KR101184159B1 - Organic compounds and organic electroluminescent devices using the same - Google Patents
Organic compounds and organic electroluminescent devices using the same Download PDFInfo
- Publication number
- KR101184159B1 KR101184159B1 KR1020090134495A KR20090134495A KR101184159B1 KR 101184159 B1 KR101184159 B1 KR 101184159B1 KR 1020090134495 A KR1020090134495 A KR 1020090134495A KR 20090134495 A KR20090134495 A KR 20090134495A KR 101184159 B1 KR101184159 B1 KR 101184159B1
- Authority
- KR
- South Korea
- Prior art keywords
- substituted
- unsubstituted
- organic
- compound
- polycyclic aromatic
- Prior art date
Links
- 150000002894 organic compounds Chemical class 0.000 title abstract description 4
- 150000001875 compounds Chemical class 0.000 claims abstract description 87
- 239000000463 material Substances 0.000 claims abstract description 55
- 238000002347 injection Methods 0.000 claims abstract description 34
- 239000007924 injection Substances 0.000 claims abstract description 34
- 230000005525 hole transport Effects 0.000 claims abstract description 12
- 239000010410 layer Substances 0.000 claims description 65
- 125000004429 atom Chemical group 0.000 claims description 59
- 125000006749 (C6-C60) aryl group Chemical group 0.000 claims description 18
- 125000001072 heteroaryl group Chemical group 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- 239000012044 organic layer Substances 0.000 claims description 18
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 claims description 17
- 125000000217 alkyl group Chemical group 0.000 claims description 16
- 125000003118 aryl group Chemical group 0.000 claims description 14
- 125000002947 alkylene group Chemical group 0.000 claims description 12
- 125000000592 heterocycloalkyl group Chemical group 0.000 claims description 11
- 229910052717 sulfur Inorganic materials 0.000 claims description 11
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 10
- 229910052805 deuterium Inorganic materials 0.000 claims description 10
- 125000003342 alkenyl group Chemical group 0.000 claims description 9
- 125000003545 alkoxy group Chemical group 0.000 claims description 9
- 125000000304 alkynyl group Chemical group 0.000 claims description 9
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 125000004122 cyclic group Chemical group 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 150000002431 hydrogen Chemical class 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 125000006751 (C6-C60) aryloxy group Chemical group 0.000 claims description 7
- 125000005103 alkyl silyl group Chemical group 0.000 claims description 6
- 238000009833 condensation Methods 0.000 claims description 6
- 230000005494 condensation Effects 0.000 claims description 6
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 4
- 125000006736 (C6-C20) aryl group Chemical group 0.000 claims description 4
- 125000006761 (C6-C60) arylene group Chemical group 0.000 claims description 4
- 125000004450 alkenylene group Chemical group 0.000 claims description 4
- 125000004419 alkynylene group Chemical group 0.000 claims description 4
- 125000005549 heteroarylene group Chemical group 0.000 claims description 4
- 125000006588 heterocycloalkylene group Chemical group 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 125000004104 aryloxy group Chemical group 0.000 claims description 3
- 150000004982 aromatic amines Chemical class 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 125000005104 aryl silyl group Chemical group 0.000 claims description 2
- 125000005266 diarylamine group Chemical group 0.000 claims description 2
- GVEPBJHOBDJJJI-RHRFEJLCSA-N fluoranthene Chemical group C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=[14CH]1 GVEPBJHOBDJJJI-RHRFEJLCSA-N 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 description 54
- 238000003786 synthesis reaction Methods 0.000 description 54
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 33
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 21
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthene Chemical compound C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000012153 distilled water Substances 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 8
- 239000000758 substrate Substances 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000000706 filtrate Substances 0.000 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 description 5
- FBGGRFWVGWJWTH-UHFFFAOYSA-N 9-azahexacyclo[10.10.1.02,10.03,8.013,18.019,23]tricosa-1,3,5,7,9,12(23),13,15,17,19,21-undecaene Chemical compound C1=CC=C2C3=CC=CC=C3C3=C2C1=C1C2=CC=CC=C2N=C1C3 FBGGRFWVGWJWTH-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 125000005842 heteroatom Chemical group 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 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
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000002019 doping agent Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 229960001866 silicon dioxide Drugs 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- CCHUZEDLHYFBQF-UHFFFAOYSA-N 16-bromo-11-phenyl-9-azahexacyclo[10.10.1.02,10.03,8.013,18.019,23]tricosa-1,3,5,7,9,12(23),13(18),14,16,19,21-undecaene Chemical compound C12=CC(Br)=CC=C2C2=C3C1=CC=CC3=C(C1=CC=CC=C1N=1)C=1C2C1=CC=CC=C1 CCHUZEDLHYFBQF-UHFFFAOYSA-N 0.000 description 2
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- SBTUBKFHTBFVRL-UHFFFAOYSA-N 2-fluoranthen-3-ylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C1=CC=C2C3=C1C=CC=C3C1=CC=CC=C12 SBTUBKFHTBFVRL-UHFFFAOYSA-N 0.000 description 2
- WSMFPMJMPZLXHV-UHFFFAOYSA-N 3-(2-methylphenyl)fluoranthene Chemical compound Cc1ccccc1-c1ccc2-c3ccccc3-c3cccc1c23 WSMFPMJMPZLXHV-UHFFFAOYSA-N 0.000 description 2
- QENGPZGAWFQWCZ-UHFFFAOYSA-N 3-Methylthiophene Chemical compound CC=1C=CSC=1 QENGPZGAWFQWCZ-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine hydrate Chemical compound O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 2
- 125000002883 imidazolyl group Chemical group 0.000 description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- -1 metal complex compounds Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229940042055 systemic antimycotics triazole derivative Drugs 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 description 1
- IWZZBBJTIUYDPZ-DVACKJPTSA-N (z)-4-hydroxypent-3-en-2-one;iridium;2-phenylpyridine Chemical compound [Ir].C\C(O)=C\C(C)=O.[C-]1=CC=CC=C1C1=CC=CC=N1.[C-]1=CC=CC=C1C1=CC=CC=N1 IWZZBBJTIUYDPZ-DVACKJPTSA-N 0.000 description 1
- JSRLURSZEMLAFO-UHFFFAOYSA-N 1,3-dibromobenzene Chemical compound BrC1=CC=CC(Br)=C1 JSRLURSZEMLAFO-UHFFFAOYSA-N 0.000 description 1
- QSSXJPIWXQTSIX-UHFFFAOYSA-N 1-bromo-2-methylbenzene Chemical compound CC1=CC=CC=C1Br QSSXJPIWXQTSIX-UHFFFAOYSA-N 0.000 description 1
- ORPVVAKYSXQCJI-UHFFFAOYSA-N 1-bromo-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Br ORPVVAKYSXQCJI-UHFFFAOYSA-N 0.000 description 1
- YDFHRBGWDLALOB-UHFFFAOYSA-N 1-bromo-3-(3-phenylphenyl)benzene Chemical group BrC1=CC=CC(C=2C=C(C=CC=2)C=2C=CC=CC=2)=C1 YDFHRBGWDLALOB-UHFFFAOYSA-N 0.000 description 1
- XNCMQRWVMWLODV-UHFFFAOYSA-N 1-phenylbenzimidazole Chemical compound C1=NC2=CC=CC=C2N1C1=CC=CC=C1 XNCMQRWVMWLODV-UHFFFAOYSA-N 0.000 description 1
- ILCPXPCDRBIAIC-UHFFFAOYSA-N 11-phenyl-9-azahexacyclo[10.10.1.02,10.03,8.013,18.019,23]tricosa-1,3,5,7,9,12(23),13,15,17,19,21-undecaene Chemical compound C1=CC=CC=C1C1C(C2=CC=CC=C2C2=CC=C3)=C2C3=C2C3=CC=CC=C3N=C21 ILCPXPCDRBIAIC-UHFFFAOYSA-N 0.000 description 1
- YFUWVSPCUFTGQN-UHFFFAOYSA-N 2-(3-bromophenyl)-1-phenylbenzimidazole Chemical compound BrC1=CC=CC(C=2N(C3=CC=CC=C3N=2)C=2C=CC=CC=2)=C1 YFUWVSPCUFTGQN-UHFFFAOYSA-N 0.000 description 1
- GEQBRULPNIVQPP-UHFFFAOYSA-N 2-[3,5-bis(1-phenylbenzimidazol-2-yl)phenyl]-1-phenylbenzimidazole Chemical compound C1=CC=CC=C1N1C2=CC=CC=C2N=C1C1=CC(C=2N(C3=CC=CC=C3N=2)C=2C=CC=CC=2)=CC(C=2N(C3=CC=CC=C3N=2)C=2C=CC=CC=2)=C1 GEQBRULPNIVQPP-UHFFFAOYSA-N 0.000 description 1
- GECBKKNKRQJNCX-UHFFFAOYSA-N 2-fluoranthen-3-yl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane Chemical compound O1C(C)(C)C(C)(C)OB1C1=CC=C2C3=C1C=CC=C3C1=CC=CC=C12 GECBKKNKRQJNCX-UHFFFAOYSA-N 0.000 description 1
- ZFINZIXSFLDZJQ-UHFFFAOYSA-N 3-(2-nitrophenyl)fluoranthene Chemical compound [O-][N+](=O)C1=CC=CC=C1C1=CC=C2C3=C1C=CC=C3C1=CC=CC=C12 ZFINZIXSFLDZJQ-UHFFFAOYSA-N 0.000 description 1
- SQTLUXJWUCHKMT-UHFFFAOYSA-N 4-bromo-n,n-diphenylaniline Chemical compound C1=CC(Br)=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 SQTLUXJWUCHKMT-UHFFFAOYSA-N 0.000 description 1
- LUHRNBITZMNZPU-UHFFFAOYSA-N 7H-fluoranthen-8-one Chemical compound C1=CC=C2C=CC=C3C=4CC(C=CC=4C1=C23)=O LUHRNBITZMNZPU-UHFFFAOYSA-N 0.000 description 1
- VIZUPBYFLORCRA-UHFFFAOYSA-N 9,10-dinaphthalen-2-ylanthracene Chemical compound C12=CC=CC=C2C(C2=CC3=CC=CC=C3C=C2)=C(C=CC=C2)C2=C1C1=CC=C(C=CC=C2)C2=C1 VIZUPBYFLORCRA-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 125000003860 C1-C20 alkoxy group Chemical group 0.000 description 1
- 125000003358 C2-C20 alkenyl group Chemical group 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 101100030361 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) pph-3 gene Proteins 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical group C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- OKJPEAGHQZHRQV-UHFFFAOYSA-N Triiodomethane Natural products IC(I)I OKJPEAGHQZHRQV-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- UOIMOAURQGEHCR-UHFFFAOYSA-N [Si].C1=CC=CC1 Chemical class [Si].C1=CC=CC1 UOIMOAURQGEHCR-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000000319 biphenyl-4-yl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- VHBFFQKBGNRLFZ-UHFFFAOYSA-N flavone Chemical class O1C2=CC=CC=C2C(=O)C=C1C1=CC=CC=C1 VHBFFQKBGNRLFZ-UHFFFAOYSA-N 0.000 description 1
- LDPCTBXVSGTSNJ-UHFFFAOYSA-N fluoranthen-3-ylboronic acid Chemical compound C12=CC=CC=C2C2=CC=CC3=C2C1=CC=C3B(O)O LDPCTBXVSGTSNJ-UHFFFAOYSA-N 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000003037 imidazol-2-yl group Chemical group [H]N1C([*])=NC([H])=C1[H] 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- 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
- 238000007641 inkjet printing Methods 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- GKQFYZWYVBQCHT-UHFFFAOYSA-N n-naphthalen-1-yl-n-[4-[4-(n-phenylanilino)phenyl]phenyl]naphthalen-1-amine Chemical compound C1=CC=CC=C1N(C=1C=CC(=CC=1)C=1C=CC(=CC=1)N(C=1C2=CC=CC=C2C=CC=1)C=1C2=CC=CC=C2C=CC=1)C1=CC=CC=C1 GKQFYZWYVBQCHT-UHFFFAOYSA-N 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 150000004866 oxadiazoles Chemical class 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 150000005041 phenanthrolines Chemical class 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 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
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000010345 tape casting 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
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 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
Images
Classifications
-
- 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
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/12—Light sources with substantially two-dimensional radiating surfaces
- H05B33/20—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the material in which the electroluminescent material is embedded
-
- 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
-
- 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]
- H10K50/14—Carrier transporting layers
-
- 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]
- H10K50/17—Carrier injection layers
-
- 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
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
- H10K85/623—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing five rings, e.g. pentacene
-
- 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
-
- 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
-
- 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
- H10K85/40—Organosilicon compounds, e.g. TIPS pentacene
Landscapes
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Optics & Photonics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Organic Chemistry (AREA)
- Electroluminescent Light Sources (AREA)
- Indole Compounds (AREA)
Abstract
본 발명은 신규한 유기 화합물 및 이를 이용한 유기 전계 발광 소자에 관한 것으로, 보다 구체적으로는 하나 이상의 플루오란텐 유도체 모이어티(moiety)를 가지면서, 대칭 혹은 비대칭 분자 구조를 가지는 화합물, 및 상기 화합물을 유기 전계 발광 소자에 적용, 바람직하게는 정공 주입층 재료, 정공 수송층 재료, 형광층 혹은 인광층의 호스트 재료, 전자 수송 및 주입 재료로 적용하여 발광효율, 휘도, 열적 안정성, 구동 전압, 수명 등의 특성이 향상된 유기 전계 발광 소자에 관한 것이다.The present invention relates to a novel organic compound and an organic electroluminescent device using the same, and more particularly, a compound having one or more fluoranthene derivative moieties and having a symmetric or asymmetric molecular structure, and the compound Applied to organic electroluminescent device, preferably applied as hole injection layer material, hole transport layer material, host material of fluorescent layer or phosphorescent layer, electron transport and injection material, such as luminous efficiency, brightness, thermal stability, driving voltage, lifetime The present invention relates to an organic electroluminescent device having improved characteristics.
유기 화합물, 발광 호스트, 유기 전계 발광 소자 Organic compound, light emitting host, organic electroluminescent device
Description
본 발명은 신규한 유기 화합물 및 이를 이용한 유기 전계 발광 소자에 관한 것으로, 보다 구체적으로는 하나 이상의 플루오란텐 유도체 모이어티(moiety)를 가지면서, 대칭 혹은 비대칭 분자 구조를 가지는 화합물, 및 상기 화합물을 유기 전계 발광 소자에 적용, 바람직하게는 정공 주입층 재료, 정공 수송층 재료, 형광 혹은 인광층의 호스트 재료, 전자 주입층 재료 및/또는 전자 수송층 재료로 적용하여 발광효율, 휘도, 열적 안정성, 구동 전압, 수명 등의 특성이 향상된 유기 전계 발광 소자에 관한 것이다.The present invention relates to a novel organic compound and an organic electroluminescent device using the same, and more particularly, a compound having one or more fluoranthene derivative moieties and having a symmetric or asymmetric molecular structure, and the compound Applied to an organic electroluminescent device, preferably applied as a hole injection layer material, a hole transport layer material, a host material of a fluorescent or phosphorescent layer, an electron injection layer material and / or an electron transport layer material, luminous efficiency, brightness, thermal stability, drive voltage The present invention relates to an organic electroluminescent device having improved characteristics, such as lifespan.
일반적으로 유기 발광 현상이란 유기 물질에 전기에너지를 가했을 때 빛이 나타나는 현상을 말한다. 즉, 양극(anode)과 음극(cathode) 사이에 유기층을 위치시키고 두 전극 사이에 전압을 걸어주게 되면 양극에서는 정공이, 음극에서는 전자가 유기층에 주입되게 된다. 주입된 정공과 전자가 만났을 때 엑시톤(exciton)이 형성되고, 이 엑시톤이 다시 바닥상태로 떨어질 때 빛이 나게 된다.In general, organic light emitting phenomenon refers to a phenomenon in which light appears when electric energy is applied to an organic material. That is, when the organic layer is positioned between the anode and the cathode and a voltage is applied between the two electrodes, holes are injected into the organic layer and electrons are injected into the cathode. When the injected holes and electrons meet, excitons are formed, and when the excitons fall back to the ground, they shine.
유기 전계 발광(electroluminescent, EL) 소자(이하, 간단히 '유기 EL 소자' 로 칭함)는 자발광 표시 소자이므로 명암비가 우수하고 시야각이 넓으며 응답시간이 빨라 고성능 디스플레이에 적합하다. Organic electroluminescent (EL) devices (hereinafter, simply referred to as 'organic EL devices') are self-luminous display devices, and thus have excellent contrast ratio, wide viewing angle, and fast response time, and are suitable for high performance displays.
1950년대 Bernanose의 유기 박막 발광 관측을 시점으로 1965년 안트라센 단결정을 이용한 청색 전기발광으로 이어진 유기 EL 소자에 대한 연구는 1987년 탕(Tang)에 의하여 정공층과 발광층의 기능층으로 나눈 적층구조의 유기 EL 소자가 제시되었고, 고효율, 고수명의 유기 EL 소자를 만들기 위하여 소자 내 각각의 특징적인 유기물 층을 도입하는 형태로 발전하여 왔으며, 이에 사용되는 특화된 물질의 개발로 이어졌다. From the observation of organic thin-film emission by Bernanose in the 1950s, the study on organic EL devices that led to blue electroluminescence using anthracene single crystals in 1965 was carried out by Tang in 1987. EL devices have been proposed, and have been developed in the form of introducing each characteristic organic material layer in the device to make high efficiency, high life organic EL devices, leading to the development of specialized materials used therein.
유기 EL 소자를 효율적으로 만들기 위한 일 방법으로서 소자내의 유기층을 단층 대신 다층 구조로 제조하는 연구가 진행되어 왔다. As one method for making an organic EL device efficiently, research has been conducted to manufacture an organic layer in the device into a multilayer structure instead of a single layer.
일반적으로 유기 EL 소자는 기판 상부에 양극(anode)이 형성되어 있고 양극 상부에 순차적으로 정공 주입층, 정공 수송층, 발광층, 전자 수송층, 전자 주입층 및 음극(cathode)이 형성되어 있는 박막 다층 구조로 되어 있다. In general, an organic EL device has a thin film multilayer structure in which an anode is formed on a substrate and a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a cathode are sequentially formed on the anode. It is.
이렇게 유기 EL 소자를 다층으로 제작하는 이유는 정공과 전자의 이동속도가 상이하며, 따라서 적절한 정공 주입층 및 수송층, 전자 수송층 및 주입층을 만들어 주면 정공과 전자가 효과적으로 전달될 수 있으며, 소자 내 정공과 전자의 균형이 이루어져 발광 효율을 높일 수 있기 때문이다. The reason why the organic EL device is manufactured in a multi-layer is that the movement speeds of the holes and the electrons are different. Therefore, if the appropriate hole injection layer, the transport layer, the electron transport layer, and the injection layer are made, the holes and the electrons can be effectively transferred. This is because the light emission efficiency can be improved by balancing the electrons.
전자 주입층에서 주입된 전자와 정공 주입층에서 전달된 정공은 발광층에서 재결합하여 엑시톤을 형성하게 되며 일중항 여기상태에서 기저 상태로 떨어지며 발광하는 것을 형광이라고 하고, 삼중항 여기상태에서 기저 상태로 떨어지는 발광을 인광이라고 한다. 이론적으로 캐리어가 발광층에서 재결합하여 엑시톤이 발생될 때 일중항과 삼중항 여기자의 비율이 1:3의 비율로 발생되게 되며, 인광을 이용할 경우 내부 양자 효율이 100%에 이를 수 있다. Electrons injected from the electron injection layer and holes transferred from the hole injection layer recombine in the emission layer to form excitons, and fall from the singlet excited state to the ground state and are called fluorescence. Luminescence is called phosphorescence. Theoretically, when the exciton is generated when the carrier is recombined in the emission layer, the ratio of singlet and triplet excitons is generated at a ratio of 1: 3, and when phosphorescence is used, the internal quantum efficiency may be 100%.
전자 수송 재료에 관한 최초의 보고는 옥사디아졸 유도체(PBD)를 들 수 있다. 이후 트리아졸 유도체(TAZ) 및 페난트롤린 유도체(BCP)가 전자 수송성을 나타낸다고 보고되었다. 전자 수송층은 유기 단분자 물질로는 전자에 대한 안정도와 전자 이동 속도가 상대적으로 우수한 유기 금속 착제들이 좋은 후보들이며, 안정성이 우수하고 전자 친화도가 큰 Alq3가 가장 우수한 것으로 보고 되었으며 지금까지도 가장 기본적으로 사용되고 있다. 또한, 종래에 공지된 전자 수송용 물질로는 산요(Sanyo)사에서 발표한 플라본(flavon)유도체 또는 치소(Chisso)사의 게르마늄 및 실리콘 사이클로펜타디엔 유도체 등이 알려져 있다. (일본공개특허공보 제1998-017860호, 일본공개특허공보 제1999-087067호). Initial reports on electron transport materials include oxadiazole derivatives (PBDs). It has since been reported that triazole derivatives (TAZ) and phenanthroline derivatives (BCP) exhibit electron transport properties. The electron transport layer is a good candidate for organometallic complexes having excellent stability and electron transfer speed as organic monomolecular materials, and Alq3 having high stability and high electron affinity has been reported to be the best candidate. It is used. In addition, conventionally known materials for electron transport include flavon derivatives published by Sanyo, germanium, and silicon cyclopentadiene derivatives of Chisso. (Japanese Laid-Open Patent Publication No. 1998-017860, Japanese Laid-Open Patent Publication No. 1999-087067).
종래의 전자 주입 및 수송 물질로는 이미다졸기, 옥사졸기, 티아졸기를 가진 유기 단분자 물질들이 많이 보고되었다. 그러나 이러한 물질들이 전자수송 물질로 보고되기 이전에 모토롤라(Motorola)사의 EU 0700917 A2에 이러한 물질들의 금속착체 화합물들이 유기 EL 소자의 청색 발광층 또는 청록색 발광층으로의 적용이 이미 보고되었다. As a conventional electron injection and transport material, many organic monomolecular materials having imidazole groups, oxazole groups, and thiazole groups have been reported. However, before these materials were reported as electron transport materials, application of metal complex compounds of these materials to Motorola blue or cyan light emitting layers has already been reported in Motorola EU 0700917 A2.
1996년도에 코닥사에서 발표하고 미국 특허 제5,645,948호에 기재된 TPBI는 이미다졸기를 가진 대표적인 전자 수송 물질로 알려져 있으며, 그 구조는 벤젠의 1,3,5 위치에 세 개의 N-페닐 벤즈이미다졸기를 함유하고 기능적으로는 전자를 전 달하는 능력뿐 아니라 발광층에서 넘어오는 정공을 차단하는 기능도 있는 것으로 보고되고 있으나, 실제 소자에 적용하기에는 열적 안정성이 낮은 문제점을 가지고 있다. TPBI, published by Kodak in 1996 and described in US Pat. No. 5,645,948, is known as a representative electron transporting material with imidazole groups, whose structure is three N-phenyl benzimides at the 1,3,5 position of benzene. It has been reported to have a function of blocking the holes coming from the light emitting layer as well as the ability to transfer the electrons functionally, but has a low thermal stability to be applied to the actual device.
인광 호스트 재료로는 CBP(4,4-dicarbazolybiphenyl)등의 카바졸 고리 화합물 등이 사용되며, 인광 게스트 재료로는 Ir, Pt 등의 중원자가 포함된 금속 착체 화합물이 널리 사용되고 있다. Carbazole ring compounds such as CBP (4,4-dicarbazolybiphenyl) are used as the phosphorescent host material, and metal complex compounds containing heavy atoms such as Ir and Pt are widely used as phosphorescent guest materials.
그러나 현재 사용되는 인광 호스트 재료인 CBP 의 경우 유리전이온도(Tg)가 110℃ 정도로 낮으며, 소자 내의 결정화가 쉽게 일어나 유기 EL 소자의 수명이 150시간 정도로 매우 짧은 단점이 있다.However, CBP, which is currently used phosphorescent host material, has a low glass transition temperature (Tg) of about 110 ° C., and crystallization within the device is easy, resulting in a very short lifetime of about 150 hours.
따라서, 본 발명의 목적은 인광 호스트 물질, 형광 호스트 물질, 정공 주입 물질, 정공 수송 물질, 전자 주입 물질 및/또는 전자 수송 물질로서 유기 EL 소자에 적용하여 구동전압을 낮추고, 발광효율, 휘도, 열적 안정성 및 소자 수명을 향상시킬 수 있는 플루오란텐 유도체 구조를 포함하는 신규 화합물을 제공하는 것이다. Accordingly, an object of the present invention is to apply the organic EL device as a phosphorescent host material, a fluorescent host material, a hole injection material, a hole transport material, an electron injection material and / or an electron transport material to lower the driving voltage, and to reduce luminous efficiency, luminance and thermal properties. It is to provide a novel compound comprising a fluoranthene derivative structure that can improve the stability and device life.
본 발명의 다른 목적은 상기 화합물을 이용한 유기 EL 소자를 제공하는 것이다.Another object of the present invention is to provide an organic EL device using the compound.
상기 목적을 달성하기 위하여 본 발명은 하기 화학식 1로 표시되는 화합물을 제공한다.The present invention to achieve the above object provides a compound represented by the following formula (1).
상기 식에서,
X는 CR13R14, O, S, S(=O), S(=O)2 및 SiR16R17로 이루어진 군에서 선택되고,
R1 내지 R14, R16 내지 R17은 각각 독립적으로 
하나 이상의 L은 각각 독립적으로 CA1A2, NA3, O, S 및 SiA4A5로 이루어진 군에서 선택되며, A1 내지 A5는 각각 독립적으로 수소, 중수소, 치환 또는 비치환된 C1-C40 알킬, 치환 또는 비치환된 C2-C40 알케닐, 치환 또는 비치환된 C2-C40 알키닐, 치환 또는 비치환된 C3-C40 사이클로알킬, 치환 또는 비치환된 핵원자수 3 내지 40의 헤테로사이클로알킬, (치환 또는 비치환된 C6-C60 아릴)C1-C40 알킬, 치환 또는 비치환된 C1-C40 알콕시, 치환 또는 비치환된 C6-C60 아릴아민, 치환 또는 비치환된 C6-C60 디아릴아민, 치환 또는 비치환된 C6-C60 아릴옥시, 치환 또는 비치환된 C6-C60 아릴, 치환 또는 비치환된 핵원자수 5 내지 60의 헤테로아릴, 치환 또는 비치환된 핵원자수 5 내지 50의 축합(fused) 폴리사이클릭 방향족 탄화수소, 또는 치환 또는 비치환된 핵원자수 5 내지 50의 축합(fused) 폴리사이클릭 방향족 헤테로환이고, A1과 A2, A4와 A5는 서로 결합하여 환상 고리를 형성할 수 있으며;
하나 이상의 Q1은 각각 독립적으로 치환 또는 비치환된 C1-C40 알킬렌, 치환 또는 비치환된 C2-C40 알케닐렌, 치환 또는 비치환된 C2-C40 알키닐렌, 치환 또는 비치환된 C3-C40 사이클로알킬렌, 치환 또는 비치환된 핵원자수 3 내지 40의 헤테로사이클로알킬렌, (치환 또는 비치환된 C6-C60 아릴) C1-C40 알킬렌, 치환 또는 비치환된 C6-C60의 -N(아릴)-, 치환 또는 비치환된 C6-C60 아릴렌, 치환 또는 비치환된 핵원자수 5 내지 60의 헤테로아릴렌, 치환 또는 비치환된 C1-C30 알킬실릴렌, 치환 또는 비치환된 C6-C60 아릴실릴렌, 치환 또는 비치환된 핵원자수 5 내지 50의 축합(fused) 폴리사이클릭 방향족 탄화수소, 또는 치환 또는 비치환된 핵원자수 5 내지 50의 축합(fused) 폴리사이클릭 방향족 헤테로환이고;
Q2는 수소, 중수소, 치환 또는 비치환된 C1-C40 알킬, 치환 또는 비치환된 C2-C40 알케닐, 치환 또는 비치환된 C2-C40 알키닐, 치환 또는 비치환된 C3-C40 사이클로알킬, 치환 또는 비치환된 핵원자수 3 내지 40의 헤테로사이클로알킬, (치환 또는 비치환된 C6-C60 아릴) C1-C40 알킬, 치환 또는 비치환된 C1-C40 알콕시, 치환 또는 비치환된 C6-C60 아릴아민, 치환 또는 비치환된 C6-C60 디아릴아민, 치환 또는 비치환된 C6-C60 아릴옥시, 치환 또는 비치환된 C6-C60 아릴, 치환 또는 비치환된 핵원자수 5 내지 60의 헤테로아릴, 치환 또는 비치환된 C1-C30 알킬실릴, 치환 또는 비치환된 C6-C60 아릴실릴, 치환 또는 비치환된 핵원자수 5 내지 50의 축합(fused) 폴리사이클릭 방향족 탄화수소, 또는 치환 또는 비치환된 핵원자수 5 내지 50의 축합(fused) 폴리사이클릭 방향족 헤테로환이며;
R1 내지 R12는 인접하는 기와 서로 결합하여 축합(fused) 지방족 고리, 축합 방향족 고리, 축합 헤테로지방족 고리 또는 축합 헤테로방향족 고리를 형성할 수 있으며;
R13과 R14, R16과 R17은 서로 결합하여 환상 고리를 형성할 수 있다.In this formula,
X is selected from the group consisting of CR 13 R 14 , O, S, S (= 0), S (= 0) 2 and SiR 16 R 17 ,
R 1 to R 14 , R 16 to R 17 are each independently
At least one L is each independently selected from the group consisting of CA 1 A 2 , NA 3 , O, S and SiA 4 A 5 , and A 1 to A 5 are each independently hydrogen, deuterium, substituted or unsubstituted C1-; C40 alkyl, substituted or unsubstituted C2-C40 alkenyl, substituted or unsubstituted C2-C40 alkynyl, substituted or unsubstituted C3-C40 cycloalkyl, substituted or unsubstituted heterocycloalkyl having 3 to 40 heteroatoms Alkyl, (substituted or unsubstituted C6-C60 aryl) C1-C40 alkyl, substituted or unsubstituted C1-C40 alkoxy, substituted or unsubstituted C6-C60 arylamine, substituted or unsubstituted C6-C60 diarylamine , Substituted or unsubstituted C6-C60 aryloxy, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted nuclear atom having 5 to 60 heteroaryl, substituted or unsubstituted nuclear atom having 5 to 50 condensation (fused) polycyclic aromatic hydrocarbons or substituted or unsubstituted 5 to 50 condensed atoms (fu sed) a polycyclic aromatic heterocycle, wherein A 1 and A 2 , A 4 and A 5 can be bonded to each other to form a cyclic ring;
At least one Q 1 is each independently substituted or unsubstituted C1-C40 alkylene, substituted or unsubstituted C2-C40 alkenylene, substituted or unsubstituted C2-C40 alkynylene, substituted or unsubstituted C3-C40 cycle Alkylene, substituted or unsubstituted heterocycloalkylene having 3 to 40 nuclear atoms, (substituted or unsubstituted C6-C60 aryl) C1-C40 alkylene, substituted or unsubstituted C6-C60 -N (aryl )-, Substituted or unsubstituted C6-C60 arylene, substituted or unsubstituted heteroarylene having 5 to 60 nuclear atoms, substituted or unsubstituted C1-C30 alkylsilylene, substituted or unsubstituted C6-C60 Arylsilylene, substituted or unsubstituted fused polycyclic aromatic hydrocarbons having 5 to 50 nuclear atoms, or substituted or unsubstituted fused polycyclic aromatic heterocycles having 5 to 50 nuclear atoms, ;
Q 2 is hydrogen, deuterium, substituted or unsubstituted C1-C40 alkyl, substituted or unsubstituted C2-C40 alkenyl, substituted or unsubstituted C2-C40 alkynyl, substituted or unsubstituted C3-C40 cycloalkyl, Substituted or unsubstituted heterocycloalkyl having 3 to 40 nuclear atoms, (substituted or unsubstituted C6-C60 aryl) C1-C40 alkyl, substituted or unsubstituted C1-C40 alkoxy, substituted or unsubstituted C6-C60 Arylamine, substituted or unsubstituted C6-C60 diarylamine, substituted or unsubstituted C6-C60 aryloxy, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted heteroaryl having 5 to 60 nuclear atoms , Substituted or unsubstituted C1-C30 alkylsilyl, substituted or unsubstituted C6-C60 arylsilyl, substituted or unsubstituted fused polycyclic aromatic hydrocarbon having 5 to 50 nuclear atoms, or substituted or unsubstituted Fused polycyclic aromatic heterocycle having 5 to 50 nuclear atoms;
R 1 to R 12 may combine with adjacent groups to form a fused aliphatic ring, a fused aromatic ring, a fused heteroaliphatic ring or a fused heteroaromatic ring;
R 13 and R 14 , R 16 and R 17 may combine with each other to form a cyclic ring.
삭제delete
삭제delete
삭제delete
삭제delete
삭제delete
삭제delete
삭제delete
또한, 본 발명은, 양극; 음극; 및 상기 양극과 음극 사이에 개재(介在)된 하나 이상의 유기층을 포함하는 유기 EL 소자로서, 상기 유기층 중 적어도 하나는 상술된 화합물을 포함하는 것을 특징으로 하는 유기 EL 소자를 제공한다.In addition, the present invention, the anode; cathode; And at least one organic layer interposed between the anode and the cathode, wherein at least one of the organic layers includes the compound described above.
본 발명에 따른 화학식 1의 화합물은 형광 특성 및 인광 특성을 모두 가질 수 있으며 열적 안정성이 우수하여 청색, 녹색, 적색의 형광 또는 인광 호스트 재료로 채택될 경우 저 전력, 고 효율, 고 휘도 및 향상된 내구성과 수명을 확보할 수 있다. 또한, 분자 내의 전자 특성 치환기와 정공 특성 치환기를 모두 포함함으로써, 양극과 음극 사이에 1층 이상의 유기층을 포함하는 유기 EL 소자의 정공 주입층, 정공 수송층, 전자 주입층 및/또는 전자 수송층 재료로도 응용될 수 있다. 따라서 본 발명의 화합물을 포함하는 유기 EL 소자는 발광성능 및 수명 면에서 크게 향상될 수 있어 풀 칼라 디스플레이 패널 등에 효과적으로 적용될 수 있다.The compound of formula 1 according to the present invention may have both fluorescence and phosphorescence properties and has excellent thermal stability, so that when adopted as a blue, green or red fluorescent or phosphorescent host material, low power, high efficiency, high brightness and improved durability And life can be secured. In addition, by including both the electron and the hole substituents in the molecule, even as a hole injection layer, a hole transport layer, an electron injection layer and / or an electron transport layer material of an organic EL device comprising at least one organic layer between the anode and the cathode Can be applied. Therefore, the organic EL device including the compound of the present invention can be greatly improved in terms of light emitting performance and lifetime, and thus can be effectively applied to a full color display panel and the like.
본 발명에 따른 화학식 1로 표시되는 화합물은 하나 이상의 플루오란텐 유도체 모이어티(moiety)를 가지면서, 대칭 혹은 비대칭 분자 구조를 가지는 화합물로서, 인광 호스트 물질, 형광 호스트 물질, 정공 주입 물질, 정공 수송 물질, 전자 주입 물질 및/또는 전자 수송 물질로서 유기 EL 소자에 사용될 수 있다.The compound represented by Formula 1 according to the present invention is a compound having one or more fluoranthene derivative moieties and having a symmetric or asymmetric molecular structure, and includes a phosphorescent host material, a fluorescent host material, a hole injection material, and a hole transporting material. It can be used in organic EL devices as materials, electron injection materials and / or electron transport materials.
본 발명의 화학식 1의 화합물에서, X는 CR13R14, O, S, S(=O), S(=O)2 및 SiR16R17로 이루어진 군에서 선택된다.
R1 내지 R14, R16 내지 R17은 각각 독립적으로 
하나 이상의 L은 각각 독립적으로 CA1A2, NA3, O, S 및 SiA4A5로 이루어진 군에서 선택되며, A1 내지 A5는 각각 독립적으로 수소, 중수소, 치환 또는 비치환된 C1-C40 알킬, 치환 또는 비치환된 C2-C40 알케닐, 치환 또는 비치환된 C2-C40 알키닐, 치환 또는 비치환된 C3-C40 사이클로알킬, 치환 또는 비치환된 핵원자수 3 내지 40의 헤테로사이클로알킬, (치환 또는 비치환된 C6-C60 아릴)C1-C40 알킬, 치환 또는 비치환된 C1-C40 알콕시, 치환 또는 비치환된 C6-C60 아릴아민, 치환 또는 비치환된 C6-C60 디아릴아민, 치환 또는 비치환된 C6-C60 아릴옥시, 치환 또는 비치환된 C6-C60 아릴, 치환 또는 비치환된 핵원자수 5 내지 60의 헤테로아릴, 치환 또는 비치환된 핵원자수 5 내지 50의 축합(fused) 폴리사이클릭 방향족 탄화수소, 또는 치환 또는 비치환된 핵원자수 5 내지 50의 축합(fused) 폴리사이클릭 방향족 헤테로환이고, A1과 A2, A4와 A5는 서로 결합하여 환상 고리를 형성할 수 있으며;
하나 이상의 Q1은 각각 독립적으로 치환 또는 비치환된 C1-C40 알킬렌, 치환 또는 비치환된 C2-C40 알케닐렌, 치환 또는 비치환된 C2-C40 알키닐렌, 치환 또는 비치환된 C3-C40 사이클로알킬렌, 치환 또는 비치환된 핵원자수 3 내지 40의 헤테로사이클로알킬렌, (치환 또는 비치환된 C6-C60 아릴) C1-C40 알킬렌, 치환 또는 비치환된 C6-C60의 -N(아릴)-, 치환 또는 비치환된 C6-C60 아릴렌, 치환 또는 비치환된 핵원자수 5 내지 60의 헤테로아릴렌, 치환 또는 비치환된 C1-C30 알킬실릴렌, 치환 또는 비치환된 C6-C60 아릴실릴렌, 치환 또는 비치환된 핵원자수 5 내지 50의 축합(fused) 폴리사이클릭 방향족 탄화수소, 또는 치환 또는 비치환된 핵원자수 5 내지 50의 축합(fused) 폴리사이클릭 방향족 헤테로환이고;
Q2는 수소, 중수소, 치환 또는 비치환된 C1-C40 알킬, 치환 또는 비치환된 C2-C40 알케닐, 치환 또는 비치환된 C2-C40 알키닐, 치환 또는 비치환된 C3-C40 사이클로알킬, 치환 또는 비치환된 핵원자수 3 내지 40의 헤테로사이클로알킬, (치환 또는 비치환된 C6-C60 아릴) C1-C40 알킬, 치환 또는 비치환된 C1-C40 알콕시, 치환 또는 비치환된 C6-C60 아릴아민, 치환 또는 비치환된 C6-C60 디아릴아민, 치환 또는 비치환된 C6-C60 아릴옥시, 치환 또는 비치환된 C6-C60 아릴, 치환 또는 비치환된 핵원자수 5 내지 60의 헤테로아릴, 치환 또는 비치환된 C1-C30 알킬실릴, 치환 또는 비치환된 C6-C60 아릴실릴, 치환 또는 비치환된 핵원자수 5 내지 50의 축합(fused) 폴리사이클릭 방향족 탄화수소, 또는 치환 또는 비치환된 핵원자수 5 내지 50의 축합(fused) 폴리사이클릭 방향족 헤테로환이다. In the compound of formula 1 of the present invention, X is selected from the group consisting of CR 13 R 14 , O, S, S (= 0), S (= 0) 2 and SiR 16 R 17 .
R 1 to R 14 , R 16 to R 17 are each independently
At least one L is each independently selected from the group consisting of CA 1 A 2 , NA 3 , O, S and SiA 4 A 5 , and A 1 to A 5 are each independently hydrogen, deuterium, substituted or unsubstituted C1-; C40 alkyl, substituted or unsubstituted C2-C40 alkenyl, substituted or unsubstituted C2-C40 alkynyl, substituted or unsubstituted C3-C40 cycloalkyl, substituted or unsubstituted heterocycloalkyl having 3 to 40 heteroatoms Alkyl, (substituted or unsubstituted C6-C60 aryl) C1-C40 alkyl, substituted or unsubstituted C1-C40 alkoxy, substituted or unsubstituted C6-C60 arylamine, substituted or unsubstituted C6-C60 diarylamine , Substituted or unsubstituted C6-C60 aryloxy, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted nuclear atom having 5 to 60 heteroaryl, substituted or unsubstituted nuclear atom having 5 to 50 condensation (fused) polycyclic aromatic hydrocarbons or substituted or unsubstituted 5 to 50 condensed atoms (fu sed) a polycyclic aromatic heterocycle, wherein A 1 and A 2 , A 4 and A 5 can be bonded to each other to form a cyclic ring;
At least one Q 1 is each independently substituted or unsubstituted C1-C40 alkylene, substituted or unsubstituted C2-C40 alkenylene, substituted or unsubstituted C2-C40 alkynylene, substituted or unsubstituted C3-C40 cycle Alkylene, substituted or unsubstituted heterocycloalkylene having 3 to 40 nuclear atoms, (substituted or unsubstituted C6-C60 aryl) C1-C40 alkylene, substituted or unsubstituted C6-C60 -N (aryl )-, Substituted or unsubstituted C6-C60 arylene, substituted or unsubstituted heteroarylene having 5 to 60 nuclear atoms, substituted or unsubstituted C1-C30 alkylsilylene, substituted or unsubstituted C6-C60 Arylsilylene, substituted or unsubstituted fused polycyclic aromatic hydrocarbons having 5 to 50 nuclear atoms, or substituted or unsubstituted fused polycyclic aromatic heterocycles having 5 to 50 nuclear atoms, ;
Q 2 is hydrogen, deuterium, substituted or unsubstituted C1-C40 alkyl, substituted or unsubstituted C2-C40 alkenyl, substituted or unsubstituted C2-C40 alkynyl, substituted or unsubstituted C3-C40 cycloalkyl, Substituted or unsubstituted heterocycloalkyl having 3 to 40 nuclear atoms, (substituted or unsubstituted C6-C60 aryl) C1-C40 alkyl, substituted or unsubstituted C1-C40 alkoxy, substituted or unsubstituted C6-C60 Arylamine, substituted or unsubstituted C6-C60 diarylamine, substituted or unsubstituted C6-C60 aryloxy, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted heteroaryl having 5 to 60 nuclear atoms , Substituted or unsubstituted C1-C30 alkylsilyl, substituted or unsubstituted C6-C60 arylsilyl, substituted or unsubstituted fused polycyclic aromatic hydrocarbon having 5 to 50 nuclear atoms, or substituted or unsubstituted Fused polycyclic aromatic heterocycle having 5 to 50 nuclear atoms.
삭제delete
바람직하게는, A1 내지 A5는 각각 독립적으로 수소, 중수소, 치환 또는 비치환된 C1-C20 알킬, 치환 또는 비치환된 C2-C20 알케닐, 치환 또는 비치환된 C2-C20 알키닐, 치환 또는 비치환된 C3-C20 사이클로알킬, 치환 또는 비치환된 핵원자수 3 내지 20의 헤테로사이클로알킬, (치환 또는 비치환된 C6-C20 아릴) C1-C20 알킬, 치환 또는 비치환된 C1-C20 알콕시, 치환 또는 비치환된 C6-C20 아릴아민, 치환 또는 비치환된 C6-C20 디아릴아민, 치환 또는 비치환된 C6-C30 아릴옥시, 치환 또는 비치환된 C6-C30 아릴, 치환 또는 비치환된 핵원자수 5 내지 30의 헤테로아릴, 치환 또는 비치환된 핵원자수 5 내지 20의 축합(fused) 폴리사이클릭 방향족 탄화수소, 또는 치환 또는 비치환된 핵원자수 5 내지 20의 축합(fused) 폴리사이클릭 방향족 헤테로환이고, A1과 A2, A4와 A5는 서로 결합하여 핵원자수 5 내지 8의 환상 고리를 형성할 수 있으며;
하나 이상의 Q1은 각각 독립적으로 치환 또는 비치환된 C1-C40 알킬렌, 치환 또는 비치환된 C2-C40 알케닐렌, 치환 또는 비치환된 C2-C40 알키닐렌, 치환 또는 비치환된 C3-C40 사이클로알킬렌, 치환 또는 비치환된 핵원자수 3 내지 40의 헤테로사이클로알킬렌, (치환 또는 비치환된 C6-C60 아릴) C1-C40 알킬렌, 치환 또는 비치환된 C6-C60의 -N(아릴)-, 치환 또는 비치환된 C6-C60 아릴렌, 치환 또는 비치환된 핵원자수 5 내지 60의 헤테로아릴렌, 치환 또는 비치환된 C1-C30 알킬실릴렌, 치환 또는 비치환된 C6-C60 아릴실릴렌, 치환 또는 비치환된 핵원자수 5 내지 50의 축합(fused) 폴리사이클릭 방향족 탄화수소, 또는 치환 또는 비치환된 핵원자수 5 내지 50의 축합(fused) 폴리사이클릭 방향족 헤테로환이고;
Q2는 수소, 중수소, 치환 또는 비치환된 C1-C40 알킬, 치환 또는 비치환된 C2-C40 알케닐, 치환 또는 비치환된 C2-C40 알키닐, 치환 또는 비치환된 C3-C40 사이클로알킬, 치환 또는 비치환된 핵원자수 3 내지 40의 헤테로사이클로알킬, (치환 또는 비치환된 C6-C60 아릴) C1-C40 알킬, 치환 또는 비치환된 C1-C40 알콕시, 치환 또는 비치환된 C6-C60 아릴아민, 치환 또는 비치환된 C6-C60 디아릴아민, 치환 또는 비치환된 C6-C60 아릴옥시, 치환 또는 비치환된 C6-C60 아릴, 치환 또는 비치환된 핵원자수 5 내지 60의 헤테로아릴, 치환 또는 비치환된 C1-C30 알킬실릴, 치환 또는 비치환된 C6-C60 아릴실릴, 치환 또는 비치환된 핵원자수 5 내지 50의 축합(fused) 폴리사이클릭 방향족 탄화수소, 또는 치환 또는 비치환된 핵원자수 5 내지 50의 축합(fused) 폴리사이클릭 방향족 헤테로환이다. Preferably, A 1 to A 5 are each independently hydrogen, deuterium, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted C2-C20 alkynyl, substituted Or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted heterocycloalkyl having 3 to 20 nuclear atoms, (substituted or unsubstituted C6-C20 aryl) C1-C20 alkyl, substituted or unsubstituted C1-C20 Alkoxy, substituted or unsubstituted C6-C20 arylamine, substituted or unsubstituted C6-C20 diarylamine, substituted or unsubstituted C6-C30 aryloxy, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted Heteroaryl having 5 to 30 heteroatoms, substituted or unsubstituted fused polycyclic aromatic hydrocarbon having 5 to 20 atoms, or substituted or unsubstituted fused 5 to 20 atoms. polycyclic aromatic heterocyclic ring, a 1 and a 2, a 4 and a 5 are bonded to each other and Nuclear atoms to form a cyclic ring of 5 to 8, and;
At least one Q 1 is each independently substituted or unsubstituted C1-C40 alkylene, substituted or unsubstituted C2-C40 alkenylene, substituted or unsubstituted C2-C40 alkynylene, substituted or unsubstituted C3-C40 cycle Alkylene, substituted or unsubstituted heterocycloalkylene having 3 to 40 nuclear atoms, (substituted or unsubstituted C6-C60 aryl) C1-C40 alkylene, substituted or unsubstituted C6-C60 -N (aryl )-, Substituted or unsubstituted C6-C60 arylene, substituted or unsubstituted heteroarylene having 5 to 60 nuclear atoms, substituted or unsubstituted C1-C30 alkylsilylene, substituted or unsubstituted C6-C60 Arylsilylene, substituted or unsubstituted fused polycyclic aromatic hydrocarbons having 5 to 50 nuclear atoms, or substituted or unsubstituted fused polycyclic aromatic heterocycles having 5 to 50 nuclear atoms, ;
Q 2 is hydrogen, deuterium, substituted or unsubstituted C1-C40 alkyl, substituted or unsubstituted C2-C40 alkenyl, substituted or unsubstituted C2-C40 alkynyl, substituted or unsubstituted C3-C40 cycloalkyl, Substituted or unsubstituted heterocycloalkyl having 3 to 40 nuclear atoms, (substituted or unsubstituted C6-C60 aryl) C1-C40 alkyl, substituted or unsubstituted C1-C40 alkoxy, substituted or unsubstituted C6-C60 Arylamine, substituted or unsubstituted C6-C60 diarylamine, substituted or unsubstituted C6-C60 aryloxy, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted heteroaryl having 5 to 60 nuclear atoms , Substituted or unsubstituted C1-C30 alkylsilyl, substituted or unsubstituted C6-C60 arylsilyl, substituted or unsubstituted fused polycyclic aromatic hydrocarbon having 5 to 50 nuclear atoms, or substituted or unsubstituted Fused polycyclic aromatic heterocycle having 5 to 50 nuclear atoms.
R1 내지 R12는 인접하는 기와 서로 결합하여, 예를 들어 핵원자수 5 내지 50의 축합(fused) 지방족 고리, 축합 방향족 고리, 축합 헤테로지방족 고리 또는 축합 헤테로방향족 고리를 형성할 수 있으며, R13과 R14, R16과 R17은 서로 결합하여 환상 고리, 예를 들어 핵원자수 5 내지 8의 환상 고리를 형성할 수 있다.R 1 to R 12 may combine with adjacent groups to form, for example, a fused aliphatic ring, a fused aromatic ring, a fused heteroaliphatic ring or a fused heteroaromatic ring of 5 to 50 nuclear atoms, and R 13 and R 14 , R 16 and R 17 may be bonded to each other to form a cyclic ring, for example, a cyclic ring having 5 to 8 nuclear atoms.
R1 내지 R14, R16 내지 R17은 각각 독립적으로 
상기 R1 내지 R14, R16 내지 R17의 알킬, 알케닐, 알키닐, 사이클로알킬, 헤테로사이클로알킬, 아릴알킬, 알콕시, 아릴아민, 디아릴아민, 아릴옥시, 아릴, 헤테로아릴, 알킬실릴, 아릴실릴, 축합 폴리사이클릭 방향족 탄화수소, 및 축합 폴리사이클릭 방향족 헤테로환은 각각 독립적으로 중수소, C1-C20 알킬, C6-C20 아릴, C6-C20 아릴아민, C6-C20 디아릴아민, 핵원자수 5 내지 30의 헤테로아릴, 핵원자수 5 내지 30의 축합 폴리사이클릭 방향족 탄화수소, 및 핵원자수 5 내지 30의 축합 폴리사이클릭 방향족 헤테로환으로 구성된 군으로부터 선택된 1 이상의 치환기로 치환될 수 있다. 이들 치환체는 C6-C20 아릴, 핵원자수 5 내지 30의 헤테로아릴 등으로 추가적으로 치환될 수 있다.Alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, arylalkyl, alkoxy, arylamine, diarylamine, aryloxy, aryl, heteroaryl, alkylsilyl of R 1 to R 14 , R 16 to R 17 , Arylsilyl, condensed polycyclic aromatic hydrocarbons, and condensed polycyclic aromatic heterocycles are each independently deuterium, C1-C20 alkyl, C6-C20 aryl, C6-C20 arylamine, C6-C20 diarylamine, nuclear atom number It may be substituted with one or more substituents selected from the group consisting of 5 to 30 heteroaryl, condensed polycyclic aromatic hydrocarbon of 5 to 30 nuclear atoms, and condensed polycyclic aromatic heterocycle of 5 to 30 nuclear atoms. These substituents may be further substituted with C6-C20 aryl, heteroaryl having 5 to 30 nuclear atoms, and the like.
하기 화학식들은 본 발명의 화학식 1의 화합물의 대표적인 예들이나, 본 발명의 화합물이 하기 예시된 것들에 한정되는 것은 아니다.The following formulas are representative examples of the compound of formula 1 of the present invention, but the compounds of the present invention are not limited to those illustrated below.
본 발명에서 사용된 "비치환된 축합 폴리사이클릭 방향족 탄화수소"는 5-내지 8-원(membered)의 방향족 고리들이 서로 축합되어 형성된, 핵원자수 5 내지 50, 바람직하게는 5 내지 20의 방향족 부위를 의미하며, 이의 비-제한적인 예로는 인덴, 플루오렌, 페난트렌 등이 있다.As used herein, an "unsubstituted condensed polycyclic aromatic hydrocarbon" is an aromatic having 5 to 50, preferably 5 to 20, atoms formed by condensation of 5- to 8-membered aromatic rings with one another. Moiety, non-limiting examples of which include indene, fluorene, phenanthrene and the like.
"비치환된 축합 폴리사이클릭 방향족 헤테로환(heterocycle)"은 5- 내지 6-원(membered)의 방향족 고리들이 서로 축합되어 핵원자수 5 내지 50, 바람직하게는 5 내지 20의 방향족 부위를 형성하되, 축합에 의해 형성된 고리들 중 적어도 하나에서 하나 이상의 탄소, 바람직하게는 1 내지 3개의 탄소가 N, O 또는 S와 같은 헤테로원자로 치환된 방향족 부위를 의미한다. 이의 비-제한적인 예로는 카바졸 등이 있다."Unsubstituted condensed polycyclic aromatic heterocycle" refers to the condensation of 5- to 6-membered aromatic rings with each other to form an aromatic moiety of 5 to 50, preferably 5 to 20, atomic atoms. By at least one of the rings formed by condensation it is meant an aromatic moiety wherein at least one carbon, preferably 1 to 3 carbons, is substituted with a heteroatom such as N, O or S. Non-limiting examples thereof include carbazole and the like.
“비치환된 헤테로사이클로알킬”은 핵원자수 3 내지 40, 바람직하게는 3 내지 20의 비-방향족 부위를 의미하며, 고리 중 하나 이상의 탄소, 바람직하게는 1 내지 3개의 탄소가 N, O 또는 S와 같은 헤테로 원자로 치환된다. 이의 비-제한적인 예로는 모르폴린, 피페라진 등이 있다. "Unsubstituted heterocycloalkyl" means a non-aromatic moiety of 3 to 40, preferably 3 to 20, atomic atoms, wherein at least one carbon in the ring, preferably 1 to 3 carbons is N, O or Substituted with a hetero atom such as S. Non-limiting examples thereof include morpholine, piperazine and the like.
"비치환된 헤테로아릴"은 핵원자수 5 내지 60, 바람직하게는 5 내지 30의 모노헤테로사이클릭 또는 폴리헤테로사이클릭 방향족 부위를 의미하며, 고리 중 하나 이상의 탄소, 바람직하게는 1 내지 3개의 탄소가 N, O 또는 S와 같은 헤테로원자로 치환된다. 2 이상의 고리가 서로 단순 부착(pendant)되거나 축합된(fused) 형태로 부착될 수 있고, 나아가 아릴기와의 축합된 형태도 포함하는 것으로 해석한다. 본 발명에서 헤테로아릴과 방향족 헤테로환은 중첩적인 의미로 사용될 수도 있다. "Unsubstituted heteroaryl" means a monoheterocyclic or polyheterocyclic aromatic moiety of 5 to 60, preferably 5 to 30, nuclear atoms, wherein at least one carbon, preferably 1 to 3 carbon atoms in the ring Carbon is substituted with a heteroatom such as N, O or S. It is understood that two or more rings may be attached in a simple or fused form to each other and further include a condensed form with an aryl group. In the present invention, heteroaryl and aromatic heterocycle may be used in an overlapping sense.
본 발명의 화학식 1의 화합물은 일반적인 합성방법에 따라 합성될 수 있다 (J. Org . Chem. 70(13): 5014-5019 (2005); J. Org . Chem. 73: 7369 (2008) 등 참조). 본 발명의 화합물에 대한 상세한 합성 과정은 후술하는 합성예에서 구체적으로 기술하도록 한다.Compounds of formula 1 of the present invention can be synthesized according to general synthetic methods (see J. Org . Chem . 70 (13): 5014-5019 (2005); J. Org . Chem . 73: 7369 (2008), etc.). ). Detailed synthesis procedures for the compounds of the present invention will be described in detail in the synthesis examples described below.
본 발명에 따른 유기 EL 소자는, 양극(anode); 음극(cathode); 및 상기 양극과 음극 사이에 개재(介在)된 1층 이상의 유기층을 포함하며, 상기 1층 이상의 유기층 중 적어도 하나는 상기 화학식 1로 표시되는 화합물을 포함하는 것을 특징으로 한다. An organic EL device according to the present invention comprises: an anode; Cathode; And at least one organic layer interposed between the anode and the cathode, wherein at least one of the at least one organic layer includes a compound represented by Chemical Formula 1.
상기 화학식 1의 화합물은 단독 또는 복수로 포함될 수 있다.The compound of Formula 1 may be included alone or in plurality.
본 발명의 화학식 1의 화합물을 포함하는 유기층은 정공 주입층, 정공 수송층, 전자 주입층, 전자 수송층 및 발광층 중 어느 하나 이상일 수 있다. 본 발명에서 발광층은 인광 도판트 재료 또는 형광 도판트 재료를 포함할 수 있다. 바람직하게는, 본 발명의 화학식 1의 화합물은 청색, 녹색, 및/또는 적색의 인광 호스트, 형광 호스트, 정공 수송 물질, 정공 주입 물질, 전자 주입 물질 및/또는 전자수송 물질로서 유기 EL 소자에 포함될 수 있다. 또한, 본 발명의 화학식 1의 화합물은 형광 게스트 물질일 수도 있다. 보다 바람직하게는 본 발명의 화학식 1의 화합물은 인광 호스트 또는 형광 호스트, 특히 바람직하게는 인광 호스트로서 유기 EL 소자에 포함될 수 있다.The organic layer including the compound of Formula 1 of the present invention may be at least one of a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, and a light emitting layer. In the present invention, the light emitting layer may include a phosphorescent dopant material or a fluorescent dopant material. Preferably, the compound of formula 1 of the present invention is included in the organic EL device as a blue, green, and / or red phosphorescent host, fluorescent host, hole transport material, hole injection material, electron injection material and / or electron transport material. Can be. In addition, the compound of formula 1 of the present invention may be a fluorescent guest material. More preferably, the compound of formula 1 of the present invention may be included in the organic EL device as a phosphorescent host or a fluorescent host, particularly preferably as a phosphorescent host.
본 발명의 화합물은 150℃ 이상의 높은 유리 전이 온도를 가지고 있어, 이러한 화합물을 유기 EL 소자의 유기층으로 사용할 경우 유기 EL 소자 내에서 결정화 가 최소화되기 때문에 소자의 구동전압을 낮출 수 있고, 발광효율, 휘도, 열적 안정성, 및 수명 특성을 개선할 수 있다.Since the compound of the present invention has a high glass transition temperature of 150 ℃ or more, when the compound is used as an organic layer of the organic EL device, since the crystallization is minimized in the organic EL device, the driving voltage of the device can be lowered, luminous efficiency, luminance , Thermal stability, and lifetime characteristics can be improved.
본 발명에 따른 유기 EL 소자 구조의 비제한적인 예를 들면, 기판, 양극, 정공 주입층, 정공 수송층, 발광층, 전자 수송층 및 음극이 순차적으로 적층된 것일 수 있으며, 이때 상기 발광층, 정공 주입층, 정공 수송층, 전자 주입층 및 전자 수송층 중 하나 이상은 상기 화학식 1로 표시되는 화합물을 포함할 수 있다. For example, a substrate, an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and a cathode may be sequentially stacked, wherein the light emitting layer, the hole injection layer, At least one of the hole transport layer, the electron injection layer, and the electron transport layer may include a compound represented by Chemical Formula 1.
또한, 본 발명에 따른 유기 EL 소자는 전술한 바와 같이 양극, 1층 이상의 유기층 및 음극이 순차적으로 적층된 구조뿐만 아니라, 전극과 유기층 계면에 절연층 또는 접착층이 삽입될 수도 있다.In addition, as described above, the organic EL device according to the present invention may not only have a structure in which an anode, at least one organic layer, and a cathode are sequentially stacked, but an insulating layer or an adhesive layer may be inserted at the interface between the electrode and the organic layer.
본 발명의 유기 EL 소자에 있어서, 상기 화학식 1의 화합물을 포함하는 상기 유기층은 진공 증착이나 용액 도포에 의하여 형성될 수 있다. 상기 용액 도포의 예로는 스핀 코팅, 딥코팅, 닥터 블레이딩, 잉크젯 프린팅 또는 열 전사법 등이 있으나, 이들에만 한정되지 않는다. In the organic EL device of the present invention, the organic layer including the compound of Formula 1 may be formed by vacuum deposition or solution coating. Examples of the solution application include spin coating, dip coating, doctor blading, inkjet printing or thermal transfer method, but is not limited thereto.
본 발명의 유기 EL 소자는, 유기층 중 1층 이상을 본 발명의 화학식 1로 표현된 화합물을 포함하도록 형성하는 것을 제외하고는, 당 기술 분야에 알려져 있는 재료 및 방법을 이용하여 유기층 및 전극을 형성할 수 있다.The organic EL device of the present invention forms an organic layer and an electrode using materials and methods known in the art, except that at least one of the organic layers is formed to include the compound represented by the formula (1) of the present invention. can do.
예컨대, 기판으로는 실리콘 웨이퍼, 석영, 유리판, 금속판, 플라스틱 필름이나 시트 등이 사용될 수 있다.For example, a silicon wafer, quartz, glass plate, metal plate, plastic film or sheet may be used as the substrate.
양극 물질로는 바나듐, 크롬, 구리, 아연, 금과 같은 금속 또는 이들의 합금; 아연산화물, 인듐산화물, 인듐 주석 산화물(ITO), 인듐 아연 산화물(IZO)과 같 은 금속 산화물; ZnO:Al 또는 SnO2:Sb와 같은 금속과 산화물의 조합물; 폴리티오펜, 폴리(3-메틸티오펜), 폴리[3,4-(에틸렌-1,2-디옥시)티오펜](PEDT), 폴리피롤 및 폴리아닐린과 같은 전도성 고분자; 또는 카본블랙 등이 있으나, 이들에만 한정되는 것은 아니다.The anode material may be a metal such as vanadium, chromium, copper, zinc, gold or an alloy thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO); Combinations of oxides with metals such as ZnO: Al or SnO 2 : Sb; Conductive polymers such as polythiophene, poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDT), polypyrrole and polyaniline; Or carbon black, but is not limited thereto.
음극 물질로는 마그네슘, 칼슘, 나트륨, 칼륨, 타이타늄, 인듐, 이트륨, 리튬, 가돌리늄, 알루미늄, 은, 주석 또는 납과 같은 금속 또는 이들의 합금; LiF/Al 또는 LiO2/Al과 같은 다층 구조 물질 등이 있으나, 이들에만 한정되는 것은 아니다.Cathode materials include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin or lead or alloys thereof; Multilayer structure materials such as LiF / Al or LiO 2 / Al, and the like, but are not limited thereto.
정공 주입층, 정공 수송층, 전자 수송층 및 전자 주입층은 특별히 한정되는 것은 아니며, 당 업계에 알려진 통상의 물질이 사용될 수 있다.The hole injection layer, the hole transport layer, the electron transport layer and the electron injection layer are not particularly limited, and conventional materials known in the art may be used.
본 발명의 일 실시예에 따른 유기 EL 소자의 개략적인 구조가 도 1에 나타나있다. 도 1을 참조하면, 기판(101), 양극(102), 정공 주입층(103), 정공 수송층(104), 발광층(105), 전자 수송층(106) 및 음극(107)이 순차적으로 적층되어 있다. A schematic structure of an organic EL device according to an embodiment of the present invention is shown in FIG. Referring to FIG. 1, the
이하 본 발명을 실시예를 통하여 상세히 설명하면 다음과 같다. 단, 하기 실시예는 본 발명을 예시하는 것일 뿐 본 발명이 하기 실시예에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail with reference to the following Examples. However, the following examples are merely to illustrate the present invention and the present invention is not limited by the following examples.
<< 합성예Synthetic example 1> 화합물 1> Compound InvInv -- 3 의3 of 합성 synthesis
<단계 1> 3-(2-<Step 1> 3- (2- nitrophenylnitrophenyl )) fluoranthenefluoranthene 의 합성Synthesis of
2-(fluoranthen-3-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (8.4 g, 25.5934 mmol), 2-bromonitrobenzene(5.69 g, 28.1527 mmol) 및 Pd(PPh3)4 (0.9 g, 0.7678 mmol)을 플라스크에 넣은 후 Toluene 200 ㎖에 용해시켰다. Na2CO3 (8.13 g)을 증류수 70 ㎖에 용해시킨 용액을 상기 플라스크에 첨가한 후 12시간 동안 환류 교반하였다. 2- (fluoranthen-3-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (8.4 g, 25.5934 mmol), 2-bromonitrobenzene (5.69 g, 28.1527 mmol) and Pd (PPh3) 4 (0.9 g, 0.7678 mmol) was added to the flask and dissolved in 200 mL of Toluene. A solution of Na 2 CO 3 (8.13 g) dissolved in 70 mL of distilled water was added to the flask, followed by stirring under reflux for 12 hours.
반응이 종결된 후, 반응 용액을 methylene chloride를 이용하여 추출 및 농축하여 실리카겔 컬럼 크로마토그래피(Hexane : MC = 4 : 1(v/v))로 정제하여 표제 화합물 (6.22 g, 75%)을 수득하였다.After the reaction was completed, the reaction solution was extracted and concentrated with methylene chloride and purified by silica gel column chromatography (Hexane: MC = 4: 1 (v / v)) to give the title compound (6.22 g, 75%). It was.
GC-Mass (이론치: 323.24 g/mol, 측정치: 323 g/mol)GC-Mass (Theoretical value: 323.24 g / mol, Measured value: 323 g / mol)
<단계 2> 8H-<Step 2> 8H- fluorenofluoreno [9,1-[9,1- bcbc ]carbazole의 합성 ] Synthesis of carbazole
상기 <단계 1>에서 합성한 화합물(6.22 g, 19.2367 mmol)을 Triethylphosphite (20 ml, 115.4202 mmol)에 용해시킨 후 4시간 동안 환류 교반하였다. The compound (6.22 g, 19.2367 mmol) synthesized in <Step 1> was dissolved in Triethylphosphite (20 ml, 115.4202 mmol) and stirred under reflux for 4 hours.
반응이 종결된 후, 생성된 고체를 필터 및 Hexane/Methylene Chloride 에서 재결정하여 표제 화합물(3.24 g, 58%)을 수득하였다.After the reaction was completed, the resulting solid was recrystallized from a filter and Hexane / Methylene Chloride to give the title compound (3.24 g, 58%).
GC-Mass (이론치: 291.35 g/mol, 측정치: 291 g/mol)GC-Mass (Theoretical value: 291.35 g / mol, Measured value: 291 g / mol)
<단계 3> 화합물 <Step 3> Compound InvInv -3의 합성Synthesis of -3
상기 <단계 2>에서 합성한 화합물(13.6 g, 46.6299 mmol), 1,3-dibromobenzene (5 g, 21.1954 mmol), Pd2(dba)3 (0.6 g, 0.6358 mmol), NaO(t-Bu) (6.1 g, 63.5862 mmol), 및 P(t-Bu)3 (0.43 g, 2.1195 mmol)을 Toluene 100 ㎖에 용해시킨 후 12시간 동안 환류 교반하였다. Compound (13.6 g, 46.6299 mmol), 1,3-dibromobenzene (5 g, 21.1954 mmol), Pd2 (dba) 3 (0.6 g, 0.6358 mmol), NaO (t-Bu) (synthesized in Step 2) ( 6.1 g, 63.5862 mmol), and P (t-Bu) 3 (0.43 g, 2.1195 mmol) were dissolved in 100 mL of Toluene and stirred at reflux for 12 hours.
반응이 종결된 후, 반응 용액을 methylene chloride를 이용하여 추출하고, 여액을 실리카겔 필터를 이용하여 농축한 다음, 실리카겔 컬럼 크로마토그래피(Hexane : MC = 2 : 1(v/v))로 정제하여 원하는 표제 화합물 Inv-3(10 g, 77%)을 수득하였다.After the reaction was completed, the reaction solution was extracted with methylene chloride, the filtrate was concentrated using a silica gel filter, purified by silica gel column chromatography (Hexane: MC = 2: 1 (v / v)) to the desired The title compound Inv-3 (10 g, 77%) was obtained.
GC-Mass (이론치: 656.77 g/mol, 측정치: 656 g/mol)GC-Mass (Theoretical value: 656.77 g / mol, Measured value: 656 g / mol)
<< 합성예Synthetic example 2> 화합물 2> compound InvInv -6의 합성Synthesis of -6
합성예 1의 <단계 2>에서 합성한 화합물 8H-fluoreno[9,1-bc]carbazole (10 g, 34.33 mmol) 및 5-bromo-m-terphenyl (12.74 g, 41.196 mmol)을 Toluene 150 ㎖에 용해시키는 것을 제외하고는 합성예 1의 <단계 3>과 동일한 방법을 수행하여 원하는 표제 화합물 Inv-6(12 g, 67%)을 수득하였다.Compound 8H-fluoreno [9,1-bc] carbazole (10 g, 34.33 mmol) and 5-bromo-m-terphenyl (12.74 g, 41.196 mmol) synthesized in <Step 2> of Synthesis Example 1 were dissolved in 150 ml of toluene. Except for dissolving, the same procedure as in <Step 3> of Synthesis Example 1 was performed to obtain the title compound Inv-6 (12 g, 67%).
GC-Mass (이론치: 519.63 g/mol, 측정치: 519 g/mol)GC-Mass (Theoretical value: 519.63 g / mol, Measured value: 519 g / mol)
<< 합성예Synthetic example 3> 화합물 3> Compound InvInv -- 9 의9 of 합성 synthesis
합성예 1의 <단계 2>에서 합성한 화합물 8H-fluoreno[9,1-bc]carbazole (10 g, 34.33 mmol) 및 2-(3-bromophenyl)-1-phenyl-1H-benzo[d]imidazole (14.4 g, 41.2 mmol)을 toluene 150 ㎖에 용해시키는 것을 제외하고는 합성예 1의 <단계 3>과 동일한 방법을 수행하여 원하는 표제 화합물 Inv-9 (11 g, 58%)을 수득하였다.Compounds 8H-fluoreno [9,1-bc] carbazole (10 g, 34.33 mmol) and 2- (3-bromophenyl) -1-phenyl-1H-benzo [d] imidazole synthesized in <Step 2> of Synthesis Example 1 Except for dissolving (14.4 g, 41.2 mmol) in 150 ml of toluene, the same procedure as in <Step 3> of Synthesis Example 1 was performed to obtain the title compound Inv-9 (11 g, 58%).
GC-Mass (이론치: 559.66 g/mol, 측정치: 559 g/mol)
<합성예 4> 화합물 Inv-10 의 합성 GC-Mass (Theoretical value: 559.66 g / mol, Measured value: 559 g / mol)
Synthesis Example 4 Synthesis of Compound Inv-10
삭제delete
합성예 1의 <단계 2>에서 합성한 화합물 8H-fluoreno[9,1-bc]carbazole (10 g, 34.33 mmol) 및 4-bromo-N,N-diphenylaniline (13.36 g, 41.2 mmol)을 Toluene 150 ㎖에 용해시키는 것을 제외하고는 합성예 1의 <단계 3>과 동일한 방법을 수행하여 원하는 표제 화합물 Inv-10 (14 g, 76%)을 수득하였다.Compound 8H-fluoreno [9,1-bc] carbazole (10 g, 34.33 mmol) and 4-bromo-N, N-diphenylaniline (13.36 g, 41.2 mmol) synthesized in <Step 2> of Synthesis Example 1 were dissolved in Toluene 150. Except for dissolving in mL, the same procedure as in <Step 3> of Synthesis Example 1 was performed to obtain the title compound Inv-10 (14 g, 76%).
GC-Mass (이론치: 534.65 g/mol, 측정치: 534 g/mol)GC-Mass (Theoretical value: 534.65 g / mol, Measured value: 534 g / mol)
<< 합성예Synthetic example 5> 화합물 5> Compound InvInv -- 22 의22 of 합성 synthesis
<단계 1> 8-<Step 1> 8- phenylphenyl -8H--8H- fluorenofluoreno [9,1-[9,1- bcbc ]carbazole의 합성] Synthesis of carbazole
합성예 1의 <단계 2>에서 합성한 화합물 8H-fluoreno[9,1-bc]carbazole (10 g, 34.33 mmol) 및 Bromobenzene (6.47 g, 41.2 mmol)을 Toluene 150 ㎖에 용해시키는 것을 제외하고는 합성예 1의 <단계 3>과 동일한 과정을 수행하여 표제 화합물(10.5 g, 83%)을 수득하였다.Except for dissolving the compound 8H-fluoreno [9,1-bc] carbazole (10 g, 34.33 mmol) and Bromobenzene (6.47 g, 41.2 mmol) synthesized in <Step 2> of Synthesis Example 1 in 150 ml of Toluene The title compound (10.5 g, 83%) was obtained by the same procedure as <Step 3> of Synthesis Example 1.
GC-Mass (이론치: 367.44 g/mol, 측정치: 367 g/mol)GC-Mass (Theoretical value: 367.44 g / mol, Measured value: 367 g / mol)
<단계 2> 5-<Step 2> 5- bromobromo -8--8- phenylphenyl -8H--8H- fluorenofluoreno [9,1-[9,1- bcbc ]carbazole의 합성] Synthesis of carbazole
상기 <단계 1>에서 합성한 화합물 8-phenyl-8H-fluoreno[9,1-bc]carbazole (5 g, 13.61 mmol)을 N,N-dimethylformamide 80 ㎖에 용해시킨 다음 N-bromosuccinimide (2.42 g, 13.61 mmol)을 첨가하였다. 혼합 용액을 80℃에서 12시간 동안 교반한 다음 증류수 200 ㎖를 첨가하였다. Compound 8-phenyl-8H-fluoreno [9,1-bc] carbazole (5 g, 13.61 mmol) synthesized in <Step 1> was dissolved in 80 ml of N, N-dimethylformamide and then N-bromosuccinimide (2.42 g, 13.61 mmol) was added. The mixed solution was stirred at 80 ° C. for 12 hours and then 200 ml of distilled water was added.
생성된 고체를 여과한 후 methylene chloride에 용해시켜 실리카겔 필터로 여과하였다. 여액을 농축시킨 후 Hexane/Methylene Chloride 로 재결정하여 표제 화합물(5 g, 82%)을 수득하였다. The resulting solid was filtered and dissolved in methylene chloride and filtered through a silica gel filter. The filtrate was concentrated and recrystallized from Hexane / Methylene Chloride to give the title compound (5 g, 82%).
GC-Mass (이론치: 446.34 g/mol, 측정치: 446 g/mol)GC-Mass (Theoretical value: 446.34 g / mol, Measured value: 446 g / mol)
<단계 3> 화합물 <Step 3> Compound InvInv -22의 합성Synthesis of -22
상기 <단계 2>에서 합성한 화합물 5-bromo-8-phenyl-8H-fluoreno[9,1- bc]carbazole (5 g, 11.2 mmol) 및 3-(1-phenyl-1H-benzo[d]imidazol-2-yl)phenylboronic acid (4.22 g, 13.44 mmol)을 Toluene 70 ㎖에 용해시킨 후 합성예 1의 <단계 1>과 동일한 과정을 수행하여 원하는 표제 화합물 Inv-22 (5.2 g, 73%)을 수득하였다.Compounds 5-bromo-8-phenyl-8H-fluoreno [9,1-bc] carbazole (5 g, 11.2 mmol) and 3- (1-phenyl-1H-benzo [d] imidazol synthesized in <Step 2> above -2-yl) phenylboronic acid (4.22 g, 13.44 mmol) was dissolved in 70 ml of Toluene, followed by the same procedure as <Step 1> of Synthesis Example 1 to obtain the title compound Inv-22 (5.2 g, 73%). Obtained.
GC-Mass (이론치: 635.75 g/mol, 측정치: 635 g/mol)GC-Mass (Theoretical value: 635.75 g / mol, Measured value: 635 g / mol)
<< 합성예Synthetic example 6> 화합물 6> Compound InvInv -24의 합성Synthesis of -24
합성예 5의 <단계 2>에서 합성한 화합물 5-bromo-8-phenyl-8H-fluoreno[9,1-bc]carbazole (5 g, 11.2 mmol) 및 2-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)pyridine (3.78 g, 13.44 mmol)을 Toluene 70 ㎖에 용해시키는 것을 제외하고는 합성예 1의 <단계 1>과 동일한 과정을 수행하여 원하는 표제 화합물 Inv-24 (4.5 g, 77%)을 수득하였다.Compounds 5-bromo-8-phenyl-8H-fluoreno [9,1-bc] carbazole (5 g, 11.2 mmol) and 2- (4- (4,4,5) synthesized in <Step 2> of Synthesis Example 5 , 5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) pyridine (3.78 g, 13.44 mmol) was dissolved in 70 ml of Toluene, and the same procedure as in <Step 1> of Synthesis Example 1 was performed. This gave the desired title compound Inv-24 (4.5 g, 77%).
GC-Mass (이론치: 520.62 g/mol, 측정치: 520 g/mol)GC-Mass (Theoretical value: 520.62 g / mol, Measured value: 520 g / mol)
<< 합성예Synthetic example 7> 화합물 7> Compound InvInv -38의 합성Synthesis of -38
<단계 1> 3-o-<Step 1> 3-o- tolylfluoranthenetolylfluoranthene 의 합성Synthesis of
Fluoranthen-3-ylboronic acid (5 g, 20.32 mmol) 및 2-bromotoluene (4.17 g, 24.38 mmol)을 Toluene 70 ㎖에 용해시키는 것을 제외하고는 합성예 1의 <단계 1>과 동일한 과정을 수행하여 표제 화합물 (4.8 g, 81%)을 수득하였다.Except for dissolving Fluoranthen-3-ylboronic acid (5 g, 20.32 mmol) and 2-bromotoluene (4.17 g, 24.38 mmol) in 70 ml of Toluene, the same procedure as in <Step 1> of Synthesis Example 1 was performed. Compound (4.8 g, 81%) was obtained.
GC-Mass (이론치: 292.37 g/mol, 측정치: 292 g/mol)GC-Mass (Theoretical value: 292.37 g / mol, Measured value: 292 g / mol)
<단계 2> 2-(<Step 2> 2- ( FluoranthenFluoranthen -3--3- ylyl )) benzoicbenzoic acidacid 의 합성Synthesis of
상기 <단계 1>에서 합성한 화합물 3-o-tolylfluoranthene (5 g, 17.1 mmol) 을 pyridine 90 ㎖에 용해시킨 다음 potassium permanganate (13.5 g)을 증류수 15 ㎖에 녹인 용액을 첨가하여 10 시간 동안 환류 교반하였다. Dissolve compound 3-o-tolylfluoranthene (5 g, 17.1 mmol) synthesized in <Step 1> in 90 ml of pyridine, and then add a solution of potassium permanganate (13.5 g) in 15 ml of distilled water and stir at reflux for 10 hours. It was.
반응이 종결된 후, 침전물을 거르고 끓는 증류수 500 ml로 침전물에 남아있는 생성물을 세척하였다. 여액을 모아 산성이 될 때까지 염산을 조금씩 첨가해 주었다. 형성된 침전물을 여과하여 걸러진 물질을 오븐에서 건조하여 표제 화합 물(3.1 g, 56%)을 수득하였다. After the reaction was completed, the precipitate was filtered off and the product remaining in the precipitate was washed with 500 ml of boiling distilled water. The filtrate was collected and hydrochloric acid was added little by little until it became acidic. The precipitate formed was filtered off and the filtered material was dried in an oven to give the title compound (3.1 g, 56%).
GC-Mass (이론치: 322.36 g/mol, 측정치: 322 g/mol)GC-Mass (Theoretical value: 322.36 g / mol, Measured value: 322 g / mol)
<단계 3> 8H-<Step 3> 8H- indenoindeno [2,1-b]fluoranthen-8-[2,1-b] fluoranthen-8- one 의one of 합성 synthesis
상기 <단계 2>에서 합성한 화합물 2-(fluoranthen-3-yl)benzoic acid (5 g, 15.51 mmol)을 PPA (10 g)에 넣은 후 130℃에서 3시간 동안 교반하였다. Compound 2- (fluoranthen-3-yl) benzoic acid (5 g, 15.51 mmol) synthesized in <Step 2> was added to PPA (10 g), followed by stirring at 130 ° C. for 3 hours.
반응이 종결된 후, 얻어진 용액을 증류수 500 ㎖에 넣고, 생성된 고체를 증류수로 수회 세척한 다음 Methanol 200 ml로 세척하여 표제 화합물(3 g, 64%)을 수득하였다.After the reaction was completed, the obtained solution was put into 500 ml of distilled water, and the resulting solid was washed several times with distilled water and then with 200 ml of Methanol to obtain the title compound (3 g, 64%).
GC-Mass (이론치: 304.34 g/mol, 측정치: 304 g/mol)GC-Mass (Theoretical value: 304.34 g / mol, Measured value: 304 g / mol)
<단계 4> 8H-<Step 4> 8H- indenoindeno [2,1-b]fluoranthene 의 합성Synthesis of [2,1-b] fluoranthene
1L 둥근바닥 플라스크에 Potassium hydroxide (69.4 g, 1.24 mol) 및 Diethylene glycol (600 ml)를 넣고 교반한 다음, 상기 <단계 3>에서 합성한 화합 물 8H-indeno[2,1-b]fluoranthen-8-one (5 g, 16.44 mmol)과 Hydrazine monohydrate (50.8 g, 1.02 mol)을 첨가하여 185℃로 가열하면서 24시간 동안 교반하였다. Potassium hydroxide (69.4 g, 1.24 mol) and diethylene glycol (600 ml) were added to a 1 L round bottom flask, followed by stirring, followed by compound 8H-indeno [2,1-b] fluoranthen-8 synthesized in <Step 3>. -one (5 g, 16.44 mmol) and Hydrazine monohydrate (50.8 g, 1.02 mol) were added thereto, followed by stirring for 24 hours while heating to 185 ° C.
반응이 종결된 후, 얼음이 담긴 2L 비이커에 반응 용액을 붓고 교반하면서 염산을 서서히 첨가하였다. 형성된 침전물을 여과하고 증류수로 수회 세척한 다음 건조하여 표제 화합물(3.5 g, 73%)을 수득하였다.After the reaction was completed, the reaction solution was poured into a 2 L beaker containing ice and hydrochloric acid was slowly added while stirring. The precipitate formed was filtered, washed several times with distilled water and dried to give the title compound (3.5 g, 73%).
GC-Mass (이론치: 290.36 g/mol, 측정치: 290 g/mol)GC-Mass (Theoretical value: 290.36 g / mol, Measured value: 290 g / mol)
<단계 5> 8,8-<Step 5> 8,8- dimethyldimethyl -8H--8H- indenoindeno [2,1-b]fluoranthene 의 합성Synthesis of [2,1-b] fluoranthene
250 ml 둥근 바닥 플라스크에 상기 <단계 4>에서 합성한 화합물 8H-indeno[2,1-b]fluoranthene (3 g, 10.32 mmol)을 넣고 진공 건조시킨 뒤 질소 가스를 충진하였다. THF 100 ml를 상기 플라스크에 넣고 -78℃로 냉각시켰다. n-Butyllithium(1.6M in Hex.) (1.65 g, 25.8 mmol)을 천천히 첨가하면서 동일 온도에서 1시간 동안 교반하였다. Iodomethane (4.74 g, 25.8 mmol)을 첨가한 후 3시간 동안 교반하였다. The compound 8H-indeno [2,1-b] fluoranthene (3 g, 10.32 mmol) synthesized in the above <Step 4> was added to a 250 ml round bottom flask and dried under vacuum and filled with nitrogen gas. 100 ml THF was placed in the flask and cooled to -78 ° C. n-Butyllithium (1.6M in Hex.) (1.65 g, 25.8 mmol) was added slowly and stirred for 1 hour at the same temperature. Iodomethane (4.74 g, 25.8 mmol) was added and stirred for 3 hours.
반응이 종결된 후, 증류수 100 ml로 세척하고 methylene chloride로 추출한 다음 magnesium sulfate로 수분을 제거하고 여액을 농축하였다. After the reaction was completed, washed with 100 ml of distilled water, extracted with methylene chloride, water was removed with magnesium sulfate and the filtrate was concentrated.
상기 반응액을 컬럼 크로마토그래피(Hexane : MC = 9 : 1(v/v))로 정제하여 표제 화합물(2.8 g, 85%)을 수득하였다.The reaction solution was purified by column chromatography (Hexane: MC = 9: 1 (v / v)) to give the title compound (2.8 g, 85%).
GC-Mass (이론치: 318.41 g/mol, 측정치: 318 g/mol)GC-Mass (Theoretical value: 318.41 g / mol, Measured value: 318 g / mol)
<단계 6> 6-<Step 6> 6- bromobromo -8,8--8,8- dimethyldimethyl -8H--8H- indenoindeno [2,1-b]fluoranthene의 합성Synthesis of [2,1-b] fluoranthene
상기 <단계 5>에서 합성한 화합물 8,8-dimethyl-8H-indeno[2,1-b]fluoranthene (5 g, 15.7 mmol)을 N,N-dimethylformamide 120 ㎖에 용해시킨 다음 N-bromosuccinimide (2.79 g, 15.7 mmol)을 첨가하였다. Compound 8,8-dimethyl-8H-indeno [2,1-b] fluoranthene (5 g, 15.7 mmol) synthesized in step <5> was dissolved in 120 ml of N, N-dimethylformamide and then N-bromosuccinimide (2.79 g, 15.7 mmol) was added.
혼합 용액을 80℃에서 12시간 동안 교반한 다음 증류수 200 ㎖를 첨가하고 생성된 고체를 여과한 후 MC 100 ml에 용해시켜 Silicagel Filter 하였다. 여액을 농축시킨 다음 Methanol/Methylene Chloride로 재결정하여 표제 화합물(5.3 g, 85%)을 수득하였다.The mixed solution was stirred at 80 ° C. for 12 hours, and then 200 ml of distilled water was added, and the resulting solid was filtered and dissolved in 100 ml of MC, followed by Silicagel Filter. The filtrate was concentrated and then recrystallized from Methanol / Methylene Chloride to give the title compound (5.3 g, 85%).
GC-Mass (이론치: 397.31 g/mol, 측정치: 397 g/mol)GC-Mass (Theoretical value: 397.31 g / mol, Measured value: 397 g / mol)
<단계 7> 화합물 <Step 7> Compound InvInv -38의 합성Synthesis of -38
상기 <단계 6>에서 합성한 화합물 6-bromo-8,8-dimethyl-8H-indeno[2,1-b]fluoranthene (5 g, 12.58 mmol) 및 N1-(biphenyl-4-yl)-N4,N4-diphenylbenzene-1,4-diamine (5.71 g, 13.84 mmol)을 Toluene 100 ml에 용해시키는 것을 제외하고는 합성예 1의 <단계 3>과 동일한 과정을 수행하여 원하는 표제 화합물 Inv-38 (7.4 g, 81%)을 수득하였다. Compound 6-bromo-8,8-dimethyl-8H-indeno [2,1-b] fluoranthene (5 g, 12.58 mmol) and N1- (biphenyl-4-yl) -N4 synthesized in the above <Step 6>, Except for dissolving N4-diphenylbenzene-1,4-diamine (5.71 g, 13.84 mmol) in 100 ml of Toluene, the same procedure as in <Step 3> of Synthesis Example 1 was carried out to obtain the title compound Inv-38 (7.4 g , 81%) was obtained.
GC-Mass (이론치: 728.92 g/mol, 측정치: 728 g/mol)GC-Mass (Theoretical value: 728.92 g / mol, Measured value: 728 g / mol)
<< 합성예Synthetic example 8> 화합물 8> Compound InvInv -42의 합성Synthesis of -42
상기 합성예 7의 <단계 6>에서 합성한 화합물 6-bromo-8,8-dimethyl-8H-indeno[2,1-b]fluoranthene (5 g, 12.58 mmol) 및 3-(1-phenyl-1H-benzo[d]imidazol-2-yl)phenylboronic acid (4.35 g, 13.84 mmol)을 Toluene 100 ml에 용해시키는 것을 제외하고는 합성예 1의 <단계 1>과 동일한 과정을 수행하여 원하는 표제 화합물 Inv-42 (5.2 g, 70%)을 수득하였다. Compounds 6-bromo-8,8-dimethyl-8H-indeno [2,1-b] fluoranthene (5 g, 12.58 mmol) and 3- (1-phenyl-1H) synthesized in <Step 6> of Synthesis Example 7 Except for dissolving -benzo [d] imidazol-2-yl) phenylboronic acid (4.35 g, 13.84 mmol) in 100 ml of Toluene, the same procedure as in <Step 1> of Synthesis Example 1 was performed. 42 (5.2 g, 70%) was obtained.
GC-Mass (이론치: 586.72 g/mol, 측정치: 586 g/mol)GC-Mass (Theoretical value: 586.72 g / mol, Measured value: 586 g / mol)
<< 실시예Example 1 내지 6> 유기 1 to 6> organic ELEL 소자의 제조 ( Fabrication of Devices 발광층으로의To the light emitting layer 적용) apply)
ITO (Indium tin oxide)가 1500Å 두께로 박막 코팅된 유리 기판을 증류수 초음파로 세척하였다. 증류수 세척이 끝나면 이소프로필 알코올, 아세톤, 메탄올 등의 용제로 초음파 세척을 하고 건조시킨 후 플라즈마 세정기로 이송시킨 다음 산소 플라즈마를 이용하여 상기 기판을 5분간 세정한 후 진공 층착기로 기판을 이송하였다. A glass substrate coated with ITO (Indium tin oxide) having a thickness of 1500 Å was washed with distilled water ultrasonically. After the washing of distilled water, ultrasonic washing with a solvent such as isopropyl alcohol, acetone, methanol, and the like was dried, transferred to a plasma cleaner, and then the substrate was cleaned for 5 minutes using an oxygen plasma, and then the substrate was transferred to a vacuum depositor.
이렇게 준비된 ITO 투명 전극 위에 NPB(40nm)/합성예 1-6에서 합성한 각각의화합물 + 10%Ir(piq)2(acac)(20nm)/BCP(10nm)/Alq3(40 nm)/LiF(1nm)/Al(200 nm) 순으로 유기 EL 소자를 제조하였다.NPB (40 nm) / each compound synthesized in Synthesis Examples 1-6 on the prepared ITO transparent electrode + 10% Ir (piq) 2 (acac) (20 nm) / BCP (10 nm) / Alq 3 (40 nm) / LiF ( An organic EL device was manufactured in the order of 1 nm) / Al (200 nm).
NPBNPB
IrIr (( piqpiq )2(acac)2 (acac)
BCPBCP
<< 비교예Comparative example 1> 유기 1> organic ELEL 소자의 제조 Manufacture of device
발광층 형성시 합성예에서 제조된 화합물 대신 CBP를 발광호스트 물질로 사용한 것을 제외하고는, 실시예 1과 동일한 방법으로 유기 EL 소자를 제조하였다.An organic EL device was manufactured in the same manner as in Example 1, except that CBP was used as a light emitting host material, instead of the compound prepared in Synthesis Example, to form an emission layer.
CBPCBP
<< 평가예Evaluation example 1> 1>
실시예 1-6 및 비교예 1에서 제조된 각각의 유기 EL 소자에 대하여 구동전압, 전류효율 및 휘도를 측정하고, 그 결과를 하기 표 1에 나타내었다. For each organic EL device manufactured in Example 1-6 and Comparative Example 1, the driving voltage, current efficiency, and luminance were measured, and the results are shown in Table 1 below.
상기 표 1에 나타낸 바와 같이, 본 발명에 따른 화합물을 사용한 유기 EL 소자(실시예 1-6)는 종래 CBP를 사용한 유기 EL 소자(비교예 1)보다 전압 및 효율 면에서 월등한 성능을 나타내는 것을 알 수 있다.As shown in Table 1, the organic EL device (Example 1-6) using the compound according to the present invention exhibits superior performance in terms of voltage and efficiency than the organic EL device (Comparative Example 1) using the conventional CBP. Able to know.
<실시예 7 내지 9, 비교예 2> 유기 EL 소자의 제조 (전자 주입 및 수송층으 로의 적용) Examples 7 to 9 and Comparative Example 2 Fabrication of Organic EL Device ( Application to Electron Injection and Transport Layer )
상기 실시예 1에서 준비된 ITO 투명 전극 위에 DS-HIL(두산社, 이하 DS-HIL로 표기)를 60 nm의 두께로 열 진공 증착하여 정공 주입층을 형성하였다. 그 위에 정공을 이송하는 물질인 N,N-di(naphthalene-1-yl)-N,N-diphenylbenzidine (NPB)를 15 nm의 두께로 증착한 후, 발광 호스트 역할을 하는 ADN(9,10-di(naphthalen-2-yl)anthracene, 이하 ADN으로 표기)와 도판트 역할을 하는 DS-405(두산社)를 사용하여 발광층을 30 nm 두께로 증착하였다. 발광층 위에 전자의 주입 및 수송 역할을 하는 물질로서 합성예 3, 5 및 8에서 각각 합성한 화합물 Inv-9(실시예 7), Inv-22(실시예 8), 및 Inv-42(실시예 9)와 비교물질인 aluminum tris(8-hydroxyquinoline)(Alq3) (비교예 2)을 각각 25 nm 의 두께로 증착하였다. 상기 전자 주입 및 수송층 위에 순차적으로 1 nm의 두께로 LiF와 200 nm의 두께의 Al을 증착하여 음극을 형성하여 유기 EL 소자를 제조하였다.On the ITO transparent electrode prepared in Example 1, the hole injection layer was formed by thermally vacuum depositing DS-HIL (Doosan Corp., hereinafter referred to as DS-HIL) to a thickness of 60 nm. After depositing 15 nm thick N, N-di (naphthalene-1-yl) -N, N-diphenylbenzidine (NPB), a hole transporting material, ADN (9,10- A light emitting layer was deposited to a thickness of 30 nm using di (naphthalen-2-yl) anthracene (hereinafter referred to as ADN) and DS-405 (Doosan Corporation) serving as a dopant. Compounds Inv-9 (Example 7), Inv-22 (Example 8), and Inv-42 (Example 9) synthesized in Synthesis Examples 3, 5, and 8, respectively, as materials for injecting and transporting electrons on the light emitting layer. ) And a comparative material, aluminum tris (8-hydroxyquinoline) (Alq3) (Comparative Example 2), were each deposited to a thickness of 25 nm. An organic EL device was fabricated by depositing LiF and Al having a thickness of 200 nm at a thickness of 1 nm sequentially on the electron injection and transport layer to form a cathode.
<< 평가예Evaluation example 2> 2>
실시예 7-9 및 비교예 2에서 제조된 각각의 유기 EL 소자에 대하여 구동전압, 전류효율 및 휘도를 측정하고, 그 결과를 하기 표 2에 나타내었다. For each organic EL device manufactured in Example 7-9 and Comparative Example 2, the driving voltage, current efficiency and luminance were measured, and the results are shown in Table 2 below.
상기 표 2에 나타낸 바와 같이, 본 발명에 따른 화합물을 사용한 유기 EL 소자(실시예 7-9)는 종래 Alq3을 사용한 유기 EL 소자(비교예 2) 보다 전압 및 효율 면에서 월등한 성능을 나타내는 것을 알 수 있다.As shown in Table 2 above, the organic EL device (Example 7-9) using the compound according to the present invention showed superior performance in terms of voltage and efficiency than the organic EL device (Comparative Example 2) using the conventional Alq3. Able to know.
<< 실시예Example 10> 유기 10> organic ELEL 소자의 제조 (정공 주입 및 Fabrication of devices (hole injection and 수송층으로의To the transport layer 적용) apply)
상기 실시예 1에서 준비된 ITO 투명 전극 위에, 합성예 7에서 합성한 화합물 Inv-38(40nm)/CBP + 10%Ir(ppy)2(acac) (20nm)/BCP(10nm)/Alq3(40 nm)/LiF(1nm)/Al(200 nm) 순으로 유기 EL 소자를 제작하였다. On the ITO transparent electrode prepared in Example 1, the compound Inv-38 (40 nm) / CBP + 10% Ir (ppy) 2 (acac) (20 nm) / BCP (10 nm) / Alq 3 (40 nm) synthesized in Synthesis Example 7 ) / LiF (1 nm) / Al (200 nm) in order to produce an organic EL device.
IrIr (( ppyppy )2(acac) 2 (acac)
<< 비교예Comparative example 3> 유기 3> organic ELEL 소자의 제조 Manufacture of device
정공 주입 및 수송층 형성시 합성예에서 제조된 화합물 대신 NPB를 사용한 것을 제외하고는, 실시예 10과 동일한 방법으로 유기 EL 소자를 제조하였다.An organic EL device was manufactured in the same manner as in Example 10, except that NPB was used instead of the compound prepared in the synthesis example in forming the hole injection and transport layer.
<< 평가예Evaluation example 3> 3>
실시예 10 및 비교예 3에서 제조된 각각의 유기 EL 소자에 대하여 구동전압, 전류효율 및 휘도를 측정하고, 그 결과를 하기 표 3에 나타내었다.
삭제delete
상기 표 3에 나타낸 바와 같이, 본 발명에 따른 화합물을 사용한 유기 EL 소자(실시예 10)는 NPB(비교예 3)와 비교하여 전압 및 효율 면에서 월등한 성능을 나타내는 것을 알 수 있다.As shown in Table 3, it can be seen that the organic EL device (Example 10) using the compound according to the present invention exhibits superior performance in terms of voltage and efficiency compared to NPB (Comparative Example 3).
도 1은 본 발명의 일 실시예에 따른 유기 EL 소자의 개략적인 단면도이다.1 is a schematic cross-sectional view of an organic EL device according to an embodiment of the present invention.
Claims (7)
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020090134495A KR101184159B1 (en) | 2009-12-30 | 2009-12-30 | Organic compounds and organic electroluminescent devices using the same |
| PCT/KR2010/009474 WO2011081429A2 (en) | 2009-12-30 | 2010-12-29 | Organic compound, and organic electroluminescent device using same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020090134495A KR101184159B1 (en) | 2009-12-30 | 2009-12-30 | Organic compounds and organic electroluminescent devices using the same |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020120029047A Division KR101274926B1 (en) | 2012-03-21 | 2012-03-21 | Organic compounds and organic electroluminescent devices using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20110077831A KR20110077831A (en) | 2011-07-07 |
| KR101184159B1 true KR101184159B1 (en) | 2012-09-18 |
Family
ID=44227031
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020090134495A KR101184159B1 (en) | 2009-12-30 | 2009-12-30 | Organic compounds and organic electroluminescent devices using the same |
Country Status (2)
| Country | Link |
|---|---|
| KR (1) | KR101184159B1 (en) |
| WO (1) | WO2011081429A2 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101553737B1 (en) | 2012-09-24 | 2015-09-16 | 주식회사 두산 | New compounds and organic electro luminescence device using the same |
| KR101793784B1 (en) | 2014-09-22 | 2017-11-06 | 주식회사 엘지화학 | Heterocyclic compound including nitrogen and organic light emitting device using the same |
| WO2018038400A1 (en) * | 2016-08-23 | 2018-03-01 | 주식회사 두산 | Organic compound and organic electroluminescence device including same |
| JP2018518472A (en) * | 2015-06-05 | 2018-07-12 | エルジー・ケム・リミテッド | Polycyclic compound and organic light emitting device including the same |
| WO2021230690A1 (en) * | 2020-05-13 | 2021-11-18 | 주식회사 엘지화학 | Novel compound and organic light-emitting element comprising same |
| KR20210139192A (en) * | 2020-05-13 | 2021-11-22 | 주식회사 엘지화학 | Novel compound and organic light emitting device comprising the same |
| WO2023113577A1 (en) * | 2021-12-17 | 2023-06-22 | 주식회사 엘지화학 | Compounds and organic light-emitting device comprising same |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104768928B (en) * | 2013-03-27 | 2018-06-08 | 出光兴产株式会社 | Condensed fluoranthene compound, material for organic electroluminescent element using same, and organic electroluminescent element and electronic device using same |
| WO2014192950A1 (en) * | 2013-05-31 | 2014-12-04 | 出光興産株式会社 | Condensed fluoranthene compound, organic electroluminescence element material including same, organic electroluminescence element using same, and electronic device |
| CN104513246A (en) * | 2013-09-30 | 2015-04-15 | 北京鼎材科技有限公司 | Anthra bicarbazole derivative and applications thereof |
| CN104649956B (en) * | 2013-12-02 | 2016-04-27 | 固安鼎材科技有限公司 | A kind of fluorenes carbazole derivative and the application in organic electroluminescence device thereof |
| KR101661592B1 (en) * | 2014-09-30 | 2016-10-04 | (주)더블유에스 | fused fluoranthene derivatives and organic electroluminescent device including the same |
| JP6755113B2 (en) * | 2016-04-11 | 2020-09-16 | 出光興産株式会社 | Organic electroluminescence element |
| KR102126101B1 (en) * | 2016-07-07 | 2020-06-23 | 주식회사 엘지화학 | Compound and organic light emitting device containing the same |
| JPWO2018088472A1 (en) | 2016-11-09 | 2019-10-03 | 出光興産株式会社 | COMPOUND, COMPOSITION, ORGANIC ELECTROLUMINESCENT DEVICE, AND ELECTRONIC DEVICE |
| CN108623479A (en) * | 2017-03-17 | 2018-10-09 | 吉林奥来德光电材料股份有限公司 | A kind of organic luminescent compounds and its preparation method and application |
| CN108623469A (en) * | 2017-03-17 | 2018-10-09 | 吉林奥来德光电材料股份有限公司 | A kind of luminophor and its preparation method and application |
| KR20200073601A (en) * | 2018-12-14 | 2020-06-24 | 엘지디스플레이 주식회사 | Organic compound, and Organic light emitting diode and Organic light emitting display device including the same |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3929337B2 (en) * | 2002-03-14 | 2007-06-13 | 三井化学株式会社 | Organic electroluminescence device |
| JP2008115131A (en) * | 2006-11-07 | 2008-05-22 | Mitsubishi Chemicals Corp | Organic compound, charge-transporting material, composition for charge-transporting material, and organic electroluminescent element |
| KR20080047209A (en) * | 2006-11-24 | 2008-05-28 | 삼성전자주식회사 | Organic light emitting compound and organic light emitting device comprising the same |
| KR20080047210A (en) * | 2006-11-24 | 2008-05-28 | 삼성전자주식회사 | Organic light emitting compound and organic light emitting device comprising the same |
-
2009
- 2009-12-30 KR KR1020090134495A patent/KR101184159B1/en active IP Right Grant
-
2010
- 2010-12-29 WO PCT/KR2010/009474 patent/WO2011081429A2/en active Application Filing
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101553737B1 (en) | 2012-09-24 | 2015-09-16 | 주식회사 두산 | New compounds and organic electro luminescence device using the same |
| KR101793784B1 (en) | 2014-09-22 | 2017-11-06 | 주식회사 엘지화학 | Heterocyclic compound including nitrogen and organic light emitting device using the same |
| JP2018518472A (en) * | 2015-06-05 | 2018-07-12 | エルジー・ケム・リミテッド | Polycyclic compound and organic light emitting device including the same |
| WO2018038400A1 (en) * | 2016-08-23 | 2018-03-01 | 주식회사 두산 | Organic compound and organic electroluminescence device including same |
| KR20240095140A (en) * | 2016-08-23 | 2024-06-25 | 솔루스첨단소재 주식회사 | Organic compounds and organic electro luminescence device comprising the same |
| KR102703998B1 (en) | 2016-08-23 | 2024-09-09 | 솔루스첨단소재 주식회사 | Organic compounds and organic electro luminescence device comprising the same |
| WO2021230690A1 (en) * | 2020-05-13 | 2021-11-18 | 주식회사 엘지화학 | Novel compound and organic light-emitting element comprising same |
| KR20210139192A (en) * | 2020-05-13 | 2021-11-22 | 주식회사 엘지화학 | Novel compound and organic light emitting device comprising the same |
| KR102546268B1 (en) | 2020-05-13 | 2023-06-21 | 주식회사 엘지화학 | Novel compound and organic light emitting device comprising the same |
| WO2023113577A1 (en) * | 2021-12-17 | 2023-06-22 | 주식회사 엘지화학 | Compounds and organic light-emitting device comprising same |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2011081429A3 (en) | 2011-12-01 |
| KR20110077831A (en) | 2011-07-07 |
| WO2011081429A2 (en) | 2011-07-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101184159B1 (en) | Organic compounds and organic electroluminescent devices using the same | |
| KR101412246B1 (en) | New compounds and organic electronic device using the same | |
| TWI464234B (en) | Compound, organic electronic element using the same, and electronic device thereof | |
| KR101408515B1 (en) | New compounds and organic electronic device using the same | |
| KR101183722B1 (en) | Triphenylene-based compounds and organic electroluminescent device comprising same | |
| KR101011857B1 (en) | Benzofluoranthene derivative and organic light emitting device using the same | |
| KR101170666B1 (en) | Bis-carbazole chemiclal and organic electroric element using the same, terminal thererof | |
| KR101473019B1 (en) | New compounds and organic electronic device using the same | |
| KR101317511B1 (en) | New compounds and organic electronic device using the same | |
| JP5242612B2 (en) | Organic light-emitting devices using new organic compounds | |
| KR101592085B1 (en) | New compounds and organic electronic device using the same | |
| KR20110123106A (en) | Organic electroluminescence derivative and device using the phenanthrocarbazole | |
| KR20110048840A (en) | Compound for organic photoelectric device and organic photoelectric device including the same | |
| WO2011025282A2 (en) | Novel organic compound and organic light-emitting device using same | |
| KR101408632B1 (en) | New compounds and organic electronic device using the same | |
| KR20110134581A (en) | Novel organic electroluminescent compounds and organic electroluminescent device using the same | |
| KR20210100352A (en) | Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof | |
| KR101170220B1 (en) | Triphenylene-based compounds and organic electroluminescent device comprising same | |
| KR102586097B1 (en) | Compound for organic optoelectronic device, organic optoelectronic device and display device | |
| KR20150014286A (en) | Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof | |
| KR20180113921A (en) | Organic light emitting device | |
| KR101274926B1 (en) | Organic compounds and organic electroluminescent devices using the same | |
| KR20160065298A (en) | Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof | |
| KR20100108505A (en) | New cycloalkene derivatives and organic electronic diode using the same | |
| KR101550523B1 (en) | New compounds and organic electronic device using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| E902 | Notification of reason for refusal | ||
| A107 | Divisional application of patent | ||
| E701 | Decision to grant or registration of patent right | ||
| GRNT | Written decision to grant | ||
| FPAY | Annual fee payment |
Payment date: 20150901 Year of fee payment: 4 |
|
| FPAY | Annual fee payment |
Payment date: 20160822 Year of fee payment: 5 |
|
| FPAY | Annual fee payment |
Payment date: 20180806 Year of fee payment: 7 |