KR20130121597A - Using triphenylamine as hole transporting mateial and organic electroluminescent device using the same - Google Patents
Using triphenylamine as hole transporting mateial and organic electroluminescent device using the sameInfo
- Publication number
- KR20130121597A KR20130121597A KR1020120044955A KR20120044955A KR20130121597A KR 20130121597 A KR20130121597 A KR 20130121597A KR 1020120044955 A KR1020120044955 A KR 1020120044955A KR 20120044955 A KR20120044955 A KR 20120044955A KR 20130121597 A KR20130121597 A KR 20130121597A
- Authority
- KR
- South Korea
- Prior art keywords
- group
- layer
- organic
- formula
- compound
- Prior art date
Links
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 title description 2
- 150000001875 compounds Chemical class 0.000 claims abstract description 40
- 239000010410 layer Substances 0.000 claims description 94
- 125000004432 carbon atom Chemical group C* 0.000 claims description 30
- 230000005525 hole transport Effects 0.000 claims description 22
- 238000002347 injection Methods 0.000 claims description 21
- 239000007924 injection Substances 0.000 claims description 21
- 239000012044 organic layer Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 18
- 125000001424 substituent group Chemical group 0.000 claims description 18
- 239000011368 organic material Substances 0.000 claims description 17
- 150000004982 aromatic amines Chemical group 0.000 claims description 16
- 125000003118 aryl group Chemical group 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- 125000003277 amino group Chemical group 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 15
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims description 12
- -1 phenoxy, phenyl Chemical group 0.000 claims description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 12
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 claims description 12
- 125000002183 isoquinolinyl group Chemical group C1(=NC=CC2=CC=CC=C12)* 0.000 claims description 11
- 230000000903 blocking effect Effects 0.000 claims description 10
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 claims description 10
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 125000001624 naphthyl group Chemical group 0.000 claims description 9
- 125000001072 heteroaryl group Chemical group 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 125000000732 arylene group Chemical group 0.000 claims description 6
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 6
- 125000005549 heteroarylene group Chemical group 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 4
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 3
- 125000006749 (C6-C60) aryl group Chemical group 0.000 claims description 3
- 125000004448 alkyl carbonyl group Chemical group 0.000 claims description 3
- 125000005129 aryl carbonyl group Chemical group 0.000 claims description 3
- 125000004104 aryloxy group Chemical group 0.000 claims description 3
- 125000004429 atom Chemical group 0.000 claims description 3
- 125000006267 biphenyl group Chemical group 0.000 claims description 3
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 238000006467 substitution reaction Methods 0.000 claims description 3
- 125000005309 thioalkoxy group Chemical group 0.000 claims description 3
- 125000005296 thioaryloxy group Chemical group 0.000 claims description 3
- ZMSZWNCJOCYFOR-UHFFFAOYSA-N 9H-fluorene styrene Chemical compound C1=CC=CC=2C3=CC=CC=C3CC12.C=CC1=CC=CC=C1 ZMSZWNCJOCYFOR-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 48
- 239000000758 substrate Substances 0.000 abstract description 7
- 239000002019 doping agent Substances 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 230000009477 glass transition Effects 0.000 abstract description 2
- 125000005264 aryl amine group Chemical group 0.000 abstract 1
- 238000002425 crystallisation Methods 0.000 abstract 1
- 230000008025 crystallization Effects 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 29
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 17
- 239000000203 mixture Substances 0.000 description 15
- 230000032258 transport Effects 0.000 description 14
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 12
- 239000012153 distilled water Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 7
- 238000000151 deposition Methods 0.000 description 7
- 239000000706 filtrate Substances 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000004770 highest occupied molecular orbital Methods 0.000 description 6
- 238000004020 luminiscence type Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 description 4
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 4
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- JNGZXGGOCLZBFB-IVCQMTBJSA-N compound E Chemical compound N([C@@H](C)C(=O)N[C@@H]1C(N(C)C2=CC=CC=C2C(C=2C=CC=CC=2)=N1)=O)C(=O)CC1=CC(F)=CC(F)=C1 JNGZXGGOCLZBFB-IVCQMTBJSA-N 0.000 description 3
- 229920001940 conductive polymer Polymers 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
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- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 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 3
- 239000002904 solvent Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- HNWFFTUWRIGBNM-UHFFFAOYSA-N 2-methyl-9,10-dinaphthalen-2-ylanthracene Chemical compound C1=CC=CC2=CC(C3=C4C=CC=CC4=C(C=4C=C5C=CC=CC5=CC=4)C4=CC=C(C=C43)C)=CC=C21 HNWFFTUWRIGBNM-UHFFFAOYSA-N 0.000 description 2
- QENGPZGAWFQWCZ-UHFFFAOYSA-N 3-Methylthiophene Chemical compound CC=1C=CSC=1 QENGPZGAWFQWCZ-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 229940126062 Compound A Drugs 0.000 description 2
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 2
- LWLSVNFEVKJDBZ-UHFFFAOYSA-N N-[4-(trifluoromethoxy)phenyl]-4-[[3-[5-(trifluoromethyl)pyridin-2-yl]oxyphenyl]methyl]piperidine-1-carboxamide Chemical compound FC(OC1=CC=C(C=C1)NC(=O)N1CCC(CC1)CC1=CC(=CC=C1)OC1=NC=C(C=C1)C(F)(F)F)(F)F LWLSVNFEVKJDBZ-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
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- 125000004093 cyano group Chemical group *C#N 0.000 description 2
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- 230000001965 increasing effect Effects 0.000 description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
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- 125000003003 spiro group Chemical group 0.000 description 2
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- 239000010409 thin film Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- CEBAHYWORUOILU-UHFFFAOYSA-N (4-cyanophenyl)boronic acid Chemical compound OB(O)C1=CC=C(C#N)C=C1 CEBAHYWORUOILU-UHFFFAOYSA-N 0.000 description 1
- JWJQEUDGBZMPAX-UHFFFAOYSA-N (9-phenylcarbazol-3-yl)boronic acid Chemical compound C12=CC=CC=C2C2=CC(B(O)O)=CC=C2N1C1=CC=CC=C1 JWJQEUDGBZMPAX-UHFFFAOYSA-N 0.000 description 1
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 description 1
- UHXOHPVVEHBKKT-UHFFFAOYSA-N 1-(2,2-diphenylethenyl)-4-[4-(2,2-diphenylethenyl)phenyl]benzene Chemical compound C=1C=C(C=2C=CC(C=C(C=3C=CC=CC=3)C=3C=CC=CC=3)=CC=2)C=CC=1C=C(C=1C=CC=CC=1)C1=CC=CC=C1 UHXOHPVVEHBKKT-UHFFFAOYSA-N 0.000 description 1
- 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 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- DMEVMYSQZPJFOK-UHFFFAOYSA-N 3,4,5,6,9,10-hexazatetracyclo[12.4.0.02,7.08,13]octadeca-1(18),2(7),3,5,8(13),9,11,14,16-nonaene Chemical group N1=NN=C2C3=CC=CC=C3C3=CC=NN=C3C2=N1 DMEVMYSQZPJFOK-UHFFFAOYSA-N 0.000 description 1
- DHDHJYNTEFLIHY-UHFFFAOYSA-N 4,7-diphenyl-1,10-phenanthroline Chemical compound C1=CC=CC=C1C1=CC=NC2=C1C=CC1=C(C=3C=CC=CC=3)C=CN=C21 DHDHJYNTEFLIHY-UHFFFAOYSA-N 0.000 description 1
- HXWWMGJBPGRWRS-CMDGGOBGSA-N 4- -2-tert-butyl-6- -4h-pyran Chemical compound O1C(C(C)(C)C)=CC(=C(C#N)C#N)C=C1\C=C\C1=CC(C(CCN2CCC3(C)C)(C)C)=C2C3=C1 HXWWMGJBPGRWRS-CMDGGOBGSA-N 0.000 description 1
- 239000005725 8-Hydroxyquinoline Substances 0.000 description 1
- OHGJAUSHXQCSQX-UHFFFAOYSA-N 9h-fluoren-2-ylboronic acid Chemical compound C1=CC=C2C3=CC=C(B(O)O)C=C3CC2=C1 OHGJAUSHXQCSQX-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
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- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
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- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
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- HUMMCEUVDBVXTQ-UHFFFAOYSA-N naphthalen-1-ylboronic acid Chemical compound C1=CC=C2C(B(O)O)=CC=CC2=C1 HUMMCEUVDBVXTQ-UHFFFAOYSA-N 0.000 description 1
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- 238000000103 photoluminescence spectrum Methods 0.000 description 1
- 229920000553 poly(phenylenevinylene) Polymers 0.000 description 1
- 229920002098 polyfluorene Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 150000003220 pyrenes Chemical class 0.000 description 1
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000007650 screen-printing Methods 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
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium(II) oxide Chemical compound [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 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
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Abstract
Description
본 발명은 비대칭 구조를 이용한 유기전계 발광소자에 관한 것으로, 보다 구체적으로 3차 아릴 아민 및 플루오렌, 카바졸, 스파이로등의 물질을 포함하는 유기전계 발광소자에 관한것이다.The present invention relates to an organic electroluminescent device using an asymmetric structure, and more particularly to an organic electroluminescent device comprising tertiary aryl amine and materials such as fluorene, carbazole, spiro and the like.
유기전계 발광소자는 1965년에 pope등에 의해 안트라센의 단결정으로부터 유기 발광물질이 처음 발견된 것을 이래로, 1987년 Tang과 Vanslyke이 유기전계발광소자 (organic light-emitting diode, OLED)의 다층 박막구조를 이용하여 고효율의 특성을 보고한 이후 OLED는 차세대 디스플레이로서의 우수한 특성뿐만 아니라 LCD 배면광 및 조명등에 사용가능한 잠재력을 가지고 있어 각광을 받으며 많은 연구가 진행되고 있다.The organic light emitting device was first discovered in 1965 by an organic light emitting material from anthracene single crystal by pope, etc. In 1987, Tang and Vanslyke used a multilayer thin film structure of organic light-emitting diode (OLED). After reporting the characteristics of high efficiency, OLED has the potential to be used for LCD back light and lighting as well as excellent characteristics as the next generation display, and many studies have been conducted.
이러한 발광재료는 크게 형광과 인광으로 나뉘며, 발광층 형성 방법은 형광 호스트(Host)에 인광(Dopant)을 도핑하는 방법과 형광 호스트에 형광 도판트를 도핑하여 양자 효율을 증가시키는 방법 및 발광체에 도판트 (DCM, DCJTB등)를 이용하여 발광파장을 장파장으로 이동시키는 방법 등이 있다. 이러한 도핑을 통해 발광 파장, 효율, 구동전압, 수명 등을 개선하려하고 있다.These light emitting materials are largely divided into fluorescence and phosphorescence, and a light emitting layer forming method includes a method of doping phosphorescent dopants in a fluorescent host, a method of increasing quantum efficiency by doping a fluorescent dopant in a fluorescent host, and a dopant in a light emitting body. (DCM, DCJTB, etc.), there is a method for moving the light emission wavelength to a long wavelength. Such doping is intended to improve the emission wavelength, efficiency, driving voltage, lifetime, and the like.
일반적인 유기 전계 발광 소자의 구조는 양극, 정공을 양극으로부터 받아들이는 정공 주입층(HIL), 정공을 이송하는 정공 수송층(HTL), 정공과 전자가 결합하여 빛을 내는 발광층 (EML), 전자를 음극으로부터 받아들여 발광층으로 전달하는 전자 수송층(ETL), 그리고 음극으로 구성되어 있다. 진공증착법에 의해 형성된 이러한 박막 구조는 정공과 전자의 이동 속도를 조절하여 발광층에서 정공과 전자의 밀도가 균형을 이루도록 하여 발광효율을 높일 수 있게 한다. 또한 유기 전계 발광 소자의 실용화 및 특성 향상을 위해서는, 상기와 같이 다층 구조로 구성할 뿐만 아니라 소자 재료 특히, 정공 전달 물질이 열적 및 전기적으로 안정적이어야 한다. The structure of a general organic EL device includes an anode, a hole injection layer (HIL) that receives holes from an anode, a hole transport layer (HTL) that transports holes, a light emitting layer (EML) that combines holes and electrons to emit light, and an electron as a cathode. It consists of an electron transport layer (ETL) and a cathode which receive from and deliver to a light emitting layer. Such a thin film structure formed by the vacuum evaporation method can adjust the moving speed of holes and electrons to balance the densities of holes and electrons in the light emitting layer, thereby enhancing the luminous efficiency. In addition, for practical use and improvement of properties of the organic EL device, not only the multilayer structure as described above, but also the device material, in particular, the hole transport material must be thermally and electrically stable.
정공전달 물질로는 현재까지 많은 진행되어 왔으며, 비교적 유기 용매에 잘 녹는것으로 확인 되어졌다. 지금까지 사용되어 왔던 정공 전달 물질에는 TPD 및 NPB등이 있으며, 각각 유리전이온도(Tg)가 60 ℃ 및 96℃로 낮기 때문에 상기와 같은 이유로 소자의 수명을 단축시킨다는 치명적인 단점이 있다.As a hole transport material, many progresses have been made so far, and it has been confirmed that it is relatively soluble in organic solvents. The hole transport materials that have been used up to now include TPD and NPB, and the glass transition temperature (Tg) is low as 60 ° C and 96 ° C, respectively.
유기전계 발광소자에 사용되는 상기 종래의 정공 전달 물질은 여전히 성능 개선이 요구되고, 따라서 소자의 수명 및 발광효율을 향상시킬 수 있는 우수한 재료에 대한 필요성이 존대한다.The conventional hole transport materials used in organic light emitting devices still need to improve performance, and thus there is a need for excellent materials that can improve the lifetime and luminous efficiency of devices.
본 발명은 상기와 같은 종래 기술의 문제점을 향상시키기 위하여 고안된 것으로 3차 아민에 비대칭 구조를 도입하여 다층 구조의 유기전계 발광소자의 전달물질로써 열안정성이 우수하고 수명이 증가될 뿐만 아니라 발광 휘도 및 효율이 우수한 유기전계 발광소자를 제공한다.The present invention is designed to improve the problems of the prior art as described above by introducing an asymmetric structure in the tertiary amine as a transfer material of the organic electroluminescent device of the multi-layer structure, excellent thermal stability and increased lifetime, as well as luminescence brightness and Provided is an organic EL device having excellent efficiency.
상기 해결하고자는 과제를 이루기 위하여 본 발명에서는, 하기 화학식1, 화학식2, 화학식3, 화학식4 로 표시되는 비대칭 구조의 3차 아릴 아민계 화합물을 제공한다. In order to achieve the above object, the present invention provides a tertiary aryl amine compound having an asymmetric structure represented by the following formula (1), (2), (3) and (4).
화학식1Formula 1
상기 화학식 1에서 Y1 및 Y2는 서로 같거나 다르고, 단일결합이거나, 또는, 치환기가 있거나 없는 탄소수 6 내지 60의 아릴렌기, 치환기가 있거나 없는 탄소수 3 내지 60의 헤테로아릴렌기 또는 치환기가 있거나 없는 플루오레일렌기이며In Formula 1, Y 1 and Y 2 may be the same as or different from each other, and may be a single bond, or an arylene group having 6 to 60 carbon atoms with or without a substituent, a heteroarylene group having 3 to 60 carbon atoms, or without a substituent. It is a fluorylene group
X는 1가 또는 2가이며, 치환기가 있거나 없는 탄소수 6 내지60의 아릴기 또는 아릴렌기, 또는 치환기가 있거난 없는 탄소수 2 내지 60의 헤테로아릴기 또는 헤테로아릴렌기이다. X is monovalent or divalent and is a C6-C60 aryl group or arylene group with or without a substituent, or a C2-C60 heteroaryl group or heteroarylene group with or without substituents.
상기 화학식 1의 X 는 X in Chemical Formula 1
상기 a1 및 a2 는 동일 또는 상이한 것으로, 각각 H, C4~C25의 아릴기, C4~C25의 헤테로아릴기, 아미노기 및 치환된 아미노기로 이루어진 군에서 선택된 어느 하나이며, A1 and a2 are the same or different, each selected from the group consisting of H, C4 ~ C25 aryl group, C4 ~ C25 heteroaryl group, amino group and substituted amino group,
상기L 은 C 또는 N이며, L is C or N,
상기L 이 N일 경우, a1는 비공유전자쌍이며, a2는 H, C1~C13의 알킬기, C4~C25의 아릴기 및 C4~C25의 헤테로아릴기로 이루어진 군에서 선택된 어느 하나이고, When L is N, a1 is a non-covalent electron pair, a2 is any one selected from the group consisting of H, an alkyl group of C1-C13, an aryl group of C4-C25, and a heteroaryl group of C4-C25,
상기L 이 C일 경우, a1 및 a2 는 동일 또는 상이한 것으로, 각각 H, C1~C13의 알킬기, C4~C25의 헤테로아릴기로 이루어진 군에서 선택된 어느 하나이거나, 상기 a1 및 a2가 C4~C20의 고리로 연결된 구조이며 다음과 같은 구조를 지닌다.
When L is C, a1 and a2 are the same or different, and each one selected from the group consisting of H, C1-C13 alkyl group and C4-C25 heteroaryl group, or a1 and a2 are C4-C20 ring It is connected to and has the following structure.
화학식 2(2)
상기 화학식 2의 L이 N인 경우, a1은 비공유전자쌍이며, a2는 H, C1~C13의 알킬기, 페닐기(phenyl), 나프틸기(naphthyl), 안트라세닐기(anthracenyl),When L in
퀴놀리닐기(quinolinyl) 및 이소퀴놀릴리닐기(isoquinolinyl)로 이루어진 군에서 선택된 어느 하나일 수 있으나, 이에 한정되는 것은 아니다. A quinolinyl group (quinolinyl) and isoquinolinyl group (isoquinolinyl) may be any one selected from the group consisting of, but is not limited thereto.
상기 화학식2의 L이 C 일 경우, a1 및 a2는 동일 또는 상이한 것으로 각각 H, C1~C13의 알킬기, 페닐기(phenyl), 나프틸기(naphthyl), 안트라세닐기(anthrac When L in
enyl), 퀴놀리닐기(quinolinyl) 및 이소퀴놀릴리닐기(isoquinolinyl)로 이루어진 군에서 선택된 어느 하나일 수 있으나, 이에 한정되는 것은 아니다.enyl), quinolinyl group (quinolinyl) and isoquinolinyl group (isoquinolinyl) may be any one selected from the group consisting of, but is not limited thereto.
화학식 1 에 있어서,In formula (1)
Y1 내지 Y2 각각 독립적으로 수소원자, 할로젠 원자, 치환 또는 비치환된 탄소수 1 내지 50의 알킬기 치환 또는 비치환된 탄소수 1 내지 50의 알콕시기, 치환 또는 비치환된 탄소수 4 내지 50의 아릴옥시기, 치환 또는 비치환된 탄소수 1 내지 50의 싸이오알콕시기, 치환 또는 비치환된 탄소수 4 내지 50의 싸이오아릴옥시기, 치환 또는 비치환된 아미노기, 치환 또는 비치환된 탄소수 4 내지 50의 아릴기, 치환 또는 비치환된 탄소수 1 내지 50의 알킬카보닐기, 또는 치환 또는 비치환된 탄소수 4 내지 50의 아릴카보닐기이며, A 내지 B에 의해 정의되는 원자 및 기는 서로 동일하거나 상이 할 수 있다.Y 1 to Y 2 Each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 50 carbon atoms, a substituted or unsubstituted aryloxy group having 4 to 50 carbon atoms, substituted or Unsubstituted thioalkoxy group having 1 to 50 carbon atoms, substituted or unsubstituted thioaryloxy group having 4 to 50 carbon atoms, substituted or unsubstituted amino group, substituted or unsubstituted aryl group having 4 to 50 carbon atoms, substitution Or an unsubstituted alkyl carbonyl group having 1 to 50 carbon atoms, or a substituted or unsubstituted arylcarbonyl group having 4 to 50 carbon atoms, and the atoms and groups defined by A to B may be the same or different from each other.
화학식1에 있어서, Y1, Y2 는 각각 독립적으로, 페닐기, 나프틸기, 비페닐기, 플루오렌기, 카바졸기에서 선택되는 아릴기 또는 이들의 방향족 고리에 C1-C4 알킬, C1-C5 알콕시, 시아노, 아민, 페녹시, 페닐, 플루오렌기 또는 할로겐이 1 내지 3개가 치환된 아릴기인 것을 특징으로 하는 화합물In Formula 1, Y1 and Y2 are each independently an aryl group selected from a phenyl group, a naphthyl group, a biphenyl group, a fluorene group, a carbazole group, or a C1-C4 alkyl, C1-C5 alkoxy, cyano to an aromatic ring thereof , Amine, phenoxy, phenyl, fluorene group or a compound characterized in that the halogen is an aryl group substituted with 1 to 3
화학식1에 있어서In Chemical Formula 1
X가 플루오렌계을 포함하고, Y1 및 Y2 는 같거나 상이할 수 있으며, 다음과 같은 구조를 지닌다.X comprises fluorene and Y 1 and Y 2 May be the same or different and have the following structure:
화학식3(3)
화학식2에 있어서In Formula 2
X가 카바졸계를 포함하고, Y1 및 Y2는 같거나 상이할 수 있으며, 다음과 같은 구조를 지닌다.
X includes a carbazole type, Y 1 and Y 2 may be the same or different, and have the following structure.
화학식4Formula 4
상기 3차 아릴 아민은 평면 패널 디스플레이, 평면 발광체, 조명용 면발광 OLED의 발광체,flexible 발광체, 복사기, 프린터, LCD 백라이트, 계량기 광원, 디스플레이판, 유기전계 발광소자(OLED), 유기태양전지(OSC), 전자종이(E-paper), 유기 감광체(OPC) 및 유기트랜지스터(OTFT) 중에서 선택된 어느 하나에 적용될 수 있으나, 이에 한정되는 것은 아니다.The tertiary aryl amines are flat panel displays, flat emitters, illuminators for surface emitting OLEDs for illumination, flexible emitters, copiers, printers, LCD backlights, meter light sources, display panels, organic light emitting diodes (OLEDs), organic solar cells (OSCs) , E-paper, an organic photoconductor (OPC), and an organic transistor (OTFT) may be applied to any one selected from, but is not limited thereto.
본 발명은 또한, 제1 전극, 제 2 전극 및 이들 전극 사이에 1 층 이상의 유기물층을 포함하며, 상기 유기물층의 적어도 1층 이상이 상기 3차 아릴 아민을 포함하는 유기전계 발광소자를 제공한다.The present invention also provides an organic electroluminescent device comprising a first electrode, a second electrode and at least one organic layer between these electrodes, wherein at least one layer of the organic layer comprises the tertiary aryl amine.
상기 1 층 이상의 유기물층은 발광층을 포함하며, 정공 주입층, 정공 수송층, 정공 저지층, 전자수송층, 및 전자 주입층으로 이루어진 군에서 선택된 1종 이상의 층을 더 포함할 수 있다.
The at least one organic layer may include a light emitting layer, and may further include at least one layer selected from the group consisting of a hole injection layer, a hole transport layer, a hole blocking layer, an electron transport layer, and an electron injection layer.
본 발명에 따른 화합물은 종래 기술의 문제점을 향상시키기 위하여 고안된 것으로, 아릴 아민에 방향족와 플로렌 헤테로 아릴기등을 도입하여 다층구조의 유기 전계발광 소자의 전달물질로써 열안정성이 우수하고 수명이 증가될 뿐만 아니라 발광 휘도 및 효율이 우수한 유기 전계 발광 소자를 제공할 수 있을 것이다. 또한 본 발명에 따른 아릴아민 유도체는 정공수송을 위한 물질 이외에 그 치환체의 종류에 따라 다양한 특성을 구비할 수 있어서 치환체에 따라 정공주입, 정공 수송, 전자 주입 및 수송의 역할을 모두 할 수 있으며, 고효율, 고색순도가 우수한 유기 전계 발광소자를 제공하여 디스플레이 산업의 기술 향상에 이바지 할 것으로 기대된다.
Compound according to the present invention is designed to improve the problems of the prior art, by introducing an aromatic and florene hetero aryl group in the aryl amine as a transport material of the organic electroluminescent device of a multi-layer structure, excellent thermal stability and increase the lifespan In addition, it will be possible to provide an organic EL device having excellent luminescence brightness and efficiency. In addition, the arylamine derivative according to the present invention may have various characteristics depending on the type of substituents in addition to the material for hole transport, and may serve as a hole injection, hole transport, electron injection and transport depending on the substituent, and high efficiency In addition, it is expected to contribute to the improvement of technology of the display industry by providing an organic EL device having excellent color purity.
본 발명에 따른 화합물은 종래 기술의 문제점을 향상시키기 위하여 고안된 것으로, 아릴 아민에 방향족와 플로렌 헤테로 아릴기등을 도입하여 다층구조의 유기 전계발광 소자의 전달물질로써 열안정성이 우수하고 수명이 증가될 뿐만 아니라 발광 휘도 및 효율이 우수한 유기 전계 발광 소자를 제공할 수 있을 것이다. 또한 본 발명에 따른 아릴아민 유도체는 정공수송을 위한 물질 이외에 그 치환체의 종류에 따라 다양한 특성을 구비할 수 있어서 치환체에 따라 정공주입, 정공 수송, 전자 주입 및 수송의 역할을 모두 할 수 있으며, 고효율, 고색순도가 우수한 유기 전계 발광소자를 제공하여 디스플레이 산업의 기술 향상에 이바지 할 것으로 기대된다.Compound according to the present invention is designed to improve the problems of the prior art, by introducing an aromatic and florene hetero aryl group in the aryl amine as a transport material of the organic electroluminescent device of a multi-layer structure, excellent thermal stability and increase the lifespan In addition, it will be possible to provide an organic EL device having excellent luminescence brightness and efficiency. In addition, the arylamine derivative according to the present invention may have various characteristics depending on the type of substituents in addition to the material for hole transport, and may serve as a hole injection, hole transport, electron injection and transport depending on the substituent, and high efficiency In addition, it is expected to contribute to the improvement of technology of the display industry by providing an organic EL device having excellent color purity.
본 발명은 하기 화학식1, 화학식2, 화학식3, 화학식4 로 표시되는 비대칭 구조의 3차 아릴 아민계 화합물을 제공한다.The present invention provides a tertiary aryl amine compound having an asymmetric structure represented by the following formula (1), (2), (3) and (4).
화학식1Formula 1
상기 화학식 1에서 Y1 및 Y2는 서로 같거나 다르고, 단일결합이거나, 또는, 치환기가 있거나 없는 탄소수 6 내지 60의 아릴렌기, 치환기가 있거나 없는 탄소수 3 내지 60의 헤테로아릴렌기 또는 치환기가 있거난 없는 플루오렌일렌기이며In Formula 1, Y 1 and Y 2 may be the same as or different from each other, and may be a single bond, or an arylene group having 6 to 60 carbon atoms with or without a substituent, a heteroarylene group having 3 to 60 carbon atoms with or without a substituent, or a substituent. No fluoreneylene group
X는 1가 또는 2가이며, 치환기가 있거나 없는 탄소수 6 내지60의 아릴기 또는 아릴렌기, 또는 치환기가 있거난 없는 탄소수 2 내지 60의 헤테로아릴기 또는 헤테로아릴렌기이다. X is monovalent or divalent and is a C6-C60 aryl group or arylene group with or without a substituent, or a C2-C60 heteroaryl group or heteroarylene group with or without substituents.
상기 화학식 1의 X 는 X in Chemical Formula 1
상기 a1 및 a2 는 동일 또는 상이한 것으로, 각각 H, C4~C25의 아릴기, C4~C25의 헤테로아릴기, 아미노기 및 치환된 아미노기로 이루어진 군에서 선택된 어느 하나이며, A1 and a2 are the same or different, each selected from the group consisting of H, C4 ~ C25 aryl group, C4 ~ C25 heteroaryl group, amino group and substituted amino group,
상기L 은 C 또는 N이며, L is C or N,
상기L 이 N일 경우, a1는 비공유전자쌍이며, a2는 H, C1~C13의 알킬기, C4~C25의 아릴기 및 C4~C25의 헤테로아릴기로 이루어진 군에서 선택된 어느 하나이고, When L is N, a1 is a non-covalent electron pair, a2 is any one selected from the group consisting of H, an alkyl group of C1-C13, an aryl group of C4-C25, and a heteroaryl group of C4-C25,
상기L 이 C일 경우, a1 및 a2 는 동일 또는 상이한 것으로, 각각 H, C1~C13의 알킬기, C4~C25의 헤테로아릴기로 이루어진 군에서 선택된 어느 하나이거나, 상기 a1 및 a2가 C4~C20의 고리로 연결된 구조이며 다음과 같은 구조를 지닌다. When L is C, a1 and a2 are the same or different, and each one selected from the group consisting of H, C1-C13 alkyl group and C4-C25 heteroaryl group, or a1 and a2 are C4-C20 ring It is connected to and has the following structure.
화학식 2(2)
상기 화학식 2의 L이 N인 경우, a1은 비공유전자쌍이며, a2는 H, C1~C13의 알킬기, 페닐기(phenyl), 나프틸기(naphthyl), 안트라세닐기(anthracenyl),When L in
퀴놀리닐기(quinolinyl) 및 이소퀴놀릴리닐기(isoquinolinyl)로 이루어진 군에서 선택된 어느 하나일 수 있으나, 이에 한정되는 것은 아니다. A quinolinyl group (quinolinyl) and isoquinolinyl group (isoquinolinyl) may be any one selected from the group consisting of, but is not limited thereto.
상기 화학식2의 L이 C 일 경우, a1 및 a2는 동일 또는 상이한 것으로 각각 H, C1~C13의 알킬기, 페닐기(phenyl), 나프틸기(naphthyl), 안트라세닐기(anthrac When L in
enyl), 퀴놀리닐기(quinolinyl) 및 이소퀴놀릴리닐기(isoquinolinyl)로 이루어진 군에서 선택된 어느 하나일 수 있으나, 이에 한정되는 것은 아니다.enyl), quinolinyl group (quinolinyl) and isoquinolinyl group (isoquinolinyl) may be any one selected from the group consisting of, but is not limited thereto.
화학식1 에 있어서,In Chemical Formula 1,
Y1 내지 Y2 각각 독립적으로 수소원자, 할로젠 원자, 치환 또는 비치환된 탄소수 1 내지 50의 알킬기 치환 또는 비치환된 탄소수 1 내지 50의 알콕시기, 치환 또는 비치환된 탄소수 4 내지 50의 아릴옥시기, 치환 또는 비치환된 탄소수 1 내지 50의 싸이오알콕시기, 치환 또는 비치환된 탄소수 4 내지 50의 싸이오아릴옥시기, 치환 또는 비치환된 아미노기, 치환 또는 비치환된 탄소수 4 내지 50의 아릴기, 치환 또는 비치환된 탄소수 1 내지 50의 알킬카보닐기, 또는 치환 또는 비치환된 탄소수 4 내지 50의 아릴카보닐기이며, A 내지 B에 의해 정의되는 원자 및 기는 서로 동일하거나 상이 할 수 있다.Y 1 to Y 2 Each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 50 carbon atoms, a substituted or unsubstituted aryloxy group having 4 to 50 carbon atoms, substituted or Unsubstituted thioalkoxy group having 1 to 50 carbon atoms, substituted or unsubstituted thioaryloxy group having 4 to 50 carbon atoms, substituted or unsubstituted amino group, substituted or unsubstituted aryl group having 4 to 50 carbon atoms, substitution Or an unsubstituted alkyl carbonyl group having 1 to 50 carbon atoms, or a substituted or unsubstituted arylcarbonyl group having 4 to 50 carbon atoms, and the atoms and groups defined by A to B may be the same or different from each other.
화학식1에 있어서, Y1, Y2 는 각각 독립적으로, 페닐기, 나프틸기, 비페닐기, 플루오렌기, 카바졸기에서 선택되는 아릴기 또는 이들의 방향족 고리에 C1-C4 알킬, C1-C5 알콕시, 시아노, 아민, 페녹시, 페닐, 플루오렌기 또는 할로겐이 1 내지 3개가 치환된 아릴기인 것을 특징으로 하는 화합물In Formula 1, Y1 and Y2 are each independently an aryl group selected from a phenyl group, a naphthyl group, a biphenyl group, a fluorene group, a carbazole group, or a C1-C4 alkyl, C1-C5 alkoxy, cyano to an aromatic ring thereof , Amine, phenoxy, phenyl, fluorene group or a compound characterized in that the halogen is an aryl group substituted with 1 to 3
화학식1에 있어서In Chemical Formula 1
X가 플루오렌계을 포함하고, Y1 및 Y2 는 같거나 상이할 수 있으며, 다음과 같은 구조를 지닌다.X comprises fluorene and Y 1 and Y 2 May be the same or different and have the following structure:
화학식3(3)
화학식2에 있어서In
X가 카바졸계를 포함하고, Y1 및 Y2는 같거나 상이할 수 있으며, 다음과 같은 구조를 지닌다.
X includes a carbazole type, Y 1 and Y 2 may be the same or different, and have the following structure.
화학식4Formula 4
도3 및 도4에는 상기 화학식1로 표시되는 3차아릴 아민의 예로 하기 화합물 B1의 UV/PL 스펙트럼 및 열적 안정성에 대한 데이터를 나타내었다.3 and 4 show data on the UV / PL spectrum and thermal stability of the following compound B1 as an example of the tertiary aryl amine represented by Chemical Formula 1.
B1 B1
상기 도 3의 UV(Ultraviolet)/PL(Photoluminescene) 스펙트럼은 OLED를 특성화하기 위하여 각 화합물이 갖는 발광 파장을 측정하는 것으로, UV를 통하여 흡수되는 파장의 빛을 조사하여 가장 발광이 잘 일어나는 파장을 측정한 그래프이다. The UV (Ultraviolet) / PL (Photoluminescene) spectrum of FIG. 3 measures the emission wavelength of each compound to characterize the OLED, and measures the wavelength at which the most emission occurs by irradiating light of the wavelength absorbed through the UV. One graph.
상기 UV(Ultraviolet)/PL(Photoluminescene) 스펙트럼은 당 업계의 공지의 방법을 통하여 얻을 수 있으며, 본 발명에서는 퀄츠(quartz)에 상기 화합물 B1이 포함된 용액을 코팅하여 제조된 고체 필름에 약 340nm 파장의 여기광을 조사하여 도 3의 스펙트럼을 얻었으며, 도 3에 도시한 바와 같이 약 433nm에서 최대 발광 피크를 가지므로 발광 효율이 우수할 것으로 기대된다. 그러나, 그 구체적 수치는 화합물의 순도, 주변 환경 등에 따라 달라질 것인바, 세부적 수치보다는 데이터의 경향이 중요하다고 할 수 있다.The UV (Ultraviolet) / PL (Photoluminescene) spectrum can be obtained through a method known in the art, in the present invention is about 340nm wavelength on a solid film prepared by coating a solution containing the compound B1 in the quartz (quartz) The spectrum of FIG. 3 was obtained by irradiating the excitation light, and since it has a maximum emission peak at about 433 nm as shown in FIG. 3, it is expected that the luminous efficiency will be excellent. However, the specific value will vary depending on the purity of the compound, the surrounding environment, etc., and thus, the trend of the data is more important than the detailed value.
상기 도4는 정공전달물질의 열안정성 특성을 알아보기 위한 것으로, 이 역시 당 업계의 공지의 방법을 통하여 평가될 수 있으며, 본 발명에서는 열중량분석법(TGA)을 이용하여 질소 분위기 하에서 팬에 일정 무게의 화합물 B1의 시료를 달아 일정한 속도로 온도를 증가시키면서 시료의 무게 변화를 측정하여 열적 안정성에 대한 데이터를 얻었다. 그 결과 도 4에 도시한 바와 같이 화합물 B1의 열분해 온도가 약 300 ℃ 이상으로 우수한 열적 안정성을 갖는 것을 확인할 수 있었으며, 이를 토대로 본 발명에 따른 상기 화학식1로 표시되는 3차 아릴 아민은 300 ℃ 정도의 고온에서도 열적 안정성을 나타냄을 확인할 수 있다.Figure 4 is to determine the thermal stability characteristics of the hole transport material, which can also be evaluated through a method known in the art, in the present invention, the thermogravimetric analysis (TGA) using a constant temperature in the fan under nitrogen atmosphere A sample of the compound B1 of weight was weighed and the temperature change was measured at a constant rate to obtain data on thermal stability. As a result, as shown in FIG. 4, it was confirmed that the thermal decomposition temperature of Compound B1 was about 300 ° C. or more, and the tertiary aryl amine represented by Formula 1 according to the present invention was about 300 ° C. It can be seen that the thermal stability is shown even at high temperature.
한편, 본 발명은 또한 상기와 같은 화학식 1의 아릴아민 화합물을 포함하는 유기전계 발광 재료를 더 제공한다. On the other hand, the present invention also provides an organic electroluminescent material comprising the arylamine compound of Formula 1 as described above.
상기 유기전계 발광 재료는 전술한 화학식 1의 아릴아민 화합물을 이용하여 한 층 이상의 유기물 층을 형성하는 것을 제외하고는, 통상의 유기전계소자의 제조방법 및 재료에 의하여 제조될 수 있다.The organic electroluminescent material may be prepared by a conventional method and material for manufacturing an organic electroluminescent device, except that at least one organic layer is formed using the arylamine compound of Formula 1 described above.
즉, 본 발명의 유기 전자소자는 제 1전극, 제 2전극 및 이들 전극사이에 배치된 1층 이상의 유기물층을 포함하며, 상기 유기물층 중 적어도 1층 이상이 본 발명의 화학식 1로 표시되는 아릴아민유도체를 포함한다. That is, the organic electronic device of the present invention includes a first electrode, a second electrode and one or more organic material layers disposed between these electrodes, and at least one or more of the organic material layers is an arylamine derivative represented by Chemical Formula 1 of the present invention. It includes.
또한 본 발명의 유기 전자소자에서 유기물층은 정공주입층, 정공수송층, 발광층, 정공저지층, 전자수송층을 포함하고, 필요에 따라 정공주입층, 정공수송층, 정공저지층, 전자수송층이 한 개 또는 두 개 층이 생략된 상태로 사용할 수 있다. In addition, in the organic electronic device of the present invention, the organic material layer includes a hole injection layer, a hole transport layer, a light emitting layer, a hole blocking layer, and an electron transport layer, and if necessary, one or two hole injection layers, hole transport layers, hole blocking layers, and electron transport layers. It can be used with the layers omitted.
본 발명의 유기 발광 소자 중 유기물층은 1층으로 이루어진 단층 구조일 수도 있으나, 발광층을 포함하는 2층 이상의 다층구조일 수도 있다. 본 발명의 유기 발광 소자 중 유기물층이 다층 구조인 경우, 이는 예컨대 정공주입층 (Hole Injection Layer), 정공수송층 (Hole Transport Layer), 발광층 (Electroluminescence Layer), 정공저지층, (Hole Blocking Layer), 전자수송층 (Electron Transport Layer) 등이 적층된 구조일 수 있다. The organic material layer of the organic light emitting device of the present invention may be a single layer structure consisting of one layer, may be a multilayer structure of two or more layers including a light emitting layer. When the organic material layer of the organic light emitting device of the present invention has a multi-layer structure, for example, it is a hole injection layer (Hole Injection Layer), a hole transport layer (Hole Transport Layer), an emission layer (Electroluminescence Layer), a hole blocking layer, (Hole Blocking Layer), electron It may have a structure in which an electron transport layer or the like is stacked.
예컨대, 본 발명의 유기 발광 소자의 구조는 도 1 내지 도 2에 나타낸 것과 같은 구조를 가질 수 있으나, 이들에만 한정되는 것은 아니다.For example, the structure of the organic light emitting device of the present invention may have a structure as shown in Figs. 1 to 2, but is not limited thereto.
예컨대, 본 발명에 따른 유기발광소자는 스퍼터링(sputtering) 이나 전자빔 증발(e-beam evaporation)과 같은 공지의 PVD(physical vapor deposition) 방법을 이용하여, 기판 상에 금속 또는 전도성을 가지는 금속 산화물 또는 이들의 합금을 증착시켜 양극을 형성하고, 그 위에 정공주입층, 정공수송층, 발광층, 정공저지층 및 전자수송층을 포함하는 유기물층을 형성한 후, 그 위에 음극으로 사용할 수 있는 물질을 증착시킴으로써 제조될 수 있다. For example, the organic light emitting device according to the present invention is a metal oxide having a metal or conductivity on a substrate or a metal oxide on a substrate using known physical vapor deposition (PVD) methods such as sputtering or e-beam evaporation It can be prepared by depositing an alloy of the anode to form an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, a hole blocking layer and an electron transport layer thereon, and then depositing a material that can be used as a cathode thereon have.
이와 같은 방법 외에도, 기판 상에 음극 물질부터 유기물층, 양극 물질을 차례로 증착시켜 유기발광소자를 만들 수도 있다.In addition to the above method, an organic light emitting device may be manufactured by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate.
상기 유기물층은 정공주입층, 정공수송층, 발광층, 정공저지층 및 전자수송층 등을 포함하는 다층 구조일 수도 있으나, 이에 한정되지 않고 단층 구조일 수 있다. 또한, 상기 유기물층은 다양한 고분자 소재를 사용하여 증착법이 아닌 용매 공정(solvent process), 예컨대 스핀 코팅, 딥 코팅, 닥터 블레이딩, 스크린 프린팅, 잉크젯 프린팅 또는 열전사법 등의 방법에 의하여 더 적은 수의 층으로 제조할 수 있다.The organic material layer may have a multi-layer structure including a hole injection layer, a hole transport layer, a light emitting layer, a hole blocking layer, and an electron transport layer, but is not limited thereto and may have a single layer structure. The organic material layer may be formed using a variety of polymer materials by a method such as a solvent process such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, .
상기 양극 물질로는 통상 유기물층으로 정공주입이 원활할 수 있도록 일함수가 큰 물질이 바람직하다. 본 발명에서 사용될 수 있는 양극 물질의 구체적인 예로는 바나듐, 크롬, 구리, 아연, 금과 같은 금속 또는 이들의 합금; 아연산화물, 인듐산화물, 인듐주석 산화물(ITO), 티타늄 산화물 (TiO), 인듐아연산화물(IZO)과 같은 금속 산화물; ZnO:Al 또는 SnO2:Sb와 같은 금속과 산화물의 조합; 폴리(3-메틸티오펜), 폴리[3,4-(에틸렌-1,2-디옥시)티오펜](PEDT), 폴리피롤 및 폴리아닐린과 같은 전도성 고분자 등이 있으나, 이들에만 한정되는 것은 아니다.As the anode material, a material having a large work function is preferably used so that hole injection can be smoothly conducted into the organic material layer. Specific examples of the cathode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), titanium oxide (TiO), and indium zinc oxide (IZO); ZnO: Al or SnO 2: a combination of a metal and an oxide such as Sb; Conductive polymers such as poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDT), polypyrrole and polyaniline.
상기 음극 물질로는 통상 유기물층으로 전자주입이 용이하도록 일함수가 작은 물질인 것이 바람직하다. 음극 물질의 구체적인 예로는 마그네슘, 칼슘, 나트륨, 칼륨, 티타늄, 인듐, 이트륨, 리튬, 가돌리늄, 알루미늄, 은, 주석 및 납과 같은 금속 또는 이들의 합금; LiAl 및 LiF/Al 또는 Li2O/Al과 같은 다층 구조 물질 등이 있으나, 이들에만 한정되는 것은 아니다.The negative electrode material is preferably a material having a small work function to facilitate electron injection into the organic material layer. Specific examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead or alloys thereof; Multilayer structures such as LiAl and LiF / Al or Li 2 O / Al, and the like, but are not limited thereto.
정공주입 물질로는 낮은 전압에서 양극으로부터 정공을 잘 주입받을 수 있는 물질로서, 정공주입 물질의 HOMO(highest occupied molecular orbital)가 양극 물질의 일함수와 주변 유기물층의 HOMO 사이인 것이 바람직하다. 또한 양극과의 표면 접착력이 좋으며, 양극의 표면 거칠기를 완화해줄 수 있는 평탄화 능력이 있는 물질이 바람직하다. 그리고 발광층의 밴드갭보다 큰 HOMO와 LUMO 값을 갖는 물질이 바람직하다. 또한 화학 구조적으로 열적 안정성이 높은 물질이 바람직하다. As the hole injecting material, it is preferable that the highest occupied molecular orbital (HOMO) of the hole injecting material be between the work function of the anode material and the HOMO of the surrounding organic layer. In addition, a material having good surface adhesion with the positive electrode and having a planarization ability that can alleviate the surface roughness of the positive electrode is preferable. And a material having HOMO and LUMO values larger than the bandgap of the light emitting layer is preferable. In addition, materials having high thermal stability in chemical structure are preferable.
정공주입 물질의 구체적인 예로는 금속 포피린(porphyrine), 올리고티오펜, 아릴아민 계열의 유기물, 헥사니트릴헥사아자트리페닐렌 계열의 유기물, 퀴나크리돈(quinacridone) 계열의 유기물, 페릴렌(perylene) 계열의 유기물, 안트라퀴논 및 폴리아닐린과 폴리티오펜 계열의 전도성 고분자 등이 있으나, 이들에만 한정되는 것은 아니다.Specific examples of the hole injecting material include metal porphyrine, oligothiophene, arylamine-based organic materials, hexanitrile hexaazatriphenylene-based organic materials, quinacridone-based organic materials, perylene , Anthraquinone, polyaniline and polythiophene-based conductive polymers, but the present invention is not limited thereto.
정공수송 물질로는 양극이나 정공주입층으로부터 정공을 수송 받아 발광층으로 옮겨줄 수 있는 물질로 정공에 대한 이동성이 큰 물질이 적합하다. 발광층의 밴드갭보다 큰 HOMO와 LUMO 값을 갖는 물질이 적합하다. 또한 화학 구조적으로 열적 안정성이 높은 물질이 적합하다. As the hole transporting material, a material capable of transporting holes from the anode or the hole injection layer to the light emitting layer and having high mobility to holes is suitable. A material having HOMO and LUMO values larger than the bandgap of the light emitting layer is suitable. Materials with high chemical stability and thermal stability are also suitable.
구체적인 예로는 아릴아민 계열의 유기물, 전도성 고분자, 및 공액 부분과 비공액 부분이 함께 있는 블록 공중합체 등이 있으나, 이들에만 한정되는 것은 아니다.Specific examples include arylamine-based organic materials, conductive polymers, and block copolymers having a conjugated portion and a non-conjugated portion together, but are not limited thereto.
발광 물질로는 정공수송층과 전자수송층으로부터 정공과 전자를 각각 수송받아 결합시킴으로써 가시광선 영역의 빛을 낼 수 있는 물질로서, 양자효율이 좋은 물질이 바람직하다. As the light emitting material, a material capable of emitting light in the visible light region by transporting and combining holes and electrons from the hole transporting layer and the electron transporting layer, respectively, is preferably a material having good quantum efficiency.
구체적인 예로는 청색 계열의 ADN 또는 MADN 및 DPVBi, BAlq 등과 녹색 계열의 Alq3 및 기타의 안트라센, 파이렌, 플루오렌, 스파이(spiro)로 플루오렌, 카르바졸, 벤족사졸, 벤즈티아졸 및 벤즈이미다졸 계열로 표시되는 화합물 및 고분자성의 폴리(p-페닐렌비닐렌), 폴리스파이로, 폴리플루오렌 등이 있으나, 이들에만 한정되는 것은 아니다.Specific examples include fluorene, carbazole, benzoxazole, benzthiazole and benzimidazole with blue ADN or MADN and DPVBi, BAlq and green Alq3 and other anthracenes, pyrenes, fluorenes, spiros, etc. Compounds represented by the series, and polymeric poly (p-phenylenevinylene), polypyro, polyfluorene, and the like, but are not limited thereto.
정공저지층 물질로는 발광의 HOMO 값보다 큰 물질이 적합하다. 또한 화학 구조적으로 열적 안정성이 높은 물질이 적합하다. As the hole blocking layer material, a material larger than the HOMO value of luminescence is suitable. Materials with high chemical stability and thermal stability are also suitable.
구체적인 예로 TPBi와 BCP가 주로 이용되며, CBP와 PBD 및 PTCBI, BPhen 등이 사용될 수 있으며, 이들에만 한정되는 것은 아니다.Specifically, TPBi and BCP are mainly used, and CBP, PBD, PTCBI, BPhen, and the like can be used, but not limited thereto.
전자수송 물질로는 음극으로부터 전자를 잘 주입 받아 발광층으로 옮겨줄 수 있는 물질로서, 전자에 대한 이동성이 큰 물질이 적합하다. As the electron transporting material, a material capable of transferring electrons from the cathode well into the light emitting layer, which is highly mobile, is suitable.
또한 화학 구조적으로 열적 안정성이 높은 물질이 적합하다. Materials with high chemical stability and thermal stability are also suitable.
구체적인 예로는 8-히드록시퀴놀린의 Al 착물; Alq3를 포함한 착물; 유기 라디칼 화합물; 히드록시플라본-금속 착물 등이 있으나, 이들에만 한정되는 것은 아니다.Specific examples include an Al complex of 8-hydroxyquinoline; Complexes containing Alq 3 ; Organic radical compounds; Hydroxyflavone-metal complexes, and the like, but are not limited thereto.
본 발명에 따른 유기발광소자는 사용되는 재료에 따라 전면 발광형, 후면 발광형 또는 양면 발광형일 수 있다. 본 발명에 따른 화합물은 유기태양전지, 유기감광체, 유기트랜지스터, 전자종이 (e-Paper) 등을 비롯한 유기전자소자에서도 유기발광소자에 적용되는 것과 유사한 원리로 작용할 수 있다. The organic light emitting device according to the present invention may be a front emission type, a back emission type, or a both-sided emission type, depending on the material used. The compound according to the present invention may act on a principle similar to that applied to organic light emitting devices in organic electronic devices including organic solar cells, organic photoconductors, organic transistors, electronic paper (e-Paper) and the like.
이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시한다. 그러나 하기의 실시예는 본 발명을 보다 쉽게 이해하기 위하여 제공되는 것일 뿐, 이에 의해 본 발명의 내용이 한정되는 것은 아니다.Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, the following examples are merely provided to more easily understand the present invention, and the contents of the present invention are not limited thereto.
본 발명의 아릴 아민 화합물은 우수한 전기적 특성 및 정공 수송 특성을 보이므로 유기전계발광소자의 정공 수송층 물질로서 유용하게 사용될 수 있다.
Since the aryl amine compound of the present invention exhibits excellent electrical and hole transport properties, it may be usefully used as a hole transport layer material of an organic light emitting device.
합성예Synthetic example 1: 화합물 A의 제조 1: Preparation of Compound A
A A
건조된 둥근플라스크에 트리페닐아민 ( 5 g, 20.38 mmol)과 엔-브로모석신이미드 ( 3.62 g, 20.38 mmol)을 클로로포름 100 ml에 넣고 70 ℃에서 4시간 환류시키면서 교반하였다.Triphenylamine (5 g, 20.38 mmol) and en-bromosuccinimide (3.62 g, 20.38 mmol) were added to 100 ml of chloroform in a dried round flask and stirred at 70 ° C. under reflux for 4 hours.
이 후 농축기를 사용하여 용매를 제거하였다. 그 후 에탄올을 이용하여 침전을 얻은 후 에탄올로 워싱하며서 필터하여 화합물 A( 5.12 g 77.4 %를 얻었다.)The solvent was then removed using a concentrator. Then, precipitated using ethanol and washed with ethanol and filtered to obtain Compound A (5.12 g 77.4%).
1H NMR (400 MHz, CDCl3): δ 7.35~7.20(m, 6H), 7.11~6.99(m, 6H), 6.97~6.90(d, 2H) 1 H NMR (400 MHz, CDCl3): δ 7.35-7.20 (m, 6H), 7.11-6.99 (m, 6H), 6.97-6.70 (d, 2H)
합성예Synthetic example 2: 화합물 B의 제조 2: Preparation of compound B
B B
건조된 둥근플라스크에 4-브로모-엔,엔-다이페닐벤젠아민 (5 g, 15.42 mmol), 요오드화칼륨 (5.12 g, 30.84 mmol), 아이오딘산칼륨 (3.3 g, 15.42 mmol)을 AcOH 150 ml에 넣고 85℃에서 5시간 동안 교반시켰다.In a dried round flask, 4-bromo-ene, ene-diphenylbenzeneamine (5 g, 15.42 mmol), potassium iodide (5.12 g, 30.84 mmol), potassium iodide (3.3 g, 15.42 mmol) was added to
이후 상온으로 냉각시키고 증류수를 넣어 반응을 종료하여 다이에틸 에테르와 증류수로 추출한 뒤, 유기층을 무수 황산마그네슘으로 건조한 후 여과하였다.After cooling to room temperature, distilled water was added to terminate the reaction, extracted with diethyl ether and distilled water, and the organic layer was dried over anhydrous magnesium sulfate and filtered.
여과된 유기층을 감압 농축하여 얻어진 혼합물을 에틸아세테이트와 헥산으로 여액층을 컬럼으로 분리하여 화합물 B( 6.8 g, 76.5 %)을 얻었다.The filtered organic layer was concentrated under reduced pressure, and the mixture was separated with ethyl acetate and hexane. The filtrate was separated by a column to obtain Compound B (6.8 g, 76.5%).
1H NMR (400 MHz, CDCl3): δ 7.39(m, 4H), 7.19(d, 2H), 6.35(d, 2H), 6.23(m, 4H) 1 H NMR (400 MHz, CDCl 3): δ 7.39 (m, 4H), 7.19 (d, 2H), 6.35 (d, 2H), 6.23 (m, 4H)
합성예Synthetic example 3: 화합물 C의 제조 3: Preparation of compound C
C C
건조된 둥근 플라스크에 트리스(다이벤질디네아세톤)다이팔라듐 ( 0.158 g, 0.17 mmol), 트라이터트-뷰틸포스핀 ( 0.05 g, 0.26 mmol)을 증류한 톨루엔 100ml에 넣고 질소 하에서 3분간 교반시킨다. 그 후 화합물 B(5 g, 8.68 mmol)을 넣고 10분간 교반시킨 후 9,9-스파이로플루오렌-2-보로닉에시드 (6.2 g, 17.3 mmol), 소듐 터트-부톡사이드 (1.251 g, 13.02 mmol)을 넣고 환류를 시키면서 교반시킨다. 이후 상온으로 냉각시키고, 메틸렌 클로라이드와 증류수로 추출한 뒤, 유기층을 무수 황산마그네슘으로 건조한 후 여과하였다.Tris (dibenzyldineacetone) dipalladium (0.158 g, 0.17 mmol) and tritert-butylphosphine (0.05 g, 0.26 mmol) were added to 100 ml of distilled toluene and stirred under nitrogen for 3 minutes in a dried round flask. Then Compound B (5 g, 8.68 mmol) was added and stirred for 10 minutes, followed by 9,9-spirofluorene-2-boronic acid (6.2 g, 17.3 mmol) and sodium tert-butoxide (1.251 g, 13.02 mmol) and stirred while refluxing. After cooling to room temperature, extracted with methylene chloride and distilled water, the organic layer was dried over anhydrous magnesium sulfate and filtered.
여과된 유기층을 감압 농축하여 얻어진 혼합물을 헥산으로 여액층을 컬럼으로 분리하여 화합물 C( 5.5 g, 66.9%)을 얻었다.The filtered organic layer was concentrated under reduced pressure, and the mixture was separated with hexane. The filtrate was separated by a column to obtain Compound C (5.5 g, 66.9%).
1H NMR (400 MHz, CDCl3): δ 7.55(d, 2H), 8.509(d, 2H), 7.40(m, 16H), 7.20~7.00(m, 16H), 6.5 (m, 4H), 6.35(d, 3H) 1 H NMR (400 MHz, CDCl3): δ 7.55 (d, 2H), 8.509 (d, 2H), 7.40 (m, 16H), 7.20-7.00 (m, 16H), 6.5 (m, 4H), 6.35 ( d, 3H)
합성예Synthetic example 4: 화합물 D의 제조 4: Preparation of compound D
D D
건조된 둥근 플라스크에 화합물 B( 5 g, 8.68 mmol), 4-시아노페닐보로닉에시드 ( 2.5 g, 17.3 mmol), 테트라키스(트리페닐포스핀)팔라듐(0) ( 0.3 g, 0.26 mmol)을 THF 100 ml에 넣고 교반을 시킨 후 2몰 탄산 칼륨 50 ml을 넣고 환류를 시키면서 교반하였다.Compound B (5 g, 8.68 mmol), 4-cyanophenylboronic acid (2.5 g, 17.3 mmol), tetrakis (triphenylphosphine) palladium (0) (0.3 g, 0.26 mmol) in a dried round flask ) Was added to 100 ml of THF and stirred, and 50 ml of 2 mol potassium carbonate was added thereto, followed by stirring under reflux.
이 후 상온으로 냉각시키고, 메틸렌 클로라이드와 증류수로 추출한 뒤, 유기층을 무수 황산마그네슘으로 건조한 후 여과하였다.After cooling to room temperature, the mixture was extracted with methylene chloride and distilled water, and then the organic layer was dried over anhydrous magnesium sulfate and filtered.
여과된 유기층을 감압 농축하여 얻어진 혼합물을 메틸렌 클로라이드와 헥산으로 여액층을 컴럼으로 분리하여 화합물 D( 4.2 g, 68.2 % )을 얻었다.The filtered organic layer was concentrated under reduced pressure, and the mixture was separated with methylene chloride and hexane, and the filtrate layer was separated with a column to obtain Compound D (4.2 g, 68.2%).
1H NMR (400 MHz, CDCl3): δ 7.90~7.84(m, 4H), 7.77(d, 2H), 7.60~7.55(m, 4H), 7.46~7.38(m, 6H), 7,28(d, 2H), 7.18(d, 3H)
1 H NMR (400 MHz, CDCl3): δ 7.90-7.84 (m, 4H), 7.77 (d, 2H), 7.60-7.55 (m, 4H), 7.46-7.38 (m, 6H), 7,28 (d , 2H), 7.18 (d, 3H)
합성예Synthetic example 5: 화합물 E의 제조 5: Preparation of Compound E
E E
건조된 둥근 플라스크에 화합물 B ( 5 g, 8.68 mmol), 1-나프틸보로닉에시드 ( 2.97g, 17.3 mmol), 테트라키스(트리페닐포스핀)팔라듐(0) ( 0.3 g, 0.26 mmol)을 THF 100 ml에 넣고 교반을 시킨 후 2몰 탄산 칼륨 50 ml을 넣고 환류를 시키면서 교반하였다. In a dried round flask, Compound B (5 g, 8.68 mmol), 1-naphthylboronic acid (2.97 g, 17.3 mmol), tetrakis (triphenylphosphine) palladium (0) (0.3 g, 0.26 mmol) After stirring into 100 ml of THF, 50 ml of 2 mol potassium carbonate was added thereto, and the mixture was stirred while refluxing.
이 후 상온으로 냉각시키고, 메틸렌 클로라이드와 증류수로 추출한 뒤, 유기층을 무수 황산마그네슘으로 건조한 후 여과하였다.After cooling to room temperature, the mixture was extracted with methylene chloride and distilled water, and then the organic layer was dried over anhydrous magnesium sulfate and filtered.
여과된 유기층을 감압 농축하여 얻어진 혼합물을 메틸렌 클로라이드와 헥산으로 여액층을 컴럼으로 분리하여 화합물 E( 3.4 g, 68.2 % )을 얻었다.The filtered organic layer was concentrated under reduced pressure, and the mixture was separated with methylene chloride and hexane, and the filtrate layer was separated with a column to obtain Compound E (3.4 g, 68.2%).
1H NMR (400 MHz, CDCl3): δ 7.90~7.84(m, 4H), 7.77(d, 2H), 7.60~7.55(m, 4H), 7.46~7.38(m, 6H), 7,28(d, 2H), 7.18(d, 4H), 7.10(d, 4H) 1 H NMR (400 MHz, CDCl3): δ 7.90-7.84 (m, 4H), 7.77 (d, 2H), 7.60-7.55 (m, 4H), 7.46-7.38 (m, 6H), 7,28 (d , 2H), 7.18 (d, 4H), 7.10 (d, 4H)
합성예Synthetic example 6: 화합물 B1의 제조 6: Preparation of Compound B1
B1 B1
건조된 둥근 플라스크에 화합물 C( 5 g, 5.25mmol),9-페닐카바졸-3-보로닉에시드 (2.25g, 7.8 mmol), 테트라키스(트리페닐포스핀)팔라듐(0) ( 0.26 g, 0.22 mmol)을 THF 100 ml에 넣고 교반을 시킨 후 2몰 탄산 칼륨 20 ml을 넣고 환류를 시키면서 교반하였다.Compound C (5 g, 5.25 mmol), 9-phenylcarbazole-3-boronic acid (2.25 g, 7.8 mmol), tetrakis (triphenylphosphine) palladium (0) (0.26 g, 0.22 mmol) was added to 100 ml of THF, followed by stirring. 20 ml of 2 mol of potassium carbonate was added thereto, followed by stirring under reflux.
이 후 상온으로 냉각시키고, 메틸렌 클로라이드와 증류수로 추출한 뒤, 유기층을 무수 황산마그네슘으로 건조한 후 여과하였다.After cooling to room temperature, the mixture was extracted with methylene chloride and distilled water, and then the organic layer was dried over anhydrous magnesium sulfate and filtered.
여과된 유기층을 감압 농축하여 얻어진 혼합물을 메틸렌 클로라이드와 헥산으로 여액층을 컴럼으로 분리하여 화합물 B1( 3.8 g, 65.2 % )을 얻었다.The filtered organic layer was concentrated under reduced pressure, and the mixture was separated with methylene chloride and hexane. The filtrate layer was separated with a column to obtain Compound B1 (3.8 g, 65.2%).
1H NMR (400 MHz, CDCl3): δ 8.55 (t, 3H), 8.42(s, 1H), 8.19(d, 2H), 7.67~7.61(t, 14H), 7.46~7.32 (m, 14H), 7.20~7.00 (m, 15H), 6.52~6.5 (m, 6H)
1 H NMR (400 MHz, CDCl 3): δ 8.55 (t, 3H), 8.42 (s, 1H), 8.19 (d, 2H), 7.67-7.61 (t, 14H), 7.46-7.32 (m, 14H), 7.20 ~ 7.00 (m, 15H), 6.52 ~ 6.5 (m, 6H)
합성예Synthetic example 7: 화합물 A5의 제조 7: Preparation of Compound A5
A5 A5
건조된 둥근 플라스크에 화합물 D ( 5 g, 9.51mmol), 9H-플루오렌-2-일-보로닉에시드 (3.39 g, 14.26mmol), 테트라키스(트리페닐포스핀)팔라듐(0) ( 0.24 g, 0.21 mmol)을 THF 100 ml에 넣고 교반을 시킨 후 2몰 탄산 칼륨 20 ml을 넣고 환류를 시키면서 교반하였다. 이 후 상온으로 냉각시키고, 메틸렌 클로라이드와 증류수로 추출한 뒤, 유기층을 무수 황산마그네슘으로 건조한 후 여과하였다.In a dried round flask, Compound D (5 g, 9.51 mmol), 9H-fluoren-2-yl-boronic acid (3.39 g, 14.26 mmol), tetrakis (triphenylphosphine) palladium (0) (0.24 g , 0.21 mmol) was added to 100 ml of THF, followed by stirring. 20 ml of 2 mol potassium carbonate was added thereto, and the mixture was stirred under reflux. After cooling to room temperature, the mixture was extracted with methylene chloride and distilled water, and then the organic layer was dried over anhydrous magnesium sulfate and filtered.
여과된 유기층을 감압 농축하여 얻어진 혼합물을 메틸렌 클로라이드와 헥산으로 여액층을 컴럼으로 분리하여 화합물 G (4.07 g, 67.5 % )을 얻었다.The filtered organic layer was concentrated under reduced pressure, and the obtained mixture was separated with methylene chloride and hexane, and the filtrate layer was separated with a column to obtain compound G (4.07 g, 67.5%).
1H NMR (400 MHz, CDCl3): δ 7.77~7.72(t, 3H), 7.60~7.55(m, 6H), 7.46~7.28(m, 17H), 7.19~7.16(d, 2H) 1.67(m, 6H)
1 H NMR (400 MHz, CDCl3): δ 7.77-7.72 (t, 3H), 7.60-7.55 (m, 6H), 7.46-7.28 (m, 17H), 7.19-7.16 (d, 2H) 1.67 (m, 6H)
합성예Synthetic example 8: 화합물 B11의 제조 8: Preparation of Compound B11
B11 B11
건조된 둥근 플라스크에 화합물 E( 5 g, 8.67mmol), 9H-카바졸(2.541 g, 7.05 mmol), 트리스(다이벤질디네아세톤)다이팔라듐(0) (340mg, 0.372mmol) 0.02eq, 트라이-터트-뷰틸포스핀 (75mg , 0.372mmol) 0.02eq 소듐 터트-부톡사이드 (2.67g, 27.84mmol) 1.5eq 을 넣고 질소를 충분히 충진시킨 후 무수 톨루엔 50ml 을 넣어 85℃에서 3시간 환류 교반을 시킨다.Compound E (5 g, 8.67 mmol), 9H-carbazole (2.541 g, 7.05 mmol), tris (dibenzyldineacetone) dipalladium (0) (340 mg, 0.372 mmol) 0.02eq, tri- Tert-butylphosphine (75mg, 0.372mmol) 0.02eq Sodium tert-butoxide (2.67g, 27.84mmol) 1.5eq was added and filled with nitrogen, 50ml of anhydrous toluene was added, and the mixture was refluxed at 85 ° C for 3 hours.
이후 상온으로 냉각시키고 증류수를 넣어 반응을 종료하여 다이에틸 에테르와 증류수로 추출한 뒤, 유기층을 무수 황산마그네슘으로 건조하여 여과하였다. 여과된 유기층을 감압 농축하여 얻어진 혼합물을 에틸아세테이트와 헥산으로 여액층을 컬럼으로 분리하여 화합물 B11 (4.4g, 77%)를 얻었다.After the reaction mixture was cooled to room temperature, distilled water was added thereto to complete the reaction. The mixture was extracted with diethyl ether and distilled water. The organic layer was dried over anhydrous magnesium sulfate and filtered. The filtered organic layer was concentrated under reduced pressure, and the mixture was separated with ethyl acetate and hexane, and the filtrate was separated by a column to obtain Compound B11 (4.4 g, 77%).
1H NMR (400 MHz, CDCl3): δ 7.77~7.72(t, 3H), 7.60~7.55(m, 6H), 7.46~7.28(m, 18H), 7.19~7.16(d, 2H), 6.52 (m, 6H)
1 H NMR (400 MHz, CDCl3): δ 7.77-7.72 (t, 3H), 7.60-7.55 (m, 6H), 7.46-7.28 (m, 18H), 7.19-7.16 (d, 2H), 6.52 (m , 6H)
실시 예1: Example 1: 유기전계Organic field 발광소자의 제조 Manufacture of light emitting device
ITO(indium tin oxide)가 1500 Å의 두께로 박막 코팅된 유리 기판을 피셔사의 세제를 녹인 2차 증류수에 넣고 초음파로 세척하였다. ITO를 30분간 세턱한 후 증류수로 2회 반복하여 초음파 세척을 10분간 진행하였다. 증류수 세척이 끝난 후 , 이소프로필알콜, 아세톤, 메탄올의 용제로 초음파 세척을 하고 건조시킨 후, 플라즈마 세정기로 이송시켰다. 산소 플라즈마를 이용하여 상기 기판을 5분간 세정한 후 진공 증착기로 기판을 이송시켰다.A glass substrate coated with a film of ITO (indium tin oxide) having a thickness of 1500 Å was placed in secondary distilled water in which Fischer's detergent was dissolved, and ultrasonically cleaned. After ITO was fined for 30 minutes, the ultrasonic cleaning was performed twice with distilled water for 10 minutes. After the distilled water was washed, it was ultrasonically washed with a solvent of isopropyl alcohol, acetone, and methanol, dried, and then transferred to a plasma cleaner. The substrate was cleaned for 5 minutes using an oxygen plasma and then transferred to a vacuum evaporator.
이렇게 준비된 ITO 투명 전극 위에 아민 계열의 ELM200을 500Å의 두께로 열 진공 증착하여 정공 주입층을 형성하였다. 그 위에 정공 수송하는 물질인 상기 합성 예 6에서 얻어진 화합물 B1(300Å)을 진공증착한 후, 발광층으로 안트라센 계열의 MADN을 300Å의 두께로 진공 증착 하였으며, 전자 수송층으로 Alq3 화합물을 300Å의 두께로 진공증착 한 후, 순차적으로 리튬 플루오라이드(LiF) 7 Å과 1000Å두께의 알루미늄을 증착하여 음극을 형성하였다. An amine-based ELM200 was thermally vacuum deposited to a thickness of 500 kPa on the prepared ITO transparent electrode to form a hole injection layer. After vacuum depositing Compound B1 (300 kPa) obtained in Synthesis Example 6 as a hole transporting material, an anthracene-based MADN was vacuum deposited to a thickness of 300 kPa as an emitting layer, and an Alq3 compound was vacuumed to a thickness of 300 kPa as an electron transporting layer. After deposition, lithium fluoride (LiF) 7 Å and 1000 Å thickness of aluminum were deposited to form a cathode.
상기의 과정에서 유기물의 증착속도는 1 Å/sec를 유지하였고, 리튬플루오라이드는 0.2 Å/sec, 알루미늄은 3~7 Å/sec의 증착속도를 유지하였다. In the above process, the deposition rate of the organic material was maintained at 1 Å / sec, the lithium fluoride was 0.2 Å / sec, and the aluminum was maintained at the deposition rate of 3-7 Å / sec.
상기에서 제조된 유기전계 발광소자의 전류밀도 50mA/cm2에서의 구동전압, 발광휘도, 발색좌표, 발광효율 등의 특성을 조사하여 표 1에 나타내었다.
Table 1 shows the characteristics of the organic electroluminescent device manufactured at the current density of 50 mA / cm 2 , such as driving voltage, luminescence brightness, coloring coordinates, and luminous efficiency.
실시 예2: Example 2: 유기전계Organic field 발광소자의 제조 Manufacture of light emitting device
정공을 수송하는 물질로 화합물 B1대신 합성예 7에서 얻어진 화합물 A5를 이용한 것을 제외하고는, 실시예 1과 동일하게 유기전계 발광소자를 제작하였다.An organic light emitting device was manufactured in the same manner as in Example 1, except that Compound A5 obtained in Synthesis Example 7 was used instead of Compound B1 as a material for transporting holes.
상기 유기전계 발광소자의 전류밀도 50 mA/cm2 에서의 구동전압, 발광휘도, 발색좌표, 발광효율 등의 특성을 조사하여 표 1에 나타내었다.The characteristics of the organic electroluminescent device at a current density of 50 mA / cm 2 , such as driving voltage, luminescence brightness, coloring coordinates, and luminous efficiency, were shown in Table 1.
비교 예1:Comparative Example 1: 유기전계Organic field 발광소자의 제조 Manufacture of light emitting device
정공을 수송하는 물질로 화합물 B1 대신 다음 화학식 6으로 표시되는 N,N'디(나프탈렌-1-일)-N,-N'디페닐벤지딘(NPB)를 이용한 것을 제외하고는, 실시예 1과 동일하게 유기전계 발광소자를 제작하였다.
Example 1 except that N, N'di (naphthalen-1-yl) -N, -N'diphenylbenzidine (NPB) represented by the following formula (6) instead of compound B1 was used as a material for transporting holes In the same manner, an organic EL device was manufactured.
화학식 66
상기에서 제조된 유기전계 발광소자의 전류밀도 50mA/cm2 에서의 구동전압, 발광휘도, 발색좌표, 발광효율 등의 특성을 조사하여 표1에 나타내었다.
The characteristics of the driving voltage, light emission luminance, color coordinate, and light emission efficiency at the current density of 50 mA / cm 2 of the organic light emitting device manufactured above are shown in Table 1 below.
본 발명에 따른 화학식1로 표시되는 비대칭 구조의 3차아릴 아민을 정공수송물질로 유기전계 발광소자에 사용한 결과를 상용화되어 있는 물질인 NPB를 유기전계 발광소자에 사용한 결과와 비교해 볼 때, 본 발명에 따른 유기전계 발광소자는 모두 구동전압이 낮으면서도 효율이 대폭 향상된 우수한 I-V-L 특성을 나타내었다. 이와 같이, 본 발명에 따르면 월등하게 홀과 전자의 이동 능력이 향상됨으로써 우수한 정공수송 및 전자 수송 능력을 바탕으로 한 저전압, 고효율, 고휘도, 장수명의 유기전계 발광소자를 제작할 수 있다.
When the result of using the tertiary aryl amine having an asymmetric structure represented by the formula (1) according to the present invention as a hole transporting material in the organic light emitting device is compared with the result of using NPB, which is a commercially available material in the organic light emitting device, All of the organic light emitting diodes exhibited excellent IVL characteristics with significantly improved efficiency while low driving voltage. As described above, according to the present invention, excellent mobility of holes and electrons is improved, and thus low-voltage, high-efficiency, high brightness, and long-life organic light emitting devices based on excellent hole transport and electron transport capabilities can be manufactured.
01 기판
02 양극
03 음극
04 정공주입층
05 정공수송층
06 발광층
07 정공저지층
08 전자수송층
09 전자주입층01 substrate
02 Anode
03 cathode
04 Hole injection layer
05 hole transport layer
06 Light emitting layer
07 Hole blocking layer
08 Electron transport layer
09 Electron injection layer
Claims (13)
화학식1
상기 화학식 1에서 Y1 및 Y2는 서로 같거나 다르고, 단일결합이거나, 또는, 치환기가 있거나 없는 탄소수 6 내지 60의 아릴렌기, 치환기가 있거나 없는 탄소수 3 내지 60의 헤테로아릴렌기 또는 치환기가 있거난 없는 플로오렌일렌기이며
X는 1가 또는 2가이며, 치환기가 있거나 없는 탄소수 6 내지60의 아릴기 또는 아릴렌기, 또는 치환기가 있거난 없는 탄소수 2 내지 60의 헤테로아릴기 또는 헤테로아릴렌기이다.Tertiary aryl amines represented by Formula 1:
Formula 1
In Formula 1, Y 1 and Y 2 may be the same as or different from each other, and may be a single bond, or an arylene group having 6 to 60 carbon atoms with or without a substituent, a heteroarylene group having 3 to 60 carbon atoms with or without a substituent, or a substituent. There is no fluorene styrene
X is monovalent or divalent and is a C6-C60 aryl group or arylene group with or without a substituent, or a C2-C60 heteroaryl group or heteroarylene group with or without substituents.
상기 a1 및 a2 는 동일 또는 상이한 것으로, 각각 H, C4~C25의 아릴기, C4~C25의 헤테로아릴기, 아미노기 및 치환된 아미노기로 이루어진 군에서 선택된 어느 하나이며,
상기L 은 C 또는 N이며,
상기L 이 N일 경우, a1는 비공유전자쌍이며, a2는 H, C1~C13의 알킬기, C4~C25의 아릴기 및 C4~C25의 헤테로아릴기로 이루어진 군에서 선택된 어느 하나이고,
상기L 이 C일 경우, a1 및 a2 는 동일 또는 상이한 것으로, 각각 H, C1~C13의 알킬기, C4~C25의 헤테로아릴기로 이루어진 군에서 선택된 어느 하나이거나, 상기 a1 및 a2가 C4~C20의 고리로 연결된 구조이며 다음과 같은 구조를 지닌다.
화학식 2
According to claim 1, wherein in Formula 1 X
A1 and a2 are the same or different, each selected from the group consisting of H, C4 ~ C25 aryl group, C4 ~ C25 heteroaryl group, amino group and substituted amino group,
L is C or N,
When L is N, a1 is a non-covalent electron pair, a2 is any one selected from the group consisting of H, an alkyl group of C1-C13, an aryl group of C4-C25, and a heteroaryl group of C4-C25,
When L is C, a1 and a2 are the same or different, and each one selected from the group consisting of H, C1-C13 alkyl group and C4-C25 heteroaryl group, or a1 and a2 are C4-C20 ring It is connected to and has the following structure.
(2)
상기 화학식 2의 L이 N인 경우, a1은 비공유전자쌍이며, a2는 H, C1~C13의 알킬기, 페닐기(phenyl), 나프틸기(naphthyl), 안트라세닐기(anthracenyl),
퀴놀리닐기(quinolinyl) 및 이소퀴놀릴리닐기(isoquinolinyl)로 이루어진 군에서 선택된 어느 하나일 수 있으나, 이에 한정되는 것은 아니다.The method according to claim 2, wherein
When L in Formula 2 is N, a1 is a non-covalent electron pair, a2 is H, C1-C13 alkyl group, phenyl group (phenyl), naphthyl group, anthracenyl group (anthracenyl),
A quinolinyl group (quinolinyl) and isoquinolinyl group (isoquinolinyl) may be any one selected from the group consisting of, but is not limited thereto.
상기 화학식 2의 L이 C 일 경우, a1 및 a2는 동일 또는 상이한 것으로 각각 H, C1~C13의 알킬기, 페닐기(phenyl), 나프틸기(naphthyl), 안트라세닐기(anthrac
enyl), 퀴놀리닐기(quinolinyl) 및 이소퀴놀릴리닐렌기(isoquinolinyl)로 이루어진 군에서 선택된 어느 하나일 수 있으나, 이에 한정되는 것은 아니다.The method according to claim 2, wherein
When L in Formula 2 is C, a1 and a2 are the same or different, and each of H, C1-C13 is an alkyl group, a phenyl group, a naphthyl group, and anthracenyl group.
enyl), quinolinyl group (quinolinyl) and isoquinolinylylene group (isoquinolinyl) may be any one selected from the group consisting of, but is not limited thereto.
Y1 내지 Y2 각각 독립적으로 수소원자, 할로젠 원자, 치환 또는 비치환된 탄소수 1 내지 50의 알킬기 치환 또는 비치환된 탄소수 1 내지 50의 알콕시기, 치환 또는 비치환된 탄소수 4 내지 50의 아릴옥시기, 치환 또는 비치환된 탄소수 1 내지 50의 싸이오알콕시기, 치환 또는 비치환된 탄소수 4 내지 50의 싸이오아릴옥시기, 치환 또는 비치환된 아미노기, 치환 또는 비치환된 탄소수 4 내지 50의 아릴기, 치환 또는 비치환된 탄소수 1 내지 50의 알킬카보닐기, 또는 치환 또는 비치환된 탄소수 4 내지 50의 아릴카보닐기이며, A 내지 B에 의해 정의되는 원자 및 기는 서로 동일하거나 상이 할 수 있다.The method of claim 1,
Y 1 to Y 2 Each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 50 carbon atoms, a substituted or unsubstituted aryloxy group having 4 to 50 carbon atoms, substituted or Unsubstituted thioalkoxy group having 1 to 50 carbon atoms, substituted or unsubstituted thioaryloxy group having 4 to 50 carbon atoms, substituted or unsubstituted amino group, substituted or unsubstituted aryl group having 4 to 50 carbon atoms, substitution Or an unsubstituted alkyl carbonyl group having 1 to 50 carbon atoms, or a substituted or unsubstituted arylcarbonyl group having 4 to 50 carbon atoms, and the atoms and groups defined by A to B may be the same or different from each other.
X가 플루오렌계을 포함하고, Y1 및 Y2 는 같거나 상이할 수 있으며, 다음과 같은 구조를 지닌다.
화학식3
X comprises fluorene and Y 1 and Y 2 May be the same or different and have the following structure:
Formula 3
X가 카바졸계를 포함하고, Y1 및 Y2는 같거나 상이할 수 있으며, 다음과 같은 구조를 지닌다.
화학식4
X includes a carbazole type, Y 1 and Y 2 may be the same or different, and have the following structure.
Formula 4
화학식5
Specific examples of the compound in Chemical Formula 3 include compounds of the following Chemical Formula 5, but the present invention is not limited thereto.
Formula 5
화학식6
Specific examples of the compound belonging to Chemical Formula 4 include compounds represented by Chemical Formula 6, but the present invention is not limited thereto.
Formula 6
상기 화합물은 평면 패널 디스플레이, 평면 발광체, 조명용 면발광 OLED의 발광체,flexble 발광체, 복사기, 프린터, LCD 백라이트, 계량기 광원, 디스플레이판, 유기전계 발광소자(OLED), 유기태양전지(OSC), 전자종이(e-paper), 유기 감광체(OPC) 및 유기트랜지스터(OTFT) 중에서 선택된 어느 하나에 적용되는 것을 특징으로 하는 3차 아릴 아민을 포함하는 화합물11. The method according to any one of claims 1 to 10,
The compound is a flat panel display, a flat light emitter, a light emitter of an illuminated surface-emitting OLED, a flexible light emitter, a copier, a printer, an LCD backlight, a meter light source, a display panel, an organic light emitting diode (OLED), an organic solar cell (OSC), an electronic paper (e-paper), an organic photoconductor (OPC) and a compound containing a tertiary aryl amine, characterized in that applied to any one selected from the organic transistor (OTFT)
상기 1층 이상의 유기물층은 발광층을 포함하며, 정공 주입층, 정공수송층, 정공 저지층, 전자 수송층 및 전자 주입층으로 이루어진 군에서 선택된 1종 이상의 층을 더 포함하는 것을 특징으로 하는 유기전계 발광소자.
13. The method of claim 12,
The at least one organic material layer includes a light emitting layer, and further comprising at least one layer selected from the group consisting of a hole injection layer, a hole transport layer, a hole blocking layer, an electron transport layer and an electron injection layer.
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