KR20210046294A - The thermally activated delayed fluorescence dopant material and organic light emitting diode comprising the same - Google Patents
The thermally activated delayed fluorescence dopant material and organic light emitting diode comprising the same Download PDFInfo
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- KR20210046294A KR20210046294A KR1020190129853A KR20190129853A KR20210046294A KR 20210046294 A KR20210046294 A KR 20210046294A KR 1020190129853 A KR1020190129853 A KR 1020190129853A KR 20190129853 A KR20190129853 A KR 20190129853A KR 20210046294 A KR20210046294 A KR 20210046294A
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- 239000000463 material Substances 0.000 title claims abstract description 47
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- 230000003111 delayed effect Effects 0.000 title description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 15
- 239000001257 hydrogen Substances 0.000 claims abstract description 15
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 8
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- 150000002367 halogens Chemical class 0.000 claims abstract description 5
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 5
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052796 boron Inorganic materials 0.000 claims abstract description 4
- 239000011574 phosphorus Chemical group 0.000 claims abstract description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 30
- 125000003118 aryl group Chemical group 0.000 claims description 16
- 125000001072 heteroaryl group Chemical group 0.000 claims description 15
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- 125000005264 aryl amine group Chemical group 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical compound [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 claims description 5
- GEQBRULPNIVQPP-UHFFFAOYSA-N 2-[3,5-bis(1-phenylbenzimidazol-2-yl)phenyl]-1-phenylbenzimidazole Chemical compound C1=CC=CC=C1N1C2=CC=CC=C2N=C1C1=CC(C=2N(C3=CC=CC=C3N=2)C=2C=CC=CC=2)=CC(C=2N(C3=CC=CC=C3N=2)C=2C=CC=CC=2)=C1 GEQBRULPNIVQPP-UHFFFAOYSA-N 0.000 claims description 4
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- 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 claims description 2
- 150000001721 carbon Chemical class 0.000 claims description 2
- NSXJEEMTGWMJPY-UHFFFAOYSA-N 9-[3-(3-carbazol-9-ylphenyl)phenyl]carbazole Chemical group C12=CC=CC=C2C2=CC=CC=C2N1C1=CC(C=2C=CC=C(C=2)N2C3=CC=CC=C3C3=CC=CC=C32)=CC=C1 NSXJEEMTGWMJPY-UHFFFAOYSA-N 0.000 claims 1
- 239000010410 layer Substances 0.000 description 77
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- 230000000052 comparative effect Effects 0.000 description 29
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- ZEEBGORNQSEQBE-UHFFFAOYSA-N [2-(3-phenylphenoxy)-6-(trifluoromethyl)pyridin-4-yl]methanamine Chemical compound C1(=CC(=CC=C1)OC1=NC(=CC(=C1)CN)C(F)(F)F)C1=CC=CC=C1 ZEEBGORNQSEQBE-UHFFFAOYSA-N 0.000 description 8
- 229940125782 compound 2 Drugs 0.000 description 8
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 8
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- 229940126214 compound 3 Drugs 0.000 description 7
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- 125000001424 substituent group Chemical group 0.000 description 6
- NSNKTSSANPWFJA-UHFFFAOYSA-N 11,12-dihydroindolo[2,3-a]carbazole Chemical compound C12=CC=CC=C2NC2=C1C=CC1=C2NC2=CC=CC=C12 NSNKTSSANPWFJA-UHFFFAOYSA-N 0.000 description 5
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- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 5
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 5
- 229940125898 compound 5 Drugs 0.000 description 5
- 229910052700 potassium Inorganic materials 0.000 description 5
- 239000011591 potassium Substances 0.000 description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 4
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- 239000007983 Tris buffer Substances 0.000 description 4
- 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 4
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- 238000000605 extraction Methods 0.000 description 4
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- 125000005842 heteroatom Chemical group 0.000 description 4
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 4
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- 230000004044 response Effects 0.000 description 4
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- 239000000243 solution Substances 0.000 description 4
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- 229910000073 phosphorus hydride Inorganic materials 0.000 description 3
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- 125000001725 pyrenyl group Chemical group 0.000 description 3
- 125000004076 pyridyl group Chemical group 0.000 description 3
- 125000000168 pyrrolyl group Chemical group 0.000 description 3
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
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- 125000005580 triphenylene group Chemical group 0.000 description 3
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- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 2
- VHQGURIJMFPBKS-UHFFFAOYSA-N 2,4,7-trinitrofluoren-9-one Chemical compound [O-][N+](=O)C1=CC([N+]([O-])=O)=C2C3=CC=C([N+](=O)[O-])C=C3C(=O)C2=C1 VHQGURIJMFPBKS-UHFFFAOYSA-N 0.000 description 2
- AWXGSYPUMWKTBR-UHFFFAOYSA-N 4-carbazol-9-yl-n,n-bis(4-carbazol-9-ylphenyl)aniline Chemical compound C12=CC=CC=C2C2=CC=CC=C2N1C1=CC=C(N(C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=C1 AWXGSYPUMWKTBR-UHFFFAOYSA-N 0.000 description 2
- SCZWJXTUYYSKGF-UHFFFAOYSA-N 5,12-dimethylquinolino[2,3-b]acridine-7,14-dione Chemical compound CN1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3N(C)C1=C2 SCZWJXTUYYSKGF-UHFFFAOYSA-N 0.000 description 2
- RAPHUPWIHDYTKU-WXUKJITCSA-N 9-ethyl-3-[(e)-2-[4-[4-[(e)-2-(9-ethylcarbazol-3-yl)ethenyl]phenyl]phenyl]ethenyl]carbazole Chemical compound C1=CC=C2C3=CC(/C=C/C4=CC=C(C=C4)C4=CC=C(C=C4)/C=C/C=4C=C5C6=CC=CC=C6N(C5=CC=4)CC)=CC=C3N(CC)C2=C1 RAPHUPWIHDYTKU-WXUKJITCSA-N 0.000 description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- 101000837344 Homo sapiens T-cell leukemia translocation-altered gene protein Proteins 0.000 description 2
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- 102100028692 T-cell leukemia translocation-altered gene protein Human genes 0.000 description 2
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- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 2
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- 125000004122 cyclic group Chemical group 0.000 description 2
- JAONJTDQXUSBGG-UHFFFAOYSA-N dialuminum;dizinc;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Al+3].[Zn+2].[Zn+2] JAONJTDQXUSBGG-UHFFFAOYSA-N 0.000 description 2
- DKHNGUNXLDCATP-UHFFFAOYSA-N dipyrazino[2,3-f:2',3'-h]quinoxaline-2,3,6,7,10,11-hexacarbonitrile Chemical compound C12=NC(C#N)=C(C#N)N=C2C2=NC(C#N)=C(C#N)N=C2C2=C1N=C(C#N)C(C#N)=N2 DKHNGUNXLDCATP-UHFFFAOYSA-N 0.000 description 2
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- SKRWFPLZQAAQSU-UHFFFAOYSA-N stibanylidynetin;hydrate Chemical compound O.[Sn].[Sb] SKRWFPLZQAAQSU-UHFFFAOYSA-N 0.000 description 2
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- 239000000758 substrate Substances 0.000 description 2
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- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 2
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- UJVRUXZYNHVVBS-UHFFFAOYSA-N 10-[10-(2-methylanilino)-10-(2-methylphenyl)-1H-anthracen-9-yl]-N,N-bis(2-methylphenyl)anthracen-9-amine Chemical compound C1(=C(C=CC=C1)C1(C2=CC=CCC2=C(C2=CC=CC=C12)C=1C2=CC=CC=C2C(=C2C=CC=CC=12)N(C1=C(C=CC=C1)C)C1=C(C=CC=C1)C)NC1=C(C=CC=C1)C)C UJVRUXZYNHVVBS-UHFFFAOYSA-N 0.000 description 1
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- ZNNWWIMRSATCKZ-UHFFFAOYSA-N 3,5,9,12,15,18-hexazatetracyclo[12.4.0.02,7.08,13]octadeca-1(18),2,4,6,8,10,12,14,16-nonaene Chemical group C1=CN=C2C3=NC=CN=C3C3=CN=CN=C3C2=N1 ZNNWWIMRSATCKZ-UHFFFAOYSA-N 0.000 description 1
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- BWGRDBSNKQABCB-UHFFFAOYSA-N 4,4-difluoro-N-[3-[3-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)-8-azabicyclo[3.2.1]octan-8-yl]-1-thiophen-2-ylpropyl]cyclohexane-1-carboxamide Chemical compound CC(C)C1=NN=C(C)N1C1CC2CCC(C1)N2CCC(NC(=O)C1CCC(F)(F)CC1)C1=CC=CS1 BWGRDBSNKQABCB-UHFFFAOYSA-N 0.000 description 1
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- YLYPIBBGWLKELC-UHFFFAOYSA-N 4-(dicyanomethylene)-2-methyl-6-(4-(dimethylamino)styryl)-4H-pyran Chemical compound C1=CC(N(C)C)=CC=C1C=CC1=CC(=C(C#N)C#N)C=C(C)O1 YLYPIBBGWLKELC-UHFFFAOYSA-N 0.000 description 1
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- 125000004429 atom Chemical group 0.000 description 1
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- 235000010290 biphenyl Nutrition 0.000 description 1
- XZCJVWCMJYNSQO-UHFFFAOYSA-N butyl pbd Chemical compound C1=CC(C(C)(C)C)=CC=C1C1=NN=C(C=2C=CC(=CC=2)C=2C=CC=CC=2)O1 XZCJVWCMJYNSQO-UHFFFAOYSA-N 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Inorganic materials [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
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- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
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- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
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- 125000000753 cycloalkyl group Chemical group 0.000 description 1
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- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical group C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
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- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
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- IMKMFBIYHXBKRX-UHFFFAOYSA-M lithium;quinoline-2-carboxylate Chemical compound [Li+].C1=CC=CC2=NC(C(=O)[O-])=CC=C21 IMKMFBIYHXBKRX-UHFFFAOYSA-M 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
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- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- ONFSYSWBTGIEQE-NBHCHVEOSA-N n,n-diphenyl-4-[(e)-2-[4-[(e)-2-[4-(n-phenylanilino)phenyl]ethenyl]phenyl]ethenyl]aniline Chemical compound C=1C=C(\C=C\C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=CC=CC=2)C=CC=1/C=C/C(C=C1)=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ONFSYSWBTGIEQE-NBHCHVEOSA-N 0.000 description 1
- ONFSYSWBTGIEQE-UHFFFAOYSA-N n,n-diphenyl-4-[2-[4-[2-[4-(n-phenylanilino)phenyl]ethenyl]phenyl]ethenyl]aniline Chemical compound C=1C=C(C=CC=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=CC=CC=2)C=CC=1C=CC(C=C1)=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ONFSYSWBTGIEQE-UHFFFAOYSA-N 0.000 description 1
- IBHBKWKFFTZAHE-UHFFFAOYSA-N n-[4-[4-(n-naphthalen-1-ylanilino)phenyl]phenyl]-n-phenylnaphthalen-1-amine Chemical compound 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
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 150000003057 platinum Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- XTUSEBKMEQERQV-UHFFFAOYSA-N propan-2-ol;hydrate Chemical compound O.CC(C)O XTUSEBKMEQERQV-UHFFFAOYSA-N 0.000 description 1
- YYMBJDOZVAITBP-UHFFFAOYSA-N rubrene Chemical compound C1=CC=CC=C1C(C1=C(C=2C=CC=CC=2)C2=CC=CC=C2C(C=2C=CC=CC=2)=C11)=C(C=CC=C2)C2=C1C1=CC=CC=C1 YYMBJDOZVAITBP-UHFFFAOYSA-N 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001443 terpenyl group Chemical group 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/12—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains three hetero rings
- C07D487/16—Peri-condensed systems
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- H01L51/0072—
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- H01L51/5024—
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
- H10K50/12—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising dopants
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1059—Heterocyclic compounds characterised by ligands containing three nitrogen atoms as heteroatoms
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- Spectroscopy & Molecular Physics (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
Description
본 발명은 형광 재료 및 이를 포함하는 유기 발광 다이오드에 관한 것으로, 보다 상세하게는 우수한 전기화학적, 열적 안정성을 가지게 되어 수명 특성이 우수하고, 낮은 구동 전압에서도 높은 발광 효율을 갖는 형광 재료 및 이를 포함하는 유기 발광 다이오드에 관한 것이다.The present invention relates to a fluorescent material and an organic light-emitting diode comprising the same, and more particularly, a fluorescent material having excellent electrochemical and thermal stability, excellent lifespan characteristics, and high luminous efficiency even at a low driving voltage, and a fluorescent material including the same. It relates to an organic light emitting diode.
유기 발광 다이오드(organic light emitting diode)는 자발광형 소자로서 시야각이 넓고 콘트라스트가 우수할 뿐 만 아니라, 응답시간이 빠르며, 휘도, 구동전압 및 응답속도 특성이 우수하고 다색화가 가능하다는 장점을 가지고 있다.Organic light-emitting diodes are self-luminous devices that not only have a wide viewing angle and excellent contrast, but also have a fast response time, excellent luminance, driving voltage, and response speed characteristics, and are capable of multicolorization. .
일반적인 유기 발광 다이오드는 애노드 및 캐소드와 상기 애노드와 캐소드 사이에 개재된 유기층을 포함할 수 있다. 상기 유기층은, 전자주입층, 정공수송층, 발광층, 전자수송층 및 전자주입층 등을 포함할 수 있다. 상기 애노드 및 캐소드 간에 전압을 인가하면, 애노드로부터 주입된 정공은 정공수송층을 경유하여 발광층으로 이동하고, 캐소드로부터 주입된 전자는 전자수송층을 경유하여 발광층으로 이동한다. 상기 정공 및 전자와 같은 캐리어들은 발광층 영역에서 재결합하여 엑시톤(exiton)을 생성하는데, 이 엑시톤이 기저상태로 변하면서 광이 생성된다. A typical organic light emitting diode may include an anode and a cathode, and an organic layer interposed between the anode and the cathode. The organic layer may include an electron injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer. When a voltage is applied between the anode and the cathode, holes injected from the anode move to the emission layer via the hole transport layer, and electrons injected from the cathode move to the emission layer via the electron transport layer. Carriers such as holes and electrons recombine in the emission layer region to generate excitons, and the excitons change to a ground state to generate light.
일반적으로 유기 발광 다이오드 구동 시 생성되는 여기자(exiton)는 확률적으로 단일항 상태가 25 %, 삼중항 상태가 75 %로 생성되며, 형광 발광 재료의 경우 단일항 상태의 25 %의 여기자에 의한 발광만 생성되어 내부 양자 효율이 최대 25 % 수준에 머무르게 된다. 이러한 특성을 개선하기 위해 삼중항 에너지를 이용할 수 있는 이리듐 또는 백금 착물을 이용하고 있으며, 우수한 양자 효율 특성을 보유하고 있는 것으로 알려져 있다. 그러나 이러한 재료들은 고가이며, 특히 청색 발광 재료의 불안정성에 기인하여 그 응용에 한계가 있다.In general, excitons generated when driving an organic light emitting diode are generated with a probability of 25% in a singlet state and 75% in a triplet state, and in the case of a fluorescent light emitting material, light emission by 25% of the excitons in the singlet state Is generated, and the internal quantum efficiency stays at the maximum level of 25%. In order to improve these characteristics, iridium or platinum complexes that can use triplet energy are used, and are known to have excellent quantum efficiency characteristics. However, these materials are expensive, and in particular, due to the instability of the blue light-emitting material, their application is limited.
상기 문제점을 해결하기 위해 최근 형광(Fluorescence) 재료가 개발되고 있고, 상기 형광 재료는 여기자의 단일항 상태와 삼중항 상태의 차이가 0.3 eV 이하이며, 이 경우 상온 또는 소자 구동 온도에 해당하는 열에 의해 삼중항 상태를 단일항 상태로 전이시켜 이론적으로는 100 %의 양자 효율을 나타낼 수 있는 것으로 보고되고 있다.In order to solve the above problem, a fluorescence material has been recently developed, and the difference between the singlet state and the triplet state of the excitons is 0.3 eV or less, and in this case, due to heat corresponding to room temperature or device driving temperature. It is reported that the quantum efficiency of 100% can theoretically be achieved by transitioning the triplet state to the singlet state.
그러나, 현재까지 개발된 형광 재료의 실제 양자 효율은 이론 양자 효율과의 차이가 매우 크므로 여전히 개선되어야 할 문제로 알려져 있다.However, the actual quantum efficiency of the fluorescent material developed so far is known to be a problem to be improved since the difference from the theoretical quantum efficiency is very large.
따라서, 삼중항 상태에서 단일항 상태로의 전이가 효율적으로 가능하여 실제 양자 효율을 개선할 수 있는 형광 재료 및 이를 포함하는 유기 발광 다이오드 개발이 절실한 상황이다.Accordingly, there is an urgent need to develop a fluorescent material and an organic light emitting diode including the same, which can effectively improve quantum efficiency by effectively enabling a transition from a triplet state to a singlet state.
상기와 같은 종래기술의 문제점을 해결하고자, 본 발명은 우수한 전기화학적, 열적 안정성을 가지게 되어 수명 특성이 우수하고, 낮은 구동 전압에서도 높은 발광 효율을 갖는 형광 재료 및 이를 포함하는 유기 발광 다이오드를 제공하는 것을 목적으로 한다. In order to solve the problems of the prior art as described above, the present invention provides a fluorescent material having excellent electrochemical and thermal stability, excellent lifespan, and high luminous efficiency even at a low driving voltage, and an organic light emitting diode including the same. It is aimed at.
본 발명의 상기 목적 및 기타 목적들은 하기 설명된 본 발명에 의하여 모두 달성될 수 있다.All of the above and other objects of the present invention can be achieved by the present invention described below.
상기의 목적을 달성하기 위하여, 본 발명은 하기 화학식 1로 표시되는 것을 특징으로 하는 형광 재료를 제공한다.In order to achieve the above object, the present invention provides a fluorescent material, characterized in that represented by the following formula (1).
[화학식 1][Formula 1]
(상기 화학식 1에서 X는 질소(N), 붕소(B) 또는 인(P)이고, Y1 내지 Y5는 독립적으로 CR6 또는 N이며, 상기 Y1 내지 Y5 중 적어도 하나는 N이고, R1, R2 및 R6는 독립적으로 수소, 할로겐, 치환 또는 비치환된 탄소수 6 내지 20의 아릴기, 치환 또는 비치환된 탄소수 5 내지 20의 헤테로아릴기, 및 치환 또는 비치환된 탄소수 6 내지 20의 아릴아민기로 이루어진 군으로부터 선택되며, R3 내지 R5는 독립적으로 수소, 치환 또는 비치환된 탄소수 1 내지 20의 알킬기, 치환 또는 비치환된 탄소수 1 내지 20의 알콕시기, 치환 또는 비치환된 탄소수 6 내지 30의 아릴기, 치환 또는 비치환된 탄소수 5 내지 30의 헤테로아릴기, 및 치환 또는 비치환된 탄소수 1 내지 20의 아민기로 이루어진 군으로부터 선택되되, l, m은 독립적으로 0 내지 2의 정수이고, n은 1 내지 3의 정수이며, l+m+n은 3 이하이다.)(In Formula 1, X is nitrogen (N), boron (B) or phosphorus (P), Y 1 to Y 5 are independently CR 6 or N, and at least one of Y 1 to Y 5 is N, R 1 , R 2 and R 6 are independently hydrogen, halogen, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 20 carbon atoms, and a substituted or unsubstituted C 6 To 20 arylamine groups, and R 3 to R 5 are independently hydrogen, a substituted or unsubstituted C 1 to C 20 alkyl group, a substituted or unsubstituted C 1 to C 20 alkoxy group, substituted or unsubstituted Is selected from the group consisting of a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 30 carbon atoms, and a substituted or unsubstituted amine group having 1 to 20 carbon atoms, l and m are independently 0 Is an integer of 2, n is an integer of 1 to 3, and l+m+n is 3 or less.)
또한 본 발명은 제 1전극; 제 2전극; 및 상기 제 1전극과 상기 제 2전극 사이에 위치하는 발광층;을 포함하며, 상기 발광층은 본 기재의 형광 재료를 포함하는 것을 특징으로 하는 유기 발광 다이오드를 제공한다.In addition, the present invention is a first electrode; A second electrode; And a light emitting layer positioned between the first electrode and the second electrode, wherein the light emitting layer includes the fluorescent material of the present invention.
본 발명에 따르면 우수한 전기화학적, 열적 안정성을 가지게 되어 수명 특성이 우수하고, 낮은 구동 전압에서도 높은 발광 효율을 갖는 형광 재료 및 이를 포함하는 유기 발광 다이오드를 제공하는 효과가 있다.According to the present invention, there is an effect of providing a fluorescent material having excellent electrochemical and thermal stability, excellent lifespan characteristics, and high luminous efficiency even at a low driving voltage, and an organic light emitting diode including the same.
이하 본 기재의 형광 재료 및 이를 포함하는 유기 발광 다이오드를 상세하게 설명한다.Hereinafter, the fluorescent material of the present disclosure and an organic light emitting diode including the same will be described in detail.
본 발명자들은 다양한 화합물을 합성하여 형광 재료에 적용할 경우 실제 양자 효율이 우수하여 이론 양자 효율에 근접하고, 결과적으로는 낮은 구동 전압에서도 높은 발광 효율을 갖을 뿐만 아니라 수명 특성 또한 우수한 것을 확인하고, 이를 토대로 연구에 더욱 매진하여 본 발명을 완성하게 되었다.The present inventors have confirmed that when various compounds are synthesized and applied to a fluorescent material, the actual quantum efficiency is excellent, which is close to the theoretical quantum efficiency, and as a result, it has not only high luminous efficiency even at a low driving voltage, but also excellent lifespan characteristics. Based on this, the present invention was completed by further focusing on research.
본 기재에서 "치환"이란 치환기, 또는 화합물 중의 적어도 하나의 수소가 할로겐, 니트로기, 탄소수 1 내지 20의 알킬기, 탄소수 3 내지 30의 시클로알킬기, 탄소수 6 내지 40의 아릴기, 탄소수 5 내지 40의 헤테로아릴기, 탄소수 1 내지 20의 알킬렌기, 5 내지 20의 시클로 알킬렌기, 탄소수 6 내지 20의 아릴렌기, 에스테르기, 에스터기, 카르보닐기, 또는 카보네이트기 등으로 치환된 것을 의미한다.In the present description, "substituted" means a substituent or at least one hydrogen in the compound is a halogen, a nitro group, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an aryl group having 6 to 40 carbon atoms, and having 5 to 40 carbon atoms. It means substituted with a heteroaryl group, an alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 5 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, an ester group, an ester group, a carbonyl group, or a carbonate group.
본 기재에서 "아릴기"란 별도의 정의가 없는 한 방향족 탄화수소 고리로부터 유도된 임의의 작용기 또는 치환기를 의미한다.In the present description, “aryl group” means any functional group or substituent derived from an aromatic hydrocarbon ring unless otherwise defined.
본 기재에서 "헤테로"란 별도의 정의가 없는 한, 하나의 작용기 내에 O, N, S 및 P로 이루어진 군에서 선택되는 헤테로 원자를 1개 내지 3개 함유하고, 나머지는 탄소 또는 수소인 것을 의미한다.In the present description, "hetero" means that one functional group contains 1 to 3 heteroatoms selected from the group consisting of O, N, S and P, and the rest is carbon or hydrogen unless otherwise defined. do.
본 기재에서 "헤테로아릴기"이란 아릴기 내에 N, O, S 및 P로 이루어진 군에서 선택되는 헤테로 원자를 1개 내지 3개 함유하고, 나머지는 탄소 또는 수소인 것을 의미한다. 상기 헤테로아릴기가 융합고리인 경우, 각각의 고리마다 상기 헤테로 원자를 1개 내지 3개 포함할 수 있다.In the present description, the term "heteroaryl group" means that the aryl group contains 1 to 3 heteroatoms selected from the group consisting of N, O, S, and P, and the remainder is carbon or hydrogen. When the heteroaryl group is a fused ring, each ring may contain 1 to 3 heteroatoms.
본 기재에서 "아릴아민기"이란 별도의 정의가 없는 한 방향족 탄화수소 고리가 질소 원자에 결합된 작용기 또는 치환기를 의미한다.As used herein, the term "arylamine group" means a functional group or a substituent in which an aromatic hydrocarbon ring is bonded to a nitrogen atom unless otherwise defined.
본 기재에서 "알킬기"란 별도의 정의가 없는 한 지방족 탄화수소기를 의미한다.In the present description, "alkyl group" means an aliphatic hydrocarbon group unless otherwise defined.
본 기재에서 "*"는 탄소 원자 또는 탄소 이외의 원자와 연결되는 부분, 즉 치환기(group)나 관능기가 연결되는 부분을 의미한다.In the present description, "*" means a part connected to a carbon atom or an atom other than carbon, that is, a part to which a substituent or a functional group is connected.
형광 재료Fluorescent material
본 발명의 형광 재료는 하기 화학식 1로 표시되는 것을 특징으로 하며, 이 경우 적색, 녹색, 청색의 발광색을 구현할 수 있고, 단일항 에너지와 삼중항 에너지의 차를 0.3 Ev 이하로 낮추는 효과가 있다.The fluorescent material of the present invention is characterized in that it is represented by the following formula (1), and in this case, it is possible to realize the luminous colors of red, green, and blue, and has an effect of lowering the difference between singlet energy and triplet energy to 0.3 Ev or less.
상기 단일항 에너지와 삼중항 에너지의 차가 작을수록 낮은 구동 전압에서도 높은 발광 효율을 갖고, 수명 특성이 향상되는 효과가 있다.The smaller the difference between the singlet energy and the triplet energy, the higher the luminous efficiency even at a low driving voltage, and the lifespan characteristics are improved.
또한, 상기 단일항 에너지와 삼중항 에너지의 차가 삼중항 에너지와 유사한 레벨을 갖게 되고, 유사한 레벨을 갖는 형광 재료를 유기 발광 다이오드에 적용할 경우 구동 전압이 낮아지는 효과가 있다.In addition, the difference between the singlet energy and the triplet energy has a level similar to that of the triplet energy, and when a fluorescent material having a similar level is applied to the organic light emitting diode, there is an effect of lowering the driving voltage.
[화학식 1][Formula 1]
(상기 화학식 1에서 X는 질소(N), 붕소(B) 또는 인(P)이고, Y1 내지 Y5는 독립적으로 CR6 또는 N이며, 상기 Y1 내지 Y5 중 적어도 하나는 N이고, R1, R2 및 R6는 독립적으로 수소, 할로겐, 치환 또는 비치환된 탄소수 6 내지 20의 아릴기, 치환 또는 비치환된 탄소수 5 내지 20의 헤테로아릴기, 및 치환 또는 비치환된 탄소수 6 내지 20의 아릴아민기로 이루어진 군으로부터 선택되며, R3 내지 R5는 독립적으로 수소, 치환 또는 비치환된 탄소수 1 내지 20의 알킬기, 치환 또는 비치환된 탄소수 1 내지 20의 알콕시기, 치환 또는 비치환된 탄소수 6 내지 30의 아릴기, 치환 또는 비치환된 탄소수 5 내지 30의 헤테로아릴기, 및 치환 또는 비치환된 탄소수 1 내지 20의 아민기로 이루어진 군으로부터 선택되되, 상기 R1 내지 R5, CN 및 고리형태를 갖는 관능기는 독립적으로, 걸쳐 있는 벤젠 고리 내 결합된 수소 중 어느 하나에 치환되며, l, m은 독립적으로 0 내지 2의 정수이고, n은 1 내지 3의 정수이며, l+m+n은 3 이하이다.)(In Formula 1, X is nitrogen (N), boron (B) or phosphorus (P), Y 1 to Y 5 are independently CR 6 or N, and at least one of Y 1 to Y 5 is N, R 1 , R 2 and R 6 are independently hydrogen, halogen, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 20 carbon atoms, and a substituted or unsubstituted C 6 To 20 arylamine groups, and R 3 to R 5 are independently hydrogen, a substituted or unsubstituted C 1 to C 20 alkyl group, a substituted or unsubstituted C 1 to C 20 alkoxy group, substituted or unsubstituted Is selected from the group consisting of a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 30 carbon atoms, and a substituted or unsubstituted amine group having 1 to 20 carbon atoms, wherein R 1 to R 5 , CN and the functional group having a cyclic form are independently substituted with any one of the hydrogens bonded in the spanning benzene ring, l and m are independently an integer of 0 to 2, n is an integer of 1 to 3, and l+ m+n is 3 or less.)
상기 화학식 1에서 고리형태를 갖는 관능기는
구체적인 예로, 상기 화학식 1에서 X는 질소(N)일 수 있고, n은 1일 수 있으며, 이 경우 전하 수송 성능이 향상되고 발광 효율 및 수명 특성이 우수한 효과가 있다.As a specific example, in Chemical Formula 1, X may be nitrogen (N) and n may be 1, and in this case, charge transport performance is improved, and luminous efficiency and lifespan characteristics are excellent.
또 다른 예로, 상기 화학식 1에서 X는 질소(N)일 수 있고, l+m은 0 내지 2의 정수일 수 있으며, 이 경우 낮은 구동 전압에서도 높은 발광 효율을 갖고, 수명 특성이 향상되는 효과가 있다.As another example, in Formula 1, X may be nitrogen (N), and l+m may be an integer of 0 to 2. In this case, there is an effect of having high luminous efficiency even at a low driving voltage and improving lifespan characteristics. .
상기 화학식 1에서 R1, R2 및 R6의 아릴기, 헤테로아릴기, 아릴아민기에 각각 도입될 수 있는 치환기는 일례로, 독립적으로 탄소수 6 내지 20의 아릴기 및 N을 1 내지 3개 함유하는 탄소수 5 내지 20의 헤테로아릴기로 이루어진 군으로부터 선택될 수 있다. Substituents that may be introduced into the aryl group, heteroaryl group, and arylamine group of R 1 , R 2 and R 6 in Formula 1 are for example, independently containing an aryl group having 6 to 20 carbon atoms and 1 to 3 N It may be selected from the group consisting of a C5 to C20 heteroaryl group.
구체적인 예로, 상기 R1, R2 및 R6의 아릴기, 헤테로아릴기, 아릴아민기에 각각 도입될 수 있는 치환기는 독립적으로 페닐기, 바이페닐기, 터퍼닐기, 나프틸기, 안트라세닐기, 페나트렌기, 파이레닐기, 트리페닐렌기 페릴레닐기, 크라이세닐기, 카바졸기, 티오펜기, 퓨란기, 피롤기, 이미다졸기, 티아졸기, 옥사졸기, 옥사디아졸기, 트리아졸기, 피리딜기, 피라다진기, 퀴놀리닐기, 이소퀴놀린기 및 아크리딜기로 이루어진 군에서 선택될 수 있다.As a specific example, the substituents each of which may be introduced into the aryl group, heteroaryl group, and arylamine group of R 1 , R 2 and R 6 are independently phenyl group, biphenyl group, terfuryl group, naphthyl group, anthracenyl group, phenathrene group , Pyrenyl group, triphenylene group perylenyl group, chrysenyl group, carbazole group, thiophene group, furan group, pyrrole group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, pyra It may be selected from the group consisting of a chopped group, a quinolinyl group, an isoquinoline group, and an acridyl group.
상기 화학식 1에서 Y1 내지 Y5는 일례로 독립적으로 CR6 또는 N이고, 상기 Y1 내지 Y5 중 적어도 하나는 N이며, 상기 R6은 탄소수 6 내지 18의 아릴기, 또는 치환 또는 비치환된 탄소수 6 내지의 18의 헤테로아릴기일 수 있고, 이 경우 전하 이동도가 높고 열적으로 매우 안정한 효과가 있다.In Formula 1, Y 1 to Y 5 are, for example, independently CR 6 or N, at least one of Y 1 to Y 5 is N, and R 6 is an aryl group having 6 to 18 carbon atoms, or a substituted or unsubstituted It may be a heteroaryl group having 6 to 18 carbon atoms, and in this case, charge mobility is high and there is a thermally very stable effect.
구체적인 예로, 상기 화학식 1에서 Y1 내지 Y5 중 1개 내지 3개는 N이고, 나머지는 CR6일 수 있으며, 이 경우 높은 유리전이온도 및 분해온도를 가짐으로써 열적으로 우수하여 구동의 안정성이 향상되는 효과가 있다.As a specific example, in Chemical Formula 1, 1 to 3 of Y 1 to Y 5 may be N, and the rest may be CR 6. In this case, since it has a high glass transition temperature and a decomposition temperature, it is thermally excellent, so that the stability of driving is improved. There is an improved effect.
바람직한 예로, 상기 R6은 페닐기, 바이페닐기, 터퍼닐기, 나프틸기, 안트라세닐기, 페나트렌기, 파이레닐기, 트리페닐렌기 페릴레닐기, 크라이세닐기, 카바졸기, 티오펜기, 퓨란기, 피롤기, 이미다졸기, 티아졸기, 옥사졸기, 옥사디아졸기, 트리아졸기, 피리딜기, 피라다진기, 퀴놀리닐기, 이소퀴놀린기 및 아크리딜기로 이루어진 군에서 선택될 수 있다.In a preferred example, R 6 is a phenyl group, a biphenyl group, a terpenyl group, a naphthyl group, an anthracenyl group, a phenathrene group, a pyrenyl group, a triphenylene group perylenyl group, a chrysenyl group, a carbazole group, a thiophene group, a furan group , A pyrrole group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a triazole group, a pyridyl group, a pyrazazine group, a quinolinyl group, an isoquinoline group, and an acridyl group.
더 바람직한 예로, 상기 R6은 페닐기, 바이페닐기, 카바졸기 및 퓨란기로 이루어진 군에서 선택될 수 있고, 상기 퓨란기는 일례로 다이벤조퓨란기일 수 있다.As a more preferred example, R 6 may be selected from the group consisting of a phenyl group, a biphenyl group, a carbazole group and a furan group, and the furan group may be a dibenzofuran group as an example.
상기 화학식 1에서 R1 및 R2는 일례로 독립적으로 수소, 탄소수 6 내지 18의 아릴기 및 탄소수 6 내지 18의 헤테로아릴기로 이루어진 군으로부터 선택될 수 있고, 이 경우 전하 수송 성능이 향상되고 발광 효율 및 수명 특성이 우수한 효과가 있다.In Chemical Formula 1, R 1 and R 2 may be independently selected from the group consisting of hydrogen, an aryl group having 6 to 18 carbon atoms, and a heteroaryl group having 6 to 18 carbon atoms, in which case charge transport performance is improved and luminous efficiency And there is an effect of excellent life characteristics.
구체적인 예로, 상기 R1 및 R2는 독립적으로 페닐기, 바이페닐기, 터퍼닐기, 나프틸기, 안트라세닐기, 페나트렌기, 파이레닐기, 트리페닐렌기 페릴레닐기, 크라이세닐기, 카바졸기, 티오펜기, 퓨란기, 피롤기, 이미다졸기, 티아졸기, 옥사졸기, 옥사디아졸기, 트리아졸기, 피리딜기, 피라다진기, 퀴놀리닐기, 이소퀴놀린기 및 아크리딜기로 이루어진 군에서 선택될 수 있고, 이 경우 낮은 구동 전압에서도 높은 발광 효율을 갖고, 수명 특성이 향상되는 효과가 있다.In a specific example, R 1 and R 2 are independently a phenyl group, a biphenyl group, a terfuryl group, a naphthyl group, an anthracenyl group, a phenatrene group, a pyrenyl group, a triphenylene group, a perylenyl group, a chrysenyl group, a carbazole group, and a thi. To be selected from the group consisting of an ofene group, a furan group, a pyrrole group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a triazole group, a pyridyl group, a pyrazazine group, a quinolinyl group, an isoquinoline group, and an acridyl group. In this case, there is an effect of having high luminous efficiency even at a low driving voltage and improving life characteristics.
바람직한 예로, 상기 R1 및 R2는 독립적으로 페닐기 또는 카바졸기일 수 있고, 이 경우 본 발명의 목적하는 효과가 가장 잘 드러난다.As a preferred example, the R 1 and R 2 may independently be a phenyl group or a carbazole group, and in this case, the desired effect of the present invention is best revealed.
상기 화학식 1에서 R3 내지 R5는 일례로 독립적으로 수소, 또는 하기 화학식 2-1 내지 2-21 중 하나일 수 있고, 이 경우 단일항 에너지와 삼중항 에너지의 차를 줄여 낮은 구동 전압에서도 높은 발광 효율을 갖는 효과가 있다.In Formula 1, R 3 to R 5 may be independently hydrogen, or one of the following Formulas 2-1 to 2-21, in this case, reducing the difference between the singlet energy and the triplet energy, so that even at a low driving voltage There is an effect of having luminous efficiency.
바람직한 예로, 상기 화학식 1에서 R3 내지 R5는 독립적으로 수소, 또는 하기 화학식 2-1, 2-19 및 2-21 중 하나일 수 있고, 이 경우 전기화학적, 열적 안정성이 우수하여 수명 특성이 우수하고 낮은 구동 전압에서도 발광 효율이 우수한 효과가 있다.As a preferred example, in Formula 1, R 3 to R 5 may independently be hydrogen, or one of the following Formulas 2-1, 2-19, and 2-21, and in this case, electrochemical and thermal stability are excellent, resulting in lifetime characteristics. It has an excellent effect of excellent luminous efficiency even at a low driving voltage.
[화학식 2-1][Formula 2-1]
[화학식 2-2][Formula 2-2]
[화학식 2-3][Formula 2-3]
[화학식 2-4][Formula 2-4]
[화학식 2-5][Formula 2-5]
[화학식 2-6][Formula 2-6]
[화학식 2-7][Formula 2-7]
[화학식 2-8][Formula 2-8]
[화학식 2-9][Formula 2-9]
[화학식 2-10][Formula 2-10]
[화학식 2-11][Chemical Formula 2-11]
[화학식 2-12][Formula 2-12]
[화학식 2-13][Formula 2-13]
[화학식 2-14][Formula 2-14]
[화학식 2-15][Formula 2-15]
[화학식 2-16][Formula 2-16]
[화학식 2-17][Formula 2-17]
[화학식 2-18][Formula 2-18]
[화학식 2-19][Chemical Formula 2-19]
[화학식 2-20][Formula 2-20]
[화학식 2-21][Formula 2-21]
상기 화학식 1은 일례로 화학식 1-1 내지 1-16 중 하나의 화학식일 수 있으나, 이에 한정되는 것은 아니며, 이 경우 단일항 에너지와 삼중항 에너지의 차이로 삼중항의 여기자(excition)가 단일항으로 이동하는 역계간전이(reverse intersystem crossing; RISC) 효과가 우수하여 발광 효율이 매우 우수하고 수명 특성이 향상되는 효과가 있다.Formula 1 may be, for example, one of Formulas 1-1 to 1-16, but is not limited thereto. In this case, the exciton of the triplet is a singlet due to the difference between the singlet energy and the triplet energy. The moving reverse intersystem crossing (RISC) effect is excellent, so that the luminous efficiency is very excellent and the lifespan characteristics are improved.
[화학식 1-1][Formula 1-1]
[화학식 1-2][Formula 1-2]
[화학식 1-3][Formula 1-3]
[화학식 1-4][Formula 1-4]
[화학식 1-5][Formula 1-5]
[화학식 1-6][Formula 1-6]
[화학식 1-7][Formula 1-7]
[화학식 1-8][Formula 1-8]
[화학식 1-9][Formula 1-9]
[화학식 1-10][Formula 1-10]
[화학식 1-11][Formula 1-11]
[화학식 1-12][Formula 1-12]
[화학식 1-13][Formula 1-13]
[화학식 1-14][Formula 1-14]
[화학식 1-15][Formula 1-15]
[화학식 1-16][Formula 1-16]
상기 형광 재료는 일례로 열 활성 지연 형광 재료일 수 있고, 이 경우 단일항 에너지와 삼중항 에너지의 차이가 적어 역계간전이가 잘 일어나게 되고 이로 인해 지연형광 효과가 향상되어 우수한 발광 효율을 발휘하는 이점이 있다.The fluorescent material may be, for example, a thermally active delayed fluorescent material, and in this case, the difference between singlet energy and triplet energy is small, so that the inverse interphase transition occurs well, thereby improving the delayed fluorescence effect, thereby exhibiting excellent luminous efficiency. There is this.
본 기재의 형광 재료는 일례로 단일항 에너지와 삼중항 에너지의 차이(△EST)가 0.3 eV 이하, 0.01 내지 0.3 eV, 또는 0.01 내지 0.2 eV일 수 있고, 이 범위 내에서 낮은 구동 전압에서도 발광 효율이 우수한 효과가 있다.The fluorescent material of the present disclosure may, for example, have a difference between singlet energy and triplet energy (ΔE ST ) of 0.3 eV or less, 0.01 to 0.3 eV, or 0.01 to 0.2 eV, and emit light even at a low driving voltage within this range. There is an effect of excellent efficiency.
상기 △EST는 UV-vis measurement는 Agilent Technologies(社) Cary 8454 UV-Vis Diode Array system 기기를 사용하여 Energy Gap(eV)를 측정하고 PL measurements는 PerkinElmer(社) LS55 Luminescence Spectrometer를 사용하여 T1(eV)를 측정하였다.The △E ST is a UV-vis measurement using an Agilent Technologies (company) Cary 8454 UV-Vis Diode Array system device to measure the Energy Gap (eV), and the PL measurements using a PerkinElmer (company) LS55 Luminescence Spectrometer, T1 ( eV) was measured.
유기 발광 다이오드Organic light emitting diode
본 기재의 유기 발광 다이오드는 일례로 제 1전극; 제 2전극; 및 상기 제 1전극과 상기 제 2전극 사이에 위치하는 발광층;을 포함할 수 있고, 상기 발광층은 본 기재의 형광 재료를 포함할 수 있으며, 이 경우 순방향 바이어스를 인가하면 제 1전극에서 정공이 발광층으로 유입되고, 제 2전극에서 전자가 발광층으로 유입되어 발광층으로 유입된 전자와 정공은 결합하여 엑시톤을 형성하고 상기 엑시톤이 기저상태로 전이하면서 광이 방출되어 시야각이 넓고 응답시간이 빠르며 휘도, 구동 전압 및 응답 속도 특성이 우수한 효과가 있다.The organic light emitting diode of the present disclosure includes, for example, a first electrode; A second electrode; And a light-emitting layer positioned between the first electrode and the second electrode, wherein the light-emitting layer may include the fluorescent material of the present disclosure. In this case, when a forward bias is applied, holes are transferred from the first electrode to the light-emitting layer. Electrons flow into the light emitting layer from the second electrode, and electrons and holes introduced into the light emitting layer are combined to form excitons, and light is emitted as the excitons transition to the ground state, so that the viewing angle is wide, the response time is fast, and the luminance, driving The voltage and response speed characteristics are excellent.
상기 방출된 광은 적색, 녹색, 청색의 발광색을 구현할 수 있고, 특히 녹색의 구현성이 우수한 효과가 있다.The emitted light may embody red, green, and blue luminous colors, and in particular, there is an effect of excellent green color.
상기 발광층은 일례로 두께가 1 내지 100 nm, 10 내지 70 nm, 15 내지 65 mm, 또는 30 내지 50 nm일 수 있고, 이 범위 내에서 실질적인 구동 전압 상승 없이 우수한 발광 특성을 나타낼 수 있다.The light emitting layer may have a thickness of 1 to 100 nm, 10 to 70 nm, 15 to 65 mm, or 30 to 50 nm, for example, and exhibit excellent light emission characteristics without a substantial increase in driving voltage within this range.
상기 제 1전극과 상기 발광층 사이에 일례로 정공전도층을 포함할 수 있고, 상기 정공전도층은 일례로 본 기재의 형광 재료를 포함할 수 있으며, 이 경우 발광 효율 및 수명 특성이 우수한 효과가 있다.Between the first electrode and the light-emitting layer, for example, a hole-conducting layer may be included, and the hole-conducting layer may include, for example, a fluorescent material of the present disclosure, and in this case, there is an effect of excellent luminous efficiency and lifetime characteristics. .
상기 정공전도층은 일례로 정공의 수송을 위한 정공수송층과 정공의 주입을 위한 정공주입층을 포함할 수 있고, 상기 정공수송층 및 정공주입층은 애노드의 일함수 준위와 발광층의 HOMO 준위 사이의 HOMO 준위를 갖는 층이며, 이 경우 애노드에서 발광층으로의 정공의 주입 또는 수송 효율을 높이는 효과가 있다.The hole conductive layer may include, for example, a hole transport layer for transporting holes and a hole injection layer for injection of holes, and the hole transport layer and the hole injection layer are HOMO between the work function level of the anode and the HOMO level of the light emitting layer. It is a layer having a level, and in this case, there is an effect of increasing the efficiency of injecting or transporting holes from the anode to the light emitting layer.
상기 정공수송층은 바람직하게 비스(N-(1-나프틸-n-페닐))벤지딘(α-NPD), N'-다이(나프탈렌-1-일)-N,N'- 바이페닐-벤지딘(NPB) 및 N,N'-바이페닐 -N,N'-비스(3-메틸페닐)-1,1'- 바이페닐-4,4'-다이아민(TPD)로 이루어진 군으로부터 선택된 1종 이상일 수 있고, 이 경우 애노드에서 발광층으로의 정공의 수송 효율을 높이는 효과가 있다.The hole transport layer is preferably bis(N-(1-naphthyl-n-phenyl))benzidine (α-NPD), N'-di(naphthalen-1-yl)-N,N'-biphenyl-benzidine ( NPB) and N,N'-biphenyl-N,N'-bis(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine (TPD) In this case, there is an effect of increasing the transport efficiency of holes from the anode to the light emitting layer.
상기 정공수송층의 두께는 일례로 10 내지 200 nm, 20 내지 150 nm, 40 내지 100 mm, 또는 60 내지 80 nm일 수 있고, 이 범위 내에서 구동 전압 상승 없이 정공 수송 특성을 향상시키는 효과가 있다.The thickness of the hole transport layer may be, for example, 10 to 200 nm, 20 to 150 nm, 40 to 100 mm, or 60 to 80 nm, and within this range, there is an effect of improving hole transport characteristics without an increase in driving voltage.
상기 정공주입층은 일례로 구리프탈로시아닌(CuPc), 4,4',4"-트리스(3- 메틸페닐아미노)트리페닐아민(m-MTDATA), 4,4',4"-트리스 (3-메틸페닐 아미노)페녹시벤젠(m-MTDAPB), 스타버스트(starburst)형 아민류인 4,4',4"-트리(N-카바졸릴)트리페닐아민(TCTA), 4,4',4"-트리스(N-(2- 나프틸)-N-페닐아미노)-트리페닐아민(2-TNATA), N'-다이(나프탈렌-1-일)-N,N'- 바이페닐-벤지딘(NPB) 및 1,4,5,8,9,11-Hexaazatriphenylene hexacarbonitrile (HAT-CN)로 이루어진 군으로부터 선택된 1종 이상일 수 있고, 이 경우 애노드에서 발광층으로의 정공의 주입 효율을 높이는 효과가 있다.The hole injection layer is, for example, copper phthalocyanine (CuPc), 4,4',4"-tris(3-methylphenylamino)triphenylamine (m-MTDATA), 4,4',4"-tris(3-methylphenyl). Amino)phenoxybenzene (m-MTDAPB), starburst type amines 4,4',4"-tri(N-carbazolyl)triphenylamine (TCTA), 4,4',4"-tris (N-(2-naphthyl)-N-phenylamino)-triphenylamine (2-TNATA), N'-di(naphthalen-1-yl)-N,N'-biphenyl-benzidine (NPB) and It may be one or more selected from the group consisting of 1,4,5,8,9,11-Hexaazatriphenylene hexacarbonitrile (HAT-CN), and in this case, there is an effect of increasing the injection efficiency of holes from the anode to the light emitting layer.
상기 정공주입층의 두께는 일례로 1 내지 50 nm, 1 내지 30 nm, 또는 5 내지 20 nm일 수 있고, 이 범위 내에서 구동 전압의 상승 없이 정공 주입 특성을 향상시키는 효과가 있다.The thickness of the hole injection layer may be 1 to 50 nm, 1 to 30 nm, or 5 to 20 nm, for example, and within this range, there is an effect of improving hole injection characteristics without an increase in driving voltage.
상기 제 2전극과 상기 발광층 사이에 일례로 전자전도층을 포함할 수 있고, 상기 전자전도층은 일례로 본 기재의 형광 재료를 포함할 수 있으며, 이 경우 수명 특성 및 발광 효율이 우수한 효과가 있다.An electron conductive layer may be included between the second electrode and the light emitting layer as an example, and the electron conductive layer may include a fluorescent material of the present invention as an example, and in this case, there is an effect of excellent lifespan characteristics and luminous efficiency. .
상기 전도전도층은 일례로 전자의 수송을 위한 전자수송층과 전자의 주입을 위한 전자주입층을 포함할 수 있고, 상기 전자수송층 및 전자주입층은 캐소드의 일함수 준위와 발광층의 LUMO 준위 사이의 LUMO 준위를 갖는 층이며, 이 경우 캐소드에서 발광층으로의 전자의 주입 또는 수송 효율을 높이는 효과가 있다.The conductive conductive layer may include, for example, an electron transport layer for transporting electrons and an electron injection layer for injection of electrons, and the electron transport layer and the electron injection layer are LUMO between the work function level of the cathode and the LUMO level of the light emitting layer. It is a layer having a level, and in this case, there is an effect of increasing the efficiency of injecting or transporting electrons from the cathode to the light emitting layer.
상기 전자수송층은 일례로 트리스(8-하이드록시퀴놀리놀라토)알루미늄(Alq3), PBD(2-(4-비페닐일)-5- (4-t-부틸페닐)-1,3,4-옥사디아졸), TNF(2,4,7-트리니트로 플루오레논), BMD 및 BND로 이루어진 군으로부터 선택된 1종 이상일 수 있고, 이 경우 캐소드에서 발광층으로의 전자 수송 효율을 높이는 효과가 있다.The electron transport layer is, for example, tris(8-hydroxyquinolinolato)aluminum (Alq3), PBD(2-(4-biphenylyl)-5-(4-t-butylphenyl)-1,3,4 -Oxadiazole), TNF (2,4,7-trinitro fluorenone), may be one or more selected from the group consisting of BMD and BND, in this case, there is an effect of increasing the electron transport efficiency from the cathode to the light emitting layer.
상기 전자수송층의 두께는 일례로 1 내지 100 nm, 10 내지 70 nm, 15 내지 65 mm, 또는 30 내지 50 nm일 수 있고, 이 범위 내에서 실질적인 구동 전압 상승 없이 전자 수송 특성을 향상시킬 수 있다.The thickness of the electron transport layer may be 1 to 100 nm, 10 to 70 nm, 15 to 65 mm, or 30 to 50 nm, for example, and within this range, electron transport characteristics may be improved without a substantial increase in driving voltage.
상기 전자주입층은 당업계에서 통상적으로 사용되는 것이면 특별히 제한되지 않으나 일례로 LiF, NaCl, CsF, Li2O, BaO, BaF2, 및 Liq(리튬 퀴놀레이트)로 이루어진 군으로부터 선택된 1종 이상일 수 있고, 이 경우 캐소드에서 발광층으로의 전자의 주입 효율을 높이는 효과가 있다.The electron injection layer is not particularly limited as long as it is commonly used in the art, but for example, it may be at least one selected from the group consisting of LiF, NaCl, CsF, Li 2 O, BaO, BaF 2 , and Liq (lithium quinolate). In this case, there is an effect of increasing the injection efficiency of electrons from the cathode to the light emitting layer.
상기 전자주입층의 두께는 일례로 0.01 내지 10 nm, 0.01 내지 5 nm, 0.05 내지 3 nm, 또는 1 내지 3 nm일 수 있으며, 이 범위 내에서 구동 전압 상승 없이 전자 주입 특성을 향상시키는 효과가 있다.The thickness of the electron injection layer may be, for example, 0.01 to 10 nm, 0.01 to 5 nm, 0.05 to 3 nm, or 1 to 3 nm, and within this range, there is an effect of improving electron injection characteristics without increasing the driving voltage. .
상기 발광층은 일례로 도펀트 물질, 호스트 물질, 또는 이들 모두를 포함하는 것일 수 있고, 이 경우 발광 효율이 크게 향상되는 이점이 있다.The light-emitting layer may include, for example, a dopant material, a host material, or both, and in this case, there is an advantage in that luminous efficiency is greatly improved.
일례로 상기 도펀트 물질이 본 기재의 형광 재료를 포함할 경우, 상기 호스트 물질은 mCP(N,N-dicarbazolyl-3,5-benzene), DPEPO((bis 2-(diphenylphosphino)phenyl] ether oxide), Alq3(트리스(8-퀴놀리노레이트)알루미늄), CBP(4,4'-N,N'-dicarbazol-biphenyl), 9,10-디(나프탈렌-2-일)안트라센, TPBI(1,3,5-tris(N-phenylbenzimidazole-2-yl)benzene)), TBADN(3-tert-부틸-9,10-디(나프트-2-일) 안트라센) 및 mCBP(3,3'-Di(9H-carbazol-9-yl)-1,1'-biphenyl)로 이루어진 군으로부터 선택된 1종 이상일 수 있으며, 이 경우 적색, 녹색, 청색의 발광색을 구현할 수 있고, 낮은 구동 전압에서도 발광 효율이 향상되는 효과가 있다.For example, when the dopant material includes the fluorescent material of the present disclosure, the host material is mCP (N,N-dicarbazolyl-3,5-benzene), DPEPO ((bis 2-(diphenylphosphino)phenyl] ether oxide), Alq3 (tris (8-quinolinolate) aluminum), CBP (4,4'-N,N'-dicarbazol-biphenyl), 9,10-di (naphthalen-2-yl) anthracene, TPBI (1,3, 5-tris(N-phenylbenzimidazole-2-yl)benzene)), TBADN(3-tert-butyl-9,10-di(naphth-2-yl) anthracene) and mCBP(3,3'-Di(9H It may be one or more selected from the group consisting of -carbazol-9-yl)-1,1'-biphenyl), and in this case, the luminous colors of red, green, and blue can be implemented, and the luminous efficiency is improved even at a low driving voltage. There is.
또 다른 일례로, 상기 호스트 물질이 본 기재의 형광 재료를 포함하는 경우, 상기 도펀트 물질은 형광 도펀트일 수 있고, 상기 형광 도펀트는 일례로 당업계에서 통상적으로 사용되는 것이면 특별히 제한되지 않으나 녹색의 형광을 발하는 형광 그린 도펀트인 것이 바람직하며, 이 경우 유기 발광 다이오드는 초형광(Hyper Fluorescence, HF) 소자일 수 있다.As another example, when the host material includes the fluorescent material of the present disclosure, the dopant material may be a fluorescent dopant, and the fluorescent dopant is not particularly limited as long as it is commonly used in the art, for example, but green fluorescence It is preferable that it is a fluorescent green dopant that emits light, and in this case, the organic light emitting diode may be a Hyper Fluorescence (HF) device.
상기 형광 도펀트는 일례로 페릴렌(perylene), TBPe(2,5,8,11-tetra-tert-butylperylene), BCzVB(1,4-bis[2-(3-N-ethylcarbazoryl)vinyl]benzene), BCzVBi(4,4'-bis(9-ethyl-3-carbazovinylene)-1,1'-biphenyl), BDAVBi(4,4'-bis[4-diphenylamino]styryl)biphenyl), DPAVB(4-(di-p-tolylamino)-4'-[(di-p-tolylamino)styryl]stilbene), DPAVBi(4,4'-bis[4-(di-p-tolylamino)styryl]bipnehyl), DSA-Ph(1-4-di-[4-(N,N-diphenyl)amino]styryl-benzene), C545T(2,3,6,7-테트라하이드로-1,1,7,7,-테트라메틸-1H,5H,11H-10(2-벤조티아졸릴)퀴놀리지노-[9,9a,1gh]쿠마린), DMQA(N,N'-디메틸-퀴나크리돈), TPA(9,10-bis[phenyl(m-tolyl)-amino]anthracene), BA-TTB(N10,N10,N10',N10'-tetra-tolyl-9,9'-bianthracene-10,10'-diamine), DCM(4-(dicyanomethylene)-2-methyl-6-[p-(dimethylamino)styryl]-4H-pyran), DCJTB(4-(Dicyanomethylene)-2-tert-butyl-6-(1,1,7,7,-tetramethyljulolidyl-9-enyl)-4H-pyran), AAAP(6-methyl-3-[3-(1,1,6,6-tetramethyl-10-oxo-2,3,5,6-tetrahydro-1H,4H,10H-11-oxa-3a-azabenzo[de]-anthracen-9-yl)acryloyl]pyran-2,4-dione), BSN(1,10-dicyano-substituted bis-styrylnaphthalene derivative) DBP(tetraphenyldibenzoperiflanthene) 및 루브렌으로 이루어진 군으로부터 선택된 1종 이상일 수 있으나 이에 한정되지 않는다.Examples of the fluorescent dopant include perylene, TBPe (2,5,8,11-tetra-tert-butylperylene), BCzVB (1,4-bis[2-(3-N-ethylcarbazoryl)vinyl]benzene) , BCzVBi(4,4'-bis(9-ethyl-3-carbazovinylene)-1,1'-biphenyl), BDAVBi(4,4'-bis[4-diphenylamino]styryl)biphenyl), DPAVB(4-( di-p-tolylamino)-4'-[(di-p-tolylamino)styryl]stilbene), DPAVBi(4,4'-bis[4-(di-p-tolylamino)styryl]bipnehyl), DSA-Ph( 1-4-di-[4-(N,N-diphenyl)amino]styryl-benzene), C545T(2,3,6,7-tetrahydro-1,1,7,7,-tetramethyl-1H, 5H,11H-10(2-benzothiazolyl)quinozino-[9,9a,1gh]coumarin), DMQA(N,N'-dimethyl-quinacridone), TPA(9,10-bis[phenyl( m-tolyl) -amino] anthracene) , BA-TTB (N 10, N 10, N 10 ', N 10'-tetra-tolyl-9,9'-bianthracene-10,10'-diamine), DCM (4 -(dicyanomethylene)-2-methyl-6-[p-(dimethylamino)styryl]-4H-pyran), DCJTB(4-(Dicyanomethylene)-2-tert-butyl-6-(1,1,7,7, -tetramethyljulolidyl-9-enyl)-4H-pyran), AAAP(6-methyl-3-[3-(1,1,6,6-tetramethyl-10-oxo-2,3,5,6-tetrahydro-1H ,4H,10H-11-oxa-3a-azabenzo[de]-anthracen-9-yl)acryloyl]pyran-2,4-dione), BSN(1,10-dicyano-substituted bis-styrylnaphthalene derivat ive) DBP (tetraphenyldibenzoperiflanthene) and rubrene may be one or more selected from the group consisting of, but is not limited thereto.
상기 형광 재료는 일례로 발광층 총 100 중량%에 대하여 10 내지 90 중량%, 10 내지 80 중량%, 또는 10 내지 70 중량%로 포함할 수 있고, 이 경우 효율이 우수한 효과가 있다.The fluorescent material may include, for example, 10 to 90% by weight, 10 to 80% by weight, or 10 to 70% by weight based on the total 100% by weight of the light emitting layer, and in this case, there is an effect of excellent efficiency.
상기 제 1전극은 일례로 애노드이고, 상기 제 2전극은 일례로 캐소드일 수 있으며, 이 경우 애노드로부터 정공이 주입되어 발광층으로 이동하고, 캐소드로부터 전자가 주입되어 발광층으로 이동하여, 상기 정공과 전자는 발광층에서 결합하여 엑시톤(exiton)을 생성하여 적색, 녹색, 청색의 발광색의 구현 효과가 우수하다.The first electrode is an anode as an example, and the second electrode may be a cathode as an example. In this case, holes are injected from the anode to move to the emission layer, and electrons are injected from the cathode to move to the emission layer, and the holes and electrons Is combined in the emission layer to generate excitons, and has excellent effect of realizing red, green, and blue emission colors.
상기 애노드는 일례로 전도성 금속 산화물, 금속 및 탄소로 이루어진 군으로부터 1종 이상을 포함할 수 있다.The anode may include, for example, one or more from the group consisting of a conductive metal oxide, a metal, and carbon.
상기 전도성 금속 산화물은 일례로 ITO(indium tin oxide), FTO(fluorine tin oxide), AZO(aluminium zinc oxide), GZO(galium zinc oxide), ATO(antimony tin oxide), IZO(indium zinc oxide), ZnO(zinc oxide) 및 OMO(oxide/metal/oxide)로 이루어진 군으로부터 선택된 1종 이상일 수 있고, 이 경우 투명성이 우수한 효과가 있다.The conductive metal oxide is, for example, indium tin oxide (ITO), fluorine tin oxide (FTO), aluminum zinc oxide (AZO), galium zinc oxide (GZO), antimony tin oxide (ATO), indium zinc oxide (IZO), and ZnO. It may be one or more selected from the group consisting of (zinc oxide) and OMO (oxide/metal/oxide), and in this case, there is an excellent effect of transparency.
상기 금속은 일례로 당업계에서 통상적으로 사용되는 것이면 특별히 제한되지 않는다.The metal is not particularly limited as long as it is commonly used in the art, for example.
상기 탄소는 일례로 흑연, 그라핀 및 탄소나노튜브로 이루어진 군으로부터 선택된 1종 이상일 수 있다.The carbon may be one or more selected from the group consisting of graphite, graphene, and carbon nanotubes, for example.
상기 캐소드는 일례로 당업계에서 통상적으로 사용되는 것이면 특별히 제한되지 않으나 일례로 알루미늄, 마그네슘, 칼슘, 나트륨, 칼륨, 인듐, 리튬, 은, 납 및 세슘으로 이루어진 군으로부터 선택된 1종 이상을 포함할 수 있다.The cathode is not particularly limited as long as it is commonly used in the art, for example, but may include at least one selected from the group consisting of aluminum, magnesium, calcium, sodium, potassium, indium, lithium, silver, lead, and cesium. have.
상기 유기 발광 다이오드는 일례로 제 1전극; 정공주입층; 정공수송층; 발광층; 전자수송층; 전자주입층; 및 제 2전극;이 순차적으로 적층된 구조일 수 있고, 바람직하게는 제 1전극과 발광층 사이에 전자차단층을, 제 2전극과 발광층 사이에 정공차단층을 추가로 더 포함할 수 있다.The organic light emitting diode may include, for example, a first electrode; Hole injection layer; Hole transport layer; Light-emitting layer; Electron transport layer; Electron injection layer; And a second electrode; may be sequentially stacked, preferably an electron blocking layer between the first electrode and the emission layer, and a hole blocking layer between the second electrode and the emission layer.
상기 유기 발광 다이오드는 일례로 발광 휘도가 4,000 cd/m2 이상, 4,000 내지 7,000 cd/m2, 또는 4,200 내지 5,500 cd/m2일 수 있고, 이 범위 내에서 우수한 발광 효율을 얻는 이점이 있다.For example, the organic light emitting diode may have an emission luminance of 4,000 cd/m 2 or more, 4,000 to 7,000 cd/m 2 , or 4,200 to 5,500 cd/m 2 , and has an advantage of obtaining excellent luminous efficiency within this range.
상기 유기 발광 다이오드는 일례로 발광 효율이 40 cd/A 이상, 40 내지 70 cd/A, 또는 42 내지 60 cd/A일 수 있다.For example, the organic light emitting diode may have a luminous efficiency of 40 cd/A or higher, 40 to 70 cd/A, or 42 to 60 cd/A.
본 기재에서 발광 휘도 및 발광 효율은 10 mA/cm2을 기준으로 평가한 값이다.In the present description, the luminance and luminous efficiency are values evaluated based on 10 mA/cm 2.
이하, 본 발명의 이해를 돕기 위하여 바람직한 합성예 및 실시예를 제시하나, 하기 합성예 및 실시예는 본 발명을 예시하는 것일 뿐 본 발명의 범주 및 기술사상 범위 내에서 다양한 변경 및 수정이 가능함은 당업자에게 있어서 명백한 것이며, 이러한 변형 및 수정이 첨부된 특허청구범위에 속하는 것도 당연한 것이다.Hereinafter, preferred synthesis examples and examples are presented to aid the understanding of the present invention, but the following synthesis examples and examples are only illustrative of the present invention, and various changes and modifications are possible within the scope and spirit of the present invention. It is obvious to those skilled in the art, and it is natural that such modifications and modifications fall within the appended claims.
[합성예][Synthesis Example]
[화합물 1][Compound 1]
화합물 1-1의 합성Synthesis of compound 1-1
4,5-디브로모-2-클로로벤조니트릴 20g (67.7 mmol), 11,12-디하이드로인돌로[2,3-a]카바졸 17.4g (67.7 mmol), 소듐터셔리부톡사이드 26g (270.8 mmol), Pd2(dba)3 6.2g (6.8 mmmol), 트리터셔리뷰틸포스핀(50% in 톨루엔) 6.6ml (13.5 mmol)을 톨루엔 350ml에 현탁시킨 후 12시간 동안 환류 교반하였다. 디클로로메탄과 증류수로 추출하고 유기층을 실리카겔 필터하였다. 유기 용액을 제거하고 실리카겔 컬럼하여 화합물 1, 10.5g (수율: 40%)을 얻었다.4,5-dibromo-2-chlorobenzonitrile 20g (67.7 mmol), 11,12-dihydroindolo[2,3-a]carbazole 17.4g (67.7 mmol), sodium tertiarybutoxide 26g ( 270.8 mmol), Pd 2 (dba) 3 6.2 g (6.8 mmmol), triturateylphosphine (50% in toluene) 6.6 ml (13.5 mmol) were suspended in 350 ml of toluene and stirred under reflux for 12 hours. Extracted with dichloromethane and distilled water, and the organic layer was filtered with silica gel. The organic solution was removed and subjected to silica gel column to obtain compound 1, 10.5g (yield: 40%).
화합물 1-2의 합성Synthesis of compound 1-2
화합물 1-1 10.5g (26.9 mmol), 비스(피나콜라토)디보론 10.8g (40.4 mmol), Pd(dba)2 0.8g (1.3 mmol), 포타슘아세테이트 5.3g (53.9 mmmol), 트리사이클로헥실포스핀 1.8g (6.5 mmol)을 1,4-다이옥산 150 ml 현탁시킨 후 12시간 동안 80°C 하에서 교반하였다. 반응 종료 후, 혼합액을 셀라이트 필터하였다. 여액을 감압 증류 후 실리카겔 컬럼하여 화합물 1-2, 10.3g (수율: 80%)을 얻었다.Compound 1-1 10.5g (26.9 mmol), bis(pinacolato) diborone 10.8g (40.4 mmol), Pd(dba) 2 0.8g (1.3 mmol), potassium acetate 5.3g (53.9 mmmol), tricyclohexyl Phosphine 1.8 g (6.5 mmol) was suspended in 150 ml of 1,4-dioxane and stirred at 80 °C for 12 hours. After completion of the reaction, the mixture was filtered through Celite. The filtrate was distilled under reduced pressure and then subjected to silica gel column to obtain Compound 1-2, 10.3 g (yield: 80%).
화합물 1의 합성Synthesis of compound 1
화합물 1-2 7g (14.5 mmol), 2-클로로-4,6-디페닐-1,3,5-트리아진 3.9g (14.5 mmol), Pd(PPh3)4 0.8g (0.7 mmol), 포타슘카보네이트 4.0g (29.1 mmmol)을 톨루엔 75 ml, 에틸알코올 15 ml, 증류수 15 ml에 현탁시킨 후 12시간 동안 환류 교반하였다. 반응이 끝난 후, 디클로로메탄과 증류수로 추출하고 유기층을 감압 증류 후 실리카겔 컬럼하여 화합물 1, 5.9g (수율: 70%)을 얻었다.Compound 1-2 7g (14.5 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine 3.9g (14.5 mmol), Pd(PPh 3 ) 4 0.8g (0.7 mmol), potassium 4.0 g (29.1 mmmol) of carbonate was suspended in 75 ml of toluene, 15 ml of ethyl alcohol, and 15 ml of distilled water, and then stirred under reflux for 12 hours. After the reaction was completed, the mixture was extracted with dichloromethane and distilled water, and the organic layer was distilled under reduced pressure and then subjected to silica gel column to obtain Compound 1, 5.9 g (yield: 70%).
[화합물 2][Compound 2]
화합물 2의 합성Synthesis of compound 2
화합물 1-2 7g (14.5 mmol), 4-클로로-2,6-디페닐피리미딘 3.9g (14.5 mmol), Pd(PPh3)4 0.8g (0.7 mmol), 포타슘카보네이트 4g (29.1 mmmol)을 톨루엔 75 ml, 에틸알코올 15 ml, 증류수 15 ml에 현탁시킨 후 12시간 동안 환류 교반하였다. 반응이 끝난 후, 디클로로메탄과 증류수로 추출하고 유기층을 감압 증류 후 실리카겔 컬럼하여 화합물 2, 6.4g (수율: 75%)을 얻었다.Compound 1-2 7g (14.5 mmol), 4-chloro-2,6-diphenylpyrimidine 3.9g (14.5 mmol), Pd(PPh 3 ) 4 0.8g (0.7 mmol), potassium carbonate 4g (29.1 mmmol) After suspending in 75 ml of toluene, 15 ml of ethyl alcohol, and 15 ml of distilled water, the mixture was stirred under reflux for 12 hours. After the reaction was completed, the mixture was extracted with dichloromethane and distilled water, and the organic layer was distilled under reduced pressure and then subjected to silica gel column to obtain Compound 2, 6.4 g (yield: 75%).
[화합물 3][Compound 3]
화합물 3의 합성Synthesis of compound 3
화합물 1-2 7g (14.5 mmol), 2―([1,1'-디페닐]-3-yl-4-클로로-6-페닐-1,3,5-트리아진 5g (14.5 mmol), Pd(PPh3)4 0.8g (0.7 mmol), 포타슘카보네이트 4g (29.1 mmmol)을 톨루엔 75 ml, 에틸알코올 15 ml, 증류수 15 ml에 현탁시킨 후 12시간 동안 환류 교반하였다. 반응이 끝난 후, 디클로로메탄과 증류수로 추출하고 유기층을 감압 증류 후 실리카겔 컬럼하여 화합물 3, 6.7g (수율: 70%)을 얻었다.Compound 1-2 7g (14.5 mmol), 2-([1,1'-diphenyl]-3-yl-4-chloro-6-phenyl-1,3,5-triazine 5g (14.5 mmol), Pd (PPh 3 ) 4 0.8 g (0.7 mmol), potassium carbonate 4 g (29.1 mmmol) were suspended in 75 ml of toluene, 15 ml of ethyl alcohol, and 15 ml of distilled water, and then stirred under reflux for 12 hours. And extracted with distilled water, the organic layer was distilled under reduced pressure, and then subjected to silica gel column to obtain Compound 3, 6.7 g (yield: 70%).
[화합물 4][Compound 4]
화합물 4-1의 합성Synthesis of compound 4-1
2,3-디브로모-4-클로로벤조니트릴 20g (67.7 mmol), 11,12-디하이드로인돌로[2,3-a]카바졸 17.4g (67.7 mmol), 소듐터셔리부톡사이드 26g (270.8 mmol), Pd2(dba)3 6.2g (6.8 mmmol), 트리터셔리뷰틸포스핀(50% in 톨루엔) 6.6ml (13.5 mmol)을 톨루엔 350ml에 현탁시킨 후 12시간 동안 환류 교반하였다. 디클로로메탄과 증류수로 추출하고 유기층을 실리카겔 필터하였다. 유기 용액을 제거하고 실리카겔 컬럼하여 화합물 4, 11.9g (수율: 45%)을 얻었다.2,3-dibromo-4-chlorobenzonitrile 20g (67.7 mmol), 11,12-dihydroindolo[2,3-a]carbazole 17.4g (67.7 mmol), sodium tertiarybutoxide 26g ( 270.8 mmol), Pd 2 (dba) 3 6.2 g (6.8 mmmol), triturateylphosphine (50% in toluene) 6.6 ml (13.5 mmol) were suspended in 350 ml of toluene and stirred under reflux for 12 hours. Extracted with dichloromethane and distilled water, and the organic layer was filtered with silica gel. The organic solution was removed and subjected to silica gel column to obtain compound 4, 11.9 g (yield: 45%).
화합물 4-2의 합성Synthesis of compound 4-2
화합물 4-1 11.9g (30.5 mmol), 비스(피나콜라토)디보론 12.2g (45.8 mmol), Pd(dba)2 0.9g (1.5 mmol), 포타슘아세테이트 6g (61 mmmol), 트리사이클로헥실포스핀 2g (7.3 mmol)을 1,4-다이옥산 150 ml 현탁시킨 후 12시간 동안 80°C 하에서 교반하였다. 반응 종료 후, 혼합액을 셀라이트 필터하였다. 여액을 감압 증류 후 실리카겔 컬럼하여 화합물 4-2, 12.5g (수율: 85%)을 얻었다.Compound 4-1 11.9g (30.5 mmol), bis(pinacolato)diborone 12.2g (45.8 mmol), Pd(dba) 2 0.9g (1.5 mmol), potassium acetate 6g (61 mmmol), tricyclohexylphos Pin 2g (7.3 mmol) was suspended in 150 ml of 1,4-dioxane and stirred at 80 °C for 12 hours. After completion of the reaction, the mixture was filtered through Celite. The filtrate was distilled under reduced pressure and then subjected to silica gel column to obtain compound 4-2, 12.5 g (yield: 85%).
화합물 4의 합성Synthesis of compound 4
화합물 4-2 7g (14.5 mmol), 2-클로로-4,6-디페닐-1,3,5-트리아진 3.9g (14.5 mmol), Pd(PPh3)4 0.8g (0.7 mmol), 포타슘카보네이트 4g (29.1 mmmol)을 톨루엔 70 ml, 에틸알코올 15 ml, 증류수 15 ml에 현탁시킨 후 12시간 동안 환류 교반하였다. 반응이 끝난 후, 디클로로메탄과 증류수로 추출하고 유기층을 감압 증류 후 실리카겔 컬럼하여 화합물 4, 5.9g (수율: 70%)을 얻었다.Compound 4-2 7g (14.5 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine 3.9g (14.5 mmol), Pd(PPh 3 ) 4 0.8g (0.7 mmol), potassium 4 g (29.1 mmmol) of carbonate was suspended in 70 ml of toluene, 15 ml of ethyl alcohol, and 15 ml of distilled water, and then stirred under reflux for 12 hours. After the reaction was completed, the mixture was extracted with dichloromethane and distilled water, and the organic layer was distilled under reduced pressure and then subjected to silica gel column to obtain Compound 4, 5.9g (yield: 70%).
[화합물 5][Compound 5]
화합물 5-1의 합성Synthesis of compound 5-1
2,3-디브로모-5-클로로-4,6-디플루오로벤조니트릴 20g (60.4 mmol), 11,12-디하이드로인돌로[2,3-a]카바졸 15.4g (60.4 mmol), 소듐터셔리부톡사이드 23.2g (241.4 mmol), Pd2(dba)3 5.5g (6 mmmol), 트리터셔리뷰틸포스핀(50% in 톨루엔) 5.85 ml (12.1 mmol)을 톨루엔 300 ml에 현탁시킨 후 12시간 동안 환류 교반하였다. 디클로로메탄과 증류수로 추출하고 유기층을 실리카겔 필터하였다. 유기 용액을 제거하고 실리카겔 컬럼하여 화합물 5, 10.3g (수율: 40%)을 얻었다.2,3-dibromo-5-chloro-4,6-difluorobenzonitrile 20g (60.4 mmol), 11,12-dihydroindolo[2,3-a]carbazole 15.4g (60.4 mmol) , Sodium tertiary butoxide 23.2g (241.4 mmol), Pd 2 (dba) 3 5.5g (6 mmmol), tritertiary phosphine (50% in toluene) 5.85 ml (12.1 mmol) suspended in 300 ml of toluene Then, the mixture was stirred under reflux for 12 hours. Extracted with dichloromethane and distilled water, and the organic layer was filtered with silica gel. The organic solution was removed and subjected to silica gel column to obtain compound 5, 10.3 g (yield: 40%).
화합물 5-2의 합성Synthesis of compound 5-2
화합물 5-1 10.3g (24.2 mmol), 카바졸 8.5g (50.8 mmol), 세슘 카보네이트 33.1g (101.6 mmol)을 다이메틸포름아마이드 120 ml에 현탁시킨 후 16시간 동안 150°C 하에서 교반하였다. 반응이 끝난 후, 디클로로메탄과 증류수로 추출하고 유기층을 감압 증류 후 실리카겔 컬럼하여 화합물 5-2, 10.4g (수율: 60%)을 얻었다.Compound 5-1 10.3g (24.2 mmol), carbazole 8.5g (50.8 mmol), cesium carbonate 33.1g (101.6 mmol) were suspended in 120 ml of dimethylformamide and then stirred at 150 °C for 16 hours. After the reaction was completed, the mixture was extracted with dichloromethane and distilled water, and the organic layer was distilled under reduced pressure and then subjected to silica gel column to obtain Compound 5-2, 10.4g (yield: 60%).
화합물 5-3의 합성Synthesis of compound 5-3
화합물 5-2 10.4g (14.5 mmol), 비스(피나콜라토)디보론 5.8g (21.6 mmol), Pd(dba)2 0.4g (0.7 mmol), 포타슘아세테이트 2.8g (28.9 mmmol), 트리사이클로헥실포스핀 1g (3.5 mmol)을 1,4-다이옥산 75 ml 현탁시킨 후 12시간 동안 80°C 하에서 교반하였다. 반응 종료 후, 혼합액을 셀라이트 필터하였다. 여액을 감압 증류 후 실리카겔 컬럼하여 화합물 5-3, 8.2g (수율: 70%)을 얻었다.Compound 5-2 10.4g (14.5 mmol), bis(pinacolato)diborone 5.8g (21.6 mmol), Pd(dba) 2 0.4g (0.7 mmol), potassium acetate 2.8g (28.9 mmmol), tricyclohexyl 1 g (3.5 mmol) of phosphine was suspended in 75 ml of 1,4-dioxane, and then stirred at 80 °C for 12 hours. After completion of the reaction, the mixture was filtered through Celite. The filtrate was distilled under reduced pressure and then subjected to silica gel column to obtain compound 5-3, 8.2g (yield: 70%).
화합물 5의 합성Synthesis of compound 5
화합물 5-3 7g (8.6 mmol), 2-클로로-4,6-디페닐-1,3,5-트리아진 2.3g (8.6 mmol), Pd(PPh3)4 0.5g (0.4 mmol), 포타슘카보네이트 2.4g (17.2 mmmol)을 톨루엔 45 ml, 에틸알코올 9 ml, 증류수 9 ml에 현탁시킨 후 12시간 동안 환류 교반하였다. 반응이 끝난 후, 디클로로메탄과 증류수로 추출하고 유기층을 감압 증류 후 실리카겔 컬럼하여 화합물 5, 5.5g (수율: 70%)을 얻었다.Compound 5-3 7g (8.6 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine 2.3g (8.6 mmol), Pd(PPh 3 ) 4 0.5g (0.4 mmol), potassium After suspending 2.4 g (17.2 mmmol) of carbonate in 45 ml of toluene, 9 ml of ethyl alcohol, and 9 ml of distilled water, the mixture was stirred under reflux for 12 hours. After the reaction was completed, the mixture was extracted with dichloromethane and distilled water, and the organic layer was distilled under reduced pressure and then subjected to silica gel column to obtain Compound 5, 5.5g (yield: 70%).
[비교 화합물 1][Comparative compound 1]
비교 화합물 1-1의 합성Synthesis of Comparative Compound 1-1
화합물 5-1 20g (74 mmol), 11,12-디하이드로인돌로[2,3-a]카바졸 19g (74 mmol), 소듐터셔리부톡사이드 28.4g (295.9 mmol), Pd2(dba)3 6.8g (7.4 mmmol), 트리터셔리뷰틸포스핀(50% in 톨루엔) 7.2 ml (14.8 mmol)을 톨루엔 370 ml에 현탁시킨 후 12시간 동안 환류 교반하였다. 디클로로메탄과 증류수로 추출하고 유기층을 실리카겔 필터하였다. 유기 용액을 제거하고 실리카겔 컬럼하여 화합물 1, 13.5g (수율: 50%)을 얻었다.Compound 5-1 20g (74 mmol), 11,12-dihydroindolo[2,3-a]carbazole 19g (74 mmol), sodium tertiarybutoxide 28.4g (295.9 mmol), Pd 2 (dba) 3 6.8g (7.4 mmmol), tritertiary phosphine (50% in toluene) 7.2 ml (14.8 mmol) were suspended in 370 ml of toluene and stirred under reflux for 12 hours. Extracted with dichloromethane and distilled water, and the organic layer was filtered with silica gel. The organic solution was removed and subjected to silica gel column to obtain compound 1, 13.5g (yield: 50%).
비교 화합물 1-2의 합성Synthesis of Comparative Compound 1-2
화합물 1-1 13.5g (37 mmol), 비스(피나콜라토)디보론 14.8g (55.5 mmol), Pd(dba)2 1.1g (1.8 mmol), 포타슘아세테이트 7.3g (74 mmmol), 트리사이클로헥실포스핀 2.5g (8.9 mmol)을 1,4-다이옥산 185 ml 현탁시킨 후 12시간 동안 80°C 하에서 교반하였다. 반응 종료 후, 혼합액을 셀라이트 필터하였다. 여액을 감압 증류 후 실리카겔 컬럼하여 비교화합물 1-2, 13.5g (수율: 80%)을 얻었다.Compound 1-1 13.5g (37 mmol), bis(pinacolato) diborone 14.8g (55.5 mmol), Pd(dba) 2 1.1g (1.8 mmol), potassium acetate 7.3g (74 mmmol), tricyclohexyl Phosphine 2.5 g (8.9 mmol) was suspended in 185 ml of 1,4-dioxane and stirred for 12 hours at 80 °C. After completion of the reaction, the mixture was filtered through Celite. The filtrate was distilled under reduced pressure and then subjected to silica gel column to obtain Comparative Compound 1-2, 13.5 g (yield: 80%).
비교 화합물 1의 합성Synthesis of Comparative Compound 1
화합물 1-2 7g (15.3 mmol), 2-클로로-4,6-디페닐-1,3,5-트리아진 4.1g (15.3 mmol), Pd(PPh3)4 0.9g (0.8 mmol), 포타슘카보네이트 4.2g (30.7 mmmol)을 톨루엔 75 ml, 에틸알코올 15 ml, 증류수 15 ml에 현탁시킨 후 12시간 동안 환류 교반하였다. 반응이 끝난 후, 디클로로메탄과 증류수로 추출하고 유기층을 감압 증류 후 실리카겔 컬럼하여 비교화합물 1, 5.6g (수율: 65%)을 얻었다.Compound 1-2 7g (15.3 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine 4.1g (15.3 mmol), Pd(PPh 3 ) 4 0.9g (0.8 mmol), potassium 4.2 g (30.7 mmmol) of carbonate was suspended in 75 ml of toluene, 15 ml of ethyl alcohol, and 15 ml of distilled water, followed by reflux agitation for 12 hours. After the reaction was completed, extraction was performed with dichloromethane and distilled water, and the organic layer was distilled under reduced pressure and then subjected to silica gel column to obtain Comparative Compound 1, 5.6 g (yield: 65%).
[비교 화합물 2][Comparative compound 2]
비교 화합물 2의 합성Synthesis of Comparative Compound 2
질소 분위기 하에서 11,12-디하이드로인돌로[2,3-a]카바졸 10g (39 mmol)을 테트라하이드라퓨란 270 ml에 현탁시킨 후 수소화나트륨(60%) 3.4g (85.8 mmol)을 소량씩 첨가하였다. 첨가가 완료된 후 1시간 동안 상온에서 교반하였다. 그 다음 테트라하이드로퓨란 80 ml에 녹인 3,4-디플루오로벤조니트릴 6g (43 mmol)을 천천히 첨가하였다. 첨가가 완료된 후 12시간 동안 55°C 하에서 교반하였다. 반응 종료 후, 과량의 증류수를 넣어 교반 한 후 디클로로메탄과 증류수로 추출하였다. 유기층을 감압 증류 후 실리카겔 컬럼하여 비교 화합물 2, 9g (수율: 65%)을 얻었다.In a nitrogen atmosphere, 10 g (39 mmol) of 11,12-dihydroindolo[2,3-a]carbazole was suspended in 270 ml of tetrahydrafuran, and 3.4 g (85.8 mmol) of sodium hydride (60%) was added in a small amount. It was added in increments. After the addition was completed, the mixture was stirred at room temperature for 1 hour. Then, 6 g (43 mmol) of 3,4-difluorobenzonitrile dissolved in 80 ml of tetrahydrofuran was slowly added. After the addition was complete, the mixture was stirred at 55°C for 12 hours. After the reaction was completed, an excess of distilled water was added and stirred, followed by extraction with dichloromethane and distilled water. The organic layer was distilled under reduced pressure and then subjected to silica gel column to obtain Comparative Compound 2, 9g (yield: 65%).
[비교 화합물 3][Comparative compound 3]
비교 화합물 3-1의 제조Preparation of Comparative Compound 3-1
2-클로로-4,6-디페닐-1,3,5-트리아진 20 g (74.7 mmol), (4-플루오로페닐)보로닉 에시드 11.5 g (82.2 mmol), Pd(PPh3)4 4.3 g (3.7 mmol), 포타슘카보네이트 20.6 g (149.4 mmol)을 톨루엔 380 ml, 에틸알코올 75 ml, 증류수 75 ml에 현탁시킨 후 12 시간 동안 환류 교반하였다. 반응이 끝난 후, 디클로로메탄과 증류수로 추출하고 유기층을 감압 증류 후 실리카겔 컬럼으로 정제하여 비교 화합물 3-1, 19.6 g (수율: 80%)을 얻었다.2-chloro-4,6-diphenyl-1,3,5-triazine 20 g (74.7 mmol), (4-fluorophenyl) boronic acid 11.5 g (82.2 mmol), Pd(PPh 3 ) 4 4.3 g (3.7 mmol) and potassium carbonate 20.6 g (149.4 mmol) were suspended in 380 ml of toluene, 75 ml of ethyl alcohol, and 75 ml of distilled water, followed by reflux stirring for 12 hours. After the reaction was completed, extraction was performed with dichloromethane and distilled water, and the organic layer was distilled under reduced pressure and purified by a silica gel column to obtain Comparative Compound 3-1, 19.6 g (yield: 80%).
비교 화합물 3의 합성Synthesis of Comparative Compound 3
비교화합물 3-1 1.96 g (5.99 mmol), 1-브로모-9H-카바졸 1.0 g (5.99 mmol), 세슘 카보네이트 3.9 g (11.97 mmol)을 디메틸포름아미드 30 ml에 현탁시킨 후 16 시간 동안 190℃ 하에서 교반하였다. 반응이 끝난 후, 디클로로메탄과 증류수로 추출하고 유기층을 감압 증류 후 실리카겔 컬럼으로 정제하여 비교 화합물 3, 2.1 g (수율: 75%)을 얻었다.Comparative compound 3-1 1.96 g (5.99 mmol), 1-bromo-9H-carbazole 1.0 g (5.99 mmol), cesium carbonate 3.9 g (11.97 mmol) were suspended in 30 ml of dimethylformamide and then 190 for 16 hours. Stirred under °C. After the reaction was completed, extraction was performed with dichloromethane and distilled water, and the organic layer was distilled under reduced pressure and purified by a silica gel column to obtain Comparative Compound 3, 2.1 g (yield: 75%).
[실시예][Example]
실시예 1 (유기 발광 다이오드의 제조) Example 1 (Manufacture of organic light emitting diode)
애노드로 사용되는 ITO (Indium Tin Oxide) glass를 IPA 및 증류수를 이용하여 30 분간 초음파 세척하고 100 ℃의 오븐에서 30 분간 건조한 후 진공 증착 장치 챔버로 이송하였다.ITO (Indium Tin Oxide) glass used as an anode was ultrasonically cleaned for 30 minutes using IPA and distilled water, dried in an oven at 100° C. for 30 minutes, and then transferred to a vacuum deposition apparatus chamber.
다음으로, ITO 기판 위에 차례로 정공 주입층(Hole Injecting Layer, HIL), 정공 수송층(Hole Transport Layer, HTL), 전자 차단층(Electron Blocking Layer, EBL), 유기 발광층(Organic Emitting Layer, OEL), 전자 수송층(Electron Transport Layer, ETL) 및 전자 주입층(Electron Injecting Layer, EIL)을 순차대로 증착하였고(0.5 ~ 1.0Å/sec, 1 × 10-7 ~ 4 × 10-7 torr), 캐소드로 Al layer을 증착하였다. 유기 발광층은 각각 호스트(mCP; N,N-dicarbazolyl-3,5-benzene) 상에 도펀트(화합물 1)를 60:40의 중량비로 포함되도록 제조하였다.Next, on the ITO substrate in turn, a hole injection layer (HIL), a hole transport layer (HTL), an electron blocking layer (EBL), an organic emission layer (OEL), and electrons A transport layer (ETL) and an electron injection layer (EIL) were sequentially deposited (0.5 to 1.0Å/sec, 1 × 10 -7 to 4 × 10 -7 torr), and an Al layer as a cathode. Was deposited. The organic emission layer was prepared to contain a dopant (Compound 1) on a host (mCP; N,N-dicarbazolyl-3,5-benzene) in a weight ratio of 60:40.
진공 증착 후 기판은 글로브 박스(Glove Box)로 옮겨져 봉지공정(Encapsulation)을 진행하여 유기 발광 소자를 제조하였다. 밀봉 부재는 내부에 BaO를 이용한 흡습제(Getter)가 구비된 글래스 캡(Glass cap)으로 구비될 수 있으며, 밀봉용 에폭시 실란트를 도포하여 UV 조사(Curing)하여 증착면으로 산소 및 수분 침투가 차단되는 것을 방지하였다.After vacuum deposition, the substrate was transferred to a glove box and encapsulated to manufacture an organic light-emitting device. The sealing member may be provided as a glass cap with a getter using BaO inside, and an epoxy sealant for sealing is applied and UV irradiation (curing) to block oxygen and moisture penetration into the deposition surface. Was prevented.
상기 실시예 1에서 사용된 성분은 하기 표 1에 나타내었다.Components used in Example 1 are shown in Table 1 below.
도펀트 : 화합물 1 내지 5 또는 비교 화합물 1, 2
호스트 : 도펀트 = 60 : 40 중량비Host: mCBP, CBP, or mCP
Dopant: Compounds 1 to 5 or Comparative Compounds 1 and 2
Host: Dopant = 60: 40 weight ratio
실시예Example 2 내지 7 및 2 to 7 and 비교예Comparative example 1 내지 5 1 to 5
상기 실시예 1에서 하기 표 2의 호스트 물질 및 도펀트 물질을 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 실시하였다.In Example 1, except that the host material and the dopant material of Table 2 were used, it was carried out in the same manner as in Example 1.
[시험예][Test Example]
상기 실시예 1 내지 7 및 비교예 1 내지 5에서 제조된 유기 발광 다이오드에 대하여, Keithley sourcemeter “2635B”, HORIBA Spectrometer“PR-655”을 이용하여 10 mA/cm2을 기준으로 발광 휘도, 발광 효율, 발광 피크를 각각 평가하여, 그 결과를 하기 표 2에 나타내었다. 상기 샘플들은 530 내지 540 ㎚ 범위에서 녹색 발광 피크값을 보여주었다.For the organic light emitting diodes prepared in Examples 1 to 7 and Comparative Examples 1 to 5, luminance and luminous efficiency based on 10 mA/cm 2 using Keithley sourcemeter “2635B” and HORIBA Spectrometer “PR-655” And the emission peaks were evaluated, respectively, and the results are shown in Table 2 below. The samples showed peak values of green emission in the range of 530 to 540 nm.
[cd/A]Luminous efficiency
[cd/A]
상기 표 1에 나타낸 바와 같이, 본 발명의 실시예 1 내지 7의 유기 발광 다이오드는 발광휘도 및 발광효율이 우수한 것을 확인할 수 있었다.As shown in Table 1, it was confirmed that the organic light emitting diodes of Examples 1 to 7 of the present invention have excellent luminance and luminous efficiency.
반면, 본 발명의 도펀트 물질을 포함하지 않는 비교예 1 내지 5의 유기 발광 다이오드의 경우 실시예 1 내지 7의 유기 발광 다이오드 대비 발광휘도 및 발광효율이 모두 저하되는 것을 확인할 수 있었다.On the other hand, in the case of the organic light-emitting diodes of Comparative Examples 1 to 5 that do not contain the dopant material of the present invention, it was confirmed that both the luminance and luminous efficiency were lowered compared to the organic light-emitting diodes of Examples 1 to 7.
Claims (10)
[화학식 1]
(상기 화학식 1에서 X는 질소(N), 붕소(B) 또는 인(P)이고, Y1 내지 Y5는 독립적으로 CR6 또는 N이며, 상기 Y1 내지 Y5 중 적어도 하나는 N이고, R1, R2 및 R6는 독립적으로 수소, 할로겐, 치환 또는 비치환된 탄소수 6 내지 20의 아릴기, 치환 또는 비치환된 탄소수 5 내지 20의 헤테로아릴기, 및 치환 또는 비치환된 탄소수 6 내지 20의 아릴아민기로 이루어진 군으로부터 선택되며, R3 내지 R5는 독립적으로 수소, 치환 또는 비치환된 탄소수 1 내지 20의 알킬기, 치환 또는 비치환된 탄소수 1 내지 20의 알콕시기, 치환 또는 비치환된 탄소수 6 내지 30의 아릴기, 치환 또는 비치환된 탄소수 5 내지 30의 헤테로아릴기, 및 치환 또는 비치환된 탄소수 1 내지 20의 아민기로 이루어진 군으로부터 선택되되, l, m은 독립적으로 0 내지 2의 정수이고, n은 1 내지 3의 정수이며, l+m+n은 3 이하이다.)
Fluorescent material, characterized in that represented by the following formula (1).
[Formula 1]
(In Formula 1, X is nitrogen (N), boron (B) or phosphorus (P), Y 1 to Y 5 are independently CR 6 or N, and at least one of Y 1 to Y 5 is N, R 1 , R 2 and R 6 are independently hydrogen, halogen, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 20 carbon atoms, and a substituted or unsubstituted C 6 To 20 arylamine groups, and R 3 to R 5 are independently hydrogen, a substituted or unsubstituted C 1 to C 20 alkyl group, a substituted or unsubstituted C 1 to C 20 alkoxy group, substituted or unsubstituted Is selected from the group consisting of a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 30 carbon atoms, and a substituted or unsubstituted amine group having 1 to 20 carbon atoms, l and m are independently 0 Is an integer of 2, n is an integer of 1 to 3, and l+m+n is 3 or less.)
상기 화학식 1에서 X는 질소(N)이고, n은 1인 것을 특징으로 하는 형광 재료.
The method of claim 1,
In Formula 1, X is nitrogen (N), and n is a fluorescent material, characterized in that 1.
상기 화학식 1에서 Y1 내지 Y5는 독립적으로 CR6 또는 N이고, 상기 Y1 내지 Y5 중 적어도 하나는 N이며, 상기 R6은 탄소수 6 내지 18의 아릴기, 또는 치환 또는 비치환된 탄소수 6 내지 18의 헤테로아릴기인 것을 특징으로 하는 형광 재료.
The method of claim 1,
In Formula 1, Y 1 to Y 5 are independently CR 6 or N, at least one of Y 1 to Y 5 is N, and R 6 is an aryl group having 6 to 18 carbon atoms, or a substituted or unsubstituted carbon number A fluorescent material characterized in that it is a 6 to 18 heteroaryl group.
상기 화학식 1에서 R1 및 R2는 독립적으로 수소, 탄소수 6 내지 18의 아릴기 및 탄소수 6 내지 18의 헤테로아릴기로 이루어진 군으로부터 선택되는 것을 특징으로 하는 형광 재료.
The method of claim 1,
In Formula 1, R 1 and R 2 are independently selected from the group consisting of hydrogen, an aryl group having 6 to 18 carbon atoms, and a heteroaryl group having 6 to 18 carbon atoms.
상기 화학식 1에서 R3 내지 R5는 독립적으로 수소, 또는 하기 화학식 2-1 내지 2-21 중 하나인 것을 특징으로 하는 형광 재료.
[화학식 2-1]
[화학식 2-2]
[화학식 2-3]
[화학식 2-4]
[화학식 2-5]
[화학식 2-6]
[화학식 2-7]
[화학식 2-8]
[화학식 2-9]
[화학식 2-10]
[화학식 2-11]
[화학식 2-12]
[화학식 2-13]
[화학식 2-14]
[화학식 2-15]
[화학식 2-16]
[화학식 2-17]
[화학식 2-18]
[화학식 2-19]
[화학식 2-20]
[화학식 2-21]
The method of claim 1,
In Formula 1, R 3 to R 5 are independently hydrogen or one of the following Formulas 2-1 to 2-21.
[Formula 2-1]
[Formula 2-2]
[Formula 2-3]
[Formula 2-4]
[Formula 2-5]
[Formula 2-6]
[Formula 2-7]
[Formula 2-8]
[Formula 2-9]
[Formula 2-10]
[Chemical Formula 2-11]
[Formula 2-12]
[Formula 2-13]
[Formula 2-14]
[Formula 2-15]
[Formula 2-16]
[Formula 2-17]
[Formula 2-18]
[Chemical Formula 2-19]
[Formula 2-20]
[Formula 2-21]
상기 화학식 1은 화학식 1-1 내지 1-16 중 하나의 화학식인 것을 특징으로 하는 형광 재료.
[화학식 1-1]
[화학식 1-2]
[화학식 1-3]
[화학식 1-4]
[화학식 1-5]
[화학식 1-6]
[화학식 1-7]
[화학식 1-8]
[화학식 1-9]
[화학식 1-10]
[화학식 1-11]
[화학식 1-12]
[화학식 1-13]
[화학식 1-14]
[화학식 1-15]
[화학식 1-16]
The method of claim 1,
Formula 1 is a fluorescent material, characterized in that one of formulas 1-1 to 1-16.
[Formula 1-1]
[Formula 1-2]
[Formula 1-3]
[Formula 1-4]
[Formula 1-5]
[Formula 1-6]
[Formula 1-7]
[Formula 1-8]
[Formula 1-9]
[Formula 1-10]
[Formula 1-11]
[Formula 1-12]
[Formula 1-13]
[Formula 1-14]
[Formula 1-15]
[Formula 1-16]
상기 발광층은 제 1항 내지 제 6항 중 어느 한 항에 따른 형광 재료를 포함하는 것을 특징으로 하는 유기 발광 다이오드.
A first electrode; A second electrode; And a light emitting layer positioned between the first electrode and the second electrode,
An organic light-emitting diode comprising the fluorescent material according to any one of claims 1 to 6 in the light-emitting layer.
상기 발광층은 도펀트 물질, 호스트 물질, 또는 이들 모두를 포함하는 것을 특징으로 하는 유기 발광 다이오드.
The method of claim 7,
The light emitting layer is an organic light emitting diode comprising a dopant material, a host material, or both.
상기 발광층은 mCP(N,N-dicarbazolyl-3,5-benzene), DPEPO((bis 2-(diphenylphosphino)phenyl] ether oxide), Alq3(트리스(8-퀴놀리노레이트)알루미늄), CBP(4,4'-N,N'-dicarbazol-biphenyl), 9,10-디(나프탈렌-2-일)안트라센, TPBI(1,3,5-tris(N-phenylbenzimidazole-2-yl)benzene)), TBADN(3-tert-부틸-9,10-디(나프트-2-일) 안트라센) 및 mCBP(3,3'-Di(9H-carbazol-9-yl)-1,1'-biphenyl)로 이루어진 군으로부터 선택된 1종 이상인 것을 특징으로 하는 유기 발광 다이오드.
The method of claim 7,
The emission layer is mCP (N,N-dicarbazolyl-3,5-benzene), DPEPO ((bis 2-(diphenylphosphino)phenyl] ether oxide), Alq3 (tris (8-quinolinolate) aluminum), CBP (4, 4'-N,N'-dicarbazol-biphenyl), 9,10-di(naphthalen-2-yl)anthracene, TPBI(1,3,5-tris(N-phenylbenzimidazole-2-yl)benzene)), TBADN (3-tert-butyl-9,10-di(naphth-2-yl) anthracene) and mCBP(3,3'-Di(9H-carbazol-9-yl)-1,1'-biphenyl) Organic light-emitting diode, characterized in that at least one selected from the group.
상기 형광 재료는 발광층 총 100 중량%에 대하여 10 내지 90 중량%로 포함하는 것을 특징으로 하는 유기 발광 다이오드.
The method of claim 7,
The fluorescent material is an organic light-emitting diode comprising 10 to 90% by weight based on the total 100% by weight of the emission layer.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114539268A (en) * | 2022-03-24 | 2022-05-27 | 郑州大学 | Cardipy dye-based lysosome targeted fluorescent probe and preparation method and application thereof |
| CN114656466A (en) * | 2022-04-16 | 2022-06-24 | 常州大学 | Benzo-fused carbazole and indolocarbazole derivative and application of benzo-fused carbazole and indolocarbazole derivative in organic electroluminescent device |
| CN115490693A (en) * | 2022-03-01 | 2022-12-20 | 陕西莱特迈思光电材料有限公司 | Organic compound, and electronic element and electronic device comprising same |
| CN116332945A (en) * | 2022-04-01 | 2023-06-27 | 陕西莱特光电材料股份有限公司 | Organic compound, and electronic component and electronic device including the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20170113808A (en) | 2016-03-25 | 2017-10-13 | 단국대학교 산학협력단 | TADF Material and OLED Having the Same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20170113808A (en) | 2016-03-25 | 2017-10-13 | 단국대학교 산학협력단 | TADF Material and OLED Having the Same |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115490693A (en) * | 2022-03-01 | 2022-12-20 | 陕西莱特迈思光电材料有限公司 | Organic compound, and electronic element and electronic device comprising same |
| CN115490693B (en) * | 2022-03-01 | 2023-11-14 | 陕西莱特迈思光电材料有限公司 | Organic compound, and electronic component and electronic device including the same |
| CN114539268A (en) * | 2022-03-24 | 2022-05-27 | 郑州大学 | Cardipy dye-based lysosome targeted fluorescent probe and preparation method and application thereof |
| CN114539268B (en) * | 2022-03-24 | 2022-12-09 | 郑州大学 | Cardipy dye-based lysosome targeted fluorescent probe and preparation method and application thereof |
| CN116332945A (en) * | 2022-04-01 | 2023-06-27 | 陕西莱特光电材料股份有限公司 | Organic compound, and electronic component and electronic device including the same |
| WO2023185039A1 (en) * | 2022-04-01 | 2023-10-05 | 陕西莱特光电材料股份有限公司 | Organic compound, and electronic element and electronic apparatus comprising same |
| CN114656466A (en) * | 2022-04-16 | 2022-06-24 | 常州大学 | Benzo-fused carbazole and indolocarbazole derivative and application of benzo-fused carbazole and indolocarbazole derivative in organic electroluminescent device |
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