CN116082285A - Aromatic amine organic compound and organic electroluminescent device prepared from same - Google Patents
Aromatic amine organic compound and organic electroluminescent device prepared from same Download PDFInfo
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- CN116082285A CN116082285A CN202111304129.8A CN202111304129A CN116082285A CN 116082285 A CN116082285 A CN 116082285A CN 202111304129 A CN202111304129 A CN 202111304129A CN 116082285 A CN116082285 A CN 116082285A
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- -1 Aromatic amine organic compound Chemical class 0.000 title claims abstract description 43
- 239000000463 material Substances 0.000 claims abstract description 102
- 230000005525 hole transport Effects 0.000 claims abstract description 42
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 11
- 238000002347 injection Methods 0.000 claims description 61
- 239000007924 injection Substances 0.000 claims description 61
- 150000001875 compounds Chemical class 0.000 claims description 30
- 230000000903 blocking effect Effects 0.000 claims description 23
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 19
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 18
- 125000001624 naphthyl group Chemical group 0.000 claims description 15
- 125000001424 substituent group Chemical group 0.000 claims description 14
- 125000004431 deuterium atom Chemical group 0.000 claims description 12
- 150000004982 aromatic amines Chemical class 0.000 claims description 11
- 235000010290 biphenyl Nutrition 0.000 claims description 9
- 239000004305 biphenyl Substances 0.000 claims description 9
- 229910052805 deuterium Inorganic materials 0.000 claims description 9
- 125000005842 heteroatom Chemical group 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- 125000004076 pyridyl group Chemical group 0.000 claims description 5
- 125000000714 pyrimidinyl group Chemical group 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 5
- 125000004988 dibenzothienyl group Chemical group C1(=CC=CC=2SC3=C(C21)C=CC=C3)* 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000004957 naphthylene group Chemical group 0.000 claims description 4
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 4
- 125000000732 arylene group Chemical group 0.000 claims description 3
- 125000006267 biphenyl group Chemical group 0.000 claims description 3
- 125000001072 heteroaryl group Chemical group 0.000 claims description 3
- 125000000623 heterocyclic group Chemical group 0.000 claims description 3
- 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 claims description 2
- 125000000499 benzofuranyl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 claims description 2
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 claims description 2
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000002541 furyl group Chemical group 0.000 claims description 2
- 125000005561 phenanthryl group Chemical group 0.000 claims description 2
- 125000001544 thienyl group Chemical group 0.000 claims description 2
- VIJYEGDOKCKUOL-UHFFFAOYSA-N 9-phenylcarbazole Chemical group C1=CC=CC=C1N1C2=CC=CC=C2C2=CC=CC=C21 VIJYEGDOKCKUOL-UHFFFAOYSA-N 0.000 claims 1
- 150000001616 biphenylenes Chemical group 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 9
- 239000010410 layer Substances 0.000 description 171
- 239000010408 film Substances 0.000 description 24
- 239000000758 substrate Substances 0.000 description 22
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 239000007858 starting material Substances 0.000 description 16
- 230000015572 biosynthetic process Effects 0.000 description 15
- 238000000034 method Methods 0.000 description 15
- 238000012360 testing method Methods 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 14
- 238000004770 highest occupied molecular orbital Methods 0.000 description 14
- 238000003786 synthesis reaction Methods 0.000 description 14
- 238000005259 measurement Methods 0.000 description 13
- 239000011368 organic material Substances 0.000 description 13
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 12
- 230000005540 biological transmission Effects 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- 238000000921 elemental analysis Methods 0.000 description 8
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000000741 silica gel Substances 0.000 description 7
- 229910002027 silica gel Inorganic materials 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 5
- 230000002349 favourable effect Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000010025 steaming Methods 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000004020 conductor Substances 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 description 4
- 238000007740 vapor deposition Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 description 3
- 239000002019 doping agent Substances 0.000 description 3
- 230000005684 electric field Effects 0.000 description 3
- 238000005538 encapsulation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 238000007738 vacuum evaporation Methods 0.000 description 3
- GHYOCDFICYLMRF-UTIIJYGPSA-N (2S,3R)-N-[(2S)-3-(cyclopenten-1-yl)-1-[(2R)-2-methyloxiran-2-yl]-1-oxopropan-2-yl]-3-hydroxy-3-(4-methoxyphenyl)-2-[[(2S)-2-[(2-morpholin-4-ylacetyl)amino]propanoyl]amino]propanamide Chemical compound C1(=CCCC1)C[C@@H](C(=O)[C@@]1(OC1)C)NC([C@H]([C@@H](C1=CC=C(C=C1)OC)O)NC([C@H](C)NC(CN1CCOCC1)=O)=O)=O GHYOCDFICYLMRF-UTIIJYGPSA-N 0.000 description 2
- VIJSPAIQWVPKQZ-BLECARSGSA-N (2s)-2-[[(2s)-2-[[(2s)-2-[[(2s)-2-[[(2s)-2-[[(2s)-2-acetamido-5-(diaminomethylideneamino)pentanoyl]amino]-4-methylpentanoyl]amino]-4,4-dimethylpentanoyl]amino]-4-methylpentanoyl]amino]propanoyl]amino]-5-(diaminomethylideneamino)pentanoic acid Chemical compound NC(=N)NCCC[C@@H](C(O)=O)NC(=O)[C@H](C)NC(=O)[C@H](CC(C)C)NC(=O)[C@H](CC(C)(C)C)NC(=O)[C@H](CC(C)C)NC(=O)[C@H](CCCNC(N)=N)NC(C)=O VIJSPAIQWVPKQZ-BLECARSGSA-N 0.000 description 2
- HUWSZNZAROKDRZ-RRLWZMAJSA-N (3r,4r)-3-azaniumyl-5-[[(2s,3r)-1-[(2s)-2,3-dicarboxypyrrolidin-1-yl]-3-methyl-1-oxopentan-2-yl]amino]-5-oxo-4-sulfanylpentane-1-sulfonate Chemical compound OS(=O)(=O)CC[C@@H](N)[C@@H](S)C(=O)N[C@@H]([C@H](C)CC)C(=O)N1CCC(C(O)=O)[C@H]1C(O)=O HUWSZNZAROKDRZ-RRLWZMAJSA-N 0.000 description 2
- KKHFRAFPESRGGD-UHFFFAOYSA-N 1,3-dimethyl-7-[3-(n-methylanilino)propyl]purine-2,6-dione Chemical compound C1=NC=2N(C)C(=O)N(C)C(=O)C=2N1CCCN(C)C1=CC=CC=C1 KKHFRAFPESRGGD-UHFFFAOYSA-N 0.000 description 2
- NPRYCHLHHVWLQZ-TURQNECASA-N 2-amino-9-[(2R,3S,4S,5R)-4-fluoro-3-hydroxy-5-(hydroxymethyl)oxolan-2-yl]-7-prop-2-ynylpurin-8-one Chemical compound NC1=NC=C2N(C(N(C2=N1)[C@@H]1O[C@@H]([C@H]([C@H]1O)F)CO)=O)CC#C NPRYCHLHHVWLQZ-TURQNECASA-N 0.000 description 2
- LFOIDLOIBZFWDO-UHFFFAOYSA-N 2-methoxy-6-[6-methoxy-4-[(3-phenylmethoxyphenyl)methoxy]-1-benzofuran-2-yl]imidazo[2,1-b][1,3,4]thiadiazole Chemical compound N1=C2SC(OC)=NN2C=C1C(OC1=CC(OC)=C2)=CC1=C2OCC(C=1)=CC=CC=1OCC1=CC=CC=C1 LFOIDLOIBZFWDO-UHFFFAOYSA-N 0.000 description 2
- QENGPZGAWFQWCZ-UHFFFAOYSA-N 3-Methylthiophene Chemical compound CC=1C=CSC=1 QENGPZGAWFQWCZ-UHFFFAOYSA-N 0.000 description 2
- VFUDMQLBKNMONU-UHFFFAOYSA-N 9-[4-(4-carbazol-9-ylphenyl)phenyl]carbazole Chemical group C12=CC=CC=C2C2=CC=CC=C2N1C1=CC=C(C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=C1 VFUDMQLBKNMONU-UHFFFAOYSA-N 0.000 description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 2
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229940125797 compound 12 Drugs 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 239000012776 electronic material Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
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- 239000000203 mixture Substances 0.000 description 2
- YGBMCLDVRUGXOV-UHFFFAOYSA-N n-[6-[6-chloro-5-[(4-fluorophenyl)sulfonylamino]pyridin-3-yl]-1,3-benzothiazol-2-yl]acetamide Chemical compound C1=C2SC(NC(=O)C)=NC2=CC=C1C(C=1)=CN=C(Cl)C=1NS(=O)(=O)C1=CC=C(F)C=C1 YGBMCLDVRUGXOV-UHFFFAOYSA-N 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 2
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920000767 polyaniline Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 238000004809 thin layer chromatography Methods 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
- 239000011787 zinc oxide Substances 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- OMDTUSYJJFBYMG-UHFFFAOYSA-N 2,4-bis(9,9-dimethylfluoren-2-yl)-6-naphthalen-2-yl-1,3,5-triazine Chemical compound C1=CC=C2C(C)(C)C3=CC(C=4N=C(N=C(N=4)C=4C=C5C=CC=CC5=CC=4)C4=CC=C5C6=CC=CC=C6C(C5=C4)(C)C)=CC=C3C2=C1 OMDTUSYJJFBYMG-UHFFFAOYSA-N 0.000 description 1
- YWWTWWDBLGSPAA-UHFFFAOYSA-N 2-(2-bromophenyl)furan Chemical compound BrC1=CC=CC=C1C1=CC=CO1 YWWTWWDBLGSPAA-UHFFFAOYSA-N 0.000 description 1
- UWRZIZXBOLBCON-UHFFFAOYSA-N 2-phenylethenamine Chemical class NC=CC1=CC=CC=C1 UWRZIZXBOLBCON-UHFFFAOYSA-N 0.000 description 1
- DMEVMYSQZPJFOK-UHFFFAOYSA-N 3,4,5,6,9,10-hexazatetracyclo[12.4.0.02,7.08,13]octadeca-1(18),2(7),3,5,8(13),9,11,14,16-nonaene Chemical compound N1=NN=C2C3=CC=CC=C3C3=CC=NN=C3C2=N1 DMEVMYSQZPJFOK-UHFFFAOYSA-N 0.000 description 1
- GOLORTLGFDVFDW-UHFFFAOYSA-N 3-(1h-benzimidazol-2-yl)-7-(diethylamino)chromen-2-one Chemical compound C1=CC=C2NC(C3=CC4=CC=C(C=C4OC3=O)N(CC)CC)=NC2=C1 GOLORTLGFDVFDW-UHFFFAOYSA-N 0.000 description 1
- AYHNRNGQKVFSAO-UHFFFAOYSA-N 4-chlorofluoren-1-one Chemical compound ClC=1C=CC(C2=CC3=CC=CC=C3C=12)=O AYHNRNGQKVFSAO-UHFFFAOYSA-N 0.000 description 1
- 229910016036 BaF 2 Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 206010041067 Small cell lung cancer Diseases 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 238000004082 amperometric method Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 125000005577 anthracene group Chemical group 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 125000005264 aryl amine group Chemical group 0.000 description 1
- 230000001174 ascending effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001556 benzimidazoles Chemical class 0.000 description 1
- 150000001562 benzopyrans Chemical class 0.000 description 1
- IPWKHHSGDUIRAH-UHFFFAOYSA-N bis(pinacolato)diboron Chemical compound O1C(C)(C)C(C)(C)OB1B1OC(C)(C)C(C)(C)O1 IPWKHHSGDUIRAH-UHFFFAOYSA-N 0.000 description 1
- UFVXQDWNSAGPHN-UHFFFAOYSA-K bis[(2-methylquinolin-8-yl)oxy]-(4-phenylphenoxy)alumane Chemical compound [Al+3].C1=CC=C([O-])C2=NC(C)=CC=C21.C1=CC=C([O-])C2=NC(C)=CC=C21.C1=CC([O-])=CC=C1C1=CC=CC=C1 UFVXQDWNSAGPHN-UHFFFAOYSA-K 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 159000000006 cesium salts Chemical class 0.000 description 1
- AYTVLULEEPNWAX-UHFFFAOYSA-N cesium;azide Chemical compound [Cs+].[N-]=[N+]=[N-] AYTVLULEEPNWAX-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
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- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- IYYZUPMFVPLQIF-ALWQSETLSA-N dibenzothiophene Chemical class C1=CC=CC=2[34S]C3=C(C=21)C=CC=C3 IYYZUPMFVPLQIF-ALWQSETLSA-N 0.000 description 1
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene sulfoxide Natural products C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 150000002220 fluorenes Chemical class 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 229940058961 hydroxyquinoline derivative for amoebiasis and other protozoal diseases Drugs 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 229940079865 intestinal antiinfectives imidazole derivative Drugs 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000007648 laser printing Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- GUWHRJQTTVADPB-UHFFFAOYSA-N lithium azide Chemical compound [Li+].[N-]=[N+]=[N-] GUWHRJQTTVADPB-UHFFFAOYSA-N 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- SKEDXQSRJSUMRP-UHFFFAOYSA-N lithium;quinolin-8-ol Chemical compound [Li].C1=CN=C2C(O)=CC=CC2=C1 SKEDXQSRJSUMRP-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 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
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 150000004866 oxadiazoles Chemical class 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- LISFMEBWQUVKPJ-UHFFFAOYSA-N quinolin-2-ol Chemical class C1=CC=C2NC(=O)C=CC2=C1 LISFMEBWQUVKPJ-UHFFFAOYSA-N 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 150000004059 quinone derivatives Chemical class 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical class [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- YYMBJDOZVAITBP-UHFFFAOYSA-N rubrene Chemical compound C1=CC=CC=C1C(C1=C(C=2C=CC=CC=2)C2=CC=CC=C2C(C=2C=CC=CC=2)=C11)=C(C=CC=C2)C2=C1C1=CC=CC=C1 YYMBJDOZVAITBP-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229940042055 systemic antimycotics triazole derivative Drugs 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- 150000007979 thiazole derivatives Chemical class 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/94—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom spiro-condensed with carbocyclic rings or ring systems, e.g. griseofulvins
-
- 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
- C07D405/02—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 two hetero rings
- C07D405/12—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 two hetero rings linked by a chain containing hetero atoms as chain links
-
- 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
- C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
- C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention discloses an arylamine organic compound and an organic electroluminescent device prepared from the same, wherein the structure of the organic compound is shown as a general formula (1):
Description
Technical Field
The invention relates to the technical field of semiconductor materials, in particular to an arylamine organic compound and an organic electroluminescent device prepared from the same.
Background
Carriers (holes and electrons) in an organic electroluminescent device (OLED) are respectively injected into the device by two electrodes of the device under the drive of an electric field, and meet and recombine and emit light in an organic light-emitting layer. High-performance organic electroluminescent devices require various organic functional materials to have good photoelectric properties. For example, a charge transport material is required to have good carrier mobility. The injection and transmission characteristics of the hole injection layer material and the hole transmission layer material used in the existing organic electroluminescent device are relatively weak, and the hole injection and transmission rates are not matched with the electron injection and transmission rates, so that the composite area is greatly deviated, and the stability of the device is not facilitated. In addition, reasonable energy level matching of the hole injection layer material and the hole transport layer material is an important factor for improving the efficiency and the service life of the device, so how to adjust the balance degree of holes and electrons and adjust the recombination region is always an important subject in the field.
Blue organic electroluminescent devices are always soft ribs in full-color OLED development, so that the efficiency, service life and other performances of blue light devices are not fully improved until now, and therefore, how to improve the performances of the devices is still a critical problem and challenge in the field. Since the blue light host materials currently used in the market are mostly electron-biased host materials, the hole transport materials are required to have excellent hole transport properties in order to adjust the carrier balance of the light emitting layer. The better the hole injection and transmission, the more the adjusting composite area is deviated to the side far away from the electron blocking layer, so that the light is emitted far away from the interface, the performance of the device is improved, and the service life of the device is prolonged. Therefore, the hole transport region material is required to have high hole injection property, high hole mobility, high electron blocking property, and high electron weatherability.
In the prior art, in a high-temperature environment, as the difference between electron mobility and hole mobility is more obvious, a blue light device shows rich electrons and holes and has poor service life in the high-temperature environment, and in order to improve the high-temperature service life of the blue light device, the mobility of a hole transport material, especially the mobility under the high-temperature condition, needs to be improved.
Disclosure of Invention
In view of the above problems in the prior art, the applicant provides an arylamine organic compound and an organic electroluminescent device prepared from the same. The organic compound has excellent hole transport capacity and thermal stability, and can simultaneously show the effects of improving the efficiency of the device and prolonging the service life of the device, in particular prolonging the high-temperature service life of the device when the aromatic amine organic compound is used for forming the hole transport material of the organic electroluminescent device.
The technical scheme of the invention is as follows: an arylamine organic compound has a structure shown in a general formula (1):
in the general formula (1), the L 1 、L 2 、L 3 Each independently represents one of a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, and a substituted or unsubstituted biphenylene group;
the Ar is as follows 1 To Ar 2 Each occurrence of C, independently represented as substituted or unsubstituted 6-30 Aryl, substituted or unsubstituted C 2-30 Heteroaryl;
m and n are respectively and independently 1,2, 3 or 4;
r represents a hydrogen atom, a deuterium atom, a phenyl group or a naphthyl group;
substituents for the substituents are deuterium atoms, methyl, ethyl, tert-butyl, adamantyl, phenyl, naphthyl or biphenyl.
The invention also provides an organic electroluminescent device which sequentially comprises an anode, a hole transmission region, a light-emitting region, an electron transmission region and a cathode, wherein the hole transmission region comprises the arylamine organic compound.
The beneficial technical effects of the invention are as follows:
the arylamine group of the arylamine organic compound is connected with a specific fluorene derivative through a specific connection site, so that the molecule of the present invention has the following advantages.
(1) The structural characteristics are favorable for keeping a stable amorphous film phase state of molecules during film formation, so that the physicochemical stability of the film phase state and the film phase state stability under the action of point forming are ensured, and further the service life stability of a device is favorable.
(2) The connection mode of the characteristics of the invention is more favorable for the distribution of HOMO on the whole molecule, thereby being easy to obtain the high carrier mobility of the material and further being easy to obtain the long-life effect of the device.
(3) Because the structural characteristics of the arylamine organic compound are favorable for improving the vitrification transfer temperature of molecules and reducing the evaporation temperature of the molecules, namely, even though the molecular weight of the structure is relatively high, the structure can ensure that the structure has relatively low evaporation temperature, the excellent performance is not only favorable for thermal evaporation of materials, but also controls the thermal decomposition rate of the materials, so that the stability of the materials in device application is improved.
Moreover, for the molecular structural formula of the aromatic amine, which is characterized by the invention, the ligand connected to the aromatic amine is optimized, so that the performance of the material is further improved, the stability and mobility of the material are improved, and meanwhile, the accurate regulation and control of the HOMO energy level of the material are facilitated, and further, the good device application effect of the material is obtained.
The organic functional material forming the OLED device not only comprises the hole injection conductive material, but also comprises the electron injection conductive material and the luminescent layer material, so that good device application effect is achieved, and good carrier balance is required to be ensured, so that the arylamine material matched with the characteristic structure disclosed by the invention also needs to be matched with specific electronic materials in order to obtain the optimal device application effect. Based on the intensive studies of the present inventors, the electronic material is preferably a material containing structural characteristics of an azabenzene, such as a triazine-based material, a pyridine-based material, a pyrazine-based material, or the like, or a derivative containing these characteristic groups. The arylamine organic compound disclosed by the invention is combined with the aza-benzene ring electron transport material, so that electrons and holes are easy to obtain an optimal balance state, the arylamine organic compound has higher efficiency and excellent service life, and particularly good high-temperature service life effect of a device is easy to obtain.
Drawings
Fig. 1 is a cross-sectional view of an organic electroluminescent device according to the present invention.
In the figure, 1 represents a substrate layer; 2 represents an anode layer; 3 represents a hole injection layer; 4 represents a hole transport layer; 5 represents an electron blocking layer; 6 represents a light emitting layer; 7 represents a hole blocking layer; 8 represents an electron transport layer; 9 denotes an electron injection layer; 10 is denoted as cathode layer; 11 denotes a cover layer.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. The following description of at least one exemplary embodiment is merely exemplary in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments in accordance with the present application. As used herein, the singular is also intended to include the plural unless the context clearly indicates otherwise, and furthermore, it is to be understood that the terms "comprises" and/or "comprising" when used in this specification are taken to specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof.
In the present invention, HOMO means the highest occupied orbital of a molecule, and LUMO means the lowest unoccupied orbital of a molecule unless otherwise specified. Furthermore, in the present invention, HOMO and LUMO energy levels are expressed in absolute values, and the comparison between energy levels is also a comparison of the magnitudes of the absolute values thereof, and those skilled in the art know that the larger the absolute value of an energy level, the lower the energy of the energy level.
In the present invention, when a layer or element is referred to as being "on" another layer or substrate, it can be directly on the other layer or substrate or intervening layers may also be present. Further, it will also be understood that when a layer is referred to as being "between" two layers, it can be the only layer between the two layers or one or more intervening layers may also be present. Like numbers refer to like elements throughout.
In the present invention, when describing electrodes and organic electroluminescent devices, as well as other structures, words of "upper", "lower", "top" and "bottom", etc., which are used to indicate orientations, indicate only orientations in a certain specific state, and do not mean that the relevant structure can only exist in the orientations; conversely, if the structure can be repositioned, for example inverted, the orientation of the structure is changed accordingly. Specifically, in the present invention, the "bottom" side of an electrode refers to the side of the electrode that is closer to the substrate during fabrication, while the opposite side that is farther from the substrate is the "top" side.
In this specification, the term "substituted" means that one or more hydrogen atoms on a given atom or group is replaced by the specified group, provided that the normal valence of the given atom is not exceeded in the present case.
In this specification, the hole feature refers to a feature that can supply electrons when an electric field is applied and is attributed to a conductive feature according to the Highest Occupied Molecular Orbital (HOMO) level, and holes formed in the anode are easily injected into and transported in the light emitting layer.
In this specification, the electron feature refers to a feature that can accept electrons when an electric field is applied and is attributed to a conductive feature according to the Lowest Unoccupied Molecular Orbital (LUMO) level, electrons formed in the cathode are easily injected into and transported in the light emitting layer.
The compound shown in the general formula (1),
in the general formula (1), the L 1 、L 2 、L 3 Each independently represents one of a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, and a substituted or unsubstituted biphenylene group;
the Ar is as follows 1 To Ar 2 Each occurrence of C, independently represented as substituted or unsubstituted 6-30 Aryl, substituted or unsubstituted C 2-30 Heteroaryl;
m and n are respectively and independently 1,2, 3 or 4;
r represents a hydrogen atom, a deuterium atom, a phenyl group or a naphthyl group;
substituents for the substituents are deuterium atoms, methyl, ethyl, tert-butyl, adamantyl, phenyl, naphthyl or biphenyl.
Preferably, the structure of the compound is shown as a general formula (2):
in the general formula (2), R 1 Represented by deuterium atom, methyl, ethyl, t-butyl, adamantyl, phenyl, naphthyl or biphenyl;
R、L 2 、L 3 、Ar 2 the definition of n is as described above.
Preferably, the structure of the compound is shown as a general formula (3):
in the general formula (3), X is O, S, C (R) 2 R 3 )、N(R 4 )，R 2 、R 3 Represented by methyl or phenyl, R 4 Represented by phenyl;
R、L 2 、L 3 、Ar 2 the definition of n is as described above.
Preferably, the Ar 1 To Ar 2 Each independently is represented by a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted dimethylfluorenyl group, a substituted or unsubstituted diphenylfluorenyl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted benzofuranyl group, a substituted or unsubstituted furanyl group, a substituted or unsubstituted benzothienyl group, a substituted or unsubstituted thienyl group, a substituted or unsubstituted fluorenyl groupN-phenylcarbazole, substituted or unsubstituted carbazolyl.
Preferably, the specific structure of the compound is any one of the following structures:
organic electroluminescent device
The invention provides an organic electroluminescent device which sequentially comprises an anode, a hole transmission region, a light-emitting region, an electron transmission region and a cathode, wherein the hole transmission region comprises an arylamine organic compound shown in a general formula (1).
Preferably, the hole transport region comprises a hole injection layer, a hole transport layer and an electron blocking layer, and the hole transport layer and/or the hole injection layer comprises an arylamine organic compound represented by the general formula (1).
Preferably, the hole transport region comprises a hole injection layer, a hole transport layer and an electron blocking layer, wherein the hole transport layer comprises an arylamine organic compound shown in the general formula (1), and the hole injection layer consists of the arylamine organic compound shown in the general formula (1) and other doping materials conventionally used for the hole injection layer.
Preferably, the electron transport region comprises an azaheterocyclic compound represented by the general formula (4):
wherein Ar is 3 、Ar 4 、Ar 5 Independently of one another, from substituted or unsubstituted C 6 -C 30 Aryl, substituted or unsubstituted C containing one or more hetero atoms 2 -C 30 One of the heterocyclic groups;
L 4 represented by single bonds, substituted or unsubstituted C 6 -C 30 Arylene, substituted or unsubstituted C containing one or more hetero atoms 2 -C 30 One of the heterocyclylene groups;
X 1 、X 2 、X 3 independently of one another, N or CH, X 1 、X 2 、X 3 Wherein at least one of them represents N;
the heteroatoms are each independently selected from N, O or S;
the substituent for the substituent group is one or more of deuterium atom, phenyl, naphthyl, biphenyl, dibenzofuranyl, dibenzothienyl, pyridyl or pyrimidinyl.
The organic electroluminescent device of the present invention may be a bottom-emission organic electroluminescent device, a top-emission organic electroluminescent device, and a stacked organic electroluminescent device, and is not particularly limited.
In the organic electroluminescent device of the present invention, any substrate commonly used for organic electroluminescent devices may also be used. Examples thereof are transparent substrates such as glass or transparent plastic substrates; an opaque substrate such as a silicon substrate; a flexible Polyimide (PI) film substrate. Different substrates have different mechanical strength, thermal stability, transparency, surface smoothness, and water repellency. The use direction of the substrate is different according to the property of the substrate. In the present invention, a transparent substrate is preferably used. The thickness of the substrate is not particularly limited.
Anode
Preferably, the anode may be formed on the substrate. In the present invention, the anode and the cathode are opposite to each other. The anode may be made of a conductor having a higher work function to aid hole injection, and may be, for example, a metal such as nickel, platinum, copper, zinc, silver, or alloys thereof; metal oxides such as zinc oxide, indium Tin Oxide (ITO), and Indium Zinc Oxide (IZO); combinations of metals and metal oxides, such as ZnO with Al or ITO with Ag; conductive polymers such as poly (3-methylthiophene), poly (3, 4- (ethylene-1, 2-dioxy) thiophene), and polyaniline, but are not limited thereto. The thickness of the anode depends on the material used, typically 50-500nm, preferably 70-300nm, and more preferably 100-200nm, and in the present invention, a combination of metal and metal oxide, ITO and Ag, is preferably used.
Cathode electrode
The cathode may be made of a conductor having a lower work function to aid electron injection, and may be, for example, a metal or an alloy thereof, such as magnesium, calcium, sodium, potassium, titanium, indium, aluminum, silver, tin, and combinations thereof; multilayer structural materials, such as LiF/Al, li 2 O/Al and BaF 2 /Ca, but is not limited thereto. The thickness of the cathode is generally 10-50nm, preferably 15-20nm, depending on the material used.
Light emitting region
In the present invention, the light emitting region may be disposed between the anode and the cathode, and may include at least one host material and at least one guest material. As the host material and the guest material of the light-emitting region of the organic electroluminescent device of the present invention, a light-emitting layer material for an organic electroluminescent device known in the art can be used. The host material may be, for example, a thiazole derivative, a benzimidazole derivative, a polydialkylfluorene derivative, or 4,4' -bis (9-Carbazolyl) Biphenyl (CBP). As host material, compounds containing anthracene groups can be used. The guest material may be, for example, quinacridone, coumarin, rubrene, perylene and derivatives thereof, benzopyran derivatives, rhodamine derivatives or aminostyrene derivatives.
In a preferred embodiment of the invention, one or two host material compounds are contained in the light-emitting region.
In a preferred embodiment of the invention, two host material compounds are included in the light emitting region, and the two host material compounds form an exciplex.
In a preferred embodiment of the invention, the host material of the light-emitting region used is selected from one or more of the following compounds BH-1 to BH-11:
in the present invention, the light emitting region may include a phosphorescent or fluorescent guest material to improve fluorescence or phosphorescence characteristics of the organic electroluminescent device. Specific examples of the phosphorescent guest material include metal complexes of iridium, platinum, and the like, and as the fluorescent guest material, those generally used in the art can be used. In a preferred embodiment of the present invention, the guest material of the light-emitting film layer used is selected from one of the following compounds BD-1 to BD-10:
in the light-emitting region of the present invention, the ratio of host material to guest material used is 99:1 to 70:30, preferably 99:1 to 85:15 and more preferably 97:3 to 87:13 on a mass basis.
The thickness of the light emitting region may be 10 to 50nm, preferably 15 to 30nm, but the thickness is not limited to this range.
Hole transport region
In the organic electroluminescent device of the present invention, a hole transport region is disposed between the anode and the light emitting region, and includes a hole injection layer, a hole transport layer, and an electron blocking layer.
Hole injection layer
The hole injection material used in the hole injection layer (also referred to as an anode interface buffer layer) is a material capable of sufficiently accepting holes from the anode at a low voltage, and the Highest Occupied Molecular Orbital (HOMO) of the hole injection material is preferably a value between the work function of the anode material and the HOMO of the adjacent organic material layer. In a preferred embodiment of the present invention, the hole injection layer is a mixed film of host organic material and P-type dopant material. In order to enable holes to be smoothly injected into the organic film layer from the anode, the HOMO energy level of the main organic material and the P-type doping material must have certain characteristics, so that the occurrence of a charge transfer state between the main material and the doping material is expected to be realized, ohmic contact between the hole injection layer and the anode is realized, and efficient injection of holes from the electrode to the hole injection layer is realized. This feature is summarized as: the difference between the HOMO energy level of the host material and the LUMO energy level of the P-type doped material is less than or equal to 0.4eV. Therefore, for hole host materials with different HOMO energy levels, different P-type doping materials are required to be selected to be matched with the hole host materials, so that ohmic contact of an interface can be realized, and the hole injection effect is improved.
Preferably, specific examples of the host organic material include: metalloporphyrin, oligothiophene, arylamine organic materials, hexanitrile hexaazabenzophenanthrene, quinacridone organic materials, perylene organic materials, anthraquinone, polyaniline and polythiophene conductive polymers; but is not limited thereto. Preferably, the host organic material is an arylamine organic compound represented by general formula (1).
Preferably, the P-type dopant material is a compound having charge conductivity selected from the group consisting of: quinone derivatives or metal oxides such as tungsten oxide and molybdenum oxide, but are not limited thereto.
In a preferred embodiment of the invention, the P-type doping material used is selected from any of the following compounds P-1 to P-8:
in one embodiment of the invention, the ratio of host organic material to P-type dopant material used is 99:1 to 95:5, preferably 99:1 to 97:3, on a mass basis.
In a preferred embodiment of the present invention, the hole injection layer is a mixed film layer of an arylamine compound and a P-type doping material, and the arylamine compound is an arylamine compound of general formula (1).
The thickness of the hole injection layer of the present invention may be 5 to 20nm, preferably 8 to 15nm, but the thickness is not limited to this range.
Hole transport layer
In the organic electroluminescent device of the present invention, a hole transport layer may be disposed over the hole injection layer. The hole transport material is suitably a material having a high hole mobility, which can accept holes from the anode or the hole injection layer and transport the holes into the light emitting layer. Specific examples thereof include: an arylamine organic compound represented by the general formula (1). In a preferred embodiment, the hole transport layer comprises the same arylamine organic compound represented by general formula (1) as the hole injection layer.
The thickness of the hole transport layer of the present invention may be 80, 100 or 200nm, preferably 100 to 150nm, but the thickness is not limited to this range.
Electron blocking layer
In the organic electroluminescent device of the present invention, an electron blocking layer may be disposed between the hole transport layer and the light emitting layer, and particularly contact the light emitting layer. The electron blocking layer is disposed to contact the light emitting layer, and thus, hole transfer at the interface of the light emitting layer and the hole transporting layer can be precisely controlled. In one embodiment of the invention, the electron blocking layer material is selected from carbazole-based aromatic amine derivatives. The thickness of the electron blocking layer may be 5 to 20nm, preferably 8 to 15nm, but the thickness is not limited to this range.
Electron transport region
In the organic electroluminescent device of the present invention, an electron transport region is disposed between the light emitting region and the cathode, and includes a hole blocking layer, an electron transport layer, and an electron injection layer, but is not limited thereto.
Electron injection layer
The electron injection layer may be disposed between the electron transport layer and the cathode. The electron injection layer material is generally a material preferably having a low work function so that electrons are easily injected into the organic functional material layer. Preferably, the electron injection layer material is an N-type metal material. As the electron injection layer material of the organic electroluminescent device of the present invention, electron injection layer materials for organic electroluminescent devices known in the art, for example, lithium; lithium salts such as lithium 8-hydroxyquinoline, lithium fluoride, lithium carbonate or lithium azide; or cesium salts, cesium fluoride, cesium carbonate or cesium azide. The thickness of the electron injection layer of the present invention may be 0.1 to 5nm, preferably 0.5 to 3nm, and more preferably 0.8 to 1.5nm, but the thickness is not limited to this range.
Electron transport layer
The electron transport layer may be disposed over the light emitting film layer or (if present) the hole blocking layer. The electron transport layer material is a material that easily receives electrons of the cathode and transfers the received electrons to the light emitting layer. Materials with high electron mobility are preferred. As the electron transport layer of the organic electroluminescent device of the present invention, electron transport layer materials for organic electroluminescent devices known in the art, for example, alq 3 Metal complexes of hydroxyquinoline derivatives represented by BAlq and LiQ, various rare earth metal complexes, triazole derivatives, triazine derivatives such as 2, 4-bis (9, 9-dimethyl-9H-fluoren-2-yl) -6- (naphthalen-2-yl) -1,3, 5-triazine (CAS No.: 1459162-51-6), and 2- (4- (9, 10-bis (naphthalen-2-yl) anthracen-2-yl) phenyl) -1-phenyl-1H-benzo [ d ]]Imidazole derivatives such as imidazole (CAS number: 561064-11-7, commonly known as LG 201), oxadiazole derivatives, and the like.
In a preferred organic electroluminescent device of the present invention, the electron transport layer comprises an azacyclic derivative of the general formula (4):
wherein Ar is 3 、Ar 4 、Ar 5 Independently of one another, from substituted or unsubstituted C 6 -C 30 Aryl, substituted or unsubstituted containing one or more hetero atomsSon C 2 -C 30 One of the heterocyclic groups;
L 4 represented by single bonds, substituted or unsubstituted C 6 -C 30 Arylene, substituted or unsubstituted C containing one or more hetero atoms 2 -C 30 One of the heterocyclylene groups;
X 1 、X 2 、X 3 independently of one another, N or CH, X 1 、X 2 、X 3 Wherein at least one of them represents N;
the heteroatoms are each independently selected from N, O or S;
the substituent for the substituent group is one or more of deuterium atom, phenyl, naphthyl, biphenyl, dibenzofuranyl, dibenzothienyl, pyridyl or pyrimidinyl.
Preferably, the Ar 3 、Ar 4 、Ar 5 Independently of each other, is represented by one of a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted pyrimidinyl group, a substituted or unsubstituted dibenzothiophene, a substituted or unsubstituted quinolinyl group;
the L is 4 Represented by a single bond, phenylene, biphenylene, or naphthylene;
the substituent for the substituent group is one or two of deuterium atom, phenyl, naphthyl, biphenyl, dibenzofuranyl, dibenzothienyl, pyridyl and pyrimidinyl.
In a preferred embodiment of the present invention, the electron transport layer comprises any one of the following compounds selected from:
in a more preferred embodiment of the present invention, the electron transport layer comprises any one of the following compounds selected from:
in a preferred embodiment of the invention, the electron transport layer comprises, in addition to the compounds of the general formula (2), further compounds conventionally used for electron transport layers, for example Alq3, liQ, preferably LiQ. In a more preferred embodiment of the present invention, the electron transport layer consists of one of the compounds of formula (2) and one of the other compounds conventionally used for electron transport layers, preferably LiQ.
The hole injection and transport rate of the hole transport region containing the aromatic amine compound of the present invention can be well matched to the electron injection and transport rate. Preferably, the hole injection and transport rate of the hole transport region containing the aromatic amine compound of the present invention can be better matched with the electron injection and transport rate of the electron transport region containing the nitrogen heterocyclic derivative of the general formula (2).
Thus, in a particular embodiment of the present invention, the use of an electron transport region comprising or consisting of one or more of the aza ring derivatives of formula (2) in combination with a hole transport region comprising the arylamine compound of the present invention achieves a relatively better technical result.
The thickness of the electron transport layer of the present invention may be 10 to 80nm, preferably 20 to 60nm, and more preferably 25 to 45nm, but the thickness is not limited to this range.
Cover layer
In order to improve the light-emitting efficiency of the organic electroluminescent device, a light extraction layer (i.e., a CPL layer, also referred to as a capping layer) may be further added to the cathode of the device. According to the optical absorption and refraction principles, the higher the refractive index of the CPL cover layer material is, the better the CPL cover layer material is, and the smaller the light absorption coefficient is, the better the CPL cover layer material is. Any material known in the art may be used as the CPL layer material, such as Alq3, or N4, N4' -diphenyl-N4, N4' -bis (9-phenyl-3-carbazolyl) biphenyl-4, 4' -diamine. The CPL coating typically has a thickness of 5-300nm, preferably 20-100nm and more preferably 40-80nm.
The organic electroluminescent device of the present invention may further include an encapsulation structure. The encapsulation structure may be a protective structure that prevents foreign substances such as moisture and oxygen from entering the organic layer of the organic electroluminescent device. The encapsulation structure may be, for example, a can, such as a glass can or a metal can; or a thin film covering the entire surface of the organic layer.
Hereinafter, an organic electroluminescent device according to an embodiment of the present invention is described.
In the drawings, the thickness of layers, films, substrates, regions, etc. are exaggerated for clarity. Like numbers refer to like elements throughout. It will be understood that when an element such as a layer, film, region or substrate is referred to as being "on" another element, it can be directly on the other element or intervening elements may also be present. In contrast, when an element is referred to as being "directly on" another element, there are no intervening elements present.
Fig. 1 is a schematic cross-sectional view of an organic electroluminescent device according to an embodiment of the present invention.
Referring to fig. 1, an organic electroluminescent device according to an embodiment of the present invention includes an anode 2 and a cathode 10 opposite to each other, a hole transport region including a hole injection layer 3, a hole transport layer 4, and an electron blocking layer 5, a light emitting layer 6, and an electron transport region including a hole blocking layer 7, an electron transport layer 8, and an electron injection layer 9, sequentially disposed between the anode 2 and the cathode 10, and a capping layer 11 disposed over a substrate 1 and the cathode under the anode 2.
The invention also relates to a method of manufacturing an organic electroluminescent device comprising sequentially laminating an anode, a hole injection layer, a hole transport layer, an electron blocking layer, an organic film layer, an electron transport layer, an electron injection layer and a cathode, and optionally a capping layer, on a substrate. In this regard, methods such as vacuum deposition, vacuum evaporation, spin coating, casting, LB method, inkjet printing, laser printing, or LITI may be used, but are not limited thereto. In the present invention, the respective layers are preferably formed by a vacuum vapor deposition method. The individual process conditions in the vacuum evaporation process can be routinely selected by those skilled in the art according to the actual needs.
The material for forming each layer according to the present invention may be used as a single layer by forming a film alone, or may be used as a single layer by forming a film after mixing with another material, or may be a laminated structure between layers formed by forming a film alone, a laminated structure between layers formed by mixing, or a laminated structure between layers formed by forming a film alone and layers formed by mixing.
The invention also relates to a full-color display device, in particular a flat panel display device, comprising the organic electroluminescent device of the invention with three pixels of red, green and blue. The display device may further include at least one thin film transistor. The thin film transistor may include a gate electrode, source and drain electrodes, a gate insulating layer, and an active layer, wherein one of the source and drain electrodes may be electrically connected to an anode of the organic electroluminescent device. The active layer may include crystalline silicon, amorphous silicon, an organic semiconductor, or an oxide semiconductor, but is not limited thereto.
Example 1: synthesis of intermediate 1
In a 250mL three-mouth bottle, adding 0.04mol of 2- (2-bromophenyl) -furan and 100mL of anhydrous tetrahydrofuran under the protection of nitrogen, cooling to-78 ℃, slowly dropwise adding 16mL of 2.5M N-butyllithium N-hexane solution, keeping the temperature and stirring for 2 hours, adding 0.044mol of 4-chlorofluorenone into the solution, then reacting for 2 hours at room temperature, slowly dropwise adding 1N hydrochloric acid solution into the reaction solution, extracting with dichloromethane, rotationally steaming the extract until no fraction exists, and passing through a neutral silica gel column to obtain an intermediate 1.LC-MS: measurement value: 341.32 ([ M+H)] + ) The method comprises the steps of carrying out a first treatment on the surface of the Accurate quality: 340.07.
example 2: synthesis of Compound 7
In a 250ml three-necked flask, under the protection of nitrogen gas, 0.01mol of raw material A-1,0.012mol of raw material B-1 and 150ml of toluene were added and mixed under stirring, and then 5X 10 was added -5 mol Pd 2 (dba) 3 ，5×10 -5 Heating 0.03mol of tri-tert-butyl phosphorus and 0.03mol of sodium tert-butoxide to 105 ℃, and carrying out reflux reaction for 24 hours, wherein a sampling point plate shows that no amino compound remains and the reaction is complete; naturally cooling to room temperature, filtering, steaming the filtrate until no fraction exists, and passing through a neutral silica gel column to obtain an intermediate M-1.LC-MS ([ M+H)] + ): measurement value: 422.25; accurate quality: 421.18.
in a 250ml three-necked flask, under the protection of nitrogen gas, 0.01mol of intermediate M-1,0.012mol of intermediate 1 and 150ml of toluene were added and mixed with stirring, and then 5X 10 was added -5 mol Pd 2 (dba) 3 ，5×10 -5 Heating 0.03mol of tri-tert-butyl phosphorus and 0.03mol of sodium tert-butoxide to 105 ℃, and carrying out reflux reaction for 24 hours, wherein a sampling point plate shows that no amino compound remains and the reaction is complete; naturally cooling to room temperature, filtering, steaming the filtrate until no fraction exists, and passing through a neutral silica gel column to obtain the compound 7. Elemental analysis structure (molecular formula C) 55 H 35 NO): theoretical value: c,91.01; h,4.86; n,1.93; test value: c,91.00; h,4.90; n,1.95.LC-MS: measurement value: 726.30 ([ M+H)](+) is carried out; accurate quality: 725.27.
example 3: synthesis of Compound 12
The synthesis procedure was as in example 2, except that starting material A-2 was used instead of starting material A-1 and starting material B-2 was used instead of starting material B-1 to give compound 12. Elemental analysis structure (molecular formula C) 51 H 33 NO 2 ): theoretical value: c,88.54; h,4.81; n,2.02; test value: c,88.59; h,4.84; n,2.01.LC-MS: measurement value: 692.36 ([ M+H)](+) is carried out; accurate quality: 691.25.
example 4: synthesis of Compound 32
In a 250ml three-necked flask, under the protection of nitrogen gas, 0.01mol of raw material C-1,0.012mol of intermediate 1 and 150ml of toluene were added and mixed with stirring, and then 5X 10 was added -5 mol Pd 2 (dba) 3 ，5×10 -5 Heating 0.03mol of tri-tert-butyl phosphorus and 0.03mol of sodium tert-butoxide to 105 ℃, and carrying out reflux reaction for 24 hours, wherein a sampling point plate shows that no amino compound remains and the reaction is complete; naturally cooling to room temperature, filtering, steaming the filtrate until no fraction is present, and passing through a neutral silica gel column to obtain the compound 32. Elemental analysis structure (molecular formula C) 50 H 35 NO): theoretical value: c,90.19; h,5.30; n,2.10; test value: c,90.14; h,5.35; n,2.13.LC-MS: measurement value: 666.41 ([ M+H)](+) is carried out; accurate quality: 665.27.
example 5: synthesis of Compound 40
The synthesis procedure was as in example 2, except that starting material A-3 was used instead of starting material A-1 and starting material B-3 was used instead of starting material B-1, to give compound 40. Elemental analysis structure (molecular formula C) 48 H 33 NO 2 ): theoretical value: c,87.91; h,5.07; n,2.14; test value: c,87.88; h,5.04; n,2.18.LC-MS: measurement value: 656.20 ([ M+H)](+) is carried out; accurate quality: 655.25.
example 6: synthesis of Compound 51
The synthesis procedure was as in example 4, except that starting material C-2 was used instead of starting material C-1 to give compound 51. Elemental analysis structure (molecular formula C) 53 H 39 NO): theoretical value: c,90.18; h,5.57; n,1.98; test value: c,90.20; h,5.61; n,1.94.LC-MS: measurement value: 706.33 ([ M+H)](+) is carried out; accurate quality: 705.30.
example 7: synthesis of Compound 54
In a 250ml three-necked flask, under the protection of nitrogen gas, 0.01mol of raw material A-4,0.012mol of raw material B-4 and 150ml of toluene were added and mixed under stirring, and then 5X 10 was added -5 mol Pd 2 (dba) 3 ，5×10 -5 Heating 0.03mol of tri-tert-butyl phosphorus and 0.03mol of sodium tert-butoxide to 105 ℃, and carrying out reflux reaction for 24 hours, wherein a sampling point plate shows that no amino compound remains and the reaction is complete; naturally cooling to room temperature, filtering, steaming the filtrate until no fraction exists, and passing through a neutral silica gel column to obtain an intermediate M-4.LC-MS: measurement value: 512.42 ([ M+H)] + ) The method comprises the steps of carrying out a first treatment on the surface of the Accurate quality: 511.21.
under nitrogen, 0.01mol of intermediate M-4 was weighed and dissolved in 150ml of Tetrahydrofuran (THF), and 0.03mol of bis (pinacolato) diboron, 1X 10 -4 Adding mol (1, 1' -bis (diphenylphosphine) ferrocene) dichloropalladium (II) and 0.03mol of potassium acetate, stirring the mixture, and heating and refluxing the mixed solution of the reactants at the reaction temperature of 80 ℃ for 10 hours; after the reaction is finished, water is added for cooling, the mixture is filtered, a filter cake is dried in a vacuum drying oven, and the obtained residue is separated and purified through a silica gel column to obtain an intermediate N-1; LC-MS: measurement value: 604.44 ([ M+H)] + ) The method comprises the steps of carrying out a first treatment on the surface of the Accurate quality: 603.33.
0.06mol of intermediate N-1 was added to a 500ml three-necked flask under a nitrogen atmosphere, and a mixed solvent (300 ml of toluene, 90ml of H was added 2 O) dissolving it, stirring for 1 hour by introducing nitrogen, then slowly adding 0.05mol of intermediate 1 and 0.1mol of K 2 CO 3 、0.005mol Pd(PPh 3 ) 4 The reaction was heated to 90℃and observed by Thin Layer Chromatography (TLC) for 8 hours until the reaction was complete. Naturally cooling to room temperature, adding water into the reaction system for extraction, separating liquid, and performing reduced pressure rotary evaporation on the organic phase until no fraction exists. The resulting material was purified by silica gel column to give compound 54. Elemental analysis junctionStructure (molecular formula C) 59 H 43 NO): theoretical value: c,90.62; h,5.54; n,1.79; test value: c,90.57; h,5.50; n,1.81.LC-MS: measurement value: 782.38 ([ M+H)](+) is carried out; accurate quality: 781.33.
example 8: synthesis of Compound 62
The synthesis procedure was as in example 2, except that starting material A-5 was used instead of starting material A-1 and starting material B-5 was used instead of starting material B-1 to give compound 62. Elemental analysis structure (molecular formula C) 64 H 47 NO): theoretical value: c,90.85; h,5.60; n,1.66; test value: c,90.88; h,5.62; n,1.64.LC-MS: measurement value: 846.24 ([ M+H)](+) is carried out; accurate quality: 845.37.
example 9: synthesis of Compound 82
The synthesis procedure was as in example 4, except that starting material C-3 was used instead of starting material C-1 to give compound 82. Elemental analysis structure (molecular formula C) 53 H 34 N 2 O): theoretical value: c,89.05; h,4.79; n,3.92; test value: c,89.08; h,4.75; n,3.90.LC-MS: measurement value: 715.21 ([ M+H)](+) is carried out; accurate quality: 714.27.
detection method
Glass transition temperature Tg: the temperature was increased at a rate of 10℃per minute as measured by differential scanning calorimetry (DSC, german fast Co., DSC204F1 differential scanning calorimeter).
HOMO energy level: the test was performed by an ionization energy measurement system (IPS 3) test, which was a vacuum environment.
Eg energy level: the test was performed by a double beam ultraviolet-visible spectrophotometer (model: TU-1901) based on the tangential line between the ultraviolet spectrophotometry (UV absorption) base line of the material single film and the ascending side of the first absorption peak, calculated using the value of the intersection point between the tangential line and the base line.
Hole mobility: the material was fabricated as a single charge device, measured using space charge (induced) limited amperometry (SCLC).
Triplet energy level T1: tested by a fluorescent-3 series fluorescence spectrometer of Horiba, the test conditions of the material were 2×10 -5 Toluene solution of mol/L.
The specific physical properties are shown in Table 1.
TABLE 1
As can be seen from the data in table 1 above, the compounds of the present invention have suitable HOMO levels, higher hole mobility and wider band gap (Eg), which helps to realize organic electroluminescent devices with high efficiency, low voltage and long lifetime.
Preparation of organic electroluminescent device
The molecular structural formula of the materials involved in the following preparation process is shown as follows:
device comparative example 1
The organic electroluminescent device is prepared according to the following steps:
as shown in fig. 1, the substrate layer 1 is washed with an anode layer 2 (Ag (100 nm)), that is, alkali washing, pure water washing, drying, and ultraviolet-ozone washing in order to remove organic residues on the surface of the anode layer. On the anode layer 2 after the above washing, HT-1 and P-1 having film thicknesses of 10nm were vapor deposited as hole injection layers 3 by a vacuum vapor deposition apparatus, and the mass ratio of HT-1 and P-1 was 97:3. Next, HT-1 was evaporated to a thickness of 117nm as a hole transport layer 4. Subsequently EB-1 was evaporated to a thickness of 10nm as an electron blocking layer 5. After the evaporation of the electron blocking material is completed, a light emitting layer 6 of the OLED light emitting device is manufactured, and the structure of the light emitting layer comprises BH-1 used by the OLED light emitting layer 6 as a main material, BD-1 as a doping material, the doping material doping ratio is 3% by weight, and the film thickness of the light emitting layer is 20nm. After the light-emitting layer 6, the deposition of HB1 was continued, and the deposited film thickness was 8nm, thereby forming a hole blocking layer 7. And continuously evaporating ET-1 and Liq on the hole blocking layer 7, wherein the mass ratio of the ET-1 to the Liq is 1:1, the vacuum evaporation film thickness of the material is 30nm, and the layer is an electron transport layer 8. On the electron transport layer 8, a LiF layer having a film thickness of 1nm, which is an electron injection layer 9, was formed by a vacuum vapor deposition apparatus. On the electron injection layer 9, an Mg/Ag electrode layer having a film thickness of 16nm was prepared by a vacuum vapor deposition apparatus, and the mass ratio of Mg to Ag was 1:9, and this layer was used as the cathode layer 10. On the cathode layer 10, 70nm of CP-1 was vacuum-deposited as the coating layer 11.
Device comparative examples 2 to 4
The procedure of device comparative example 1 was conducted except that the organic materials in the hole injection layer and the hole transport layer were replaced with the organic materials shown in table 2, respectively.
Device examples 1 to 13
The procedure of device comparative example 1 was conducted except that the organic materials in the hole injection layer, the hole transport layer, or the electron transport layer were replaced with the organic materials shown in table 2, respectively.
TABLE 2
Taking example 1 row as an example in the table above, the "P-1:7=3:9710 nm" in the second column table indicates that the hole injection layer uses the compound 7 and the P-type doping material P-1, and the weight ratio of the P-type doping material to the compound 7 is 3:9710nm represents the thickness of the layer; the third column of the tables, "7117nm" indicates that the material used was compound 7, and the layer thickness was 117nm. And so on in other tables.
After the OLED light-emitting device was fabricated as described above, the cathode and anode were connected using a well-known driving circuit, and various properties of the device were measured. The results of measuring the performance of the devices of examples 1 to 13 and comparative examples 1 to 4 are shown in Table 3.
TABLE 3 Table 3
Note that: LT95 refers to the time taken for the device brightness to decay to 95% of the original brightness at a brightness of 1500 nits;
voltage, current efficiency and color coordinates were tested using an IVL (current-voltage-brightness) test system (fresco scientific instruments, su-state); the current density was 10mA/cm 2 ；
The life test system is an EAS-62C OLED life test system of japan systems research limited.
The high temperature life is that the device has a current density of 10mA/cm at 80 DEG C 2 The time for the brightness of the device to decay to 80% of the original brightness is shortened;
from the results of comparative examples 1 to 4 in Table 3, examples 1 to 13 of devices show that the use of the arylamine organic compounds of the present invention as hole injection and hole transport layer materials effectively improves the efficiency and lifetime of devices, especially the high temperature lifetime of devices, due to their higher carrier transport rate.
Claims (10)
1. An arylamine organic compound is characterized in that the structure of the compound is shown as a general formula (1):
in the general formula (1), the L 1 、L 2 、L 3 Each independently represents one of a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, and a substituted or unsubstituted biphenylene group;
the Ar is as follows 1 To Ar 2 Each occurrence of C, independently represented as substituted or unsubstituted 6-30 Aryl, substituted or unsubstituted C 2-30 Heteroaryl;
m and n are respectively and independently 1,2, 3 or 4;
r represents a hydrogen atom, a deuterium atom, a phenyl group or a naphthyl group;
substituents for the substituents are deuterium atoms, methyl, ethyl, tert-butyl, adamantyl, phenyl, naphthyl or biphenyl.
2. The aromatic amine-based organic compound according to claim 1, wherein the structure of the compound is represented by the general formula (2):
in the general formula (2), R 1 Represented by deuterium atom, methyl, ethyl, t-butyl, adamantyl, phenyl, naphthyl or biphenyl;
R、L 2 、L 3 、Ar 2 n is defined as 1.
3. The aromatic amine-based organic compound according to claim 1, wherein the structure of the compound is represented by the general formula (3):
in the general formula (3), X is O, S, C (R) 2 R 3 )、N(R 4 )，R 2 、R 3 Represented by methyl or phenyl, R 4 Represented by phenyl;
R、L 2 、L 3 、Ar 2 n is defined as 1.
4. The aromatic amine-based organic compound according to claim 1, wherein Ar 1 To Ar 2 Each independently represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted dimethylfluorenyl group, a substituted or unsubstituted diphenylfluorenyl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted benzofuranyl group, a substituted or unsubstituted furanyl group, a substituted or unsubstituted benzothienyl group, a substituted or unsubstituted thienyl group, a substituted or unsubstituted N-phenylcarbazole group, or a substituted or unsubstituted carbazolyl group.
5. The aromatic amine-based organic compound according to claim 1, wherein the specific structure of the compound is any one of the following structures:
6. an organic electroluminescent device comprising, in order, an anode, a hole transport region, a light emitting region, an electron transport region, and a cathode, characterized in that the hole transport region comprises the aromatic amine-based organic compound according to any one of claims 1 to 5.
7. The organic electroluminescent device according to claim 6, wherein the hole transport region comprises a hole injection layer, a hole transport layer, and an electron blocking layer, and the hole transport layer and/or the hole injection layer comprises the aromatic amine-based organic compound according to any one of claims 1 to 5.
8. The organic electroluminescent device according to claim 6, wherein the hole transport region comprises a hole injection layer, a hole transport layer, and an electron blocking layer, the hole transport layer comprising the aromatic amine-type organic compound according to any one of claims 1 to 5, and the hole injection layer is composed of the aromatic amine-type organic compound according to any one of claims 1 to 5 and other doping materials for the hole injection layer.
9. The organic electroluminescent device according to claim 6, wherein the electron transport region comprises an aza-heterocyclic compound represented by general formula (4):
wherein Ar is 3 、Ar 4 、Ar 5 Independently of one another, from substituted or unsubstituted C 6 -C 30 Aryl, substituted or unsubstituted C containing one or more hetero atoms 2 -C 30 One of the heterocyclic groups;
L 4 represented by single bonds, substituted or unsubstituted C 6 -C 30 Arylene, substituted or unsubstituted C containing one or more hetero atoms 2 -C 30 One of the heterocyclylene groups;
X 1 、X 2 、X 3 independently of one another, N or CH, X 1 、X 2 、X 3 Wherein at least one of them represents N;
the heteroatoms are each independently selected from N, O or S;
the substituent for the substituent group is one or more of deuterium atom, phenyl, naphthyl, biphenyl, dibenzofuranyl, dibenzothienyl, pyridyl or pyrimidinyl.
10. The organic electroluminescent device according to claim 9, wherein the aza-cycle compound represented by the general formula (4) is represented by the following structure:
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107614494A (en) * | 2015-10-06 | 2018-01-19 | 株式会社Lg化学 | Spiro-compound and the organic luminescent device for including it |
| CN107635983A (en) * | 2015-10-06 | 2018-01-26 | 株式会社Lg化学 | Spiral shell ring-based compounds and the Organic Light Emitting Diode for including it |
| WO2020036171A1 (en) * | 2018-08-17 | 2020-02-20 | 富士フイルム株式会社 | Sensor |
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2021
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107614494A (en) * | 2015-10-06 | 2018-01-19 | 株式会社Lg化学 | Spiro-compound and the organic luminescent device for including it |
| CN107635983A (en) * | 2015-10-06 | 2018-01-26 | 株式会社Lg化学 | Spiral shell ring-based compounds and the Organic Light Emitting Diode for including it |
| WO2020036171A1 (en) * | 2018-08-17 | 2020-02-20 | 富士フイルム株式会社 | Sensor |
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