일도를 저하시키는 특성이 있는바, 이는 소자수명에 큰 영향을 미치는 것으로 보고되고 있다. 또한, OLED 소자는 주로 증착 방법에 의해 형성되는데, 증착시 오랫동안 견딜 수 있는 재료, 즉 내열특성이 강한 재료 개발이 필요한 실정이다. On the other hand, while delaying penetration and diffusion of the metal oxide from the anode electrode (ITO), which is one of the causes of shortening the life of the organic electronic device, to the organic layer, stable characteristics such as Joule heating, It is necessary to develop a hole injection layer material having a temperature. The low glass transition temperature of the hole transport layer material has a property of lowering the uniformity of the surface of the thin film when the device is driven, which has been reported to have a great influence on the lifetime of the device. In addition, OLED devices are mainly formed by a deposition method, and it is necessary to develop a material that can withstand a long period of time, that is, a material having high heat resistance characteristics.
즉, 유기전기소자가 갖는 우수한 특징들을 충분히 발휘하기 위해서는 소자 내 유기물층을 이루는 물질, 예컨대 정공주입 물질, 정공수송 물질, 발광 물질, 전자수송 물질, 전자주입 물질, 발광보조층 물질 등이 안정하고 효율적인 재료에 의하여 뒷받침되는 것이 선행되어야 하나, 아직까지 안정되고 효율적인 유기전기소자용 유기물층 재료의 개발이 충분히 이루어지지 않은 상태이다. 따라서, 새로운 재료의 개발이 계속 요구되고 있으며, 특히 발광보조층과 정공수송층의 재료에 대한 개발이 절실히 요구되고 있다. That is, in order to sufficiently exhibit the excellent characteristics of the organic electronic device, a material constituting the organic material layer in the device such as a hole injecting material, a hole transporting material, a light emitting material, an electron transporting material, an electron injecting material, However, the development of a stable and efficient organic material layer for an organic electric device has not been sufficiently developed yet. Therefore, development of new materials is continuously required, and development of materials for the light emission-assisting layer and the hole transporting layer is urgently required.
본 발명은 소자의 높은 발광효율, 낮은 구동전압, 고내열성, 색순도 및 수명을 향상시킬 수 있는 화합물, 이를 이용한 유기전기소자 및 그 전자장치를 제공하는 것을 목적으로 한다.It is an object of the present invention to provide a compound capable of improving a high luminous efficiency, a low driving voltage, a high heat resistance, a color purity and a lifetime of the device, an organic electric device using the same, and an electronic device thereof.
일 측면에서, 본 발명은 하기 화학식으로 표시되는 화합물을 제공한다.In one aspect, the invention provides compounds represented by the formula:
다른 측면에서, 본 발명은 상기 화학식으로 표시되는 화합물을 이용한 유기전기소자 및 그 전자장치를 제공한다.In another aspect, the present invention provides an organic electronic device using the compound represented by the above formula and an electronic device thereof.
본 발명에 따른 화합물을 이용함으로써 소자의 높은 발광효율, 낮은 구동전압, 고내열성을 달성할 수 있고, 소자의 색순도 및 수명을 크게 향상시킬 수 있다. By using the compound according to the present invention, it is possible to achieve a high luminous efficiency, a low driving voltage, and a high heat resistance of the device, and can greatly improve the color purity and lifetime of the device.
도 1은 본 발명에 따른 유기전기발광소자의 예시도이다. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is an illustration of an organic electroluminescent device according to the present invention. FIG.
이하, 본 발명의 실시예를 첨부된 도면을 참조하여 상세하게 설명한다.DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.
각 도면의 구성요소들에 참조부호를 부가함에 있어서, 동일한 구성요소들에 대해서는 비록 다른 도면상에 표시되더라도 가능한 한 동일한 부호를 가지도록 하고 있음에 유의해야 한다. 또한, 본 발명을 설명함에 있어, 관련된 공지 구성 또는 기능에 대한 구체적인 설명이 본 발명의 요지를 흐릴 수 있다고 판단되는 경우에는 그 상세한 설명은 생략한다.It should be noted that, in adding reference numerals to the constituent elements of the drawings, the same constituent elements are denoted by the same reference numerals even though they are shown in different drawings. In the following description of the present invention, a detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear.
또한, 본 발명의 구성 요소를 설명하는 데 있어서, 제 1, 제 2, A, B, (a), (b) 등의 용어를 사용할 수 있다. 이러한 용어는 그 구성 요소를 다른 구성 요소와 구별하기 위한 것일 뿐, 그 용어에 의해 해당 구성 요소의 본질이나 차례 또는 순서 등이 한정되지 않는다. 어떤 구성 요소가 다른 구성요소에 "연결", "결합" 또는 "접속"된다고 기재된 경우, 그 구성 요소는 그 다른 구성요소에 직접적으로 연결되거나 또는 접속될 수 있지만, 각 구성 요소 사이에 또 다른 구성 요소가 "연결", "결합" 또는 "접속"될 수도 있다고 이해되어야 할 것이다.In describing the components of the present invention, terms such as first, second, A, B, (a), and (b) may be used. These terms are intended to distinguish the constituent elements from other constituent elements, and the terms do not limit the nature, order or order of the constituent elements. When a component is described as being "connected", "coupled", or "connected" to another component, the component may be directly connected to or connected to the other component, It should be understood that an element may be "connected," "coupled," or "connected."
본 명세서 및 첨부된 청구의 범위에서 사용된 바와 같이, 달리 언급하지 않는 한, 하기 용어의 의미는 하기와 같다.As used in this specification and the appended claims, unless stated otherwise, the following terms have the following meanings:
본 명세서에서 사용된 용어 "할로" 또는 "할로겐"은 다른 설명이 없는 한 불소(F), 브롬(Br), 염소(Cl) 또는 요오드(I)이다.The term " halo "or" halogen ", as used herein, unless otherwise indicated, is fluorine (F), bromine (Br), chlorine (Cl) or iodine (I).
본 발명에 사용된 용어 "알킬" 또는 "알킬기"는 다른 설명이 없는 한 1 내지 60의 탄소수의 단일결합을 가지며, 직쇄 알킬기, 분지쇄 알킬기, 사이클로알킬(지환족)기, 알킬-치환된 사이클로알킬기, 사이클로알킬-치환된 알킬기를 비롯한 포화 지방족 작용기의 라디칼을 의미한다.As used herein, the term "alkyl" or "alkyl group " refers to a straight or branched Quot; means a radical of a saturated aliphatic group, including an alkyl group, a cycloalkyl-substituted alkyl group.
본 발명에 사용된 용어 "할로알킬기" 또는 "할로겐알킬기"는 다른 설명이 없는 한 할로겐으로 치환된 알킬기를 의미한다.The term "haloalkyl group" or "halogenalkyl group" as used in the present invention means an alkyl group substituted with halogen unless otherwise stated.
본 발명에 사용된 용어 "헤테로알킬기"는 알킬기를 구성하는 탄소 원자 중 하나 이상이 헤테로원자로 대체된 것을 의미한다.The term "heteroalkyl group" as used herein means that at least one of the carbon atoms constituting the alkyl group is replaced by a heteroatom.
본 발명에 사용된 용어 "알켄일기" 또는 "알킨일기"는 다른 설명이 없는 한 각각 2 내지 60의 탄소수의 이중결합 또는 삼중결합을 가지며, 직쇄형 또는 측쇄형 사슬기를 포함하며, 여기에 제한되는 것은 아니다. The term "alkenyl group" or "alkynyl group ", as used herein, unless otherwise indicated, each have a double bond or triple bond of from 2 to 60 carbon atoms and include straight chain or branched chain groups, It is not.
본 발명에 사용된 용어 "시클로알킬"은 다른 설명이 없는 한 3 내지 60의 탄소수를 갖는 고리를 형성하는 알킬을 의미하며, 여기에 제한되는 것은 아니다. The term "cycloalkyl" as used herein, unless otherwise specified, means alkyl which forms a ring having from 3 to 60 carbon atoms, but is not limited thereto.
본 발명에 사용된 용어 "알콕실기", "알콕시기", 또는 "알킬옥시기"는 산소 라디칼이 부착된 알킬기를 의미하며, 다른 설명이 없는 한 1 내지 60의 탄소수를 가지며, 여기에 제한되는 것은 아니다. The term "alkoxyl group "," alkoxy group ", or "alkyloxy group" used in the present invention means an alkyl group to which an oxygen radical is attached and, unless otherwise stated, has a carbon number of 1 to 60, It is not.
본 발명에 사용된 용어 "알켄옥실기", "알켄옥시기", "알켄일옥실기", 또는 "알켄일옥시기"는 산소 라디칼이 부착된 알켄일기를 의미하며, 다른 설명이 없는 한 2 내지 60의 탄소수를 가지며, 여기에 제한되는 것은 아니다. The term "alkenoyl group "," alkenoyl group ", "alkenyloxy group ", or" alkenyloxy group "as used in the present invention means an alkenyl group to which an oxygen radical is attached, , But is not limited thereto.
본 발명에 사용된 용어 "아릴옥실기" 또는 "아릴옥시기"는 산소 라디칼이 부착된 아릴기를 의미하며, 다른 설명이 없는 한 6 내지 60의 탄소수를 가지며, 여기에 제한되는 것은 아니다. As used herein, the term "aryloxyl group" or "aryloxy group" refers to an aryl group attached to an oxygen radical and, unless otherwise stated, has a carbon number of 6 to 60, but is not limited thereto.
본 발명에 사용된 용어 "아릴기" 및 "아릴렌기"는 다른 설명이 없는 한 각각 6 내지 60의 탄소수를 가지며, 이에 제한되는 것은 아니다. 본 발명에서 아릴기 또는 아릴렌기는 단일 고리 또는 다중 고리의 방향족을 의미하며, 이웃한 치환기가 결합 또는 반응에 참여하여 형성된 방향족 고리를 포함한다. 예컨대, 아릴기는 페닐기, 비페닐기, 플루오렌기, 스파이로플루오렌기일 수 있다. The terms "aryl group" and "arylene group ", as used in the present invention, each have 6 to 60 carbon atoms, but are not limited thereto. In the present invention, an aryl group or an arylene group means a single ring or a multicyclic aromatic group, and neighboring substituents include aromatic rings formed by bonding or participating in the reaction. For example, the aryl group may be a phenyl group, a biphenyl group, a fluorene group, or a spirobifluorene group.
접두사 "아릴" 또는 "아르"는 아릴기로 치환된 라디칼을 의미한다. 예를 들어 아릴알킬기는 아릴기로 치환된 알킬기이며, 아릴알켄일기는 아릴기로 치환된 알켄일기이며, 아릴기로 치환된 라디칼은 본 명세서에서 설명한 탄소수를 가진다.The prefix "aryl" or "ar" means a radical substituted with an aryl group. For example, the arylalkyl group is an alkyl group substituted with an aryl group, the arylalkenyl group is an alkenyl group substituted with an aryl group, and the radical substituted with an aryl group has the carbon number described in the present specification.
또한 접두사가 연속으로 명명되는 경우 먼저 기재된 순서대로 치환기가 나열되는 것을 의미한다. 예를 들어, 아릴알콕시기의 경우 아릴기로 치환된 알콕시기를 의미하며, 알콕실카르보닐기의 경우 알콕실기로 치환된 카르보닐기를 의미하며, 또한 아릴카르보닐알켄일기의 경우 아릴카르보닐기로 치환된 알켄일기를 의미하며 여기서 아릴카르보닐기는 아릴기로 치환된 카르보닐기이다.Also, if prefixes are named consecutively, it means that the substituents are listed in the order listed first. For example, the arylalkoxy group means an alkoxy group substituted with an aryl group, the alkoxycarbonyl group means a carbonyl group substituted with an alkoxyl group, and in the case of an arylcarbonylalkenyl group, an alkenyl group substituted with an arylcarbonyl group means Wherein the arylcarbonyl group is a carbonyl group substituted with an aryl group.
본 명세서에서 사용된 용어 "헤테로알킬"은 다른 설명이 없는 한 하나 이상의 헤테로원자를 포함하는 알킬을 의미한다. 본 발명에 사용된 용어 "헤테로아릴기" 또는 "헤테로아릴렌기"는 다른 설명이 없는 한 각각 하나 이상의 헤테로원자를 포함하는 탄소수 2 내지 60의 아릴기 또는 아릴렌기를 의미하며, 여기에 제한되는 것은 아니며, 단일 고리 및 다중 고리 중 적어도 하나를 포함하며, 이웃한 작용기기가 결합하여 형성될 수도 있다.The term "heteroalkyl ", as used herein, unless otherwise indicated, means an alkyl comprising one or more heteroatoms. The term "heteroaryl group" or "heteroarylene group" as used in the present invention means an aryl or arylene group having 2 to 60 carbon atoms each containing at least one heteroatom unless otherwise specified, And includes at least one of a single ring and a multi-ring, and neighboring functional devices may be formed in combination.
본 발명에 사용된 용어 "헤테로고리기"는 다른 설명이 없는 한 하나 이상의 헤테로원자를 포함하고, 2 내지 60의 탄소수를 가지며, 단일 고리 및 다중 고리 중 적어도 하나를 포함하며, 헤테로지방족 고리 및 헤테로방향족 고리를 포함한다. 이웃한 작용기가 결합하여 형성될 수도 있다. The term "heterocyclic group ", as used herein, unless otherwise indicated, includes one or more heteroatoms, has from 2 to 60 carbon atoms, includes at least one of a single ring and multiple rings and includes a heteroaliphatic ring and hetero Aromatic rings. Adjacent functional groups may be combined and formed.
본 명세서에서 사용된 용어 "헤테로원자"는 다른 설명이 없는 한 N, O, S, P 또는 Si를 나타낸다. As used herein, the term "heteroatom " refers to N, O, S, P or Si unless otherwise stated.
또한 "헤테로고리기"는, 고리를 형성하는 탄소 대신 SO2를 포함하는 고리도 포함할 수 있다. 예컨대, "헤테로고리기"는 다음 화합물을 포함한다. The "heterocyclic group" may also include a ring containing SO 2 in place of the carbon forming the ring. For example, the "heterocyclic group" includes the following compounds.
다른 설명이 없는 한, 본 발명에 사용된 용어 "지방족"은 탄소수 1 내지 60의 지방족 탄화수소를 의미하며, "지방족고리"는 탄소수 3 내지 60의 지방족 탄화수소 고리를 의미한다. Unless otherwise stated, the term "aliphatic" as used herein means an aliphatic hydrocarbon having 1 to 60 carbon atoms and an "aliphatic ring" means an aliphatic hydrocarbon ring having 3 to 60 carbon atoms.
다른 설명이 없는 한, 본 발명에 사용된 용어 "고리"는 탄소수 3 내지 60의 지방족고리 또는 탄소수 6 내지 60의 방향족고리 또는 탄소수 2 내지 60의 헤테로고리 또는 이들의 조합으로 이루어진 융합 고리를 말하며, 포화 또는 불포화 고리를 포함한다.Unless otherwise specified, the term "ring" as used herein refers to a fused ring consisting of an aliphatic ring of 3 to 60 carbon atoms or an aromatic ring of 6 to 60 carbon atoms or a heterocycle of 2 to 60 carbon atoms, or combinations thereof, Saturated or unsaturated ring.
전술한 헤테로화합물 이외의 그 밖의 다른 헤테로화합물 또는 헤테로라디칼은 하나 이상의 헤테로원자를 포함하며, 여기에 제한되는 것은 아니다. Other hetero-compounds or hetero-radicals other than the above-mentioned hetero-compounds include, but are not limited to, one or more heteroatoms.
다른 설명이 없는 한, 본 발명에 사용된 용어 "카르보닐"이란 -COR'로 표시되는 것이며, 여기서 R'은 수소, 탄소수 1 내지 20 의 알킬기, 탄소수 6 내지 30 의 아릴기, 탄소수 3 내지 30의 사이클로알킬기, 탄소수 2 내지 20의 알켄일기, 탄소수 2 내지 20의 알킨일기, 또는 이들의 조합인 것이다.Unless otherwise specified, the term "carbonyl" as used herein refers to -COR ', wherein R' is hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, A cycloalkyl group of 2 to 20 carbon atoms, an alkenyl group of 2 to 20 carbon atoms, an alkynyl group of 2 to 20 carbon atoms, or a combination thereof.
다른 설명이 없는 한, 본 발명에 사용된 용어 "에테르"란 -R-O-R'로 표시되는 것이며, 여기서 R 또는 R'은 각각 서로 독립적으로 수소, 탄소수 1 내지 20의 알킬기, 탄소수 6 내지 30의 아릴기, 탄소수 3 내지 30의 사이클로알킬기, 탄소수 2 내지 20의 알켄일기, 탄소수 2 내지 20의 알킨일기, 또는 이들의 조합인 것이다.Unless otherwise indicated, the term "ether" used in the present invention refers to -RO-R 'wherein R or R' are each independently of the other hydrogen, an alkyl group of 1-20 carbon atoms, An aryl group, a cycloalkyl group having 3 to 30 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, or a combination thereof.
또한 명시적인 설명이 없는 한, 본 발명에서 사용된 용어 "치환 또는 비치환된"에서 "치환"은 중수소, 할로겐, 아미노기, 니트릴기, 니트로기, C1~C20의 알킬기, C1~C20의 알콕실기, C1~C20의 알킬아민기, C1~C20의 알킬티오펜기, C6~C20의 아릴티오펜기, C2~C20의 알켄일기, C2~C20의 알킨일기, C3~C20의 시클로알킬기, C6~C20의 아릴기, 중수소로 치환된 C6~C20의 아릴기, C8~C20의 아릴알켄일기, 실란기, 붕소기, 게르마늄기, 및 C2~C20의 헤테로고리기로 이루어진 군으로부터 선택되는 1개 이상의 치환기로 치환됨을 의미하며, 이들 치환기에 제한되는 것은 아니다. One also no explicit description, the terms in the "unsubstituted or substituted", "substituted" is heavy hydrogen, a halogen, an amino group, a nitrile group, a nitro group, C 1 ~ C 20 alkyl group, C 1 ~ C for use in the present invention 20 alkoxy group, C 1 ~ C 20 alkyl amine group, C 1 ~ C 20 alkyl thiophene group, C 6 ~ C 20 aryl thiophene group, C 2 ~ C 20 alkenyl group, C 2 ~ C of 20 alkynyl, C 3 ~ C 20 cycloalkyl group, C 6 ~ C 20 aryl group, of a C 6 ~ C 20 substituted by deuterium aryl group, a C 8 ~ C 20 aryl alkenyl group, a silane group, a boron Means a group substituted with at least one substituent selected from the group consisting of a halogen atom, a halogen atom, a cyano group, a germanium group, and a C 2 to C 20 heterocyclic group.
또한 명시적인 설명이 없는 한, 본 발명에서 사용되는 화학식은 하기 화학식의 지수 정의에 의한 치환기 정의와 동일하게 적용된다.Unless otherwise expressly stated, the formula used in the present invention is applied in the same manner as the definition of the substituent by the definition of the index of the following formula.
여기서, a가 0의 정수인 경우 치환기 R1은 부존재하며, a가 1의 정수인 경우 하나의 치환기 R1은 벤젠 고리를 형성하는 탄소 중 어느 하나의 탄소에 결합하며, a가 2 또는 3의 정수인 경우 각각 다음과 같이 결합하며 이때 R1은 서로 동일하거나 다를 수 있으며, a가 4 내지 6의 정수인 경우 이와 유사한 방식으로 벤젠 고리의 탄소에 결합하며, 한편 벤젠 고리를 형성하는 탄소에 결합된 수소의 표시는 생략한다.When a is an integer of 0, substituent R 1 is absent. When a is an integer of 1, one substituent R 1 is bonded to any one of carbon atoms forming a benzene ring, and when a is an integer of 2 or 3 each coupled as follows: and wherein R 1 may be the same or different from each other, a is the case of 4 to 6 integer, and bonded to the carbon of the benzene ring in a similar way, while the display of the hydrogen bonded to the carbon to form a benzene ring Is omitted.
도 1은 본 발명에 일 실시예에 따른 유기전기소자에 대한 예시도이다.1 is an illustration of an organic electroluminescent device according to an embodiment of the present invention.
도 1을 참조하면, 본 발명에 따른 유기전기소자(100)는 기판(110) 상에 형성된 제 1전극(120), 제 2전극(180) 및 제 1전극(110)과 제 2전극(180) 사이에 본 발명에 따른 화합물을 포함하는 유기물층을 구비한다. 이때, 제 1전극(120)은 애노드(양극)이고, 제 2전극(180)은 캐소드(음극)일 수 있으며, 인버트형의 경우에는 제 1전극이 캐소드이고 제 2전극이 애노드일 수 있다.1, an
유기물층은 제 1전극(120) 상에 순차적으로 정공주입층(130), 정공수송층(140), 발광층(150), 전자수송층(160) 및 전자주입층(170)을 포함할 수 있다. 이때, 발광층(150)을 제외한 나머지 층들이 형성되지 않을 수 있다. 정공저지층, 전자저지층, 발광보조층(151), 버퍼층(141) 등을 더 포함할 수도 있고, 전자수송층(160) 등이 정공저지층의 역할을 할 수도 있을 것이다. The organic material layer may include a hole injecting layer 130, a hole transporting layer 140, a light emitting layer 150, an electron transporting layer 160, and an electron injecting layer 170 sequentially on the first electrode 120. At this time, the remaining layers except the light emitting layer 150 may not be formed. An electron blocking layer, a light emitting auxiliary layer 151, a buffer layer 141, and the like, and the electron transport layer 160 may serve as a hole blocking layer.
또한, 미도시하였지만, 본 발명에 따른 유기전기소자는 제 1전극과 제 2전극 중 적어도 일면 중 상기 유기물층과 반대되는 일면에 형성된 보호층 또는 광효율 개선층(Capping layer)을 더 포함할 수 있다. Also, although not shown, the organic electroluminescent device according to the present invention may further include a protective layer or a light-efficiency-improving layer formed on at least one surface of the first electrode and the second electrode opposite to the organic material layer.
상기 유기물층에 적용되는 본 발명에 따른 화합물은 정공주입층(130), 정공수송층(140), 전자수송층(160), 전자주입층(170), 발광층(150)의 호스트 또는 도펀트 또는 광효율 개선층의 재료로 사용될 수 있을 것이다. 바람직하게는, 본 발명의 화합물은 발광층(150), 정공수송층(140) 및/또는 발광보조층(151)으로 사용될 수 있을 것이다.The compound according to the present invention applied to the organic material layer may be a host or a dopant of the hole injection layer 130, the hole transport layer 140, the electron transport layer 160, the electron injection layer 170, It can be used as a material. Preferably, the compound of the present invention may be used as the light emitting layer 150, the hole transporting layer 140 and / or the light emitting auxiliary layer 151.
한편, 동일한 코어일지라도 어느 위치에 어느 치환기를 결합시키냐에 따라 밴드갭(band gap), 전기적 특성, 계면 특성 등이 달라질 수 있으므로, 코어의 선택 및 이에 결합된 서브(sub)-치환체의 조합도 아주 중요하며, 특히 각 유기물층 간의 에너지 준위 및 T1 값, 물질의 고유특성(이동도, 계면특성 등) 등이 최적의 조합을 이루었을 때 긴 수명과 높은 효율을 동시에 달성할 수 있다.On the other hand, since the band gap, the electrical characteristics, the interface characteristics, and the like can be changed depending on which substituent is bonded at any position even in the same core, the selection of the core and the combination of the sub- Especially when the optimum combination of energy level and T1 value between the organic layers, intrinsic properties (mobility, interface characteristics, etc.) of the materials are achieved, long lifetime and high efficiency can be achieved at the same time.
이미 설명한 것과 같이, 최근 유기 전기 발광소자에 있어 정공수송층에서의 발광 문제를 해결하기 위해서는 정공수송층과 발광층 사이에 발광보조층이 형성하는 것이 바람직하며, 각각의 발광층(R, G, B)에 따른 서로 다른 발광보조층의 개발이 필요한 시점이다. 한편, 발광보조층의 경우 정공수송층 및 발광층(호스트)과의 상호관계를 파악해야하므로 유사한 코어를 사용하더라도 사용되는 유기물층이 달라지면 그 특징을 유추하기는 매우 어려울 것이다. As described above, in order to solve the emission problem in the hole transporting layer in recent organic electroluminescent devices, it is preferable that a light emitting auxiliary layer is formed between the hole transporting layer and the light emitting layer, and the light emitting layer (R, G, B) It is necessary to develop different luminescent auxiliary layers. On the other hand, in the case of the light-emission-assisting layer, it is difficult to deduce the characteristics of the organic layer to be used even if a similar core is used because the relationship between the hole-transport layer and the light-emitting layer (host)
따라서, 본 발명에서는 화학식 1로 표시되는 화합물을 사용하여 발광층 또는 발광보조층을 형성함으로써 각 유기물층 간의 에너지 레벨(level) 및 T1 값, 물질의 고유특성(mobility, 계면특성 등) 등을 최적화하여 유기전기소자의 수명 및 효율을 동시에 향상시킬 수 있다. Accordingly, in the present invention, by forming the light emitting layer or the light emitting auxiliary layer using the compound represented by the general formula (1), the energy level and T1 value between each organic material layer, the mobility of the material, It is possible to simultaneously improve the lifetime and efficiency of the electric element.
본 발명의 일 실시예에 따른 유기전기발광소자는 PVD(physical vapor deposition) 방법을 이용하여 제조될 수 있다. 예컨대, 기판 상에 금속 또는 전도성을 가지는 금속 산화물 또는 이들의 합금을 증착시켜 양극(120)을 형성하고, 그 위에 정공주입층(130), 정공수송층(140), 발광층(150), 전자수송층(160) 및 전자주입층(170)을 포함하는 유기물층을 형성한 후, 그 위에 음극(180)으로 사용할 수 있는 물질을 증착시킴으로써 제조될 수 있다.The organic electroluminescent device according to an embodiment of the present invention can be manufactured using a physical vapor deposition (PVD) method. For example, the anode 120 is formed by depositing a metal or a conductive metal oxide or an alloy thereof on a substrate, and a hole injecting layer 130, a hole transporting layer 140, a light emitting layer 150, and an electron transporting layer 160 and an electron injection layer 170, and then depositing a material usable as the cathode 180 on the organic layer.
또한, 유기물층은 다양한 고분자 소재를 사용하여 증착법이 아닌 용액 공정 또는 솔벤트 프로세스(solvent process), 예컨대 스핀코팅 공정, 노즐 프린팅 공정, 잉크젯 프린팅 공정, 슬롯코팅 공정, 딥코팅 공정, 롤투롤 공정, 닥터 블레이딩 공정, 스크린 프린팅 공정, 또는 열 전사법 등의 방법에 의하여 더 적은 수의 층으로 제조할 수 있다. 본 발명에 따른 유기물층은 다양한 방법으로 형성될 수 있으므로, 그 형성방법에 의해 본 발명의 권리범위가 제한되는 것은 아니다.In addition, the organic material layer may be formed using a variety of polymer materials, not a vapor deposition method, or a solution process or a solvent process such as a spin coating process, a nozzle printing process, an inkjet printing process, a slot coating process, a dip coating process, It is possible to produce a smaller number of layers by a method such as a dipping process, a screen printing process, or a thermal transfer process. Since the organic material layer according to the present invention can be formed by various methods, the scope of the present invention is not limited by the forming method.
본 발명에 따른 유기전기소자는 사용되는 재료에 따라 전면 발광형, 후면 발광형 또는 양면 발광형일 수 있다.The organic electroluminescent device according to the present invention may be of a top emission type, a back emission type, or a both-sided emission type, depending on the material used.
WOLED(White Organic Light Emitting Device)는 고해상도 실현이 용이하고 공정성이 우수한 한편, 기존의 LCD의 칼라필터 기술을 이용하여 제조될 수 있는 이점이 있다. 주로 백라이트 장치로 사용되는 백색 유기발광소자에 대한 다양한 구조들이 제안되고 특허화되고 있다. 대표적으로, R(Red), G(Green), B(Blue) 발광부들을 상호평면적으로 병렬배치(side-by-side) 방식, R, G, B 발광층이 상하로 적층되는 적층(stacking) 방식이 있고, 청색(B) 유기발광층에 의한 전계발광과 이로부터의 광을 이용하여 무기형광체의 자발광(photo-luminescence)을 이용하는 색변환물질(color conversion material, CCM) 방식 등이 있는데, 본 발명은 이러한 WOLED에도 적용될 수 있을 것이다.WOLED (White Organic Light Emitting Device) has advantages of high resolution realization and fairness, and can be manufactured using existing color filter technology of LCD. Various structures for a white organic light emitting device mainly used as a backlight device have been proposed and patented. Typically, a stacking method in which R (Red), G (Green) and B (Blue) light emitting parts are arranged side by side, and R, G and B light emitting layers are stacked up and down , And a color conversion material (CCM) method using photo-luminescence of an inorganic phosphor by using electroluminescence by a blue (B) organic light emitting layer and light from the electroluminescent material. Can be applied to such WOLED.
또한, 본 발명에 따른 유기전기소자는 유기전기발광소자(OLED), 유기태양전지, 유기감광체(OPC), 유기트랜지스터(유기 TFT), 단색 또는 백색 조명용 소자 중 하나일 수 있다.The organic electroluminescent device according to the present invention may be one of an organic electroluminescent (OLED), an organic solar cell, an organic photoconductor (OPC), an organic transistor (organic TFT), and a monochromatic or white illumination device.
본 발명의 다른 실시예는 상술한 본 발명의 유기전기소자를 포함하는 디스플레이장치와, 이 디스플레이장치를 제어하는 제어부를 포함하는 전자장치를 포함할 수 있다. 이때, 전자장치는 현재 또는 장래의 유무선 통신단말일 수 있으며, 휴대폰 등의 이동 통신 단말기, PDA, 전자사전, PMP, 리모콘, 네비게이션, 게임기, 각종 TV, 각종 컴퓨터 등 모든 전자장치를 포함한다.Another embodiment of the present invention can include an electronic device including a display device including the above-described organic electronic device of the present invention and a control unit for controlling the display device. The electronic device may be a current or future wired or wireless communication terminal and includes all electronic devices such as a mobile communication terminal such as a mobile phone, a PDA, an electronic dictionary, a PMP, a remote controller, a navigation device, a game machine, various TVs, and various computers.
이하, 본 발명의 일 측면에 따른 화합물에 대하여 설명한다.Hereinafter, the compound according to one aspect of the present invention will be described.
본 발명의 일측면에 따른 화합물은 하기 화학식 1로 표시된다.A compound according to one aspect of the present invention is represented by the following formula (1).
<화학식 1> ≪ Formula 1 >
상기 화학식 1에서,In Formula 1,
Ar1 내지 Ar4는 ⅰ) 서로 독립적으로 C6~C60의 아릴기; 플루오렌일기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C60의 헤테로고리기; C3~C60의 지방족고리와 C6~C60의 방향족고리의 융합고리기; C1~C50의 알킬기; C2~C20의 알켄일기; C2~C20의 알킨일기; C1~C30의 알콕실기; C6~C30의 아릴옥시기; 및 -L'-N(R')(R");로 이루어진 군에서 선택되거나, 또는 ⅱ) Ar1과 Ar2가 서로 결합하여 고리를 형성할 수 있다. 구체적으로 Ar1 내지 Ar4는 페닐, 바이페닐, 나프틸, 플루오렌, 피리딘, 피리미딘, 카바졸, 벤조싸이오펜 등일 수 있다.Ar 1 to Ar 4 are independently selected from the group consisting of (i) independently of one another a C 6 to C 60 aryl group; A fluorenyl group; A C 2 to C 60 heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P; A fused ring group of an aliphatic ring of C 3 to C 60 and an aromatic ring of C 6 to C 60 ; A C 1 to C 50 alkyl group; An alkenyl group having 2 to 20 carbon atoms; An alkynyl group having 2 to 20 carbon atoms; A C 1 to C 30 alkoxyl group; An aryloxy group of C 6 to C 30 ; And (ii) Ar 1 and Ar 2 may be bonded to each other to form a ring. Specifically, Ar 1 to Ar 4 are each independently selected from the group consisting of phenyl , Biphenyl, naphthyl, fluorene, pyridine, pyrimidine, carbazole, benzothiophene and the like.
a 및 d는 서로 독립적으로 0 내지 4의 정수이며, b 및 c는 서로 독립적으로 0 내지 3의 정수이다.a and d are independently an integer of 0 to 4, and b and c are independently of each other an integer of 0 to 3;
R1 내지 R4는 ⅰ) 서로 독립적으로 중수소; 할로겐; C6~C60의 아릴기; 플루오렌일기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C60의 헤테로고리기; C3~C60의 지방족고리와 C6~C60의 방향족고리의 융합고리기; C1~C50의 알킬기; C2~C20의 알켄일기; C2~C20의 알킨일기; C1~C30의 알콕실기; C6~C30의 아릴옥시기; 및 -L'-N(R')(R");로 이루어진 군에서 선택되거나, 또는 ⅱ) 이웃한 기끼리 서로 결합하여 고리를 형성할 수 있다.R 1 to R 4 are independently selected from the group consisting of: i) deuterium independently of one another; halogen; A C 6 to C 60 aryl group; A fluorenyl group; A C 2 to C 60 heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P; A fused ring group of an aliphatic ring of C 3 to C 60 and an aromatic ring of C 6 to C 60 ; A C 1 to C 50 alkyl group; An alkenyl group having 2 to 20 carbon atoms; An alkynyl group having 2 to 20 carbon atoms; A C 1 to C 30 alkoxyl group; An aryloxy group of C 6 to C 30 ; And -L'-N (R ') (R "); or ii) neighboring groups may be bonded to each other to form a ring.
여기서 상기 고리는 탄소수 3 내지 60의 지방족고리 또는 탄소수 6 내지 60의 방향족고리 또는 탄소수 2 내지 60의 헤테로고리 또는 이들의 조합으로 이루어진 융합 고리를 말하며, 포화 또는 불포화 고리를 포함한다.Wherein said ring is a fused ring consisting of an aliphatic ring having 3 to 60 carbon atoms or an aromatic ring having 6 to 60 carbon atoms or a heterocyclic ring having 2 to 60 carbon atoms, or a combination thereof, and includes a saturated or unsaturated ring.
상기 L'은 단일결합; C6~C60의 아릴렌기; 플루오렌일렌기; C3~C60의 지방족고리와 C6~C60의 방향족고리의 융합고리기; 및 C2~C60의 헤테로고리기;로 이루어진 군에서 선택된다.L 'is a single bond; An arylene group having 6 to 60 carbon atoms; A fluorenylene group; A fused ring group of an aliphatic ring of C 3 to C 60 and an aromatic ring of C 6 to C 60 ; And a C 2 to C 60 heterocyclic group.
상기 R' 및 R"는 서로 독립적으로 C6~C60의 아릴기; 플루오렌일기; C3~C60의 지방족고리와 C6~C60의 방향족고리의 융합고리기; 및 O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C60의 헤테로고리기;로 이루어진 군에서 선택된다.Wherein R 'and R "are independently selected from C 6 ~ C aryl group of 60 to each other; fluorene group; C 3 ~ fused ring group of an aromatic ring of C 60 of aliphatic rings and C 6 ~ C 60; and O, N, And a C 2 to C 60 heterocyclic group containing at least one heteroatom selected from S, Si, and P;
여기서, 상기 아릴기, 플루오렌일기, 헤테로고리기, 융합고리기, 알킬기, 알켄일기, 알킨일기, 알콕실기, 아릴옥시기, 아릴렌기, 플루오렌일렌기가 하나 이상의 치환기로 더 치환되는 경우에는 각각 중수소; 할로겐; 실란기; 실록산기; 붕소기; 게르마늄기; 시아노기; 니트로기; -L'-N(R')(R"); C1~C20의 알킬싸이오기; C1~C20의 알콕실기; C1~C20의 알킬기; C2~C20의 알켄일기; C2~C20의 알킨일기; C6~C20의 아릴기; 중수소로 치환된 C6~C20의 아릴기; 플루오렌일기; C2~C20의 헤테로고리기; C3~C20의 시클로알킬기; C7~C20의 아릴알킬기 및 C8~C20의 아릴알켄일기로 이루어진 군에서 선택된 하나 이상의 치환기로 더 치환될 수 있다.When the aryl group, the fluorenyl group, the heterocyclic group, the fused ring group, the alkyl group, the alkenyl group, the alkynyl group, the alkoxyl group, the aryloxy group, the arylene group and the fluorenylene group are further substituted with one or more substituents, heavy hydrogen; halogen; A silane group; Siloxyl group; Boron group; Germanium group; Cyano; A nitro group; -L ' -N (R ') (R "); An alkyl thio group of C 1 to C 20 ; A C 1 to C 20 alkoxyl group; An alkyl group having 1 to 20 carbon atoms; An alkenyl group having 2 to 20 carbon atoms; An alkynyl group having 2 to 20 carbon atoms; C 6 -C 20 An aryl group; A C 6 -C 20 aryl group substituted by deuterium; A fluorenyl group; A heterocyclic group of C 2 ~ C 20; A C 3 to C 20 cycloalkyl group; An arylalkyl group having 7 to 20 carbon atoms and an arylalkenyl group having 8 to 20 carbon atoms.
구체적으로, 상기 화학식 1로 표시되는 화합물은 하기 화학식 2 또는 화학식 3으로 표시될 수 있다.Specifically, the compound represented by Formula 1 may be represented by Formula 2 or Formula 3 below.
<화학식 2> <화학식 3> ≪ Formula 2 > < EMI ID =
상기 화학식 2 및 3에서, Ar1 ~ Ar4, R1 ~ R4, a, b, c 및 d는 상기 화학식 1에서 정의된 것과 동일하게 정의된다.In Formulas 2 and 3, Ar 1 to Ar 4 , R 1 to R 4 , a, b, c, and d are defined as defined in Formula 1.
보다 구체적으로, 상기 화학식 1 내지 화학식 3으로 표시되는 화합물은 하기 화합물 중 어느 하나일 수 있다.More specifically, the compounds represented by Chemical Formulas 1 to 3 may be any of the following compounds.
다른 실시예로서, 본 발명은 상기 화학식 1로 표시되는 유기전기소자용 화합물을 제공한다.In another embodiment, the present invention provides a compound for an organic electroluminescent device represented by the general formula (1).
또 다른 실시예에서, 본 발명은 상기 화학식 1로 표시되는 화합물을 함유하는 유기전기소자를 제공한다.In another embodiment, the present invention provides an organic electronic device containing the compound represented by the above formula (1).
이때, 유기전기소자는 제 1전극; 제 2전극; 및 상기 제 1전극과 제 2전극 사이에 위치하는 유기물층;을 포함할 수 있으며, 유기물층은 화학식 1로 표시되는 화합물을 포함할 수 있으며, 화학식 1은 유기물층의 정공주입층, 정공수송층, 발광보조층 또는 발광층 중 적어도 하나의 층에 함유될 수 있을 것이다. 즉, 화학식 1로 표시되는 화합물은 정공주입층, 정공수송층, 발광보조층 또는 발광층의 재료로 사용될 수 있다. 구체적으로, 유기물층에 상기 화학식 2 내지 화학식 8로 표시되는 화합물 중 하나를 포함하는 유기전기소자를 제공하며, 보다 구체적으로, 본 발명은 상기 유기물층에 상기 개별 화학식으로 표시되는 화합물을 포함하는 유기전기소자를 제공한다.The organic electroluminescent device includes a first electrode; A second electrode; And an organic material layer disposed between the first electrode and the second electrode. The organic material layer may include a compound represented by Formula 1, wherein Formula 1 is a hole injecting layer, a hole transporting layer, Or the light-emitting layer. That is, the compound represented by the formula (1) can be used as a material for the hole injection layer, the hole transport layer, the light emission assisting layer or the light emitting layer. Specifically, the present invention provides an organic electronic device including one of the compounds represented by Chemical Formulas 2 to 8 in the organic material layer, and more specifically, the present invention provides an organic electronic device including the organic compound Lt; / RTI >
본 발명의 또 다른 실시예에서, 본 발명은 상기 제 1전극의 일측면 중 상기 유기물층과 반대되는 일측 또는 상기 제 2전극의 일측면 중 상기 유기물층과 반대되는 일측 중 적어도 하나에 형성되는 광효율 개선층을 더 포함하는 유기전기소자를 제공한다.In another embodiment of the present invention, the light efficiency improving layer is formed on at least one side of the one side of the first electrode opposite to the organic layer, or one side of the one side of the second electrode opposite to the organic layer, And an organic electroluminescent device.
이하에서, 본 발명에 따른 화학식으로 표시되는 화합물의 합성예 및 유기전기소자의 제조예에 관하여 실시예를 들어 구체적으로 설명하지만, 본 발명이 하기의 실시예로 한정되는 것은 아니다.Hereinafter, the synthesis examples of the compound represented by the formula according to the present invention and the production example of the organic electric device will be concretely described by way of examples, but the present invention is not limited to the following examples.
합성예Synthetic example
본 발명에 따른 화합물(Final Product)은 하기 반응식 1과 같이 Sub 1과 Sub 2를 반응시켜 제조되나 이에 한정되는 것은 아니다.The compound according to the present invention (Final Product) is prepared by reacting Sub 1 and Sub 2 as shown in Reaction Scheme 1 below, but is not limited thereto.
<반응식 1><Reaction Scheme 1>
Ⅰ. Ⅰ. SubSub 1의 합성 Synthesis of 1
반응식 1의 sub 1은 하기 반응식 2의 반응경로에 의해 합성될 수 있으며 이에 한정된 것은 아니다. Sub 1 of Scheme 1 can be synthesized by the reaction path of Scheme 2 below, but is not limited thereto.
<반응식 2><Reaction Scheme 2>
(1) (One) SubSub 1-3 합성 1-3 synthesis
둥근바닥플라스크에 Sub 1-1 (1당량), Sub 1-2 (1당량), Pd2(dba)3 (0.05당량), PPh3 (0.1당량), NaOt-Bu (3당량), toluene (10.5mL / sub1-1 1mmol)을 넣은 후에 100℃에서 반응을 진행시킨다. 반응이 완료되면 ether와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 유기물을 silicagel column 및 재결정하여 Sub 1-3을 얻었다.Pd 2 (dba) 3 (0.05 eq.), PPh 3 (0.1 eq.), NaO t- Bu (3 eq.), Toluene (10.5 mL / sub 1-1 1 mmol), and the reaction was allowed to proceed at 100 ° C. After the reaction was completed, the reaction mixture was extracted with ether and water. The organic layer was dried over MgSO 4 and concentrated. Subsequently, the resulting organic material was subjected to silicagel column and recrystallization to obtain Sub 1-3.
(2) (2) SubSub 1-4 합성 1-4 Synthesis
Sub 1-3 (1당량)을 무수 Ether에 녹이고, 반응물의 온도를 -78℃로 낮추고, n-BuLi (2.5M in hexane) (1.1당량)을 천천히 적가하고 난 후, 반응물을 30분 동안 교반시켰다. 그 후 다시 반응물의 온도를 -78℃로 낮추고 Triisopropylborate (1.5당량)를 적가하였다. 상온에서 교반한 뒤 물을 넣어 희석시키고 2N HCl을 넣어준다. 반응이 완료되면 ethyl acetate와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 유기물을 silicagel column 및 재결정하여 Sub 1-4를 얻었다. Sub 1-3 (1 eq.) Was dissolved in anhydrous ether, the temperature of the reaction was lowered to -78 ° C and n-BuLi (2.5 M in hexane) (1.1 eq.) Was slowly added dropwise and the reaction was stirred for 30 minutes . The temperature of the reaction was then lowered to -78 ° C and triisopropylborate (1.5 eq.) Was added dropwise. After stirring at room temperature, dilute with water and add 2N HCl. After completion of the reaction, the reaction mixture was extracted with ethyl acetate and water. The organic layer was dried over MgSO 4 and concentrated. Subsequently, the resulting organic matter was subjected to silicagel column and recrystallization to obtain Sub 1-4.
(3) (3) SubSub 1-6 합성 1-6 synthesis
둥근바닥플라스크에 Sub 1-4 (1당량)을 넣고, Sub 1-5 (1당량), Pd(PPh3)4 (0.03당량), NaOH (3당량), THF (3mL / 1mmol), 물 (1.5mL / 1mmol)을 넣는다. 그런 후에 80℃~90℃ 상태에서 가열 환류시킨다. 반응이 완료되면 상온에서 증류수를 넣어 희석시키고 메틸렌클로라이드와 물로 추출한다. 유기층을 MgSO4로 건조하여 농축한 후 생성된 화합물을 silicagel column 및 재결정하여 Sub 1-6을 얻었다.Sub 1-5 (1 eq.), Pd (PPh 3 ) 4 (0.03 eq.), NaOH (3 eq.), THF (3 mL / 1.5 mL / 1 mmol). Then, the mixture is heated to reflux at 80 ° C to 90 ° C. When the reaction is complete, dilute with distilled water at room temperature and extract with methylene chloride and water. The organic layer was dried over MgSO 4 and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain Sub 1-6.
(4) (4) SubSub 1 합성 1 synthesis
둥근바닥플라스크에 Sub 1-6 (1당량)을 넣고, Sub 1-7 (1당량), Pd(PPh3)4 (0.03당량), NaOH (3당량), THF (3mL / 1mmol), 물 (1.5mL / 1mmol)을 넣는다. 그런 후에 80℃~90℃ 상태에서 가열 환류시킨다. 반응이 완료되면 상온에서 증류수를 넣어 희석시키고 메틸렌클로라이드와 물로 추출한다. 유기층을 MgSO4로 건조하여 농축한 후 생성된 화합물을 silicagel column 및 재결정하여 Sub 1을 얻었다.Sub 1-6 (1 eq.), Pd (PPh 3 ) 4 (0.03 eq.), NaOH (3 eq.), THF (3 mL / 1.5 mL / 1 mmol). Then, the mixture is heated to reflux at 80 ° C to 90 ° C. When the reaction is complete, dilute with distilled water at room temperature and extract with methylene chloride and water. The organic layer was dried over MgSO 4 and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain Sub 1.
1. One. SubSub 1(1)의 합성 Synthesis of 1 (1)
(1) (One) SubSub 1-3-1 합성 1-3-1 Synthesis
둥근바닥플라스크에 Sub 1-1-1 (4.9g, 20mmol), Sub 1-2-1 (4.1g, 20mmol), Pd2(dba)3 (0.9g, 1mmol), PPh3 (0.5g, 2mmol), NaOt-Bu (5.8g, 60mmol), toluene (210mL)을 넣은 후에 100℃에서 반응을 진행시킨다. 반응이 완료되면 ether와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 유기물을 silicagel column 및 재결정하여 Sub 1-3-1을 5.4g (수율: 84%) 얻었다.Sub 1-1-1 (4.9 g, 20 mmol), Sub 1-2-1 (4.1 g, 20 mmol), Pd 2 (dba) 3 (0.9 g, 1 mmol), PPh 3 (0.5 g, ), NaO t- Bu (5.8 g, 60 mmol), and toluene (210 mL), and the reaction was allowed to proceed at 100 ° C. After the reaction was completed, the reaction mixture was extracted with ether and water. The organic layer was dried over MgSO 4 and concentrated. The resulting organic material was subjected to silicagel column and recrystallization to obtain 5.4 g (yield: 84%) of Sub 1-3-1.
(2) (2) SubSub 1-4-1 합성 1-4-1 Synthesis
Sub 1-3-1 (6.4g, 20mmol)을 무수 Ether에 녹이고, 반응물의 온도를 -78℃로 낮추고, n-BuLi (2.5M in hexane) (1.4g, 22mmol)을 천천히 적가하고 난 후, 반응물을 30분 동안 교반시켰다. 그 후 다시 반응물의 온도를 -78℃로 낮추고 Triisopropyl borate (5.6g, 30mmol)를 적가하였다. 상온에서 교반한 뒤 물을 넣어 희석시키고 2N HCl을 넣어준다. 반응이 완료되면 ethyl acetate와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 유기물을 silicagel column 및 재결정하여 Sub 1-4-1을 4.5g (수율: 78%) 얻었다.Sub 1-3-1 (6.4g, 20mmol) was dissolved in anhydrous ether, the temperature of the reaction was lowered to -78 ° C and n-BuLi (2.5M in hexane) (1.4g, 22mmol) The reaction was stirred for 30 minutes. The temperature of the reaction was then lowered to -78 ° C and triisopropyl borate (5.6 g, 30 mmol) was added dropwise. After stirring at room temperature, dilute with water and add 2N HCl. After the reaction was completed, the reaction mixture was extracted with ethyl acetate and water. The organic layer was dried over MgSO 4 and concentrated. The resulting organic material was subjected to silicagel column and recrystallization to obtain 4.5 g (yield: 78%) of Sub 1-4-1.
(3) (3) SubSub 1-6-1 합성 1-6-1 synthesis
둥근바닥플라스크에 Sub 1-4-1 (5.7g, 20mmol)을 넣고, Sub 1-5-1 (6.3g, 20mmol), Pd(PPh3)4 (0.7g, 0.6mmol), NaOH (2.4g, 60mmol), THF (60mL), 물 (30mL)을 넣는다. 그런 후에 80℃~90℃ 상태에서 가열 환류시킨다. 반응이 완료되면 상온에서 증류수를 넣어 희석시키고 메틸렌클로라이드와 물로 추출한다. 유기층을 MgSO4로 건조하여 농축한 후 생성된 화합물을 silicagel column 및 재결정하여 Sub 1-6-1을 6.8g (수율: 71%) 얻었다.Sub 1-5-1 (6.3 g, 20 mmol), Pd (PPh 3 ) 4 (0.7 g, 0.6 mmol) and NaOH (2.4 g, 20 mmol) were placed in a round bottom flask, , 60 mmol), THF (60 mL) and water (30 mL). Then, the mixture is heated to reflux at 80 ° C to 90 ° C. When the reaction is complete, dilute with distilled water at room temperature and extract with methylene chloride and water. The organic layer was dried over MgSO 4 and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 6.8 g (yield: 71%) of Sub 1-6-1.
(4) (4) SubSub 1(1) 합성 1 (1) Synthesis
둥근바닥플라스크에 Sub 1-6-1 (9.5g, 20mmol)을 넣고, Sub 1-7-1 (5.7g, 20mmol), Pd(PPh3)4 (0.7g, 0.6mmol), NaOH (2.4g, 60mmol), THF (60mL), 물 (30mL)을 넣는다. 그런 후에 80℃~90℃ 상태에서 가열 환류시킨다. 반응이 완료되면 상온에서 증류수를 넣어 희석시키고 메틸렌클로라이드와 물로 추출한다. 유기층을 MgSO4로 건조하여 농축한 후 생성된 화합물을 silicagel column 및 재결정하여 Sub 1(1)을 8.7g (수율: 68%) 얻었다.Put Sub 1-6-1 (9.5g, 20mmol) in a round bottom flask, Sub 1-7-1 (5.7g, 20mmol) , Pd (PPh 3) 4 (0.7g, 0.6mmol), NaOH (2.4g , 60 mmol), THF (60 mL) and water (30 mL). Then, the mixture is heated to reflux at 80 ° C to 90 ° C. When the reaction is complete, dilute with distilled water at room temperature and extract with methylene chloride and water. The organic layer was dried over MgSO 4 and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 8.7 g (Yield: 68%) of Sub 1 (1).
2. 2. SubSub 1(7)의 합성 Synthesis of 1 (7)
둥근바닥플라스크에 Sub 1-6-1 (9.5g, 20mmol)을 넣고, Sub 1-7-2 (7.9g, 20mmol), Pd(PPh3)4 (0.7g, 0.6mmol), NaOH (2.4g, 60mmol), THF (60mL), 물 (30mL)을 넣는다. 그런 후에 80℃~90℃ 상태에서 가열 환류시킨다. 반응이 완료되면 상온에서 증류수를 넣어 희석시키고 메틸렌클로라이드와 물로 추출한다. 유기층을 MgSO4로 건조하여 농축한 후 생성된 화합물을 silicagel column 및 재결정하여 Sub 1(7)을 9.8g (수율: 66%) 얻었다.Sub-1-7-2 (7.9 g, 20 mmol), Pd (PPh 3 ) 4 (0.7 g, 0.6 mmol) and NaOH (2.4 g, 20 mmol) were placed in a round bottom flask. , 60 mmol), THF (60 mL) and water (30 mL). Then, the mixture is heated to reflux at 80 ° C to 90 ° C. When the reaction is complete, dilute with distilled water at room temperature and extract with methylene chloride and water. The organic layer was dried over MgSO 4 and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 9.8 g (yield: 66%) of Sub 1 (7).
3. 3. SubSub 1(10)의 합성 Synthesis of 1 (10)
둥근바닥플라스크에 Sub 1-6-1 (9.5g, 20mmol)을 넣고, Sub 1-7-3 (6.7g, 20mmol), Pd(PPh3)4 (0.7g, 0.6mmol), NaOH (2.4g, 60mmol), THF (60mL), 물 (30mL)을 넣는다. 그런 후에 80℃~90℃ 상태에서 가열 환류시킨다. 반응이 완료되면 상온에서 증류수를 넣어 희석시키고 메틸렌클로라이드와 물로 추출한다. 유기층을 MgSO4로 건조하여 농축한 후 생성된 화합물을 silicagel column 및 재결정하여 Sub 1(10)을 9.0g (수율: 65%) 얻었다.Put Sub 1-6-1 (9.5g, 20mmol) in a round bottom flask, Sub 1-7-3 (6.7g, 20mmol) , Pd (PPh 3) 4 (0.7g, 0.6mmol), NaOH (2.4g , 60 mmol), THF (60 mL) and water (30 mL). Then, the mixture is heated to reflux at 80 ° C to 90 ° C. When the reaction is complete, dilute with distilled water at room temperature and extract with methylene chloride and water. The organic layer was dried over MgSO 4 and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 9.0 g (yield: 65%) of Sub 1 (10).
한편, Sub 1의 예시는 다음과 같으나 이에 한정되는 것은 아니며, 이들의 FD-MS는 하기 표 1과 같다.Examples of Sub 1 include, but are not limited to, the following FD-MSs.
[표 1][Table 1]
Ⅱ. Ⅱ. SubSub 2의 합성 Synthesis of 2
상기 반응식 1의 Sub 2는 하기 반응식 3의 반응경로에 의해 합성될 수 있으나 이에 한정되는 것은 아니다.Sub 2 of Reaction Scheme 1 can be synthesized by the reaction path of the following Reaction Scheme 3, but is not limited thereto.
<반응식 3><Reaction Scheme 3>
둥근바닥플라스크에 Sub 2-1 (1당량), Sub 2-2 (1당량), Pd2(dba)3 (0.05당량), PPh3 (0.1당량), NaOt-Bu (3당량), toluene (10.5mL / sub1-1 1mmol)을 넣은 후에 100℃에서 반응을 진행시킨다. 반응이 완료되면 ether와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 유기물을 silicagel column 및 재결정하여 Sub 2를 얻었다.Sub 2-1 (1 eq), Sub 2-2 (1 eq), Pd 2 (dba) 3 (0.05 eq), PPh 3 (0.1 eq), NaO t- Bu (3 eq) (10.5 mL / sub 1-1 1 mmol), and the reaction was allowed to proceed at 100 ° C. After the reaction was completed, the reaction mixture was extracted with ether and water. The organic layer was dried over MgSO 4 and concentrated. Subsequently, the resulting organic material was subjected to silicagel column and recrystallization to obtain Sub 2.
1. One. SubSub 2-9의 합성 Synthesis of 2-9
둥근바닥플라스크에 Sub 2-1-1 (1.9g, 20mmol), Sub 2-2-1 (5.5g, 20mmol), Pd2(dba)3 (0.9g, 1mmol), PPh3 (0.5g, 2mmol), NaOt-Bu (5.8g, 60mmol), toluene (210mL)을 각각 첨가한 뒤, 100℃에서 24시간 교반환류시킨다. ether와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 유기물을 silicagel column 및 재결정하여 Sub 2-9를 5.2g (수율: 64%) 얻었다.Sub 2-1-1 (1.9 g, 20 mmol), Sub 2-2-1 (5.5 g, 20 mmol), Pd 2 (dba) 3 (0.9 g, 1 mmol), PPh 3 (0.5 g, ), NaO t- Bu (5.8 g, 60 mmol) and toluene (210 mL) were added, and the mixture was refluxed at 100 ° C for 24 hours. ether and water. The organic layer was dried over MgSO 4 and concentrated. The resulting organic material was subjected to silicagel column and recrystallization to obtain 5.2 g (yield: 64%) of Sub 2-9.
2. 2. SubSub 2-14의 합성 Synthesis of 2-14
둥근바닥플라스크에 Sub 2-1-2 (1.9g, 20mmol), Sub 2-2-2 (4.1g, 20mmol), Pd2(dba)3 (0.9g, 1mmol), PPh3 (0.5g, 2mmol), NaOt-Bu (5.8g, 60mmol), toluene (210mL)을 각각 첨가한 뒤, 100℃에서 24시간 교반환류시킨다. ether와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 유기물을 silicagel column 및 재결정하여 Sub 2-14를 2.6g (수율: 60%) 얻었다.Sub 2-1-2 (1.9 g, 20 mmol), Sub 2-2-2 (4.1 g, 20 mmol), Pd 2 (dba) 3 (0.9 g, 1 mmol), PPh 3 (0.5 g, ), NaO t- Bu (5.8 g, 60 mmol) and toluene (210 mL) were added, and the mixture was refluxed at 100 ° C for 24 hours. ether and water. The organic layer was dried over MgSO 4 and concentrated. The resulting organic material was subjected to silicagel column and recrystallization to obtain 2.6 g (yield: 60%) of Sub 2-14.
3. 3. SubSub 2-28의 합성 Synthesis of 2-28
둥근바닥플라스크에 Sub 2-1-3 (3.4g, 20mmol), Sub 2-2-3 (4.7g, 20mmol), Pd2(dba)3 (0.9g, 1mmol), PPh3 (0.5g, 2mmol), NaOt-Bu (5.8g, 60mmol), toluene (210mL)을 각각 첨가한 뒤, 100℃에서 24시간 교반환류시킨다. ether와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 유기물을 silicagel column 및 재결정하여 Sub 2-28을 4.2g (수율: 65%) 얻었다.Sub 2-1-3 (3.4 g, 20 mmol), Sub 2-2-3 (4.7 g, 20 mmol), Pd 2 (dba) 3 (0.9 g, 1 mmol), PPh 3 (0.5 g, ), NaO t- Bu (5.8 g, 60 mmol) and toluene (210 mL) were added, and the mixture was refluxed at 100 ° C for 24 hours. ether and water. The organic layer was dried over MgSO 4 and concentrated. The resulting organic material was purified by silicagel column and recrystallized to obtain 4.2 g (yield: 65%) of Sub 2-28.
한편, Sub 2의 예시는 다음과 같으나 이에 한정되는 것은 아니며, 이들의 FD-MS는 하기 표2와 같다.Meanwhile, examples of Sub 2 are as follows but are not limited thereto, and their FD-MSs are shown in Table 2 below.
[표 2][Table 2]
Ⅲ. 최종 생성물(Ⅲ. The final product ( FinalFinal ProductProduct )의 합성) Synthesis of
둥근바닥플라스크에 Sub 1 (1당량), Sub 2 (1당량), Pd2(dba)3 (0.05당량), PPh3 (0.1당량), NaOt-Bu (3당량), toluene (10.5mL / sub1-1 1mmol)을 넣은 후에 100℃에서 반응을 진행시킨다. 반응이 완료되면 ether와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 유기물을 silicagel column 및 재결정하여 최종 생성물을 얻었다.Pd 2 (dba) 3 (0.05 eq.), PPh 3 (0.1 eq.), NaO t- Bu (3 eq.), Toluene (10.5 mL / sub1-1, 1 mmol), and the reaction was allowed to proceed at 100 < 0 > C. After the reaction was completed, the reaction mixture was extracted with ether and water. The organic layer was dried over MgSO 4 and concentrated. The resulting organic material was subjected to silicagel column and recrystallization to obtain final product.
1. 1-34의 합성1. Synthesis of 1-34
둥근바닥플라스크에 Sub 1(1) (12.8g, 20mmol), Sub 2-28 (6.4g, 20mmol), Pd2(dba)3 (0.9g, 1mmol), PPh3 (0.5g, 2mmol), NaOt-Bu (5.8g, 60mmol), toluene (210mL)을 각각 첨가한 뒤, 100℃에서 24시간 교반환류시킨다. ether와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 유기물을 silicagel column 및 재결정하여 1-34를 13.0g (수율: 74%) 얻었다.(1.2 g, 20 mmol), Sub 2-28 (6.4 g, 20 mmol), Pd 2 (dba) 3 (0.9 g, 1 mmol), PPh 3 (0.5 g, 2 mmol), NaO t- Bu (5.8 g, 60 mmol) and toluene (210 mL) were added thereto, and the mixture was refluxed at 100 ° C for 24 hours. ether and water. The organic layer was dried over MgSO 4 and concentrated. The resulting organic material was purified by silicagel column and recrystallized to obtain 13.0 g (yield: 74%) of 1-34.
2. 1-40의 합성2. Synthesis of 1-40
둥근바닥플라스크에 Sub 1(1) (12.8g, 20mmol), Sub 2-32 (7.2g, 20mmol), Pd2(dba)3 (0.9g, 1mmol), PPh3 (0.5g, 2mmol), NaOt-Bu (5.8g, 60mmol), toluene (210mL)을 각각 첨가한 뒤, 100℃에서 24시간 교반환류시킨다. ether와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 유기물을 silicagel column 및 재결정하여 1-40을 13.8g (수율: 75%) 얻었다.(1.2 g, 20 mmol), Sub 2-32 (7.2 g, 20 mmol), Pd 2 (dba) 3 (0.9 g, 1 mmol), PPh 3 (0.5 g, 2 mmol), NaO t- Bu (5.8 g, 60 mmol) and toluene (210 mL) were added thereto, and the mixture was refluxed at 100 ° C for 24 hours. ether and water. The organic layer was dried over MgSO 4 and concentrated. The resulting organic material was purified by silicagel column and recrystallized to obtain 13.8 g (yield: 75%) of 1-40.
3. 1-49의 합성3. Synthesis of 1-49
둥근바닥플라스크에Sub 1(9) (13.8g, 20mmol), Sub 2-1 (3.4g, 20mmol), Pd2(dba)3 (0.9g, 1mmol), PPh3 (0.5g, 2mmol), NaOt-Bu (5.8g, 60mmol), toluene (210mL)을 각각 첨가한 뒤, 100℃에서 24시간 교반환류시킨다. ether와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 유기물을 silicagel column 및 재결정하여 1-49를 11.8g (수율: 76%) 얻었다.Sub 1 (9) (13.8 g, 20 mmol), Sub 2-1 (3.4 g, 20 mmol), Pd 2 (dba) 3 (0.9 g, 1 mmol), PPh 3 (0.5 g, 2 mmol) t- Bu (5.8 g, 60 mmol) and toluene (210 mL) were added thereto, and the mixture was refluxed at 100 ° C for 24 hours. ether and water. The organic layer was dried over MgSO 4 and concentrated. The resulting organic material was purified by silicagel column and recrystallized to obtain 11.8 g (yield: 76%) of 1-49.
4. 1-61의 합성4. Synthesis of 1-61
둥근바닥플라스크에Sub 1(1) (12.8g, 20mmol), Sub 2-51 (3.3g, 20mmol), Pd2(dba)3 (0.9g, 1mmol), PPh3 (0.5g, 2mmol), NaOt-Bu (5.8g, 60mmol), toluene (210mL)을 각각 첨가한 뒤, 100℃에서 24시간 교반환류시킨다. ether와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 유기물을 silicagel column 및 재결정하여 1-61을 10.6g (수율: 73%) 얻었다.Sub 1 (1) (12.8 g, 20 mmol), Sub 2-51 (3.3 g, 20 mmol), Pd 2 (dba) 3 (0.9 g, 1 mmol), PPh 3 (0.5 g, 2 mmol), NaO t- Bu (5.8 g, 60 mmol) and toluene (210 mL) were added thereto, and the mixture was refluxed at 100 ° C for 24 hours. ether and water. The organic layer was dried over MgSO 4 and concentrated. The resulting organic material was purified by silicagel column and recrystallized to obtain 10.61 g (yield: 73%) of 1-61.
5. 2-7의 합성5. Synthesis of 2-7
둥근바닥플라스크에 Sub 1(2) (12.8g, 20mmol), Sub 2-52 (6.5g, 20mmol), Pd2(dba)3 (0.9g, 1mmol), PPh3 (0.5g, 2mmol), NaOt-Bu (5.8g, 60mmol), toluene (210mL)을 각각 첨가한 뒤, 100℃에서 24시간 교반환류시킨다. ether와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 유기물을 silicagel column 및 재결정하여 2-7을 12.3g (수율: 70%) 얻었다.Sub 2 (12.8 g, 20 mmol), Sub 2-52 (6.5 g, 20 mmol), Pd 2 (dba) 3 (0.9 g, 1 mmol), PPh 3 (0.5 g, 2 mmol), NaO t- Bu (5.8 g, 60 mmol) and toluene (210 mL) were added thereto, and the mixture was refluxed at 100 ° C for 24 hours. ether and water. The organic layer was dried over MgSO 4 and concentrated. The resulting organic material was purified by silicagel column and recrystallized to obtain 12.3 g (yield: 70%) of 2-7.
6. 2-34의 합성6. Synthesis of 2-34
둥근바닥플라스크에 Sub 1(2) (12.8g, 20mmol), Sub 2-28 (6.4g, 20mmol), Pd2(dba)3 (0.9g, 1mmol), PPh3 (0.5g, 2mmol), NaOt-Bu (5.8g, 60mmol), toluene (210mL)을 각각 첨가한 뒤, 100℃에서 24시간 교반환류시킨다. ether와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 유기물을 silicagel column 및 재결정하여 2-34를 13.4g (수율: 76%) 얻었다.Sub 2 (12.8 g, 20 mmol), Sub 2-28 (6.4 g, 20 mmol), Pd 2 (dba) 3 (0.9 g, 1 mmol), PPh 3 (0.5 g, 2 mmol), NaO t- Bu (5.8 g, 60 mmol) and toluene (210 mL) were added thereto, and the mixture was refluxed at 100 ° C for 24 hours. ether and water. The organic layer was dried over MgSO 4 and concentrated. The resulting organic material was purified by silicagel column and recrystallized to obtain 13.4 g (yield: 76%) of 2-34.
7. 2-61의 합성7. Synthesis of 2-61
둥근바닥플라스크에 Sub 1(2) (12.8g, 20mmol), Sub 2-51 (3.3g, 20mmol), Pd2(dba)3 (0.9g, 1mmol), PPh3 (0.5g, 2mmol), NaOt-Bu (5.8g, 60mmol), toluene (210mL)을 각각 첨가한 뒤, 100℃에서 24시간 교반환류시킨다. ether와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 유기물을 silicagel column 및 재결정하여 2-61을 10.5g (수율: 72%) 얻었다.Sub 2 (12.8 g, 20 mmol), Sub 2-51 (3.3 g, 20 mmol), Pd 2 (dba) 3 (0.9 g, 1 mmol), PPh 3 (0.5 g, 2 mmol), NaO t- Bu (5.8 g, 60 mmol) and toluene (210 mL) were added thereto, and the mixture was refluxed at 100 ° C for 24 hours. ether and water. The organic layer was dried over MgSO 4 and concentrated. The resulting organic material was subjected to silicagel column and recrystallization to obtain 10.5 g (yield: 72%) of 2-61.
한편, 상기와 같은 합성예에 따라 제조된 본 발명의 화합물 1-1 내지 1-68, 2-1 내지 2-68의 FD-MS 값은 하기 표 3과 같다The FD-MS values of the compounds 1-1 to 1-68 and 2-1 to 2-68 of the present invention prepared according to the above synthesis examples are shown in Table 3 below
[표 3][Table 3]
유기전기소자의 제조평가Evaluation of manufacturing of organic electric device
[[ 실시예Example 1] 그린유기전기발광소자( 1] Green organic electroluminescent device ( 정공수송층Hole transport layer ))
본 발명의 화합물을 정공수송층 물질로 사용하여 통상적인 방법에 따라 유기전기발광소자를 제작하였다. 먼저, 유기 기판에 형성된 ITO층(양극) 상에 N1-(naphthalen-2-yl)-N4,N4-bis(4-(naphthalen-2-yl(phenyl)amino)phenyl)-N1-phenylbenzene-1,4-diamine (이하 "2-TNATA"로 약기함)을 60nm 두께로 진공증착하여 정공주입층을 형성한 후, 상기 정공주입층 상에 본 발명의 화합물 1-1을 60nm 두께로 진공증착하여 정공수송층을 형성하였다. 이어서, 상기 정공수송층 상에 4,4'-N,N'-dicarbazole-biphenyl (이하 "CBP"로 약기함)을 호스트로, tris(2-phenylpyridine)-iridium (이하 "Ir(ppy)3"으로 약기함)을 도판트로 하여 90:10 중량비로 도핑하여 30nm 두께로 진공증착하여 발광층을 형성하였다. 이어서, 상기 발광층 상에 (1,1'비스페닐)-4-올레이토)비스(2-메틸-8-퀴놀린올레이토)알루미늄(이하 "BAlq"로 약기함)을 10nm 두께로 진공증착하여 정공저지층을 형성하고, 상기 정공저지층 상에 트리스(8-퀴놀리놀)알루미늄 (이하 "Alq3"로 약기함)을 40nm 두께로 진공증착하여 전자수송층을 형성하였다. 이후, 할로젠화 알칼리 금속인 LiF를 0.2nm 두께로 증착하여 전자주입층을 형성하고, 이어서 Al을 150nm의 두께로 증착하여 음극을 형성함으로써 유기전기발광소자를 제조하였다.An organic electroluminescent device was fabricated according to a conventional method using the compound of the present invention as a hole transport layer material. First, N 1 on the ITO layer (anode) formed on an organic substrate - (naphthalen-2-yl) -N 4, N 4 -bis (4- (naphthalen-2-yl (phenyl) amino) phenyl) -N 1 (hereinafter abbreviated as " 2-TNATA ") was vacuum-deposited to a thickness of 60 nm to form a hole injecting layer, and Compound 1-1 of the present invention was coated on the hole injecting layer to a thickness of 60 nm To form a hole transporting layer. Then, tris (2-phenylpyridine) -iridium (hereinafter referred to as "Ir (ppy) 3 ") was added as a host to 4,4'-N, N'-dicarbazole- biphenyl (hereinafter abbreviated as "CBP") on the hole- ) As a dopant was doped at a weight ratio of 90:10, followed by vacuum evaporation to a thickness of 30 nm to form a light emitting layer. Subsequently, aluminum (1,1'bisphenyl) -4-oleato) bis (2-methyl-8-quinolinolato) aluminum (hereinafter abbreviated as "BAlq") was vacuum deposited on the light- forming a blocking layer, and a tris (8-quinolinol) aluminum (hereinafter abbreviated as "Alq 3") on the hole blocking layer to form an electron transport layer was vacuum deposited to a thickness of 40nm. Thereafter, LiF, which is an alkali metal halide, was deposited to a thickness of 0.2 nm to form an electron injection layer, and then Al was deposited to a thickness of 150 nm to form a cathode. Thus, an organic electroluminescent device was manufactured.
[[ 실시예Example 2] 내지 [ 2] to [ 실시예Example 14] 그린유기전기발광소자( 14] green organic electroluminescent device 정공수송층Hole transport layer ))
정공수송층 물질로 본 발명의 화합물 1-1 대신 하기 표 4에 기재된 본 발명의 화합물 1-2~1-4, 1-34, 1-35, 1-40, 2-1~2-4, 2-34, 2-35, 2-40을 사용한 점을 제외하고는 상기 실시예 1과 동일한 방법으로 유기전기발광소자를 제조하였다.The compounds 1-2 to 1-4, 1-34, 1-35, 1-40, 2-1 to 2-4 and 2 of the present invention shown in Table 4 below were used instead of the compound 1-1 of the present invention as the hole transport layer material -34, 2-35, and 2-40 were used as the organic electroluminescent devices.
[[ 비교예Comparative Example 1] One]
정공수송층 물질로 본 발명의 화합물 1-1 대신 하기 비교화합물 A를 사용한 점을 제외하고는 상기 실시예 1과 동일한 방법으로 유기전기발광소자를 제조하였다.An organic electroluminescent device was prepared in the same manner as in Example 1, except that the following compound A was used instead of the compound 1-1 of the present invention as a hole transport layer material.
<비교화합물 A>≪ Comparative Compound A >
[[ 비교예Comparative Example 2] 2]
정공수송층 물질로 본 발명의 화합물 1-1 대신 하기 비교화합물 B를 사용한 점을 제외하고는 상기 실시예 1과 동일한 방법으로 유기전기발광소자를 제조하였다.An organic electroluminescence device was prepared in the same manner as in Example 1, except that the following compound B was used instead of the compound 1-1 of the present invention as the hole transport layer material.
<비교화합물 B>≪ Comparative Compound B >
[[ 비교예Comparative Example 3] 3]
정공수송층 물질로 본 발명의 화합물 1-1 대신 하기 비교화합물 C를 사용한 점을 제외하고는 상기 실시예 1과 동일한 방법으로 유기전기발광소자를 제조하였다.An organic electroluminescence device was prepared in the same manner as in Example 1, except that the following compound C was used in place of the compound 1-1 of the present invention as a hole transport layer material.
<비교화합물 C><Comparative compound C>
본 발명의 실시예 1 내지 실시예 14, 비교예 1 내지 비교예 3에 의해 제조된 유기전기발광소자들에 순바이어스 직류전압을 가하여 포토리서치 (photoresearch)사의 PR-650으로 전기발광(EL) 특성을 측정하였으며, 5000cd/㎡ 기준 휘도에서 맥사이언스사에서 제조된 수명 측정 장비를 통해 T95 수명을 측정하였다. 그 측정 결과는 하기 표 4와 같다.Electruminescence (EL) characteristics were measured with a photoresearch PR-650 by applying a forward bias DC voltage to the organic electroluminescent devices manufactured in Examples 1 to 14 and Comparative Examples 1 to 3 of the present invention And T95 lifetime was measured by a life measuring device manufactured by Mac Science Inc. at a luminance of 5000 cd / m 2. The measurement results are shown in Table 4 below.
[표 4][Table 4]
상기 표 4의 결과로부터 알 수 있듯이, 본 발명의 화합물을 정공수송층의 재료로 사용한 유기전기발광소자는 비교화합물 A 내지 C를 정공수송층의 재료로 사용한 유기전기발광소자에 비해 구동전압, 발광효율 및 수명이 현저히 개선되었다.As can be seen from the results of Table 4, the organic electroluminescent device using the compound of the present invention as the material of the hole transport layer has a higher driving voltage, luminescent efficiency, and light emitting efficiency than the organic electroluminescent device using Comparative Compounds A to C as the material of the hole transport layer. The life span was significantly improved.
즉, NPB인 비교화합물 A및 카바졸(Carbazole) 1개가 연결된 비교화합물 B를 정공수송층의 재료로 사용한 소자보다 카바졸이 2개가 연결된 비교화합물 C와 본 발명의 화합물을 정공수송층 재료로 사용한 소자가 구동전압, 효율 및 수명 면에서 우수한 결과를 나타내었다. 또한, 2개의 카바졸이 각각 3번 위치에 연결기를 통해 연결된 비교화합물 C를 정공수송층 재료로 사용한 소자보다 2개의 카바졸이 각각 2번, 3번 위치 또는 2번, 2번 위치에 연결기를 통해 연결된 본 발명의 화합물을 정공수송층의 재료로 사용한 소자가 효율 및 수명은 비슷하지만 더 낮은 구동전압을 갖는 결과를 나타내었다. 이는 카바졸의 연결 개수, 연결 위치, 또는 다른 치환기의 종류에 따라 화합물의 특성이 현저히 달라지고 또한 이들 화합물을 적용한 소자의 특성도 현저히 달라질 수 있음을 시사하고 있다.
That is, Comparative Compound C, in which two carbazoles are connected, and a device using the compound of the present invention as a hole transporting layer material, compared with an element using Comparative Compound A, which is NPB, and Comparative Compound B, in which one carbazole is connected, And showed excellent results in terms of driving voltage, efficiency and life span. Further, two carbazoles are bonded to the positions 2, 3 or 2 and 2, respectively, of the device using the comparative compound C, in which the two carbazoles are respectively connected to the position 3 through the connecting group, as the hole transport layer material, The device using the compound of the present invention as a material of the hole transport layer showed the same efficiency and lifetime but a lower driving voltage. This suggests that the characteristics of the compound vary significantly depending on the number of carbazole bonds, the position of coupling, or the type of other substituent, and the characteristics of the device to which these compounds are applied may be significantly different.
[[ 실시예Example 15] 레드유기전기발광소자( 15] Red Organic Electroluminescent Device ( 발광보조층The light- ))
본 발명의 화합물을 발광보조층 물질로 사용하여 통상적인 방법에 따라 유기전기발광소자를 제작하였다. 먼저, 유기 기판에 형성된 ITO층(양극) 상에 2-TNATA를 60nm 두께로 진공증착하여 정공주입층을 형성한 후, 상기 정공주입층 상에 4,4-비스[N-(1-나프틸)-N-페닐아미노]비페닐 (이하 “NPD”로 약기함)을 60nm 두께로 진공증착하여 정공수송층을 형성하였다. 이어서, 상기 정공수송층 상에 본 발명의 화합물 1-1을 20nm 두께로 진공증착하여 발광보조층을 형성하고, 상기 발광보조층 상에 CBP를 호스트로, bis-(1-phenylisoquinolyl)iridium(Ⅲ)acetylacetonate (이하 “(piq)2Ir(acac)”로 약기함)를 도판트로 하여 95:5 중량비로 도핑하여 30nm 두께로 진공증착하여 발광층을 형성하였다. 이어서, 상기 발광층 상에 BAlq를 10nm 두께로 진공증착하여 정공저지층을 형성하고, 상기 정공저지층 상에 Alq3을 40nm 두께로 진공증착하여 전자수송층을 형성하였다. 이후, 할로젠화 알칼리 금속인 LiF를 0.2nm 두께로 증착하여 전자주입층을 형성하고, 이어서 Al을 150nm의 두께로 증착하여 음극을 형성함으로써 유기전기발광소자를 제조하였다.An organic electroluminescent device was fabricated according to a conventional method using the compound of the present invention as a light emitting auxiliary layer material. First, 2-TNATA was vacuum deposited on the ITO layer (anode) formed on the organic substrate to a thickness of 60 nm to form a hole injection layer, and 4,4-bis [N- (1-naphthyl ) -N-phenylamino] biphenyl (hereinafter abbreviated as " NPD ") was vacuum deposited to a thickness of 60 nm to form a hole transport layer. Subsequently, Compound 1-1 of the present invention was vacuum-deposited on the hole transport layer to a thickness of 20 nm to form a light-emission-assisting layer, and bis- (1-phenylisoquinolyl) iridium (III) acetylacetonate (hereinafter abbreviated as " (piq) 2 Ir (acac) ") as a dopant at a weight ratio of 95: 5 and vacuum evaporated to a thickness of 30 nm to form a light emitting layer. Subsequently, BAlq was vacuum deposited on the light emitting layer to form a hole blocking layer to form a hole blocking layer, and Alq 3 was vacuum deposited to a thickness of 40 nm on the hole blocking layer to form an electron transporting layer. Thereafter, LiF, which is an alkali metal halide, was deposited to a thickness of 0.2 nm to form an electron injection layer, and then Al was deposited to a thickness of 150 nm to form a cathode. Thus, an organic electroluminescent device was manufactured.
[[ 실시예Example 16] 내지 [ 16] to [ 실시예Example 150] 레드유기전기발광소자( 150] red organic electroluminescent device ( 발광보조층The light- ))
발광보조층 물질로 본 발명의 화합물 1-1 대신 하기 표 5에 기재된 본 발명의 화합물 1-2~1-68, 2-1~2-68을 사용한 점을 제외하고는 상기 실시예 15와 동일한 방법으로 유기전기발광소자를 제조하였다.As the luminescent auxiliary layer material, the same compounds as those of Example 15 were used, except that the compounds 1-2 to 1-68 and 2-1 to 2-68 of the present invention described in the following Table 5 were used instead of the compound 1-1 of the present invention Thereby preparing an organic electroluminescent device.
[[ 비교예Comparative Example 4] 4]
발광보조층을 형성하지 않은 점을 제외하고는 상기 실시예 15와 동일한 방법으로 유기전기발광소자를 제조하였다.An organic electroluminescent device was prepared in the same manner as in Example 15 except that no luminescent auxiliary layer was formed.
[[ 비교예Comparative Example 5] 5]
발광보조층 물질로 본 발명의 화합물 1-1 대신 상기 비교화합물 A를 사용한 점을 제외하고는 상기 실시예 15와 동일한 방법으로 유기전기발광소자를 제조하였다. An organic electroluminescent device was prepared in the same manner as in Example 15, except that the compound A was used in place of the compound 1-1 of the present invention as the luminescent auxiliary layer material.
[[ 비교예Comparative Example 6] 6]
발광보조층 물질로 본 발명의 화합물 1-1 대신 상기 비교화합물 B를 사용한 점을 제외하고는 상기 실시예 15와 동일한 방법으로 유기전기발광소자를 제조하였다.An organic electroluminescence device was prepared in the same manner as in Example 15, except that the compound B was used instead of the compound 1-1 of the present invention as the luminescent auxiliary layer material.
[[ 비교예Comparative Example 7] 7]
발광보조층 물질로 본 발명의 화합물 1-1 대신 상기 비교화합물 C를 사용한 점을 제외하고는 상기 실시예 15와 동일한 방법으로 유기전기발광소자를 제조하였다.An organic electroluminescent device was prepared in the same manner as in Example 15, except that the compound C was used instead of the compound 1-1 of the present invention as the luminescent auxiliary layer material.
본 발명의 실시예 15 내지 실시예 150, 비교예 4 내지 비교예 7에 의해 제조된 유기전기발광소자들에 순바이어스 직류전압을 가하여 포토리서치 (photoresearch)사의 PR-650으로 전기발광(EL) 특성을 측정하였으며, 2500cd/㎡ 기준 휘도에서 맥사이언스사에서 제조된 수명 측정 장비를 통해 T95 수명을 측정하였다. 그 측정 결과는 하기 표 5와 같다.Electruminescence (EL) characteristics were measured with a photoresearch PR-650 by applying a forward bias DC voltage to the organic electroluminescent devices manufactured in Examples 15 to 150 and Comparative Examples 4 to 7 of the present invention And the T95 lifetime was measured using a life measuring device manufactured by Mac Science Inc. at a luminance of 2500 cd / m 2. The measurement results are shown in Table 5 below.
[표 5][Table 5]
[[ 실시예Example 151] 그린유기전기발광소자( 151] green organic electroluminescent device 발광보조층The light- ))
본 발명의 화합물을 발광보조층 물질로 사용하여 통상적인 방법에 따라 유기전기발광소자를 제작하였다. 먼저, 유기 기판에 형성된 ITO층(양극) 상에 2-TNATA를 60nm 두께로 진공증착하여 정공주입층을 형성한 후, 상기 정공주입층 상에 NPD를 60nm 두께로 진공증착하여 정공수송층을 형성하였다. 이어서, 상기 정공수송층 상에 본 발명의 화합물 1-1을 20nm 두께로 진공증착하여 발광보조층을 형성하고, 상기 발광보조층 상에 CBP를 호스트로, Ir(ppy)3을 도판트로 하여 95:5 중량비로 도핑하여 30nm 두께로 진공증착하여 발광층을 형성하였다. 이어서, 상기 발광층 상에 BAlq를 10nm 두께로 진공증착하여 정공저지층을 형성하고, 상기 정공저지층 상에 Alq3을 40nm 두께로 진공증착하여 전자수송층을 형성하였다. 이후, 할로젠화 알칼리 금속인 LiF를 0.2nm 두께로 증착하여 전자주입층을 형성하고, 이어서 Al을 150nm의 두께로 증착하여 음극을 형성함으로써 유기전기발광소자를 제조하였다.An organic electroluminescent device was fabricated according to a conventional method using the compound of the present invention as a light emitting auxiliary layer material. First, 2-TNATA was vacuum deposited on the ITO layer (anode) formed on the organic substrate to form a hole injection layer, and then a hole transport layer was formed by vacuum depositing NPD on the hole injection layer to a thickness of 60 nm . Subsequently, Compound 1-1 of the present invention was vacuum deposited on the hole transport layer to form a light emitting auxiliary layer. CBP was used as a host and Ir (ppy) 3 was used as a dopant. 5, and vacuum evaporated to a thickness of 30 nm to form a light emitting layer. Subsequently, BAlq was vacuum deposited on the light emitting layer to form a hole blocking layer to form a hole blocking layer, and Alq 3 was vacuum deposited to a thickness of 40 nm on the hole blocking layer to form an electron transporting layer. Thereafter, LiF, which is an alkali metal halide, was deposited to a thickness of 0.2 nm to form an electron injection layer, and then Al was deposited to a thickness of 150 nm to form a cathode. Thus, an organic electroluminescent device was manufactured.
[[ 실시예Example 152] 내지 [ 152] to [ 실시예Example 286] 그린유기전기발광소자( 286] green organic electroluminescent device 발광보조층The light- ))
발광보조층 물질로 본 발명의 화합물 1-1 대신 하기 표 6에 기재된 본 발명의 화합물 1-2~1-68, 2-1~2-68을 사용한 점을 제외하고는 상기 실시예 151과 동일한 방법으로 유기전기발광소자를 제조하였다.The same procedure as in Example 151 was repeated except that the compounds 1-1 to 1-68 and 2-1 to 2-68 of the present invention described in the following Table 6 were used instead of the compound 1-1 of the present invention as the luminescent auxiliary layer material Thereby preparing an organic electroluminescent device.
[[ 비교예Comparative Example 8] 8]
발광보조층을 형성하지 않은 점을 제외하고는 상기 실시예 151과 동일한 방법으로 유기전기발광소자를 제조하였다.An organic electroluminescent device was prepared in the same manner as in Example 151 except that no light-emitting auxiliary layer was formed.
[[ 비교예Comparative Example 9] 9]
발광보조층 물질로 본 발명의 화합물 1-1 대신 상기 비교화합물 A를 사용한 점을 제외하고는 상기 실시예 151과 동일한 방법으로 유기전기발광소자를 제조하였다.An organic electroluminescent device was prepared in the same manner as in Example 151, except that the compound A was used instead of the compound 1-1 of the present invention as the luminescent auxiliary layer material.
[[ 비교예Comparative Example 10] 10]
발광보조층 물질로 본 발명의 화합물 1-1 대신 상기 비교화합물 B를 사용한 점을 제외하고는 상기 실시예 151과 동일한 방법으로 유기전기발광소자를 제조하였다.An organic electroluminescent device was prepared in the same manner as in Example 151, except that the compound B was used instead of the compound 1-1 of the present invention as the luminescent auxiliary layer material.
[[ 비교예Comparative Example 11] 11]
발광보조층 물질로 본 발명의 화합물 1-1 대신 상기 비교화합물 C를 사용한 점을 제외하고는 상기 실시예 151과 동일한 방법으로 유기전기발광소자를 제조하였다.An organic electroluminescent device was prepared in the same manner as in Example 151, except that the compound C was used instead of the compound 1-1 of the present invention as the luminescent auxiliary layer material.
본 발명의 실시예 151 내지 실시예 286, 비교예 8 내지 비교예 11에 의해 제조된 유기전기발광소자들에 순바이어스 직류전압을 가하여 포토리서치(photoresearch)사의 PR-650으로 전기발광(EL) 특성을 측정하였으며, 5000cd/㎡ 기준 휘도에서 맥사이언스사에서 제조된 수명 측정 장비를 통해 T95 수명을 측정하였다. 그 측정 결과는 하기 표 6과 같다.Electruminescence (EL) characteristics were measured with a photoresearch PR-650 by applying a forward bias DC voltage to the organic electroluminescent devices manufactured in Examples 151 to 286 and Comparative Examples 8 to 11 of the present invention And T95 lifetime was measured by a life measuring device manufactured by Mac Science Inc. at a luminance of 5000 cd / m 2. The measurement results are shown in Table 6 below.
[표 6]][Table 6]]
[[ 실시예Example 287] 블루유기전기발광소자( 287] Blue organic electroluminescent device ( 발광보조층The light- ))
본 발명의 화합물을 발광보조층 물질로 사용하여 통상적인 방법에 따라 유기전기발광소자를 제작하였다. 먼저, 유기 기판에 형성된 ITO층(양극) 상에 2-TNATA를 60nm 두께로 진공증착하여 정공주입층을 형성한 후, 상기 정공주입층 상에 NPD를 60nm 두께로 진공증착하여 정공수송층을 형성하였다. 이어서, 상기 정공수송층 상에 본 발명의 화합물 1-1을 20nm 두께로 진공증착하여 발광보조층을 형성하고, 상기 발광보조층 상에 9,10-di(naphthalen-2-yl)anthracene을 호스트로, BD-052X (Idemitsukosan 제조)를 도판트로 하여 93:7 중량비로 도핑하여 30nm 두께로 진공증착하여 발광층을 형성하였다. 이어서, 상기 발광층 상에 BAlq를 10nm 두께로 진공증착하여 정공저지층을 형성하고, 상기 정공저지층 상에 Alq3을 40nm 두께로 진공증착하여 전자수송층을 형성하였다. 이후, 할로젠화 알칼리 금속인 LiF를 0.2nm 두께로 증착하여 전자주입층을 형성하고, 이어서 Al을 150nm의 두께로 증착하여 음극을 형성함으로써 유기전기발광소자를 제조하였다.An organic electroluminescent device was fabricated according to a conventional method using the compound of the present invention as a light emitting auxiliary layer material. First, 2-TNATA was vacuum deposited on the ITO layer (anode) formed on the organic substrate to form a hole injection layer, and then a hole transport layer was formed by vacuum depositing NPD on the hole injection layer to a thickness of 60 nm . Subsequently, the compound 1-1 of the present invention was vacuum-deposited to a thickness of 20 nm on the hole transport layer to form a light emission-assisting layer, and 9,10-di (naphthalen-2-yl) anthracene was hosted on the light- , BD-052X (manufactured by Idemitsukosan) as a dopant and doped in a weight ratio of 93: 7, followed by vacuum evaporation to a thickness of 30 nm to form a light emitting layer. Subsequently, BAlq was vacuum deposited on the light emitting layer to form a hole blocking layer to form a hole blocking layer, and Alq 3 was vacuum deposited to a thickness of 40 nm on the hole blocking layer to form an electron transporting layer. Thereafter, LiF, which is an alkali metal halide, was deposited to a thickness of 0.2 nm to form an electron injection layer, and then Al was deposited to a thickness of 150 nm to form a cathode. Thus, an organic electroluminescent device was manufactured.
[[ 실시예Example 288] 내지 [ 288] to [ 실시예Example 422] 블루유기전기발광소자( 422] Blue organic electroluminescent device ( 발광보조층The light- ))
발광보조층 물질로 본 발명의 화합물 1-1 대신 하기 표 7에 기재된 본 발명의 화합물 1-2~1-68, 2-1~2-68을 사용한 점을 제외하고는 상기 실시예 287과 동일한 방법으로 유기전기발광소자를 제조하였다.The same procedure as in Example 287 was repeated except that the compounds 1-2 to 1-68 and 2-1 to 2-68 of the present invention described in the following Table 7 were used instead of the compound 1-1 of the present invention as the luminescent auxiliary layer material Thereby preparing an organic electroluminescent device.
[[ 비교예Comparative Example 12] 12]
발광보조층을 형성하지 않은 점을 제외하고는 상기 실시예 287과 동일한 방법으로 유기전기발광소자를 제조하였다.An organic EL device was prepared in the same manner as in Example 287 except that no light-emitting auxiliary layer was formed.
[[ 비교예Comparative Example 13] 13]
발광보조층 물질로 본 발명의 화합물 1-1 대신 상기 비교화합물 A를 사용한 점을 제외하고는 상기 실시예 287과 동일한 방법으로 유기전기발광소자를 제조하였다.An organic electroluminescent device was prepared in the same manner as in Example 287, except that the compound A was used instead of the compound 1-1 of the present invention as the luminescent auxiliary layer material.
[[ 비교예Comparative Example 14] 14]
발광보조층 물질로 본 발명의 화합물 1-1 대신 상기 비교화합물 B를 사용한 점을 제외하고는 상기 실시예 287과 동일한 방법으로 유기전기발광소자를 제조하였다.An organic electroluminescent device was prepared in the same manner as in Example 287, except that the compound B was used instead of the compound 1-1 of the present invention as the luminescent auxiliary layer material.
[[ 비교예Comparative Example 15] 15]
발광보조층 물질로 본 발명의 화합물 1-1 대신 상기 비교화합물 C를 사용한 점을 제외하고는 상기 실시예 287과 동일한 방법으로 유기전기발광소자를 제조하였다.An organic electroluminescent device was prepared in the same manner as in Example 287, except that the compound C was used instead of the compound 1-1 of the present invention as the luminescent auxiliary layer material.
본 발명의 실시예 287 내지 실시예 422, 비교예 12 내지 비교예 15에 의해 제조된 유기전기발광소자들에 순바이어스 직류전압을 가하여 포토리서치(photoresearch)사의 PR-650으로 전기발광(EL) 특성을 측정하였으며, 500cd/㎡ 기준 휘도에서 맥사이언스사에서 제조된 수명 측정 장비를 통해 T95 수명을 측정하였다. 그 측정 결과는 하기 표 7과 같다.Electruminescence (EL) characteristics of the organic electroluminescent devices prepared in Examples 287 to 422 and Comparative Examples 12 to 15 of the present invention were evaluated by applying a forward bias DC voltage to PR-650 of a photoresearch company And the T95 lifetime was measured using a life measuring device manufactured by Mac Science Inc. at a luminance of 500 cd / m 2. The measurement results are shown in Table 7 below.
[표 7][Table 7]
상기 표 5, 표 6 및 표 7의 결과로부터 알 수 있듯이, 본 발명의 화합물을 발광보조층의 재료로 사용한 유기전기발광소자는 발광보조층을 형성하지 않은 유기전기발광소자와 비교화합물 A 내지 C를 발광보조층의 재료로 사용한 유기전기발광소자에 비하여 구동전압, 발광효율 및 수명이 현저히 개선되었다.As can be seen from the results of Tables 5, 6 and 7, the organic electroluminescence device using the compound of the present invention as the material of the light-emission-assisting layer can be manufactured by mixing the organic electroluminescence device without the light- Emitting efficiency and life span as compared with the organic electroluminescent device using the organic electroluminescent material as the material of the light-emission assisting layer.
즉, 발광보조층을 형성하지 않은 소자보다 비교화합물 A 내지 C, 본 발명의 화합물을 발광보조층의 재료로 사용한 소자가 발광효율 및 수명이 향상되었음을 확인할 수 있으며, 또한, 비교화합물 A, B를 발광보조층 재료로 사용한 소자보다 2개의 카바졸이 연결된 비교화합물 C와 본 발명의 화합물을 발광보조층의 재료로 사용한 소자가 효율과 수명 면에서 월등히 우수한 결과를 확인하였다. 이는 2개의 카바졸이 연결기를 통해 연결된 화합물들이 단독으로 발광보조층으로 사용될 경우 높은 T1 에너지 레벨과 깊은 HOMO 에너지 레벨을 갖게 되는데 이로 인해 정공과 전자가 전하균형 (charge balance)을 이루고 정공수송층 계면이 아닌 발광층 내부에서 발광이 이루어져 더 높은 효율 및 수명을 극대화시켜주기 때문인 것으로 판단된다.That is, it can be seen that devices using Comparative Compounds A to C and the compound of the present invention as a material of the light-emission assisting layer have improved luminescence efficiency and lifetime, compared with the device not having the luminescent auxiliary layer, and Comparative Compounds A and B It was confirmed that the device using the comparative compound C in which two carbazoles are connected and the compound of the present invention as a material of the light emitting auxiliary layer, which are superior to the device used as the light emitting auxiliary layer material, are far superior in terms of efficiency and life span. This is because when the compounds connected through the two carbazoles are individually used as a light emitting auxiliary layer, they have a high T1 energy level and a deep HOMO energy level, so that the holes and electrons have a charge balance and a hole transport layer interface Emitting layer is formed within the light emitting layer, thereby maximizing the efficiency and lifetime.
또한, 비교화합물 A 내지 C를 발광보조층의 재료로 사용한 비교예 5 내지 7, 9 내지 11, 13 내지 15처럼 일반적으로 발광보조층을 사용하였을 경우, 발광보조층을 사용하지 않았을 때보다 효율 및 수명은 향상되지만 구동전압이 높아지는 현상을 확인할 수 있다. 그러나 본 발명의 화합물을 발광보조층의 재료로 사용한 소자의 결과를 보면 효율 및 수명은 향상시키면서 구동전압은 높아지지 않음을 확인하였다. 즉 본 발명의 화합물을 발광보조층의 재료로 사용한 소자는 효율과 수명을 향상시켜줌과 동시에 구동전압도 높아지지 않고 동등하거나 낮아져 소비전력을 감소시킬 수 있는 가장 우수한 결과를 나타내었다. 이는 상기 표 4에서 설명한 것과 같이 카바졸의 연결 개수, 연결 위치, 또는 다른 치환기의 종류에 따라 화합물의 특성이 현저히 달라지고 또한 이들 화합물을 적용한 소자의 특성도 현저히 달라질 수 있음을 시사하고 있다.In addition, when the light-emission-assisting layer was generally used as Comparative Examples 5 to 7, 9 to 11, and 13 to 15 in which Comparative Compounds A to C were used as materials for the light-emission-assisting layer, The lifetime is improved but the driving voltage is increased. However, the results of the device using the compound of the present invention as the material of the light-emitting auxiliary layer show that the driving voltage is not increased while improving the efficiency and lifetime. That is, the device using the compound of the present invention as the material of the light-emitting auxiliary layer improves the efficiency and lifetime, and at the same time, the driving voltage is not increased, which is equal to or lower than that of the device. This suggests that the characteristics of the compound are significantly different depending on the number of carbazole bonds, the position of coupling, or the kind of other substituent, as described in Table 4 above, and the characteristics of the device to which these compounds are applied may also be significantly different.
이상의 설명은 본 발명을 예시적으로 설명한 것에 불과한 것으로, 본 발명이 속하는 기술분야에서 통상의 지식을 가지는 자라면 본 발명의 본질적인 특성에서 벗어나지 않는 범위에서 다양한 변형이 가능할 것이다. 따라서, 본 명세서에 개시된 실시예들은 본 발명을 한정하기 위한 것이 아니라 설명하기 위한 것이고, 이러한 실시예에 의하여 본 발명의 사상과 범위가 한정되는 것은 아니다. 본 발명의 보호범위는 아래의 청구범위에 의하여 해석되어야 하며, 그와 동등한 범위 내에 있는 모든 기술은 본 발명의 권리범위에 포함하는 것으로 해석되어야 할 것이다.While the present invention has been described with reference to exemplary embodiments, it is to be understood that the invention is not limited to the disclosed exemplary embodiments. Accordingly, the embodiments disclosed herein are intended to be illustrative rather than limiting, and the spirit and scope of the present invention is not limited by these embodiments. The scope of protection of the present invention should be construed according to the following claims, and all the techniques within the scope of the same should be construed as being included in the scope of the present invention.
100: 유기전기소자
110: 기판
120: 제 1전극
130: 정공주입층
140: 정공수송층
141: 버퍼층
150: 발광층
151: 발광보조층
160: 전자수송층
170: 전자주입층
180: 제 2전극100: organic electric element 110: substrate
120: first electrode 130: hole injection layer
140: Hole transport layer 141: Buffer layer
150: light emitting layer 151: light emitting auxiliary layer
160: electron transport layer 170: electron injection layer
180: second electrode
Claims (10)
<화학식 1>
[상기 화학식 1에서,
Ar1 내지 Ar4는 ⅰ) 서로 독립적으로 C6~C60의 아릴기; 플루오렌일기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C60의 헤테로고리기; C3~C60의 지방족고리와 C6~C60의 방향족고리의 융합고리기; C1~C50의 알킬기; C2~C20의 알켄일기; C2~C20의 알킨일기; C1~C30의 알콕실기; C6~C30의 아릴옥시기; 및 -L'-N(R')(R");로 이루어진 군에서 선택되거나, 또는 ⅱ) Ar1과 Ar2가 서로 결합하여 고리를 형성하며,
a 및 d는 서로 독립적으로 0 내지 4의 정수이며,
b 및 c는 서로 독립적으로 0 내지 3의 정수이며,
R1 내지 R4는 ⅰ) 서로 독립적으로 중수소; 할로겐; C6~C60의 아릴기; 플루오렌일기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C60의 헤테로고리기; C3~C60의 지방족고리와 C6~C60의 방향족고리의 융합고리기; C1~C50의 알킬기; C2~C20의 알켄일기; C2~C20의 알킨일기; C1~C30의 알콕실기; C6~C30의 아릴옥시기; 및 -L'-N(R')(R");로 이루어진 군에서 선택되거나, 또는 ⅱ) 이웃한 기끼리 서로 결합하여 고리를 형성하며,
상기 L'은 단일결합; C6~C60의 아릴렌기; 플루오렌일렌기; C3~C60의 지방족고리와 C6~C60의 방향족고리의 융합고리기; 및 C2~C60의 헤테로고리기;로 이루어진 군에서 선택되며,
상기 R' 및 R"는 서로 독립적으로 C6~C60의 아릴기; 플루오렌일기; C3~C60의 지방족고리와 C6~C60의 방향족고리의 융합고리기; 및 O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C60의 헤테로고리기;로 이루어진 군에서 선택된다.
여기서, 상기 아릴기, 플루오렌일기, 헤테로고리기, 융합고리기, 알킬기, 알켄일기, 알킨일기, 알콕실기, 아릴옥시기, 아릴렌기, 플루오렌일렌기가 하나 이상의 치환기로 더 치환되는 경우에는 각각 중수소; 할로겐; 실란기; 실록산기; 붕소기; 게르마늄기; 시아노기; 니트로기; -L'-N(R')(R"); C1~C20의 알킬싸이오기; C1~C20의 알콕실기; C1~C20의 알킬기; C2~C20의 알켄일기; C2~C20의 알킨일기; C6~C20의 아릴기; 중수소로 치환된 C6~C20의 아릴기; 플루오렌일기; C2~C20의 헤테로고리기; C3~C20의 시클로알킬기; C7~C20의 아릴알킬기; 및 C8~C20의 아릴알켄일기;로 이루어진 군에서 선택된 하나 이상의 치환기로 더 치환된다.]A compound represented by the following formula (1).
≪ Formula 1 >
[In the above formula (1)
Ar 1 to Ar 4 are independently selected from the group consisting of (i) independently of one another a C 6 to C 60 aryl group; A fluorenyl group; A C 2 to C 60 heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P; A fused ring group of an aliphatic ring of C 3 to C 60 and an aromatic ring of C 6 to C 60 ; A C 1 to C 50 alkyl group; An alkenyl group having 2 to 20 carbon atoms; An alkynyl group having 2 to 20 carbon atoms; A C 1 to C 30 alkoxyl group; An aryloxy group of C 6 to C 30 ; And -L'-N (R ') (R "); or ii) Ar 1 and Ar 2 are bonded to each other to form a ring,
a and d are each independently an integer of 0 to 4,
b and c are each independently an integer of 0 to 3,
R 1 to R 4 are independently selected from the group consisting of: i) deuterium independently of one another; halogen; A C 6 to C 60 aryl group; A fluorenyl group; A C 2 to C 60 heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P; A fused ring group of an aliphatic ring of C 3 to C 60 and an aromatic ring of C 6 to C 60 ; A C 1 to C 50 alkyl group; An alkenyl group having 2 to 20 carbon atoms; An alkynyl group having 2 to 20 carbon atoms; A C 1 to C 30 alkoxyl group; An aryloxy group of C 6 to C 30 ; And -L'-N (R ') (R "); or ii) the neighboring groups are bonded to each other to form a ring,
L 'is a single bond; An arylene group having 6 to 60 carbon atoms; A fluorenylene group; A fused ring group of an aliphatic ring of C 3 to C 60 and an aromatic ring of C 6 to C 60 ; And a C 2 to C 60 heterocyclic group,
Wherein R 'and R "are independently selected from C 6 ~ C aryl group of 60 to each other; fluorene group; C 3 ~ fused ring group of an aromatic ring of C 60 of aliphatic rings and C 6 ~ C 60; and O, N, And a C 2 to C 60 heterocyclic group containing at least one heteroatom selected from S, Si, and P;
When the aryl group, the fluorenyl group, the heterocyclic group, the fused ring group, the alkyl group, the alkenyl group, the alkynyl group, the alkoxyl group, the aryloxy group, the arylene group and the fluorenylene group are further substituted with one or more substituents, heavy hydrogen; halogen; A silane group; Siloxyl group; Boron group; Germanium group; Cyano; A nitro group; -L ' -N (R ') (R "); An alkyl thio group of C 1 to C 20 ; A C 1 to C 20 alkoxyl group; An alkyl group having 1 to 20 carbon atoms; An alkenyl group having 2 to 20 carbon atoms; An alkynyl group having 2 to 20 carbon atoms; C 6 -C 20 An aryl group; A C 6 -C 20 aryl group substituted by deuterium; A fluorenyl group; A heterocyclic group of C 2 ~ C 20; A C 3 to C 20 cycloalkyl group; An arylalkyl group of C 7 to C 20 ; And an arylalkenyl group having from 8 to 20 carbon atoms.
하기 화학식 2 또는 화학식 3으로 표시되는 것을 특징으로 하는 화합물.
<화학식 2> <화학식 3>
[상기 화학식 2 및 3에서, Ar1 ~ Ar4, R1 ~ R4, a, b, c 및 d는 제 1항에서 정의된 것과 동일하다.]The method according to claim 1,
A compound represented by the following formula (2) or (3).
≪ Formula 2 >< EMI ID =
[Wherein Ar 1 to Ar 4 , R 1 to R 4 , a, b, c and d are the same as defined in claim 1]
하기 화합물 중 하나인 것을 특징으로 하는 화합물.
The method according to claim 1,
Lt; / RTI > is one of the following compounds.
제 1전극; 제 2전극; 및 상기 제 1전극과 제 2전극 사이에 위치하는 유기물층;을 포함하며, 상기 화합물이 상기 유기물층에 함유되는 것을 특징으로 하는 유기전기소자.5. The method of claim 4,
A first electrode; A second electrode; And an organic material layer disposed between the first electrode and the second electrode, wherein the compound is contained in the organic material layer.
상기 화합물은 상기 유기물층의 정공주입층, 정공수송층, 발광보조층 또는 발광층 중 적어도 하나의 층에 함유되는 것을 특징으로 하는 유기전기소자.6. The method of claim 5,
Wherein the compound is contained in at least one of the hole injecting layer, the hole transporting layer, the luminescent auxiliary layer or the luminescent layer of the organic material layer.
상기 제 1전극과 제 2전극의 일면 중 상기 유기물층과 반대되는 적어도 일면에 형성되는 광효율 개선층을 더 포함하는 유기전기소자.6. The method of claim 5,
Further comprising a light-efficiency-improvement layer formed on at least one side of the one surface of the first electrode and the second electrode opposite to the organic material layer.
상기 유기물층은 스핀코팅 공정, 노즐 프린팅 공정, 잉크젯 프린팅 공정, 슬롯코팅 공정, 딥코팅 공정 또는 롤투롤 공정에 의해 형성되는 것을 특징으로 하는 유기전기소자.6. The method of claim 5,
Wherein the organic material layer is formed by a spin coating process, a nozzle printing process, an inkjet printing process, a slot coating process, a dip coating process or a roll-to-roll process.
상기 디스플레이장치를 구동하는 제어부;를 포함하는 전자장치.A display device including the organic electroluminescent device of claim 4; And
And a control unit for driving the display device.
상기 유기전기소자는 유기전기발광소자(OLED), 유기태양전지, 유기감광체(OPC), 유기트랜지스터(유기 TFT), 및 단색 또는 백색 조명용 소자 중 적어도 하나인 것을 특징으로 하는 전자장치.10. The method of claim 9,
Wherein the organic electronic device is at least one of an organic electroluminescent device (OLED), an organic solar cell, an organic photoconductor (OPC), an organic transistor (organic TFT), and a monochromatic or white illumination device.
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US20160043329A1 (en) * | 2014-08-05 | 2016-02-11 | Samsung Electronics Co., Ltd. | Organic compound, and organic thin film and electronic device |
KR20160066339A (en) * | 2014-12-02 | 2016-06-10 | 주식회사 두산 | Organic compounds and organic electro luminescence device comprising the same |
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KR101303894B1 (en) * | 2004-12-28 | 2013-09-05 | 가부시키가이샤 한도오따이 에네루기 켄큐쇼 | Carbazole derivative, and light-emitting element and light-emitting device using the carbazole derivative |
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KR101072817B1 (en) * | 2011-02-21 | 2011-10-14 | 덕산하이메탈(주) | Chemical and organic electronic element using the same, electronic device thereof |
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US20160043329A1 (en) * | 2014-08-05 | 2016-02-11 | Samsung Electronics Co., Ltd. | Organic compound, and organic thin film and electronic device |
US9941478B2 (en) * | 2014-08-05 | 2018-04-10 | Samsung Electronic Co., Ltd. | Organic compound, and organic thin film and electronic device |
US10516116B2 (en) | 2014-08-05 | 2019-12-24 | Samsung Electronics Co., Ltd. | Organic compound, and organic thin film and electronic device |
KR20160066339A (en) * | 2014-12-02 | 2016-06-10 | 주식회사 두산 | Organic compounds and organic electro luminescence device comprising the same |
JP2019505478A (en) * | 2015-12-08 | 2019-02-28 | ヒソン・マテリアル・リミテッドHeesung Material Ltd. | Heterocyclic compound and organic light emitting device using the same |
CN108689913A (en) * | 2017-04-05 | 2018-10-23 | 东进世美肯株式会社 | Compounds and organic luminescent device comprising it |
CN112479978A (en) * | 2019-09-11 | 2021-03-12 | 江苏三月光电科技有限公司 | Organic compound with carbazole derivative as core and application thereof |
CN112479978B (en) * | 2019-09-11 | 2023-11-28 | 江苏三月科技股份有限公司 | Organic compound with carbazole derivative as core and application thereof |
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KR102126201B1 (en) | 2020-06-24 |
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