WO2015170930A1 - An electron transport material and an organic electroluminescence device comprising the same - Google Patents
An electron transport material and an organic electroluminescence device comprising the same Download PDFInfo
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- WO2015170930A1 WO2015170930A1 PCT/KR2015/004640 KR2015004640W WO2015170930A1 WO 2015170930 A1 WO2015170930 A1 WO 2015170930A1 KR 2015004640 W KR2015004640 W KR 2015004640W WO 2015170930 A1 WO2015170930 A1 WO 2015170930A1
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- Prior art keywords
- substituted
- unsubstituted
- aryl
- membered heteroaryl
- alkyl
- Prior art date
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- 239000000463 material Substances 0.000 title claims abstract description 77
- 238000005401 electroluminescence Methods 0.000 title description 2
- 150000001875 compounds Chemical class 0.000 claims abstract description 51
- 125000001072 heteroaryl group Chemical group 0.000 claims description 65
- 125000003118 aryl group Chemical group 0.000 claims description 50
- 125000006736 (C6-C20) aryl group Chemical group 0.000 claims description 39
- 125000000923 (C1-C30) alkyl group Chemical group 0.000 claims description 30
- 239000002019 doping agent Substances 0.000 claims description 20
- 125000004432 carbon atom Chemical group C* 0.000 claims description 19
- 125000002950 monocyclic group Chemical group 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 125000005104 aryl silyl group Chemical group 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 17
- 239000001257 hydrogen Substances 0.000 claims description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims description 17
- 125000002723 alicyclic group Chemical group 0.000 claims description 15
- 229910052760 oxygen Inorganic materials 0.000 claims description 15
- 125000003367 polycyclic group Chemical group 0.000 claims description 15
- 229910052717 sulfur Inorganic materials 0.000 claims description 15
- 125000005842 heteroatom Chemical group 0.000 claims description 14
- 125000005103 alkyl silyl group Chemical group 0.000 claims description 12
- 125000001769 aryl amino group Chemical group 0.000 claims description 12
- 150000002431 hydrogen Chemical class 0.000 claims description 12
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 10
- 229910052736 halogen Inorganic materials 0.000 claims description 10
- 150000002367 halogens Chemical class 0.000 claims description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 125000005549 heteroarylene group Chemical group 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 230000002829 reductive effect Effects 0.000 claims description 9
- 125000001424 substituent group Chemical group 0.000 claims description 9
- 239000011593 sulfur Substances 0.000 claims description 9
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 8
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 8
- 229910052805 deuterium Inorganic materials 0.000 claims description 8
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 8
- 125000003282 alkyl amino group Chemical group 0.000 claims description 7
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 7
- 150000002910 rare earth metals Chemical class 0.000 claims description 7
- 125000006835 (C6-C20) arylene group Chemical group 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 150000001340 alkali metals Chemical class 0.000 claims description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 5
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 229910052796 boron Inorganic materials 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 125000000304 alkynyl group Chemical group 0.000 claims description 4
- 125000006822 tri(C1-C30) alkylsilyl group Chemical group 0.000 claims description 4
- 125000000739 C2-C30 alkenyl group Chemical group 0.000 claims description 3
- 125000000732 arylene group Chemical group 0.000 claims description 3
- 125000000592 heterocycloalkyl group Chemical group 0.000 claims description 3
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 claims description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Natural products C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 claims description 2
- 229910001508 alkali metal halide Inorganic materials 0.000 claims description 2
- 150000008045 alkali metal halides Chemical class 0.000 claims description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 2
- 229910001615 alkaline earth metal halide Inorganic materials 0.000 claims description 2
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims description 2
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 2
- 125000004947 alkyl aryl amino group Chemical group 0.000 claims description 2
- 125000004448 alkyl carbonyl group Chemical group 0.000 claims description 2
- 125000004414 alkyl thio group Chemical group 0.000 claims description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N anhydrous quinoline Natural products N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 125000005129 aryl carbonyl group Chemical group 0.000 claims description 2
- 125000005110 aryl thio group Chemical group 0.000 claims description 2
- 125000004104 aryloxy group Chemical group 0.000 claims description 2
- XSCHRSMBECNVNS-UHFFFAOYSA-N benzopyrazine Natural products N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 125000000392 cycloalkenyl group Chemical group 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 150000005054 naphthyridines Chemical class 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 150000005041 phenanthrolines Chemical class 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 150000003216 pyrazines Chemical class 0.000 claims description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 150000003222 pyridines Chemical class 0.000 claims description 2
- 150000003230 pyrimidines Chemical class 0.000 claims description 2
- 150000003248 quinolines Chemical class 0.000 claims description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 2
- 125000005415 substituted alkoxy group Chemical group 0.000 claims description 2
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 2
- 125000003107 substituted aryl group Chemical group 0.000 claims description 2
- 125000005346 substituted cycloalkyl group Chemical group 0.000 claims description 2
- 150000003918 triazines Chemical class 0.000 claims description 2
- 150000003246 quinazolines Chemical class 0.000 claims 1
- 150000003252 quinoxalines Chemical class 0.000 claims 1
- 239000010410 layer Substances 0.000 description 101
- 230000032258 transport Effects 0.000 description 53
- 238000002347 injection Methods 0.000 description 20
- 239000007924 injection Substances 0.000 description 20
- -1 2-methylbut-2-enyl Chemical group 0.000 description 14
- 239000012044 organic layer Substances 0.000 description 14
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 230000005525 hole transport Effects 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- 230000000903 blocking effect Effects 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 238000000151 deposition Methods 0.000 description 10
- 239000002904 solvent Substances 0.000 description 7
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 229940093499 ethyl acetate Drugs 0.000 description 4
- 235000019439 ethyl acetate Nutrition 0.000 description 4
- 238000004770 highest occupied molecular orbital Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZEEBGORNQSEQBE-UHFFFAOYSA-N [2-(3-phenylphenoxy)-6-(trifluoromethyl)pyridin-4-yl]methanamine Chemical compound C1(=CC(=CC=C1)OC1=NC(=CC(=C1)CN)C(F)(F)F)C1=CC=CC=C1 ZEEBGORNQSEQBE-UHFFFAOYSA-N 0.000 description 3
- ABRVLXLNVJHDRQ-UHFFFAOYSA-N [2-pyridin-3-yl-6-(trifluoromethyl)pyridin-4-yl]methanamine Chemical compound FC(C1=CC(=CC(=N1)C=1C=NC=CC=1)CN)(F)F ABRVLXLNVJHDRQ-UHFFFAOYSA-N 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 150000004770 chalcogenides Chemical class 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 3
- 229910001507 metal halide Inorganic materials 0.000 description 3
- 150000005309 metal halides Chemical class 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 238000003775 Density Functional Theory Methods 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 2
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 230000005281 excited state Effects 0.000 description 2
- WUNJCKOTXFSWBK-UHFFFAOYSA-N indeno[2,1-a]carbazole Chemical group C1=CC=C2C=C3C4=NC5=CC=CC=C5C4=CC=C3C2=C1 WUNJCKOTXFSWBK-UHFFFAOYSA-N 0.000 description 2
- IMKMFBIYHXBKRX-UHFFFAOYSA-M lithium;quinoline-2-carboxylate Chemical compound [Li+].C1=CC=CC2=NC(C(=O)[O-])=CC=C21 IMKMFBIYHXBKRX-UHFFFAOYSA-M 0.000 description 2
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 125000002294 quinazolinyl group Chemical group N1=C(N=CC2=CC=CC=C12)* 0.000 description 2
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 125000001935 tetracenyl group Chemical group C1(=CC=CC2=CC3=CC4=CC=CC=C4C=C3C=C12)* 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 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 2
- 238000002061 vacuum sublimation Methods 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 125000004973 1-butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000004972 1-butynyl group Chemical group [H]C([H])([H])C([H])([H])C#C* 0.000 description 1
- 125000006017 1-propenyl group Chemical group 0.000 description 1
- 125000000530 1-propynyl group Chemical group [H]C([H])([H])C#C* 0.000 description 1
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 1
- STTGYIUESPWXOW-UHFFFAOYSA-N 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline Chemical compound C=12C=CC3=C(C=4C=CC=CC=4)C=C(C)N=C3C2=NC(C)=CC=1C1=CC=CC=C1 STTGYIUESPWXOW-UHFFFAOYSA-N 0.000 description 1
- WNXNWOBGPRKOJF-UHFFFAOYSA-N 2-bromo-9,9-diphenylfluorene Chemical compound C12=CC(Br)=CC=C2C2=CC=CC=C2C1(C=1C=CC=CC=1)C1=CC=CC=C1 WNXNWOBGPRKOJF-UHFFFAOYSA-N 0.000 description 1
- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 description 1
- 125000000069 2-butynyl group Chemical group [H]C([H])([H])C#CC([H])([H])* 0.000 description 1
- AKCRQHGQIJBRMN-UHFFFAOYSA-N 2-chloroaniline Chemical compound NC1=CC=CC=C1Cl AKCRQHGQIJBRMN-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 1
- 125000004975 3-butenyl group Chemical group C(CC=C)* 0.000 description 1
- 125000000474 3-butynyl group Chemical group [H]C#CC([H])([H])C([H])([H])* 0.000 description 1
- GJWBRYKOJMOBHH-UHFFFAOYSA-N 9,9-dimethyl-n-[4-(9-phenylcarbazol-3-yl)phenyl]-n-(4-phenylphenyl)fluoren-2-amine Chemical compound C1=C2C(C)(C)C3=CC=CC=C3C2=CC=C1N(C=1C=CC(=CC=1)C=1C=C2C3=CC=CC=C3N(C=3C=CC=CC=3)C2=CC=1)C(C=C1)=CC=C1C1=CC=CC=C1 GJWBRYKOJMOBHH-UHFFFAOYSA-N 0.000 description 1
- BYPCJJONRMPERB-UHFFFAOYSA-N C1(=CC(=CC=C1)C1=NC(=NC(=N1)Cl)C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound C1(=CC(=CC=C1)C1=NC(=NC(=N1)Cl)C1=CC=CC=C1)C1=CC=CC=C1 BYPCJJONRMPERB-UHFFFAOYSA-N 0.000 description 1
- UJOBWOGCFQCDNV-UHFFFAOYSA-N Carbazole Natural products C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- KOPBYBDAPCDYFK-UHFFFAOYSA-N Cs2O Inorganic materials [O-2].[Cs+].[Cs+] KOPBYBDAPCDYFK-UHFFFAOYSA-N 0.000 description 1
- 101000687716 Drosophila melanogaster SWI/SNF-related matrix-associated actin-dependent regulator of chromatin subfamily A containing DEAD/H box 1 homolog Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 101000687741 Mus musculus SWI/SNF-related matrix-associated actin-dependent regulator of chromatin subfamily A containing DEAD/H box 1 Proteins 0.000 description 1
- 229910003564 SiAlON Inorganic materials 0.000 description 1
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 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
- 150000001450 anions Chemical class 0.000 description 1
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 1
- 125000002047 benzodioxolyl group Chemical group O1OC(C2=C1C=CC=C2)* 0.000 description 1
- 125000000499 benzofuranyl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 125000005874 benzothiadiazolyl group Chemical group 0.000 description 1
- 125000001164 benzothiazolyl group Chemical group S1C(=NC2=C1C=CC=C2)* 0.000 description 1
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 125000004541 benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 description 1
- ZDZHCHYQNPQSGG-UHFFFAOYSA-N binaphthyl group Chemical group C1(=CC=CC2=CC=CC=C12)C1=CC=CC2=CC=CC=C12 ZDZHCHYQNPQSGG-UHFFFAOYSA-N 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
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- 125000006267 biphenyl group Chemical group 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- VOZBMWWMIQGZGM-UHFFFAOYSA-N c(cc1)ccc1-[n]1c(-c(cc2)ccc2-c(cc2)cc3c2c(-c2cc(cccc4)c4cc2)c(cccc2)c2c3-c2cc(cccc3)c3cc2)nc2ccccc12 Chemical compound c(cc1)ccc1-[n]1c(-c(cc2)ccc2-c(cc2)cc3c2c(-c2cc(cccc4)c4cc2)c(cccc2)c2c3-c2cc(cccc3)c3cc2)nc2ccccc12 VOZBMWWMIQGZGM-UHFFFAOYSA-N 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000002676 chrysenyl group Chemical group C1(=CC=CC=2C3=CC=C4C=CC=CC4=C3C=CC12)* 0.000 description 1
- 125000000259 cinnolinyl group Chemical group N1=NC(=CC2=CC=CC=C12)* 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 125000005299 dibenzofluorenyl group Chemical group C1(=CC=CC2=C3C(=C4C=5C=CC=CC5CC4=C21)C=CC=C3)* 0.000 description 1
- 125000005509 dibenzothiophenyl group Chemical group 0.000 description 1
- AKUNKIJLSDQFLS-UHFFFAOYSA-M dicesium;hydroxide Chemical compound [OH-].[Cs+].[Cs+] AKUNKIJLSDQFLS-UHFFFAOYSA-M 0.000 description 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 125000003914 fluoranthenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC=C4C1=C23)* 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000003838 furazanyl group Chemical group 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 125000003453 indazolyl group Chemical group N1N=C(C2=C1C=CC=C2)* 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 125000001041 indolyl group Chemical group 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 125000001977 isobenzofuranyl group Chemical group C=1(OC=C2C=CC=CC12)* 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000000904 isoindolyl group Chemical group C=1(NC=C2C=CC=CC12)* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000005956 isoquinolyl group Chemical group 0.000 description 1
- 125000001786 isothiazolyl group Chemical group 0.000 description 1
- 125000000842 isoxazolyl group Chemical group 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Inorganic materials [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- MESMXXUBQDBBSR-UHFFFAOYSA-N n,9-diphenyl-n-[4-[4-(n-(9-phenylcarbazol-3-yl)anilino)phenyl]phenyl]carbazol-3-amine Chemical compound C1=CC=CC=C1N(C=1C=C2C3=CC=CC=C3N(C=3C=CC=CC=3)C2=CC=1)C1=CC=C(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=C3C4=CC=CC=C4N(C=4C=CC=CC=4)C3=CC=2)C=C1 MESMXXUBQDBBSR-UHFFFAOYSA-N 0.000 description 1
- LCPYTQFVQRPZCV-UHFFFAOYSA-N n-[4-(4-carbazol-9-ylphenyl)phenyl]-4-phenyl-n-(4-phenylphenyl)aniline Chemical compound C1=CC=CC=C1C1=CC=C(N(C=2C=CC(=CC=2)C=2C=CC=CC=2)C=2C=CC(=CC=2)C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=C1 LCPYTQFVQRPZCV-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000001715 oxadiazolyl group Chemical group 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- 125000001792 phenanthrenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C=CC12)* 0.000 description 1
- 125000004934 phenanthridinyl group Chemical group C1(=CC=CC2=NC=C3C=CC=CC3=C12)* 0.000 description 1
- 125000001644 phenoxazinyl group Chemical group C1(=CC=CC=2OC3=CC=CC=C3NC12)* 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 125000001725 pyrenyl group Chemical group 0.000 description 1
- 125000002098 pyridazinyl group Chemical group 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 125000005493 quinolyl group Chemical group 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- ORFSSYGWXNGVFB-UHFFFAOYSA-N sodium 4-amino-6-[[4-[4-[(8-amino-1-hydroxy-5,7-disulfonaphthalen-2-yl)diazenyl]-3-methoxyphenyl]-2-methoxyphenyl]diazenyl]-5-hydroxynaphthalene-1,3-disulfonic acid Chemical compound COC1=C(C=CC(=C1)C2=CC(=C(C=C2)N=NC3=C(C4=C(C=C3)C(=CC(=C4N)S(=O)(=O)O)S(=O)(=O)O)O)OC)N=NC5=C(C6=C(C=C5)C(=CC(=C6N)S(=O)(=O)O)S(=O)(=O)O)O.[Na+] ORFSSYGWXNGVFB-UHFFFAOYSA-N 0.000 description 1
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- RAOIDOHSFRTOEL-UHFFFAOYSA-N tetrahydrothiophene Chemical compound C1CCSC1 RAOIDOHSFRTOEL-UHFFFAOYSA-N 0.000 description 1
- 125000005247 tetrazinyl group Chemical group N1=NN=NC(=C1)* 0.000 description 1
- 125000003831 tetrazolyl group Chemical group 0.000 description 1
- 125000001113 thiadiazolyl group Chemical group 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 125000004306 triazinyl group Chemical group 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- 125000003960 triphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C3=CC=CC=C3C12)* 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
- C07D403/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
- C07D403/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a carbon chain containing aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
- C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
-
- 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
- H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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- 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
- H10K50/16—Electron transporting layers
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
- H10K50/16—Electron transporting layers
- H10K50/165—Electron transporting layers comprising dopants
Definitions
- the present invention relates to an electron transport material having improved electron transport ability, and an organic electroluminescent device comprising the same.
- An electroluminescent (EL) device is a self-light-emitting device with the advantages of providing a wider viewing angle, a greater contrast ratio, and a faster response time.
- the first organic EL device was developed by Eastman Kodak, by using small aromatic diamine molecules and aluminum complexes as materials for forming a light-emitting layer (see Appl. Phys. Lett. 51, 913, 1987).
- An organic EL device changes electric energy into light by the injection of a charge into an organic light-emitting material, and commonly comprises an anode, a cathode, and an organic layer formed between the two electrodes.
- the organic layer of the organic EL device may be composed of a hole injection layer (HIL), a hole transport layer (HTL), an electron blocking layer (EBL), a light-emitting layer (EML) (containing host and dopant materials), an electron buffer layer, a hole blocking layer (HBL), an electron transport layer (ETL), an electron injection layer (EIL), etc.; the materials used in the organic layer can be classified into a hole injection material, a hole transport material, an electron blocking material, a light-emitting material, an electron buffer material, a hole blocking material, an electron transport material, an electron injection material, etc., depending on functions.
- the organic EL device In the organic EL device, holes from an anode and electrons from a cathode are injected into a light-emitting layer by electric voltage, and an exciton having high energy is produced by the recombination of the holes and electrons.
- the organic light-emitting compound moves into an excited state by the energy and emits light from energy when the organic light-emitting compound returns to the ground state from the excited state.
- the most important factor determining luminous efficiency in an organic EL device is light-emitting materials.
- the light-emitting materials are required to have the following features: high quantum efficiency, high movement degree of an electron and a hole, and uniformality and stability of the formed light-emitting material layer.
- the light-emitting material is classified into blue, green, and red light-emitting materials according to the light-emitting color, and further includes yellow or orange light-emitting materials. Furthermore, the light-emitting material is classified into a host material and a dopant material in a functional aspect. Recently, an urgent task is the development of an organic EL device having high efficiency and long lifespan.
- a host material should have high purity and a suitable molecular weight in order to be deposited under vacuum. Furthermore, a host material is required to have high glass transition temperature and pyrolysis temperature for guaranteeing thermal stability, high electrochemical stability for long lifespan, easy formability of an amorphous thin film, good adhesion with adjacent layers, and no movement between layers.
- an electron transport material actively transports electrons from a cathode to a light-emitting layer and inhibits transport of holes which are not recombined in the light-emitting layer to increase recombination opportunity of holes and electrons in the light-emitting layer.
- electron-affinitive materials are used as an electron transport material.
- Organic metal complexes having light-emitting function such as Alq 3 are excellent in transporting electrons, and thus have been conventionally used as an electron transport material.
- Alq 3 has problems in that it moves to other layers and shows reduction of color purity when used in blue light-emitting devices. Therefore, new electron transport materials have been required, which do not have the above problems, are highly electron-affinitive, and quickly transport electrons in organic EL devices to provide organic EL devices having high luminous efficiency.
- Korean Patent Appln. Laying-Open No. KR 2010-0130197 A discloses a compound wherein a nitrogen-containing heterocycle is bonded to a nitrogen atom of an indenocarbazole backbone. However, it fails to disclose an organic EL device using the compound as an electron transport material.
- the present inventors found that high efficiency and long lifespan of an organic EL device are provided when using a compound of a specific structure having an indenocarbazole backbone wherein a nitrogen atom of the carbazole is bonded to a nitrogen-containing heterocycle as an electron transport material.
- the objective of the present invention is to provide an electron transport material which can produce an organic EL device having high efficiency and long lifespan.
- A represents a substituted or unsubstituted 5- to 30-membered heteroaryl
- L represents a single bond, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted 5- to 30-membered heteroarylene;
- X represents CR 11 R 12 ;
- R 1 and R 2 each independently represent hydrogen, deuterium, a halogen, a cyano, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted 5- to 30-membered heteroaryl, a substituted or unsubstituted (C6-C30)aryl(C1-C30)alkyl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C1-C30)alkoxy, a substituted or unsubstituted (C1-C30)alkylsilyl, a substituted or unsubstituted (C6-C30)arylsilyl, a substituted or unsubstituted (C6-C30)aryl(C1-C30)alkylsilyl, a substituted
- R 3 represents hydrogen, deuterium, a halogen, a cyano, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted 5- to 30-membered heteroaryl; or are linked to an adjacent substituent(s) to form a mono- or polycyclic (C3-C30) alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen, and sulfur;
- R 11 and R 12 each independently represent a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted 5- to 30-membered heteroaryl; or are linked to each other to form a mono- or polycyclic (C3-C30) alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen, and sulfur;
- a and b each independently represent an integer of 1 to 4, where a or b is an integer of 2 or more, each of R 1 and each of R 2 may be the same or different;
- c represents an integer of 1 to 2, where c is 2, each of R 3 may be the same or different;
- an organic EL device with high efficiency and long lifespan is provided, and it is possible to produce a display device or a lighting device using the organic EL device.
- Figure 1 illustrates a schematic sectional view of an organic electroluminescent device comprising the electron transport layer comprising the electron transport material according to one embodiment of the present invention.
- Figure 2 illustrates a comparison of current efficiency between an organic electroluminescent device according to one embodiment of the present invention and a conventional organic electroluminescent device.
- Figure 3 illustrates an energy gap relationship among the layers of the organic electroluminescent device according to one embodiment of the present invention.
- (C1-C30)alkyl is meant to be a linear or branched alkyl having 1 to 30 carbon atoms, in which the number of carbon atoms is preferably 1 to 10, more preferably 1 to 6, and includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc.
- (C2-C30)alkenyl is meant to be a linear or branched alkenyl having 2 to 30 carbon atoms, in which the number of carbon atoms is preferably 2 to 20, more preferably 2 to 10, and includes vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methylbut-2-enyl, etc.
- (C2-C30)alkynyl is a linear or branched alkynyl having 2 to 30 carbon atoms, in which the number of carbon atoms is preferably 2 to 20, more preferably 2 to 10, and includes ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methylpent-2-ynyl, etc.
- (C3-C30)cycloalkyl is a mono- or polycyclic hydrocarbon having 3 to 30 carbon atoms, in which the number of carbon atoms is preferably 3 to 20, more preferably 3 to 7, and includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.
- (C6-C30)aryl(ene) is a monocyclic or fused ring derived from an aromatic hydrocarbon having 6 to 30 carbon atoms, in which the number of carbon atoms is preferably 6 to 20, more preferably 6 to 15, and includes phenyl, biphenyl, terphenyl, naphthyl, binaphthyl, phenylnaphthyl, naphthylphenyl, fluorenyl, phenylfluorenyl, benzofluorenyl, dibenzofluorenyl, phenanthrenyl, phenylphenanthrenyl, anthracenyl, indenyl, triphenylenyl, pyrenyl, tetracenyl, perylenyl, chrysenyl, naphthacenyl, fluoranthenyl, etc.
- the compound of formula 1 may be represented by one of the following formulae 2 to 7:
- A, L, R 1 to R 3 , R 11 , R 12 , a, b, and c are as defined in formula 1.
- substituted in the expression “substituted or unsubstituted” means that a hydrogen atom in a certain functional group is replaced with another atom or group, i.e., a substituent.
- A represents a substituted or unsubstituted 5- to 30-membered heteroaryl; preferably represents a substituted or unsubstituted 5- to 20-membered heteroaryl; and more preferably represents an unsubstituted 5- to 20-membered heteroaryl, a 5- to 20-membered heteroaryl substituted with a 5- to 20-membered heteroaryl unsubstituted or substituted with a (C6-C20)aryl, a 5- to 20-membered heteroaryl substituted with a (C6-C20)aryl, a 5- to 20-membered heteroaryl substituted with a (C6-C20)aryl substituted with a 5- to 20-membered heteroaryl, a 5- to 20-membered heteroaryl substituted with a (C6-C20)aryl substituted with a tri(C1-C6)alkylsilyl, a 5- to 20-membered heteroaryl substituted with a (C6
- the 5- to 30-membered heteroaryl is preferably a nitrogen-containing heteroaryl, and more preferably a substituted or unsubstituted pyridine, a substituted or unsubstituted pyrimidine, a substituted or unsubstituted triazine, a substituted or unsubstituted pyrazine, a substituted or unsubstituted quinoline, a substituted or unsubstituted quinazoline, a substituted or unsubstituted quinoxaline, a substituted or unsubstituted naphthyridine, or a substituted or unsubstituted phenanthroline.
- L represents a single bond, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted 5- to 30-membered heteroarylene; preferably represents a single bond, a substituted or unsubstituted (C6-C20)arylene, or a substituted or unsubstituted 5- to 20-membered heteroarylene; and more preferably represents a single bond, an unsubstituted (C6-C20)arylene, or an unsubstituted 5- to 20-membered heteroarylene.
- X represents CR 11 R 12 .
- R 1 and R 2 each independently represent hydrogen, deuterium, a halogen, a cyano, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted 5- to 30-membered heteroaryl, a substituted or unsubstituted (C6-C30)aryl(C1-C30)alkyl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C1-C30)alkoxy, a substituted or unsubstituted (C1-C30)alkylsilyl, a substituted or unsubstituted (C6-C30)arylsilyl, a substituted or unsubstituted (C6-C30)aryl(C1-C30)alkylsilyl, a substituted
- R 3 represents hydrogen, deuterium, a halogen, a cyano, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted 5- to 30-membered heteroaryl; or are linked to an adjacent substituent(s) to form a mono- or polycyclic (C3-C30) alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen, and sulfur; and preferably represents hydrogen.
- R 11 and R 12 each independently represent a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted 5- to 30-membered heteroaryl; or are linked to each other to form a mono- or polycyclic (C3-C30) alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen, and sulfur; preferably each independently represent a substituted or unsubstituted (C1-C6)alkyl, or a substituted or unsubstituted (C6-C20)aryl; or are linked to each other to form a mono- or polycyclic (C5-C20) alicyclic or aromatic ring; and more preferably each independently represent an unsubstituted (C1-C6)alkyl, or an unsubstituted (C6-C20)aryl; or
- a and b each independently represent an integer of 1 to 4, preferably an integer of 1 to 2, where a or b is an integer of 2 or more, each of R 1 and each of R 2 may be the same or different.
- c represents an integer of 1 to 2, and preferably 1.
- A represents a substituted or unsubstituted 5- to 20-membered heteroaryl
- L represents a single bond, a substituted or unsubstituted (C6-C20)arylene, or a substituted or unsubstituted 5- to 20-membered heteroarylene
- X represents CR 11 R 12
- R 1 and R 2 each independently represent hydrogen, a substituted or unsubstituted (C6-C20)aryl, or a substituted or unsubstituted 5- to 20-membered heteroaryl
- R 3 represents hydrogen
- R 11 and R 12 each independently represent a substituted or unsubstituted (C1-C6)alkyl, or a substituted or unsubstituted (C6-C20)aryl, or are linked to each other to form a mono- or polycyclic (C5-C20) alicyclic or aromatic ring
- a and b each independently represent an integer of 1 to 2;
- A represents an unsubstituted 5- to 20-membered heteroaryl, a 5- to 20-membered heteroaryl substituted with a 5- to 20-membered heteroaryl unsubstituted or substituted with a (C6-C20)aryl, a 5- to 20-membered heteroaryl substituted with a (C6-C20)aryl, a 5- to 20-membered heteroaryl substituted with a (C6-C20)aryl substituted with a 5- to 20-membered heteroaryl, a 5- to 20-membered heteroaryl substituted with a (C6-C20)aryl substituted with a tri(C1-C6)alkylsilyl, a 5- to 20-membered heteroaryl substituted with a (C6-C20)aryl substituted with a tri(C6-C20)arylsilyl, or a 5- to 20-membered heteroaryl substituted
- the compound of formula 1 may be selected from the group consisting of the following compounds, but is not limited thereto:
- the compound of formula 1 comprised in the electron transport material according to the present invention can be prepared by known methods to one skilled in the art, and can be prepared, for example, according to the following reaction scheme:
- A, L, X, R 1 to R 3 , a, b, and c are as defined in formula 1, and Hal represents a halogen.
- the present invention provides an electron transport material comprising the compound of formula 1, and an organic EL device comprising the material.
- the electron transport material can be comprised of the compound of formula 1 alone, or can be a mixture or composition for an electron transport layer which further comprises conventional materials generally included in electron transport materials.
- Figure 1 illustrates a schematic sectional view of an organic electroluminescent device comprising the electron transport layer comprising the electron transport material according to one embodiment of the present invention.
- the organic EL device comprises an anode; a cathode; and at least one organic layer between the two electrodes, wherein the organic layer comprises a light-emitting layer which contains a host and a dopant.
- the light-emitting layer emits light, which may be a single layer or multi-layers having two or more layers.
- the doping concentration of the dopant compound to the host compound in the light-emitting layer is preferably less than 20 wt%.
- the organic EL device of the present invention may comprise an electron transport material in the organic layer and use a reductive dopant as a dopant of the light-emitting layer.
- the reductive dopant is one or more selected from the group consisting of alkali metals, alkaline-earth metals, rare-earth metals, alkali metal oxides, alkali metal halides, alkaline-earth metal oxides, alkaline-earth metal halides, rare-earth metal oxides, rare-earth metal halides, organic complexes of an alkali metal, organic complexes of an alkaline-earth metal, and organic complexes of a rare-earth metal.
- the organic EL device of the present invention may further include at least one compound selected from the group consisting of arylamine-based compounds and styrylarylamine-based compounds in the organic layer.
- an organic layer may further comprise at least one metal selected from the group consisting of metals of Group 1, metals of Group 2, transition metals of the 4 th period, transition metals of the 5 th period, lanthanides, and organic metals of d-transition elements of the Periodic Table, or at least one complex compound comprising the metal.
- a surface layer selected from a chalcogenide layer, a metal halide layer, and a metal oxide layer may be placed on an inner surface(s) of one or both electrode(s).
- a chalcogenide (including oxides) layer of silicon or aluminum is placed on an anode surface of a light-emitting medium layer, and a metal halide layer or metal oxide layer is placed on a cathode surface of an electroluminescent medium layer.
- the surface layer provides operating stability for the organic EL device.
- the chalcogenide includes SiO X (1 ⁇ X ⁇ 2), AlO X (1 ⁇ X ⁇ 1.5), SiON, SiAlON, etc.;
- the metal halide includes LiF, MgF 2 , CaF 2 , a rare earth metal fluoride, etc.; and the metal oxide includes Cs 2 O, Li 2 O, MgO, SrO, BaO, CaO, etc.
- a hole injection layer (HIL), a hole transport layer (HTL), an electron blocking layer (EBL), or their combinations can be used between the anode and the light-emitting layer.
- the hole injection layer may be multi-layers in order to lower the hole injection barrier (or hole injection voltage) from the anode to the hole transport layer or the electron blocking layer, wherein each of the multi-layers simultaneously may use two compounds.
- the hole transport layer or the electron blocking layer may also be multi-layers.
- An electron buffer layer a hole blocking layer (HBL), an electron transport layer (ETL), an electron injection layer (EIL), or their combinations can be used between the light-emitting layer and the cathode.
- the electron buffer layer may be multi-layers in order to control the injection of the electron and improve the interface properties between the light-emitting layer and the electron injection layer, wherein each of the multi-layers simultaneously may use two compounds.
- the hole blocking layer or the electron transport layer may also be multi-layers, wherein each of the multi-layers may use a multi-component of compounds.
- a mixed region of an electron transport compound and a reductive dopant, or a mixed region of a hole transport compound and an oxidative dopant may be placed on at least one surface of a pair of electrodes.
- the electron transport compound is reduced to an anion, and thus it becomes easier to inject and transport electrons from the mixed region to the light-emitting medium.
- the hole transport compound is oxidized to a cation, and thus it becomes easier to inject and transport holes from the mixed region to the light-emitting medium.
- the oxidative dopant includes various Lewis acids and acceptor compounds; and the reductive dopant includes alkali metals, alkali metal compounds, alkaline earth metals, rare-earth metals, and mixtures thereof.
- the reductive dopant layer may be employed as a charge-generating layer to prepare an organic EL device having two or more light-emitting layers and emitting white light.
- each layer constituting the organic EL device of the present invention dry film-forming methods such as vacuum deposition, sputtering, plasma, ion plating methods, etc., or wet film-forming methods such as spin coating, dip coating, flow coating methods, etc., can be used.
- dry film-forming methods such as vacuum deposition, sputtering, plasma, ion plating methods, etc.
- wet film-forming methods such as spin coating, dip coating, flow coating methods, etc.
- a thin film is formed by dissolving or dispersing the material constituting each layer in suitable solvents, such as ethanol, chloroform, tetrahydrofuran, dioxane, etc.
- suitable solvents such as ethanol, chloroform, tetrahydrofuran, dioxane, etc.
- the solvents are not specifically limited as long as the material constituting each layer is soluble or dispersible in the solvents, which do not cause any problems in forming a layer.
- An OLED device was produced using the electron transport material of the present invention.
- a transparent electrode indium tin oxide (ITO) thin film (15 ⁇ /sq) on a glass substrate for an OLED device (Geomatec Co.. LTD., Japan) was subjected to an ultrasonic washing with trichloroethylene, acetone, ethanol, and distilled water, sequentially, and was then stored in isopropanol.
- the ITO substrate was then mounted on a substrate holder of a vacuum vapor depositing apparatus.
- N 4 ,N 4' -diphenyl-N 4 ,N 4' -bis(9-phenyl-9H-carbazol-3-yl)-[1,1'-biphenyl]-4,4'-diamine was introduced into a cell of the vacuum vapor depositing apparatus, and the pressure in the chamber of the apparatus was then controlled to 10 -6 torr. Thereafter, an electric current was applied to the cell to evaporate the introduced material, thereby forming hole injection layer 1 having a thickness of 60 nm on the ITO substrate.
- 1,4,5,8,9,12-hexaazatriphenylene-hexacarbonitrile was then introduced into another cell of the vacuum vapor depositing apparatus, and an electric current was applied to the cell to evaporate the introduced material, thereby forming hole injection layer 2 having a thickness of 5 nm on hole injection layer 1.
- N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-9H-fluorene-2-amine was introduced into one cell of the vacuum vapor depositing apparatus. Thereafter, an electric current was applied to the cell to evaporate the introduced material, thereby forming hole transport layer 1 having a thickness of 20 nm on hole injection layer 2.
- N,N-di([1,1'-biphenyl]-4-yl)-4'-(9H-carbazol-9-yl)-[1,1'-biphenyl]-4-amine was then introduced into another cell of the vacuum vapor depositing apparatus, and an electric current was applied to the cell to evaporate the introduced material, thereby forming hole transport layer 2 having a thickness of 5 nm on hole transport layer 1.
- BH-1 as a host was introduced into one cell of the vacuum vapor depositing apparatus and BD-1 as a dopant was introduced into another cell.
- the two materials were evaporated at a different rate and the dopant was deposited in a doping amount of 2 wt%, based on the total weight of the host and dopant, to form a light-emitting layer having a thickness of 20 nm on the hole transport layer.
- Compound ETL-75 was then evaporated on one cell to form an electron transport layer having a thickness of 35 nm on the light-emitting layer.
- an Al cathode having a thickness of 80 nm was then deposited by another vacuum vapor deposition apparatus on the electron injection layer.
- All the materials used for producing the OLED device were purified by vacuum sublimation at 10 -6 torr prior to use.
- An OLED device was produced in the same manner as in Device Example 1, except that compound ETL-78 was used in the electron transport layer.
- An OLED device was produced in the same manner as in Device Example 1, except that compound ETL-80 was used in the electron transport layer.
- An OLED device was produced in the same manner as in Device Example 1, except that compound ETL-84 was used in the electron transport layer.
- Comparative Example 1 Production of an OLED device comprising a conventional electron transport material
- An OLED device was produced in the same manner as in Device Example 1, except that the following comparative compound was used in the electron transport layer.
- the data of the above Device Examples 1 to 4 and Comparative Example 1 were determined under the condition of ⁇ electron affinity of the electron transport layer (Ab) > electron affinity of the host (Ah) ⁇ .
- the electron transport layers of Device Examples 1 to 4 have higher LUMO (lowest unoccupied molecular orbital) than that of Comparative Example 1.
- the devices according to the present invention have a large barrier between the light-emitting layer and the electron transport layer in the process of transporting electrons compared with the device of Comparative Example 1.
- the devices of the present invention have lower driving voltage and higher efficiency than the device of Comparative Example 1.
- LUMO energy value and HOMO (highest occupied molecular orbital) energy value have inherently negative numbers, but LUMO energy value and HOMO energy value in the present invention are conveniently expressed in their absolute values. Furthermore, the comparison between LUMO energy values is based on their absolute values. LUMO energy value and HOMO energy value in the present invention are calculated by Density Functional Theory (DFT).
- DFT Density Functional Theory
- the organic electroluminescent compound of the present invention has lower driving voltage, higher efficiency, and longer lifespan than the conventional material.
- the compound of the present invention is regarded as showing color coordinates being the closest to pure blue compared with the comparative compound of Comparative Example 1.
- EOD Electron Only Device
- the device was produced as follows: Barium, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP) were introduced into a cell in a vacuum vapor depositing apparatus. Thereafter, an electric current was applied to the cell to evaporate the introduced materials, thereby forming a hole blocking layer (HBL) having a thickness of 10 nm on the ITO substrate. Next, BH-1 as a host was introduced into one cell of the vacuum vapor depositing apparatus, and BD-1 as a dopant was introduced into another cell.
- BCP Barium, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline
- HBL hole blocking layer
- the two materials were evaporated at a different rate and the dopant was deposited in a doping amount of 2 wt%, based on the total weight of the host and dopant, to form a light-emitting layer having a thickness of 20 nm on a hole transport layer.
- the compounds in the table below were then evaporated to form an electron transport layer having a thickness of 33 nm on the light-emitting layer.
- an Al cathode having a thickness of 80 nm was then deposited by another vacuum vapor deposition apparatus on the electron injection layer.
- All the materials used for producing the OLED device were purified by vacuum sublimation at 10 -6 torr prior to use. Voltages at 10 and 50 mA/cm 2 according to each electron transport material are shown in Table 3 below.
- the compounds of the present invention have faster electron current characteristics at both voltages (10 and 50 mA/cm 2 ) than the comparative compound.
- the EOD verified that the compounds of the present invention were suitable to provide low driving voltage and high efficiency of the device.
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Abstract
The present invention relates to an organic electroluminescent device comprising an electron transport material which comprises a compound having a specific structure. The organic electroluminescent device comprising the electron transport material of the present invention provides low driving voltage, high luminous efficiency, excellent lifespan characteristics, and excellent color coordination to efficiently emit blue light.
Description
The present invention relates to an electron transport material having improved electron transport ability, and an organic electroluminescent device comprising the same.
An electroluminescent (EL) device is a self-light-emitting device with the advantages of providing a wider viewing angle, a greater contrast ratio, and a faster response time. The first organic EL device was developed by Eastman Kodak, by using small aromatic diamine molecules and aluminum complexes as materials for forming a light-emitting layer (see Appl. Phys. Lett. 51, 913, 1987).
An organic EL device changes electric energy into light by the injection of a charge into an organic light-emitting material, and commonly comprises an anode, a cathode, and an organic layer formed between the two electrodes. The organic layer of the organic EL device may be composed of a hole injection layer (HIL), a hole transport layer (HTL), an electron blocking layer (EBL), a light-emitting layer (EML) (containing host and dopant materials), an electron buffer layer, a hole blocking layer (HBL), an electron transport layer (ETL), an electron injection layer (EIL), etc.; the materials used in the organic layer can be classified into a hole injection material, a hole transport material, an electron blocking material, a light-emitting material, an electron buffer material, a hole blocking material, an electron transport material, an electron injection material, etc., depending on functions. In the organic EL device, holes from an anode and electrons from a cathode are injected into a light-emitting layer by electric voltage, and an exciton having high energy is produced by the recombination of the holes and electrons. The organic light-emitting compound moves into an excited state by the energy and emits light from energy when the organic light-emitting compound returns to the ground state from the excited state.
The most important factor determining luminous efficiency in an organic EL device is light-emitting materials. The light-emitting materials are required to have the following features: high quantum efficiency, high movement degree of an electron and a hole, and uniformality and stability of the formed light-emitting material layer. The light-emitting material is classified into blue, green, and red light-emitting materials according to the light-emitting color, and further includes yellow or orange light-emitting materials. Furthermore, the light-emitting material is classified into a host material and a dopant material in a functional aspect. Recently, an urgent task is the development of an organic EL device having high efficiency and long lifespan. In particular, the development of highly excellent light-emitting material over conventional materials is urgently required, considering the EL properties necessary for medium- and large-sized OLED panels. For this, preferably, as a solvent in a solid state and an energy transmitter, a host material should have high purity and a suitable molecular weight in order to be deposited under vacuum. Furthermore, a host material is required to have high glass transition temperature and pyrolysis temperature for guaranteeing thermal stability, high electrochemical stability for long lifespan, easy formability of an amorphous thin film, good adhesion with adjacent layers, and no movement between layers.
Meanwhile, in an organic EL device, an electron transport material actively transports electrons from a cathode to a light-emitting layer and inhibits transport of holes which are not recombined in the light-emitting layer to increase recombination opportunity of holes and electrons in the light-emitting layer. Thus, electron-affinitive materials are used as an electron transport material. Organic metal complexes having light-emitting function such as Alq3 are excellent in transporting electrons, and thus have been conventionally used as an electron transport material. However, Alq3 has problems in that it moves to other layers and shows reduction of color purity when used in blue light-emitting devices. Therefore, new electron transport materials have been required, which do not have the above problems, are highly electron-affinitive, and quickly transport electrons in organic EL devices to provide organic EL devices having high luminous efficiency.
Korean Patent Appln. Laying-Open No. KR 2010-0130197 A discloses a compound wherein a nitrogen-containing heterocycle is bonded to a nitrogen atom of an indenocarbazole backbone. However, it fails to disclose an organic EL device using the compound as an electron transport material.
The present inventors found that high efficiency and long lifespan of an organic EL device are provided when using a compound of a specific structure having an indenocarbazole backbone wherein a nitrogen atom of the carbazole is bonded to a nitrogen-containing heterocycle as an electron transport material.
The objective of the present invention is to provide an electron transport material which can produce an organic EL device having high efficiency and long lifespan.
The above objective can be achieved by an electron transport material comprising the compound represented by the following formula 1:
wherein
A represents a substituted or unsubstituted 5- to 30-membered heteroaryl;
L represents a single bond, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted 5- to 30-membered heteroarylene;
X represents CR11R12;
R1 and R2 each independently represent hydrogen, deuterium, a halogen, a cyano, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted 5- to 30-membered heteroaryl, a substituted or unsubstituted (C6-C30)aryl(C1-C30)alkyl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C1-C30)alkoxy, a substituted or unsubstituted (C1-C30)alkylsilyl, a substituted or unsubstituted (C6-C30)arylsilyl, a substituted or unsubstituted (C6-C30)aryl(C1-C30)alkylsilyl, a substituted or unsubstituted (C1-C30)alkylamino, a substituted or unsubstituted (C6-C30)arylamino, or a substituted or unsubstituted (C1-C30)alkyl(C6-C30)arylamino; or are linked to an adjacent substituent(s) to form a mono- or polycyclic (C3-C30) alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen, and sulfur;
R3 represents hydrogen, deuterium, a halogen, a cyano, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted 5- to 30-membered heteroaryl; or are linked to an adjacent substituent(s) to form a mono- or polycyclic (C3-C30) alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen, and sulfur;
R11 and R12 each independently represent a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted 5- to 30-membered heteroaryl; or are linked to each other to form a mono- or polycyclic (C3-C30) alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen, and sulfur;
a and b each independently represent an integer of 1 to 4, where a or b is an integer of 2 or more, each of R1 and each of R2 may be the same or different;
c represents an integer of 1 to 2, where c is 2, each of R3 may be the same or different; and
the heteroaryl(ene) contains at least one hetero atom selected from B, N, O, S, P(=O), Si, and P.
By using the electron transport material according to the present invention, an organic EL device with high efficiency and long lifespan is provided, and it is possible to produce a display device or a lighting device using the organic EL device.
Figure 1 illustrates a schematic sectional view of an organic electroluminescent device comprising the electron transport layer comprising the electron transport material according to one embodiment of the present invention.
Figure 2 illustrates a comparison of current efficiency between an organic electroluminescent device according to one embodiment of the present invention and a conventional organic electroluminescent device.
Figure 3 illustrates an energy gap relationship among the layers of the organic electroluminescent device according to one embodiment of the present invention.
Hereinafter, the present invention will be described in detail. However, the following description is intended to explain the invention, and is not meant in any way to restrict the scope of the invention.
Hereinafter, the compound represented by formula 1 will be described in detail.
Herein, “(C1-C30)alkyl” is meant to be a linear or branched alkyl having 1 to 30 carbon atoms, in which the number of carbon atoms is preferably 1 to 10, more preferably 1 to 6, and includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc. “(C2-C30)alkenyl” is meant to be a linear or branched alkenyl having 2 to 30 carbon atoms, in which the number of carbon atoms is preferably 2 to 20, more preferably 2 to 10, and includes vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methylbut-2-enyl, etc. “(C2-C30)alkynyl” is a linear or branched alkynyl having 2 to 30 carbon atoms, in which the number of carbon atoms is preferably 2 to 20, more preferably 2 to 10, and includes ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methylpent-2-ynyl, etc. “(C3-C30)cycloalkyl” is a mono- or polycyclic hydrocarbon having 3 to 30 carbon atoms, in which the number of carbon atoms is preferably 3 to 20, more preferably 3 to 7, and includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc. “3- to 7-membered heterocycloalkyl” is a cycloalkyl having at least one heteroatom selected from B, N, O, S, P(=O), Si, and P, preferably O, S, and N, and 3 to 7 ring backbone atoms, and includes tetrahydrofuran, pyrrolidine, thiolan, tetrahydropyran, etc. “(C6-C30)aryl(ene)” is a monocyclic or fused ring derived from an aromatic hydrocarbon having 6 to 30 carbon atoms, in which the number of carbon atoms is preferably 6 to 20, more preferably 6 to 15, and includes phenyl, biphenyl, terphenyl, naphthyl, binaphthyl, phenylnaphthyl, naphthylphenyl, fluorenyl, phenylfluorenyl, benzofluorenyl, dibenzofluorenyl, phenanthrenyl, phenylphenanthrenyl, anthracenyl, indenyl, triphenylenyl, pyrenyl, tetracenyl, perylenyl, chrysenyl, naphthacenyl, fluoranthenyl, etc. “5- to 30-membered heteroaryl(ene)” is an aryl group having at least one, preferably 1 to 4 heteroatoms selected from the group consisting of B, N, O, S, P(=O), Si, and P, and 5 to 30 ring backbone atoms; is a monocyclic ring, or a fused ring condensed with at least one benzene ring; may be partially saturated; may be one formed by linking at least one heteroaryl or aryl group to a heteroaryl group via a single bond(s); and includes a monocyclic ring-type heteroaryl including furyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, etc., and a fused ring-type heteroaryl including benzofuranyl, benzothiophenyl, isobenzofuranyl, dibenzofuranyl, dibenzothiophenyl, benzonaphthothiophenyl, benzimidazolyl, benzothiazolyl, benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, carbazolyl, phenoxazinyl, phenanthridinyl, benzodioxolyl, etc. “Halogen” includes F, Cl, Br, and I.
The compound of formula 1 may be represented by one of the following formulae 2 to 7:
wherein A, L, R1 to R3, R11, R12, a, b, and c are as defined in formula 1.
Herein, “substituted” in the expression “substituted or unsubstituted” means that a hydrogen atom in a certain functional group is replaced with another atom or group, i.e., a substituent. The substituents of the substituted alkyl, the substituted alkoxy, the substituted cycloalkyl, the substituted aryl(ene), the substituted heteroaryl(ene), the substituted alkylsilyl, the substituted arylsilyl, the substituted arylalkylsilyl, the substituted arylamino, the substituted alkylamino, the substituted alkylarylamino, and the substituted arylalkyl in A, L, R1 to R3, R11, and R12 each independently are at least one selected from the group consisting of deuterium, a halogen, a cyano, a carboxyl, a nitro, a hydroxyl, a (C1-C30)alkyl, a halo(C1-C30)alkyl, a (C2-C30)alkenyl, a (C2-C30)alkynyl, a (C1-C30)alkoxy, a (C1-C30)alkylthio, a (C3-C30)cycloalkyl, a (C3-C30)cycloalkenyl, a 3- to 7-membered heterocycloalkyl, a (C6-C30)aryloxy, a (C6-C30)arylthio, a 3- to 30-membered heteroaryl unsubstituted or substituted with a (C6-C30)aryl, a (C6-C30)aryl, a (C6-C30)aryl substituted with a 3- to 30-membered heteroaryl, a (C6-C30)aryl substituted with a tri(C1-C30)alkylsilyl, a (C6-C30)aryl substituted with a tri(C6-C30)arylsilyl, a tri(C1-C30)alkylsilyl, a tri(C6-C30)arylsilyl, a di(C1-C30)alkyl(C6-C30)arylsilyl, a (C1-C30)alkyldi(C6-C30)arylsilyl, an amino, a mono- or di- (C1-C30)alkylamino, a mono- or di- (C6-C30)arylamino, a (C1-C30)alkyl(C6-C30)arylamino, a (C1-C30)alkylcarbonyl, a (C1-C30)alkoxycarbonyl, a (C6-C30)arylcarbonyl, a di(C6-C30)arylboronyl, a di(C1-C30)alkylboronyl, a (C1-C30)alkyl(C6-C30)arylboronyl, a (C6-C30)aryl(C1-C30)alkyl, and a (C1-C30)alkyl(C6-C30)aryl; and preferably each independently are at least one selected from the group consisting of a 5- to 20-membered heteroaryl unsubstituted or substituted with a (C6-C20)aryl, a (C6-C20)aryl, a (C6-C20)aryl substituted with a 5- to 20-membered heteroaryl, a (C6-C20)aryl substituted with a tri(C1-C6)alkylsilyl, a (C6-C20)aryl substituted with a tri(C6-C20)arylsilyl, and a (C1-C6)alkyl(C6-C20)aryl.
In formula 1, A represents a substituted or unsubstituted 5- to 30-membered heteroaryl; preferably represents a substituted or unsubstituted 5- to 20-membered heteroaryl; and more preferably represents an unsubstituted 5- to 20-membered heteroaryl, a 5- to 20-membered heteroaryl substituted with a 5- to 20-membered heteroaryl unsubstituted or substituted with a (C6-C20)aryl, a 5- to 20-membered heteroaryl substituted with a (C6-C20)aryl, a 5- to 20-membered heteroaryl substituted with a (C6-C20)aryl substituted with a 5- to 20-membered heteroaryl, a 5- to 20-membered heteroaryl substituted with a (C6-C20)aryl substituted with a tri(C1-C6)alkylsilyl, a 5- to 20-membered heteroaryl substituted with a (C6-C20)aryl substituted with a tri(C6-C20)arylsilyl, or a 5- to 20-membered heteroaryl substituted with a (C1-C6)alkyl(C6-C20)aryl.
In the definition of A, the 5- to 30-membered heteroaryl is preferably a nitrogen-containing heteroaryl, and more preferably a substituted or unsubstituted pyridine, a substituted or unsubstituted pyrimidine, a substituted or unsubstituted triazine, a substituted or unsubstituted pyrazine, a substituted or unsubstituted quinoline, a substituted or unsubstituted quinazoline, a substituted or unsubstituted quinoxaline, a substituted or unsubstituted naphthyridine, or a substituted or unsubstituted phenanthroline.
L represents a single bond, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted 5- to 30-membered heteroarylene; preferably represents a single bond, a substituted or unsubstituted (C6-C20)arylene, or a substituted or unsubstituted 5- to 20-membered heteroarylene; and more preferably represents a single bond, an unsubstituted (C6-C20)arylene, or an unsubstituted 5- to 20-membered heteroarylene.
X represents CR11R12.
R1 and R2 each independently represent hydrogen, deuterium, a halogen, a cyano, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted 5- to 30-membered heteroaryl, a substituted or unsubstituted (C6-C30)aryl(C1-C30)alkyl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C1-C30)alkoxy, a substituted or unsubstituted (C1-C30)alkylsilyl, a substituted or unsubstituted (C6-C30)arylsilyl, a substituted or unsubstituted (C6-C30)aryl(C1-C30)alkylsilyl, a substituted or unsubstituted (C1-C30)alkylamino, a substituted or unsubstituted (C6-C30)arylamino, or a substituted or unsubstituted (C1-C30)alkyl(C6-C30)arylamino; or are linked to an adjacent substituent(s) to form a mono- or polycyclic (C3-C30) alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen, and sulfur; preferably each independently represent hydrogen, a substituted or unsubstituted (C6-C20)aryl, or a substituted or unsubstituted 5- to 20-membered heteroaryl; and more preferably each independently represent hydrogen, a (C6-C20)aryl unsubstituted or substituted with a (C6-C12)aryl, or a 5- to 20-membered heteroaryl unsubstituted or substituted with a (C6-C20)aryl.
R3 represents hydrogen, deuterium, a halogen, a cyano, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted 5- to 30-membered heteroaryl; or are linked to an adjacent substituent(s) to form a mono- or polycyclic (C3-C30) alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen, and sulfur; and preferably represents hydrogen.
R11 and R12 each independently represent a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted 5- to 30-membered heteroaryl; or are linked to each other to form a mono- or polycyclic (C3-C30) alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen, and sulfur; preferably each independently represent a substituted or unsubstituted (C1-C6)alkyl, or a substituted or unsubstituted (C6-C20)aryl; or are linked to each other to form a mono- or polycyclic (C5-C20) alicyclic or aromatic ring; and more preferably each independently represent an unsubstituted (C1-C6)alkyl, or an unsubstituted (C6-C20)aryl; or are linked to each other to form a mono- or polycyclic (C5-C20) alicyclic or aromatic ring.
a and b each independently represent an integer of 1 to 4, preferably an integer of 1 to 2, where a or b is an integer of 2 or more, each of R1 and each of R2 may be the same or different.
c represents an integer of 1 to 2, and preferably 1.
The heteroaryl(ene) contains at least one hetero atom selected from B, N, O, S, P(=O), Si, and P.
According to one embodiment of the present invention, in formula 1, A represents a substituted or unsubstituted 5- to 20-membered heteroaryl; L represents a single bond, a substituted or unsubstituted (C6-C20)arylene, or a substituted or unsubstituted 5- to 20-membered heteroarylene; X represents CR11R12; R1 and R2 each independently represent hydrogen, a substituted or unsubstituted (C6-C20)aryl, or a substituted or unsubstituted 5- to 20-membered heteroaryl; R3 represents hydrogen; R11 and R12 each independently represent a substituted or unsubstituted (C1-C6)alkyl, or a substituted or unsubstituted (C6-C20)aryl, or are linked to each other to form a mono- or polycyclic (C5-C20) alicyclic or aromatic ring; a and b each independently represent an integer of 1 to 2; and c represents 1.
According to another embodiment of the present invention, in formula 1, A represents an unsubstituted 5- to 20-membered heteroaryl, a 5- to 20-membered heteroaryl substituted with a 5- to 20-membered heteroaryl unsubstituted or substituted with a (C6-C20)aryl, a 5- to 20-membered heteroaryl substituted with a (C6-C20)aryl, a 5- to 20-membered heteroaryl substituted with a (C6-C20)aryl substituted with a 5- to 20-membered heteroaryl, a 5- to 20-membered heteroaryl substituted with a (C6-C20)aryl substituted with a tri(C1-C6)alkylsilyl, a 5- to 20-membered heteroaryl substituted with a (C6-C20)aryl substituted with a tri(C6-C20)arylsilyl, or a 5- to 20-membered heteroaryl substituted with a (C1-C6)alkyl(C6-C20)aryl; L represents a single bond, an unsubstituted (C6-C20)arylene, or an unsubstituted 5- to 20-membered heteroarylene; X represents CR11R12; R1 and R2 each independently represent hydrogen, a (C6-C20)aryl unsubstituted or substituted with a (C6-C12)aryl, or a 5- to 20-membered heteroaryl unsubstituted or substituted with a (C6-C20)aryl; R3 represents hydrogen; R11 and R12 each independently represent an unsubstituted (C1-C6)alkyl, or an unsubstituted (C6-C20)aryl, or are linked to each other to form a mono- or polycyclic (C5-C20) alicyclic or aromatic ring; a and b each independently represent an integer of 1 to 2; and c represents 1.
The compound of formula 1 may be selected from the group consisting of the following compounds, but is not limited thereto:
The compound of formula 1 comprised in the electron transport material according to the present invention can be prepared by known methods to one skilled in the art, and can be prepared, for example, according to the following reaction scheme:
wherein
A, L, X, R1 to R3, a, b, and c are as defined in formula 1, and Hal represents a halogen.
The present invention provides an electron transport material comprising the compound of formula 1, and an organic EL device comprising the material. The electron transport material can be comprised of the compound of formula 1 alone, or can be a mixture or composition for an electron transport layer which further comprises conventional materials generally included in electron transport materials.
Figure 1 illustrates a schematic sectional view of an organic electroluminescent device comprising the electron transport layer comprising the electron transport material according to one embodiment of the present invention.
The organic EL device according to the present invention comprises an anode; a cathode; and at least one organic layer between the two electrodes, wherein the organic layer comprises a light-emitting layer which contains a host and a dopant. The light-emitting layer emits light, which may be a single layer or multi-layers having two or more layers. The doping concentration of the dopant compound to the host compound in the light-emitting layer is preferably less than 20 wt%.
The organic EL device of the present invention may comprise an electron transport material in the organic layer and use a reductive dopant as a dopant of the light-emitting layer. The reductive dopant is one or more selected from the group consisting of alkali metals, alkaline-earth metals, rare-earth metals, alkali metal oxides, alkali metal halides, alkaline-earth metal oxides, alkaline-earth metal halides, rare-earth metal oxides, rare-earth metal halides, organic complexes of an alkali metal, organic complexes of an alkaline-earth metal, and organic complexes of a rare-earth metal.
The organic EL device of the present invention may further include at least one compound selected from the group consisting of arylamine-based compounds and styrylarylamine-based compounds in the organic layer.
In the organic EL device of the present invention, an organic layer may further comprise at least one metal selected from the group consisting of metals of Group 1, metals of Group 2, transition metals of the 4th period, transition metals of the 5th period, lanthanides, and organic metals of d-transition elements of the Periodic Table, or at least one complex compound comprising the metal.
Preferably, in the organic EL device of the present invention, at least one layer (hereinafter, "a surface layer”) selected from a chalcogenide layer, a metal halide layer, and a metal oxide layer may be placed on an inner surface(s) of one or both electrode(s). Specifically, it is preferred that a chalcogenide (including oxides) layer of silicon or aluminum is placed on an anode surface of a light-emitting medium layer, and a metal halide layer or metal oxide layer is placed on a cathode surface of an electroluminescent medium layer. The surface layer provides operating stability for the organic EL device. Preferably, the chalcogenide includes SiOX (1≤X≤2), AlOX (1≤X≤1.5), SiON, SiAlON, etc.; the metal halide includes LiF, MgF2, CaF2, a rare earth metal fluoride, etc.; and the metal oxide includes Cs2O, Li2O, MgO, SrO, BaO, CaO, etc.
A hole injection layer (HIL), a hole transport layer (HTL), an electron blocking layer (EBL), or their combinations can be used between the anode and the light-emitting layer. The hole injection layer may be multi-layers in order to lower the hole injection barrier (or hole injection voltage) from the anode to the hole transport layer or the electron blocking layer, wherein each of the multi-layers simultaneously may use two compounds. The hole transport layer or the electron blocking layer may also be multi-layers.
An electron buffer layer, a hole blocking layer (HBL), an electron transport layer (ETL), an electron injection layer (EIL), or their combinations can be used between the light-emitting layer and the cathode. The electron buffer layer may be multi-layers in order to control the injection of the electron and improve the interface properties between the light-emitting layer and the electron injection layer, wherein each of the multi-layers simultaneously may use two compounds. The hole blocking layer or the electron transport layer may also be multi-layers, wherein each of the multi-layers may use a multi-component of compounds.
Preferably, in the organic EL device of the present invention, a mixed region of an electron transport compound and a reductive dopant, or a mixed region of a hole transport compound and an oxidative dopant may be placed on at least one surface of a pair of electrodes. In this case, the electron transport compound is reduced to an anion, and thus it becomes easier to inject and transport electrons from the mixed region to the light-emitting medium. Furthermore, the hole transport compound is oxidized to a cation, and thus it becomes easier to inject and transport holes from the mixed region to the light-emitting medium. Preferably, the oxidative dopant includes various Lewis acids and acceptor compounds; and the reductive dopant includes alkali metals, alkali metal compounds, alkaline earth metals, rare-earth metals, and mixtures thereof. The reductive dopant layer may be employed as a charge-generating layer to prepare an organic EL device having two or more light-emitting layers and emitting white light.
In order to form each layer constituting the organic EL device of the present invention, dry film-forming methods such as vacuum deposition, sputtering, plasma, ion plating methods, etc., or wet film-forming methods such as spin coating, dip coating, flow coating methods, etc., can be used.
When using a wet film-forming method, a thin film is formed by dissolving or dispersing the material constituting each layer in suitable solvents, such as ethanol, chloroform, tetrahydrofuran, dioxane, etc. The solvents are not specifically limited as long as the material constituting each layer is soluble or dispersible in the solvents, which do not cause any problems in forming a layer.
Hereinafter, the compounds of the present invention, the preparation method thereof, and luminous properties of devices comprising the electron transport material comprising the compound will be explained in detail with reference to the following examples.
Example 1: Preparation of compound ETL-75
Preparation of compound 1-1
After introducing 2-bromo-9,9-diphenyl-9H-fluorene (8 g, 0.020 mol), 2-chloroaniline (3.1 mL, 0.030 mol), Pd(OAc)2 (181 mg, 0.805 mol), P(t-Bu)3 (50%) (0.8 mL, 1.61 mmol), NaOt-Bu (4.8 g, 0.056 mol), and toluene 58 mL in a flask, the mixture was stirred at 140°C for 4 hours. After the reaction, the mixture was washed with distilled water, and an organic layer was extracted with ethylacetate (EA). The organic layer was then dried with MgSO4, the solvent was removed with a rotary evaporator, and the remaining product was purified with column chromatography to obtain compound 1-1 (7.3 g, 82%).
Preparation of compound 1-2
After introducing compound 1-1 (7.3 g, 0.016 mol) in a flask, Pd(OAc)2 (190 mg, 0.84 mmol), tricyclohexylphosphonium tetrafluoroborate (620 mg, 0.0016 mol), Cs2CO3 (16 g, 0.050 mol), and dimethylacetamide (DMA) 85 mL were added to the mixture. The reactant mixture was heated to 190°C and stirred for 5 hours. After the reaction, the mixture was washed with distilled water, and an organic layer was extracted with EA. The organic layer was then dried with MgSO4, the solvent was removed with a rotary evaporator, and the remaining product was purified with column chromatography to obtain compound 1-2 (4.8 g, 59%).
Preparation of compound ETL-75
After introducing compound 1-2 (4.8 g, 0.011 mol) in a flask, 2-([1,1'-biphenyl]-3-yl)-4-chloro-6-phenyl-1,3,5-triazine (4.8 g, 0.014 mol), dimethylaminopyridine (DMAP) (720 mg, 0.005 mmol), K2CO3 (4.0 g, 0.029 mol), and dimethylformamide (DMF) 120 mL were added to the mixture. The reactant mixture was heated to 120°C and stirred for 3 hours. After the reaction, the mixture was washed with distilled water, and an organic layer was extracted with EA. The organic layer was then dried with MgSO4, the solvent was removed with a rotary evaporator, and the remaining product was purified with column chromatography to obtain compound ETL-75 (6.9 g, 82%).
Compounds ETL-1 to ETL-86 were prepared using the same synthetic method of Example 1. Among them, specific physical property data of the representative compounds are shown in Table 1 as follows:
Device Example 1: Production of an OLED device comprising the electron transport material according to the present invention
An OLED device was produced using the electron transport material of the present invention. A transparent electrode indium tin oxide (ITO) thin film (15 Ω/sq) on a glass substrate for an OLED device (Geomatec Co.. LTD., Japan) was subjected to an ultrasonic washing with trichloroethylene, acetone, ethanol, and distilled water, sequentially, and was then stored in isopropanol. The ITO substrate was then mounted on a substrate holder of a vacuum vapor depositing apparatus. N4,N4'-diphenyl-N4,N4'-bis(9-phenyl-9H-carbazol-3-yl)-[1,1'-biphenyl]-4,4'-diamine was introduced into a cell of the vacuum vapor depositing apparatus, and the pressure in the chamber of the apparatus was then controlled to 10-6 torr. Thereafter, an electric current was applied to the cell to evaporate the introduced material, thereby forming hole injection layer 1 having a thickness of 60 nm on the ITO substrate. 1,4,5,8,9,12-hexaazatriphenylene-hexacarbonitrile was then introduced into another cell of the vacuum vapor depositing apparatus, and an electric current was applied to the cell to evaporate the introduced material, thereby forming hole injection layer 2 having a thickness of 5 nm on hole injection layer 1. N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-9H-fluorene-2-amine was introduced into one cell of the vacuum vapor depositing apparatus. Thereafter, an electric current was applied to the cell to evaporate the introduced material, thereby forming hole transport layer 1 having a thickness of 20 nm on hole injection layer 2. N,N-di([1,1'-biphenyl]-4-yl)-4'-(9H-carbazol-9-yl)-[1,1'-biphenyl]-4-amine was then introduced into another cell of the vacuum vapor depositing apparatus, and an electric current was applied to the cell to evaporate the introduced material, thereby forming hole transport layer 2 having a thickness of 5 nm on hole transport layer 1. Thereafter, BH-1 as a host was introduced into one cell of the vacuum vapor depositing apparatus and BD-1 as a dopant was introduced into another cell. The two materials were evaporated at a different rate and the dopant was deposited in a doping amount of 2 wt%, based on the total weight of the host and dopant, to form a light-emitting layer having a thickness of 20 nm on the hole transport layer. Compound ETL-75 was then evaporated on one cell to form an electron transport layer having a thickness of 35 nm on the light-emitting layer. After depositing lithium quinolate having a thickness of 4 nm as an electron injection layer on the electron transport layer, an Al cathode having a thickness of 80 nm was then deposited by another vacuum vapor deposition apparatus on the electron injection layer. Thus, an OLED device was produced. All the materials used for producing the OLED device were purified by vacuum sublimation at 10-6 torr prior to use.
Device Example 2: Production of an OLED device comprising the electron transport material according to the present invention
An OLED device was produced in the same manner as in Device Example 1, except that compound ETL-78 was used in the electron transport layer.
Device Example 3: Production of an OLED device comprising the electron transport material according to the present invention
An OLED device was produced in the same manner as in Device Example 1, except that compound ETL-80 was used in the electron transport layer.
Device Example 4: Production of an OLED device comprising the electron transport material according to the present invention
An OLED device was produced in the same manner as in Device Example 1, except that compound ETL-84 was used in the electron transport layer.
Comparative Example 1: Production of an OLED device comprising a conventional electron transport material
An OLED device was produced in the same manner as in Device Example 1, except that the following comparative compound was used in the electron transport layer.
The current efficiencies according to luminance values of the OLED devices produced above are shown in Fig. 2.
Furthermore, driving voltage at a luminance of 1,000 nit, luminous efficiency, CIE color coordinate, and the time taken for the luminance at 2,000 nit to be reduced from 100% to 90% at a constant current of the OLEDs produced as above are shown in Table 2 below.
The data of the above Device Examples 1 to 4 and Comparative Example 1 were determined under the condition of 「electron affinity of the electron transport layer (Ab) > electron affinity of the host (Ah)」. The electron transport layers of Device Examples 1 to 4 have higher LUMO (lowest unoccupied molecular orbital) than that of Comparative Example 1. As depicted in Fig. 3, the devices according to the present invention have a large barrier between the light-emitting layer and the electron transport layer in the process of transporting electrons compared with the device of Comparative Example 1. However, in accordance with the fast electron current characteristic of the diphenyl structure, the devices of the present invention have lower driving voltage and higher efficiency than the device of Comparative Example 1.
LUMO energy value and HOMO (highest occupied molecular orbital) energy value have inherently negative numbers, but LUMO energy value and HOMO energy value in the present invention are conveniently expressed in their absolute values. Furthermore, the comparison between LUMO energy values is based on their absolute values. LUMO energy value and HOMO energy value in the present invention are calculated by Density Functional Theory (DFT).
The organic electroluminescent compound of the present invention has lower driving voltage, higher efficiency, and longer lifespan than the conventional material.
In addition, the movement of excitons produced in the light-emitting layer and hole carriers are efficiently restricted as shown in Fig. 3. According to this, the compound of the present invention is regarded as showing color coordinates being the closest to pure blue compared with the comparative compound of Comparative Example 1.
Comparison of electron current characteristic of the comparative compound and the compound of the present invention
In order to demonstrate fast electron current characteristic of the electron transport layer in the devices according to the present invention, voltage property was compared by preparing an Electron Only Device (EOD).
The device was produced as follows: Barium, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP) were introduced into a cell in a vacuum vapor depositing apparatus. Thereafter, an electric current was applied to the cell to evaporate the introduced materials, thereby forming a hole blocking layer (HBL) having a thickness of 10 nm on the ITO substrate. Next, BH-1 as a host was introduced into one cell of the vacuum vapor depositing apparatus, and BD-1 as a dopant was introduced into another cell. The two materials were evaporated at a different rate and the dopant was deposited in a doping amount of 2 wt%, based on the total weight of the host and dopant, to form a light-emitting layer having a thickness of 20 nm on a hole transport layer. The compounds in the table below were then evaporated to form an electron transport layer having a thickness of 33 nm on the light-emitting layer. After depositing lithium quinolate having a thickness of 4 nm as an electron injection layer on the electron transport layer, an Al cathode having a thickness of 80 nm was then deposited by another vacuum vapor deposition apparatus on the electron injection layer. Thus, an OLED device was produced. All the materials used for producing the OLED device were purified by vacuum sublimation at 10-6 torr prior to use. Voltages at 10 and 50 mA/cm2 according to each electron transport material are shown in Table 3 below.
As shown in Table 3 above, the compounds of the present invention have faster electron current characteristics at both voltages (10 and 50 mA/cm2) than the comparative compound. The EOD verified that the compounds of the present invention were suitable to provide low driving voltage and high efficiency of the device.
Claims (10)
- An electron transport material comprising a compound represented by the following formula 1:
whereinA represents a substituted or unsubstituted 5- to 30-membered heteroaryl;L represents a single bond, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted 5- to 30-membered heteroarylene;X represents CR11R12;R1 and R2 each independently represent hydrogen, deuterium, a halogen, a cyano, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted 5- to 30-membered heteroaryl, a substituted or unsubstituted (C6-C30)aryl(C1-C30)alkyl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C1-C30)alkoxy, a substituted or unsubstituted (C1-C30)alkylsilyl, a substituted or unsubstituted (C6-C30)arylsilyl, a substituted or unsubstituted (C6-C30)aryl(C1-C30)alkylsilyl, a substituted or unsubstituted (C1-C30)alkylamino, a substituted or unsubstituted (C6-C30)arylamino, or a substituted or unsubstituted (C1-C30)alkyl(C6-C30)arylamino; or are linked to an adjacent substituent(s) to form a mono- or polycyclic (C3-C30) alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen, and sulfur;R3 represents hydrogen, deuterium, a halogen, a cyano, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted 5- to 30-membered heteroaryl; or are linked to an adjacent substituent(s) to form a mono- or polycyclic (C3-C30) alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen, and sulfur;R11 and R12 each independently represent a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted 5- to 30-membered heteroaryl; or are linked to each other to form a mono- or polycyclic (C3-C30) alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen, and sulfur;a and b each independently represent an integer of 1 to 4, where a or b is an integer of 2 or more, each of R1 and each of R2 may be the same or different;c represents an integer of 1 to 2, where c is 2, each of R3 may be the same or different; andthe heteroaryl(ene) contains at least one hetero atom selected from B, N, O, S, P(=O), Si, and P. - The electron transport material according to claim 1, wherein formula 1 is represented by one of the following formulae 2 to 7:
wherein A, L, R1 to R3, R11, R12, a, b, and c are as defined in claim 1. - The electron transport material according to claim 1, wherein the substituents of the substituted alkyl, the substituted alkoxy, the substituted cycloalkyl, the substituted aryl(ene), the substituted heteroaryl(ene), the substituted alkylsilyl, the substituted arylsilyl, the substituted arylalkylsilyl, the substituted arylamino, the substituted alkylamino, the substituted alkylarylamino, and the substituted arylalkyl in A, L, R1 to R3, R11, and R12 each independently are at least one selected from the group consisting of deuterium, a halogen, a cyano, a carboxyl, a nitro, a hydroxyl, a (C1-C30)alkyl, a halo(C1-C30)alkyl, a (C2-C30)alkenyl, a (C2-C30)alkynyl, a (C1-C30)alkoxy, a (C1-C30)alkylthio, a (C3-C30)cycloalkyl, a (C3-C30)cycloalkenyl, a 3- to 7-membered heterocycloalkyl, a (C6-C30)aryloxy, a (C6-C30)arylthio, a 3- to 30-membered heteroaryl unsubstituted or substituted with a (C6-C30)aryl, a (C6-C30)aryl, a (C6-C30)aryl substituted with a 3- to 30-membered heteroaryl, a (C6-C30)aryl substituted with a tri(C1-C30)alkylsilyl, a (C6-C30)aryl substituted with a tri(C6-C30)arylsilyl, a tri(C1-C30)alkylsilyl, a tri(C6-C30)arylsilyl, a di(C1-C30)alkyl(C6-C30)arylsilyl, a (C1-C30)alkyldi(C6-C30)arylsilyl, an amino, a mono- or di- (C1-C30)alkylamino, a mono- or di- (C6-C30)arylamino, a (C1-C30)alkyl(C6-C30)arylamino, a (C1-C30)alkylcarbonyl, a (C1-C30)alkoxycarbonyl, a (C6-C30)arylcarbonyl, a di(C6-C30)arylboronyl, a di(C1-C30)alkylboronyl, a (C1-C30)alkyl(C6-C30)arylboronyl, a (C6-C30)aryl(C1-C30)alkyl, and a (C1-C30)alkyl(C6-C30)aryl.
- The electron transport material according to claim 1, whereinA represents a substituted or unsubstituted 5- to 20-membered heteroaryl;L represents a single bond, a substituted or unsubstituted (C6-C20)arylene, or a substituted or unsubstituted 5- to 20-membered heteroarylene;X represents CR11R12;R1 and R2 each independently represent hydrogen, a substituted or unsubstituted (C6-C20)aryl, or a substituted or unsubstituted 5- to 20-membered heteroaryl;R3 represents hydrogen;R11 and R12 each independently represent a substituted or unsubstituted (C1-C6)alkyl, or a substituted or unsubstituted (C6-C20)aryl; or are linked to each other to form a mono- or polycyclic (C5-C20) alicyclic or aromatic ring;a and b each independently represent an integer of 1 to 2; andc represents 1.
- The electron transport material according to claim 1, whereinA represents an unsubstituted 5- to 20-membered heteroaryl, a 5- to 20-membered heteroaryl substituted with a 5- to 20-membered heteroaryl unsubstituted or substituted with a (C6-C20)aryl, a 5- to 20-membered heteroaryl substituted with a (C6-C20)aryl, a 5- to 20-membered heteroaryl substituted with a (C6-C20)aryl substituted with a 5- to 20-membered heteroaryl, a 5- to 20-membered heteroaryl substituted with a (C6-C20)aryl substituted with a tri(C1-C6)alkylsilyl, a 5- to 20-membered heteroaryl substituted with a (C6-C20)aryl substituted with a tri(C6-C20)arylsilyl, or a 5- to 20-membered heteroaryl substituted with a (C1-C6)alkyl(C6-C20)aryl;L represents a single bond, an unsubstituted (C6-C20)arylene, or an unsubstituted 5- to 20-membered heteroarylene;X represents CR11R12;R1 and R2 each independently represent hydrogen, a (C6-C20)aryl unsubstituted or substituted with a (C6-C12)aryl, or a 5- to 20-membered heteroaryl unsubstituted or substituted with a (C6-C20)aryl;R3 represents hydrogen;R11 and R12 each independently represent an unsubstituted (C1-C6)alkyl, or an unsubstituted (C6-C20)aryl; or are linked to each other to form a mono- or polycyclic (C5-C20) alicyclic or aromatic ring;a and b each independently represent an integer of 1 to 2; andc represents 1.
- The electron transport material according to claim 1, wherein A represents a substituted or unsubstituted pyridine, a substituted or unsubstituted pyrimidine, a substituted or unsubstituted triazine, a substituted or unsubstituted pyrazine, a substituted or unsubstituted quinoline, a substituted or unsubstituted quinazoline, a substituted or unsubstituted quinoxaline, a substituted or unsubstituted naphthyridine, or a substituted or unsubstituted phenanthroline.
- The electron transport material according to claim 1, wherein the compound represented by formula 1 is selected from the group consisting of:
- An organic electroluminescent device comprising the electron transport material according to claim 1.
- The organic electroluminescent device according to claim 8, further comprising a reductive dopant.
- The organic electroluminescent device according to claim 9, wherein the reductive dopant is at least one selected from the group consisting of alkali metals, alkaline-earth metals, rare-earth metals, alkali metal oxides, alkali metal halides, alkaline-earth metal oxides, alkaline-earth metal halides, rare-earth metal oxides, rare-earth metal halides, organic complexes of an alkali metal, organic complexes of an alkaline-earth metal, and organic complexes of a rare-earth metal.
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| CN201580023005.9A CN106458997A (en) | 2014-05-08 | 2015-05-08 | An electron transport material and an organic electroluminescence device comprising the same |
| US15/309,233 US20170077415A1 (en) | 2014-05-08 | 2015-05-08 | An electron transport material and an organic electroluminescence device comprising the same |
| EP15788763.9A EP3140299A4 (en) | 2014-05-08 | 2015-05-08 | An electron transport material and an organic electroluminescence device comprising the same |
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| KR1020150063687A KR20150128590A (en) | 2014-05-08 | 2015-05-07 | An electron transport material and an organic electroluminescence device comprising the same |
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| CN108780849A (en) * | 2016-03-15 | 2018-11-09 | 新日铁住金化学株式会社 | Organic electroluminescent device |
| JP2019023183A (en) * | 2017-07-14 | 2019-02-14 | サイノラ ゲゼルシャフト ミット ベシュレンクテル ハフツング | Organic molecules in particular for use in optoelectronic devices |
| JP2019186571A (en) * | 2014-05-23 | 2019-10-24 | 株式会社半導体エネルギー研究所 | Light-emitting element, light-emitting device, electronic device, and lighting device |
| CN113508113A (en) * | 2019-01-30 | 2021-10-15 | 诺瓦尔德股份有限公司 | Composition, organic semiconductor layer and electronic device |
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| EP3432378A4 (en) * | 2016-03-15 | 2019-11-20 | NIPPON STEEL Chemical & Material Co., Ltd. | Organic electroluminescent element |
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| CN113508113A (en) * | 2019-01-30 | 2021-10-15 | 诺瓦尔德股份有限公司 | Composition, organic semiconductor layer and electronic device |
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