CN117777038A - Organic electroluminescent material, preparation method thereof and organic electroluminescent device - Google Patents
Organic electroluminescent material, preparation method thereof and organic electroluminescent device Download PDFInfo
- Publication number
- CN117777038A CN117777038A CN202410216773.7A CN202410216773A CN117777038A CN 117777038 A CN117777038 A CN 117777038A CN 202410216773 A CN202410216773 A CN 202410216773A CN 117777038 A CN117777038 A CN 117777038A
- Authority
- CN
- China
- Prior art keywords
- organic electroluminescent
- electroluminescent material
- substituted
- layer
- electron
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000463 material Substances 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title abstract description 9
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000006467 substitution reaction Methods 0.000 claims abstract description 15
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 14
- 125000001624 naphthyl group Chemical group 0.000 claims abstract description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- -1 phenyl-substituted naphthyl Chemical group 0.000 claims description 16
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 235000010290 biphenyl Nutrition 0.000 claims description 7
- 239000004305 biphenyl Substances 0.000 claims description 7
- 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 6
- 150000002431 hydrogen Chemical class 0.000 claims description 5
- 125000005561 phenanthryl group Chemical group 0.000 claims description 5
- 125000005842 heteroatom Chemical group 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- 125000004802 cyanophenyl group Chemical group 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 abstract description 9
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 abstract description 7
- 238000009826 distribution Methods 0.000 abstract description 5
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 abstract description 4
- 238000009792 diffusion process Methods 0.000 abstract description 3
- 230000002035 prolonged effect Effects 0.000 abstract description 3
- 230000005855 radiation Effects 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 88
- 239000000376 reactant Substances 0.000 description 30
- 238000006243 chemical reaction Methods 0.000 description 27
- 150000001875 compounds Chemical class 0.000 description 25
- 230000032258 transport Effects 0.000 description 24
- 238000002347 injection Methods 0.000 description 22
- 239000007924 injection Substances 0.000 description 22
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- 239000012044 organic layer Substances 0.000 description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 17
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- 238000004440 column chromatography Methods 0.000 description 14
- 239000012153 distilled water Substances 0.000 description 14
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 13
- 239000002904 solvent Substances 0.000 description 13
- 238000001035 drying Methods 0.000 description 12
- 229940125904 compound 1 Drugs 0.000 description 11
- 239000002019 doping agent Substances 0.000 description 10
- 238000001704 evaporation Methods 0.000 description 10
- 230000005525 hole transport Effects 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 239000012046 mixed solvent Substances 0.000 description 7
- 229910052763 palladium Inorganic materials 0.000 description 7
- 125000001424 substituent group Chemical group 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- 230000000903 blocking effect Effects 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000000151 deposition Methods 0.000 description 6
- 230000008021 deposition Effects 0.000 description 6
- 230000008020 evaporation Effects 0.000 description 6
- 230000006870 function Effects 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000000746 purification Methods 0.000 description 6
- 238000007740 vapor deposition Methods 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 239000008096 xylene Substances 0.000 description 5
- QRXMUCSWCMTJGU-UHFFFAOYSA-N 5-bromo-4-chloro-3-indolyl phosphate Chemical compound C1=C(Br)C(Cl)=C2C(OP(O)(=O)O)=CNC2=C1 QRXMUCSWCMTJGU-UHFFFAOYSA-N 0.000 description 4
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 125000003367 polycyclic group Chemical group 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 3
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- 229910052688 Gadolinium Inorganic materials 0.000 description 2
- 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 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 101150003085 Pdcl gene Proteins 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 229940125782 compound 2 Drugs 0.000 description 2
- 229940126214 compound 3 Drugs 0.000 description 2
- 229940125898 compound 5 Drugs 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- GWNFQAKCJYEJEW-UHFFFAOYSA-N ethyl 3-[8-[[4-methyl-5-[(3-methyl-4-oxophthalazin-1-yl)methyl]-1,2,4-triazol-3-yl]sulfanyl]octanoylamino]benzoate Chemical compound CCOC(=O)C1=CC(NC(=O)CCCCCCCSC2=NN=C(CC3=NN(C)C(=O)C4=CC=CC=C34)N2C)=CC=C1 GWNFQAKCJYEJEW-UHFFFAOYSA-N 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 150000002219 fluoranthenes Chemical class 0.000 description 2
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 125000001072 heteroaryl group Chemical group 0.000 description 2
- 150000002391 heterocyclic compounds Chemical class 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical compound C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 235000011056 potassium acetate Nutrition 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 150000003852 triazoles Chemical class 0.000 description 2
- YWWDBCBWQNCYNR-UHFFFAOYSA-N trimethylphosphine Chemical compound CP(C)C YWWDBCBWQNCYNR-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 2
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 description 1
- UWRZIZXBOLBCON-VOTSOKGWSA-N (e)-2-phenylethenamine Chemical class N\C=C\C1=CC=CC=C1 UWRZIZXBOLBCON-VOTSOKGWSA-N 0.000 description 1
- NMCHMWFTPROZGB-UHFFFAOYSA-N 6-cyclohexyl-1-phenyl-2,4,6-tri(propan-2-yl)cyclohexa-1,3-diene Chemical group CC(C)C(C1)(C2CCCCC2)C(C2=CC=CC=C2)=C(C(C)C)C=C1C(C)C NMCHMWFTPROZGB-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 238000006443 Buchwald-Hartwig cross coupling reaction Methods 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 238000006069 Suzuki reaction reaction Methods 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- RLQZDQWRKWNWPP-UHFFFAOYSA-N [K].P(OC1=CC=CC=C1)(OC1=CC=CC=C1)=O Chemical compound [K].P(OC1=CC=CC=C1)(OC1=CC=CC=C1)=O RLQZDQWRKWNWPP-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 150000001454 anthracenes Chemical class 0.000 description 1
- RJGDLRCDCYRQOQ-UHFFFAOYSA-N anthrone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3CC2=C1 RJGDLRCDCYRQOQ-UHFFFAOYSA-N 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000000499 benzofuranyl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000001638 boron Chemical class 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000000609 carbazolyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- NXQGGXCHGDYOHB-UHFFFAOYSA-L cyclopenta-1,4-dien-1-yl(diphenyl)phosphane;dichloropalladium;iron(2+) Chemical compound [Fe+2].Cl[Pd]Cl.[CH-]1C=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1.[CH-]1C=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 NXQGGXCHGDYOHB-UHFFFAOYSA-L 0.000 description 1
- 150000004826 dibenzofurans Chemical class 0.000 description 1
- 125000005509 dibenzothiophenyl group Chemical group 0.000 description 1
- YNHIGQDRGKUECZ-UHFFFAOYSA-N dichloropalladium;triphenylphosphanium Chemical compound Cl[Pd]Cl.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-N 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 230000004313 glare Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 238000004770 highest occupied molecular orbital Methods 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 125000001977 isobenzofuranyl group Chemical group C=1(OC=C2C=CC=CC12)* 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 238000006138 lithiation reaction Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- 150000002964 pentacenes Chemical class 0.000 description 1
- FVDOBFPYBSDRKH-UHFFFAOYSA-N perylene-3,4,9,10-tetracarboxylic acid Chemical compound C=12C3=CC=C(C(O)=O)C2=C(C(O)=O)C=CC=1C1=CC=C(C(O)=O)C2=C1C3=CC=C2C(=O)O FVDOBFPYBSDRKH-UHFFFAOYSA-N 0.000 description 1
- 150000002987 phenanthrenes Chemical class 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 108091008695 photoreceptors Proteins 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 238000005036 potential barrier Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003220 pyrenes Chemical class 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 229940083082 pyrimidine derivative acting on arteriolar smooth muscle Drugs 0.000 description 1
- 150000003230 pyrimidines Chemical class 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-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
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Electroluminescent Light Sources (AREA)
Abstract
The application is applicable to the technical field of materials, and provides an organic electroluminescent material, a preparation method thereof and an organic electroluminescent device. The organic electroluminescent material provided by the application consists of 3 main parts: triazine, cyano groups substituted on phenyl and R 1 ，R 2 The above groups are simultaneously connected with 1,2 or 2,3 positions of naphthalene; wherein R is introduced while cyano is substituted on phenyl 1 ，R 2 While maintaining cyano electron withdrawing capability, the rigidity and the planarity of molecules are ensured, the molecules are combined with triazine or pyrimidine on the other side to regulate electron hole distribution, balance electron withdrawing capability at two ends, improve electron mobility, further improve the luminous efficiency of the device and reduce driving voltage; 1 on naphthalene , 2 bits or 2 , The 3-bit substitution can improve the triplet state energy level, so that electron holes are quickly recombined in the light-emitting layer to form excitons, the exciton combination position is in the main body part, a large amount of exciton diffusion and non-radiation loss are avoided, and the service life of the device is prolonged.
Description
Technical Field
The application belongs to the technical field of materials, and particularly relates to an organic electroluminescent material, a preparation method thereof and an organic electroluminescent device.
Background
An organic light-emitting device (OLED) refers to a photovoltaic device that emits light under the excitation of an electric field or current using an organic material. The OLED has the characteristics of active light emission, high contrast ratio, wide viewing angle, high response speed, uniform light emission, high color gamut, no glare, easy realization of flexible display, simple preparation process and the like, and is considered as an ideal next-generation display and illumination technology.
An organic electroluminescent device using an organic light emitting phenomenon generally has a structure including an anode and a cathode and an organic layer therebetween. Such as a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), a light emitting layer, an Electron Transport Layer (ETL), and an Electron Injection Layer (EIL). The hole transport layer is embedded between the anode and the light-emitting layer, and the electron transport layer is embedded between the cathode and the light-emitting layer, so that not only can the injection barrier of carriers be reduced and the transport rate of the carriers be balanced, but also excitons can be limited to the light-emitting layer, and the light-emitting efficiency of the device is improved.
The structure of the electron transport material used as the electron transport layer at present usually contains nitrogen-containing heterocycle such as pyridine, pyrimidine, oxadiazole, triazole, imidazole and the like with electron transport performance as an electron withdrawing group, but the general organic electroluminescent material has low electron mobility and higher hole mobility, so that the electron-hole in the luminescent device is unbalanced, thereby causing the problems of reduced device efficiency, poor stability, short service life and the like.
Therefore, developing an organic electroluminescent device with high mobility electron transport material to make the organic electroluminescent device have low driving voltage, high efficiency and long service life is a technical problem that needs to be solved by those skilled in the art.
Disclosure of Invention
An object of the embodiments of the present application is to provide an organic electroluminescent material, which is composed of 3 main parts: triazine, cyano groups substituted on phenyl and R 1 ，R 2 The groups are simultaneously connected with 1,2 or 2,3 positions of naphthalene, and the prepared organic electroluminescent device has the technical effects of improving the efficiency of the luminescent device, prolonging the service life and reducing the driving voltage.
The embodiment of the application is realized in such a way that the structure of the organic electroluminescent material is shown as a formula I:；
wherein,
L 1 ，L 2 the substitution positions on naphthalene are 1, 2-position combination or 2, 3-position combination;
L 1 ，L 2 each independently selected from the group consisting of a bond, substituted or unsubstituted C6-aryl of C24, heteroaryl of C3-C24, substituted or unsubstituted, the heteroatoms of which are selected from oxygen, nitrogen, sulfur;
Z 1 -Z 3 at least one N and the rest are C;
Ar 1 ，Ar 2 each independently selected from a bond, a substituted or unsubstituted C6-C24 aryl, a substituted or unsubstituted C3-C24 heteroaryl;
R 1 ，R 2 each independently selected from hydrogen, substituted or unsubstituted C6-C24 aryl, and R 1 And R is R 2 Are not hydrogen at the same time;
the 1,2 and 2,3 substitution positions on naphthalene are defined as follows:。
another object of the present application is an organic electroluminescent device comprising an electron transport layer comprising the organic electroluminescent material described above.
The beneficial effects of this application: the organic electroluminescent material provided by the application consists of 3 main parts: triazine, cyano groups substituted on phenyl and R 1 ，R 2 The groups are simultaneously connected with 1,2 or 2,3 positions of naphthalene, and the organic electroluminescent device prepared by the groups has the technical effects of improving the efficiency of the luminescent device, prolonging the service life and reducing the driving voltage. In one aspect, the present application introduces R simultaneously with the substitution of cyano on phenyl 1 ，R 2 The method has the advantages that the strong electron withdrawing capability of the cyanide base is maintained, meanwhile, the rigidity and the flatness of molecules are ensured, the molecules and triazine or pyrimidine on the other side are combined to act together, the electron hole distribution is regulated, the electron withdrawing capability at two ends is balanced, the cyanide base has a large electron distribution characteristic, the electron mobility is improved, the luminous efficiency is further improved, and the driving voltage is reduced; on the other hand, 1 on naphthalene of the present application , 2 bits or 2 , The 3-bit substitution can improve the triplet state energy level, so that electron holes can be quickly combined in the light-emitting layer to form excitons, and meanwhile, the exciton combination position is in the main body part, so that a large amount of exciton diffusion and non-radiation loss are avoided, and the service life of the OLED device is prolonged.
Drawings
Fig. 1 is a nuclear magnetic resonance hydrogen spectrum of compound 1 provided in example 1 of the present application.
Detailed Description
In order to make the objects, technical solutions and advantages of the present application more apparent, the present application will be further described in detail with reference to the accompanying drawings and examples. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the present application.
The structure of the organic electroluminescent material provided by the application is shown as the following formula I:；
wherein,
L 1 ，L 2 the substitution positions on naphthalene are 1, 2-position combination or 2, 3-position combination;
L 1 ，L 2 each independently selected from a bond, a substituted or unsubstituted C6-C24 aryl, a substituted or unsubstituted C3-C24 heteroaryl, and a heteroatom selected from oxygen, nitrogen, and sulfur;
Z 1 -Z 3 at least one N and the rest are C;
Ar 1 ，Ar 2 each independently selected from the group consisting of a bond, a substituted or unsubstituted C6-C24 aryl, a substituted or unsubstituted C3-C24 heteroaryl;
R 1 ，R 2 each independently selected from hydrogen, substituted or unsubstituted C6-C24 aryl, and R 1 And R is R 2 Not both hydrogen.
Further, the formula I has a structure shown in formulas I-a to I-c:
；
wherein,
Z 1 -Z 3 2 or 3N;
L 1 、L 2 each independently selected from a bond or a group substituted at a substitutable position:
。
Ar 1 ，Ar 2 independently selected from the group consisting of substitution at a substitutable position:
。
R 1 ，R 2 selected from hydrogen or a group R 1 -R 2 Not both hydrogen, substitution at substitutable positions:
。
further, L 1 ，L 2 Selected from the group consisting of a bond, phenyl, naphthyl, biphenyl, terphenyl, phenanthryl, phenyl-substituted naphthyl.
Further, ar 1 ，Ar 2 Selected from phenyl, naphthyl, biphenyl, terphenyl, phenyl-substituted naphthyl, methylphenyl, cyanophenyl, dimethylfluorenyl, dibenzofuranyl.
Further, R 1 ，R 2 Selected from phenyl, naphthyl, biphenyl, terphenyl, phenyl-substituted naphthyl, phenanthryl.
The number of carbon atoms of a substituent in the term "substituted or unsubstituted" means the number of carbon atoms constituting the substituent when unsubstituted, irrespective of the number of carbon atoms in the substituent.
The term "substituted or unsubstituted" means substituted with one, two or more substituents selected from the group consisting of: cyano, methyl, ethyl, propyl, butyl, tert-butyl, cyclopentane, cyclohexane, phenyl, biphenyl, naphthyl, fluorenyl, dimethylfluorenyl, phenanthryl, triphenylenyl, furanyl, thienyl, pyrrolyl, pyridyl, benzofuranyl, benzothienyl, isobenzofuranyl, dibenzofuranyl, dibenzothiophenyl, or a substituent attached by two or more of the substituents shown above, or not having a substituent.
Aryl refers to monocyclic aromatic hydrocarbon groups and polycyclic aromatic ring systems, a polycyclic ring may have two or more rings in which two carbons are common to two adjoining rings (the rings being "fused").
Heteroaryl groups include monocyclic aromatic groups and polycyclic aromatic ring systems of at least one heteroatom including, but not limited to O, S, N, P, B, si and Se.
The 1,2 and 2,3 substitution positions on naphthalene are defined as follows:。
the compound represented by formula I may be specifically exemplified by, but not limited to, the following compounds.
/>
/>
/>
/>
/>
/>
/>
/>
/>
。
The organic electroluminescent materials of the present application can be prepared by synthetic methods known to those skilled in the art. Preferably, the present application also provides a synthetic route of the organic electroluminescent material shown in formula I, as follows:
in the above, L 1 、L 2 、Ar 1 、Ar 2 、Z 1 -Z 3 、R 1 、R 2 Hal as defined in formula I above 1 Independently selected from bromine or iodine; r ', rr ' ' are independently selected fromOr->Wherein is the attachment site.
The preparation method comprises the following steps:
step 1: n (N) 2 Under protection, adding reactant A-I (1.0 eq), reactant F-I (1.1-1.4 eq), palladium catalyst (0.01-0.05 eq), alkali (2.1-2.4 eq), phosphorus ligand (0.02-0.15 eq) or palladium catalyst (0.01-0.05 eq), alkali (2.1-2.4 eq) into a mixed solvent of toluene, ethanol and water (volume ratio of 2-4:1:1), heating to 85-95 ℃, reacting for 8-12h, extracting the obtained product by introducing distilled water and DCM into the obtained product at room temperature after the reaction is completed, and using MgSO 4 After drying the organic layer, the solvent was removed using a rotary evaporator. Purifying by column chromatography to obtain intermediate C-I;
step 2: after adding intermediate C-I (1.0 eq) and reactant D-I (1.1-1.3 eq) to a reaction vessel and dissolving in xylene, adding palladium catalyst (0.01-0.05 eq), phosphorus ligand (0.02-0.15 eq), alkali (2.0-2.4 eq) or palladium catalyst (0.01-0.05 eq) and alkali (2.1-2.4 eq) under the protection of nitrogen; after the addition, the reaction temperature is slowly increased to 130-140 ℃, and the mixture is stirred for 8-12h; the resultant was extracted by introducing distilled water and ethyl acetate thereto at room temperature, and then treated with MgSO 4 After drying the organic layer, the solvent was removed using a rotary evaporator and purified by column chromatography to obtain compound formula I.
Wherein the palladium catalyst may be: tris (dibenzylideneacetone) dipalladium: pd (Pd) 2 (dba) 3 Tetrakis (triphenylphosphine) palladium: pd (PPh) 3 ) 4 Palladium dichloride: pdCl 2 1,1' -bis (diphenylphosphino) ferrocene palladium dichloride: pdCl 2 (dppf), palladium acetate: pd (OAc) 2 Bis (triphenylphosphine) palladium dichloride: pd (PPh) 3 ) 2 Cl 2 Any one or a combination of at least two of these.
The phosphine ligand may be: tri-tert-butylphosphine: p (t-Bu) 3 2-cyclohexyl-2, 4, 6-triisopropylbiphenyl: x-phos, triethylphosphine: PET (polyethylene terephthalate) 3 Trimethylphosphine: PMe 3 Triphenylphosphine: PPh (PPh) 3 Potassium diphenylphosphonate: KPPh (Key performance improvement) 2 。
The base may be: potassium acetate: acOK, K 2 CO 3 、K 3 PO 4 、Na 2 CO 3 、CsF、Cs 2 CO 3 Or sodium tert-butoxide: any one or a combination of at least two of t-BuONa.
For complex raw materials not disclosed, the complex raw materials are synthesized by adopting a classical Suzuki coupling reaction, a Buchwald-Hartwig coupling reaction and a lithiation reaction, and are applied to the application.
The series of palladium catalytic coupling reactions performed in the application utilize the difference that the activity of I and Br is larger than that of Cl on one hand, control reaction sites by controlling reaction conditions on the other hand, and purify the reaction by using column chromatography or a silica gel funnel to remove byproducts so as to obtain the target compound. The following are referred to in the common general knowledge:
transition metal organic chemistry (original sixth edition), robert H-Crabtree (Robert H. Crabtree), press: publication time of Shanghai Shandong university Press: 2017-09-00, ISBN:978-7-5628-5111-0, page 388.
Organic chemistry and photoelectric Material Experimental Instructions, chen Runfeng, press: university of east south Press, publication time: 2019-11-00, ISBN:9787564184230, page 174.
The technical solutions in the embodiments of the present application will be clearly and completely described below in conjunction with the organic electroluminescent material of the present application, and it is apparent that the described embodiments are only some embodiments of the present application, but not all embodiments.
In addition, it should be noted that the numerical values set forth in the following examples are as precise as possible, but those skilled in the art will understand that each numerical value should be construed as a divisor rather than an absolute precise numerical value due to measurement errors and experimental operation problems that cannot be avoided.
Example 1: synthesis of Compound 1
CAS: reactant a-1:1345345-08-5
CAS: reactant B-1:2378552-11-3
CAS: reactant D-1:2173320-52-8
Step 1: n (N) 2 Under protection, the reaction vessel was charged with reactant A-1 (1.0 eq), reactant B-1 (1.2 eq), pd (PPh) 4 (0.02 eq) and K 2 CO 3 (2.2 eq) in a mixed solvent of toluene, ethanol, water (volume ratio 3:1:1), heating to 90 ℃, reacting for 8h, after the reaction was completed, extracting the resultant by introducing distilled water and DCM into the resultant at room temperature, and after using MgSO 4 After drying the organic layer, the solvent was removed using a rotary evaporator. Purification by column chromatography gave intermediate C-1 (yield: 76.6%, test value MS (ESI, M/Z): [ M+H ]]+= 470.15）；
Step 2: after adding intermediate C-1 (1.0 eq) and reactant D-1 (1.1 eq) to the reaction vessel and dissolving in xylene, pd (OAc) was added under nitrogen protection 2 (0.02 eq) and X-Phos (0.04 eq), cs 2 CO 3 (2.3 eq); after the addition, the reaction temperature was slowly raised to 130 ℃, and the mixture was stirred for 10h; the resultant was extracted by introducing distilled water and ethyl acetate thereto at room temperature, and then treated with MgSO 4 After drying the organic layer, the solvent was removed using a rotary evaporator, and purified by column chromatography to obtain compound 1 (yield: 60.3%, test value MS (ESI, M/Z): [ M+H ]]+= 689.27）。
Characterization:
the nuclear magnetic resonance hydrogen spectrum of the compound 1 is shown in fig. 1.
HPLC purity: > 99.7%.
Elemental analysis:
theoretical value: c, 87.18, H, 4.68, N, 8.13;
test value: c, 86.98, H, 4:86, N, 8.24.
Example 2: synthesis of Compound 76
CAS: reactant B-76:1421694-50-9
CAS: reactant D-76:2977291-71-5
Step 1: n (N) 2 Under protection, the reaction vessel was charged with reactant A-76 (1.0 eq), reactant B-76 (1.2 eq), pd (PPh) 4 (0.02 eq) and K 2 CO 3 (2.2 eq) in a mixed solvent of toluene, ethanol, water (volume ratio 3:1:1), heating to 90 ℃, reacting for 8h, after the reaction was completed, extracting the resultant by introducing distilled water and DCM into the resultant at room temperature, and after using MgSO 4 After drying the organic layer, the solvent was removed using a rotary evaporator. Purification by column chromatography gave intermediate C-76 (yield: 80.3%, test value MS (ESI, M/Z): [ M+H ]]+= 470.16）；
Step 2: after adding intermediate C-76 (1.0 eq) and reactant D-76 (1.1 eq) to the reaction vessel and dissolving in xylene, pd (OAc) was added under nitrogen protection 2 (0.02 eq) and X-Phos (0.04 eq), cs 2 CO 3 (2.3 eq); after the addition, the reaction temperature was slowly raised to 130 ℃, and the mixture was stirred for 10h; the resultant was extracted by introducing distilled water and ethyl acetate thereto at room temperature, and then treated with MgSO 4 After drying the organic layer, the solvent was removed using a rotary evaporator, and purified by column chromatography to obtain compound 76 (yield: 65.6%, test value MS (ESI, M/Z): [ M+H ]]+= 729.30）。
Characterization:
HPLC purity: > 99.8%.
Elemental analysis:
theoretical value: c, 87.33, H, 4.98, N, 7.69;
test value: c, 87.06, H, 5.20, N, 7.78.
Example 3: synthesis of Compound 201
/>
CAS: reactant a-201:1821675-79-9
CAS: reactant B-201:71436-66-3
Step 1: n (N) 2 Under protection, the reaction vessel was charged with reactant A-201 (1.0 eq), reactant B-201 (1.2 eq), pd (PPh) 4 (0.02 eq) and K 2 CO 3 (2.2 eq) in a mixed solvent of toluene, ethanol, water (volume ratio 3:1:1), heating to 90 ℃, reacting for 8h, after the reaction was completed, extracting the resultant by introducing distilled water and DCM into the resultant at room temperature, and after using MgSO 4 After drying the organic layer, the solvent was removed using a rotary evaporator. Purification by column chromatography gave intermediate C-201 (yield: 59.5%, test value MS (ESI, M/Z): [ M+H ]]+= 622.23）；
Step 2: n (N) 2 Under protection, intermediate c-201 (1.0 eq), reactant d-201 (1.1 eq), pdCl 2 (dppf) (0.02 eq) and potassium acetate (2.5 eq) were dissolved in DMF and heated to 90℃for 8h. The solvent was removed using a rotary evaporator, the residue was stirred with methylene chloride, filtered, and the remaining material was purified by column chromatography to give reactant B-201 (yield: 88.1%, test value MS (ESI, M/Z): [ M+H ]]+= 714.34）。
Step 3: n (N) 2 Under protection, the reaction vessel was charged with reactant A-201 (1.0 eq), reactant B-201 (1.2 eq), pd (PPh) 4 (0.02 eq) and K 2 CO 3 (2.2 eq) in a mixed solvent of toluene, ethanol, water (volume ratio 3:1:1), heating to 90 ℃, reacting for 8h, after the reaction was completed, extracting the resultant by introducing distilled water and DCM into the resultant at room temperature, and after using MgSO 4 After drying the organic layer, the solvent was removed using a rotary evaporator. Purification by column chromatography gave intermediate C-201 (yield: 86.5%, test value MS (ESI, M/Z): [ M+H ]]+= 774.27）；
Step 4: after adding intermediate C-201 (1.0 eq) and reactant D-201 (1.1 eq) to the reaction vessel and dissolving in xylene, pd (OAc) was added under nitrogen protection 2 (0.02 eq) and X-Phos (0.04 eq), cs 2 CO 3 (2.3 eq); after the addition, the reaction temperature was slowly raised to 130 ℃, and the mixture was stirred for 10h; the resultant was extracted by introducing distilled water and ethyl acetate thereto at room temperature, and then treated with MgSO 4 After drying the organic layer, the solvent was removed using a rotary evaporator, and purified by column chromatography to obtain compound 201 (yield: 73.8%, test value MS (ESI, M/Z): [ M+H ]]+=993.41）。
Characterization:
HPLC purity: > 99.7%.
Elemental analysis:
theoretical value: c, 89.49, H, 4.87, N, 5.64;
test value: c, 89.50, H, 4.98, N, 5.72.
Example 4: synthesis of Compound 276
CAS: reactants a-276:872041-85-5
CAS: reactants b-276:13214-70-5
Step 1: n (N) 2 Under protection, the reaction vessel was charged with reactants a-276 (1.0 eq), b-276 (1.1 eq), pd (PPh) 4 (0.02 eq) and K 2 CO 3 (2.2 eq) in a mixed solvent of toluene, ethanol, water (volume ratio 3:1:1), heating to 85 ℃, reacting for 8h, after the reaction was completed, extracting the resultant by introducing distilled water and DCM into the resultant at room temperature, and after using MgSO 4 After drying the organic layer, the solvent was removed using a rotary evaporator. Purification by column chromatography gave reactant B-276 (yield: 77.7%, test value MS (ESI, M/Z): [ M+H ]]+= 317.12）；
Step 2: n (N) 2 Under protection, the reaction vessel was charged with reactant A-276 (1.0 eq), reactant B-276 (1.1 eq), pd (PPh) 4 (0.02 eq) and K 2 CO 3 (2.2 eq) in a mixed solvent of toluene, ethanol, water (volume ratio 3:1:1), heating to 90 ℃, reacting for 8h, after the reaction was completed, extracting the resultant by introducing distilled water and DCM into the resultant at room temperature, and after using MgSO 4 After drying the organic layer, the solvent was removed using a rotary evaporator. Purification by column chromatography gave intermediate C-276 (yield: 69.3%, test value MS (ESI, M/Z): [ M+H ]]+=471.16）；
Step 3: after adding intermediate C-276 (1.0 eq) and reactant D-276 (1.3 eq) to xylene in a reaction vessel, pd (OAc) was added under nitrogen protection 2 (0.02 eq) and X-Phos (0.04 eq), cs 2 CO 3 (2.3 eq); after the addition, the reaction temperature was slowly raised to 135 ℃ and the mixture was stirred for 8h; the resultant was extracted by introducing distilled water and ethyl acetate thereto at room temperature, and then treated with MgSO 4 After drying the organic layer, the solvent was removed using a rotary evaporator, and purified by column chromatography to obtain compound 276 (yield: 75.4%, test value MS (ESI, M/Z): [ M+H ]]+= 690.28）。
Characterization:
HPLC purity: > 99.6%.
Elemental analysis:
theoretical value: c, 85.32, H, 4.53, N, 10.15;
test value: c, 85.10, H, 4.75, N, 10.23.
Examples 5 to 65: the synthesis of the following compounds, the molecular formulas and mass spectra of which are shown in table 1 below, was accomplished with reference to the synthesis methods of the examples of the present application. The mass spectrometer model adopted in the mass spectrum test is Waters XEVO TQD, and the ESI source test is low-precision.
/>
/>
Further, since other compounds of the present application can be obtained by referring to the synthetic methods of the examples listed above, they are not exemplified herein.
The present application provides an organic electroluminescent device that may have a structure including a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting auxiliary layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, a capping layer, and the like as an organic layer. However, the structure of the organic light emitting element is not limited thereto, and may include a smaller or larger number of organic layers.
According to one embodiment of the present disclosure, the organic layer has an electron transport layer, and the compound of formula I prepared herein is used as a material for the electron transport layer.
In the case of producing an organic light-emitting device, the compound represented by the formula I may be formed by vacuum vapor deposition or solution coating. The solution coating method is, but not limited to, spin coating, dip coating, blade coating, ink jet printing, screen printing, spray coating, roll coating, and the like.
The organic light emitting element of the present application may be of a top emission type, a bottom emission type, or a bi-directional emission type, depending on the materials used.
The device described herein may be used in organic light emitting devices, organic solar cells, electronic paper, organic photoreceptors, or organic thin film transistors.
As the anode material, a material having a large work function is generally preferable in order to allow holes to be smoothly injected into the organic layer. Specific examples of the anode material that can be used in the present application include metals such as vanadium, chromium, copper, zinc, and gold, and alloys thereof; metal oxides such as zinc oxide, indium Tin Oxide (ITO), and Indium Zinc Oxide (IZO); znO A1 or SnO 2 A combination of metals such as Sb and the like and oxides; and conductive polymers such as polypyrrole and polyaniline.
The hole injection layer is preferably a p-doped hole injection layer, by which is meant a hole injection layer doped with a p-dopant. A p-dopant is a material capable of imparting p-type semiconductor characteristics. The p-type semiconductor property means a property of injecting holes or transporting holes at the HOMO level, that is, a property of a material having high hole conductivity.
The hole transporting material is a material capable of receiving holes from the anode or the hole injecting layer and transporting the holes to the light emitting layer, and has high hole mobility. The hole transporting material may be selected from arylamine derivatives, conductive polymers, block copolymers having both conjugated and non-conjugated portions, and the like.
A light-emitting auxiliary layer (multilayer hole-transporting layer) is interposed between the hole-transporting layer and the light-emitting layer. The light-emitting auxiliary layer mainly functions as an auxiliary hole transport layer, and is therefore sometimes also referred to as a second hole transport layer. The light emitting auxiliary layer enables holes transferred from the anode to smoothly move to the light emitting layer, and can block electrons transferred from the cathode to confine electrons in the light emitting layer, reduce potential barrier between the hole transporting layer and the light emitting layer, reduce driving voltage of the organic electroluminescent device, further increase utilization ratio of holes, thereby improving luminous efficiency and lifetime of the device.
The light-emitting substance of the light-emitting layer is a substance capable of receiving and binding holes and electrons from the hole-transporting layer and the electron-transporting layer, respectively, to emit light in the visible light region, and is preferably a substance having high quantum efficiency for fluorescence or phosphorescence.
The light emitting layer may include a host material and a dopant material.
The mass ratio of the host material to the doping material is 90-99.5:0.5-10.
The host material includes aromatic condensed ring derivatives, heterocyclic compounds, and the like. Specifically, examples of the aromatic condensed ring derivative include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, and the like, and examples of the heterocyclic compound include carbazole derivatives, dibenzofuran derivatives, pyrimidine derivatives, and the like.
The dopant materials herein include fluorescent doping and phosphorescent doping. May be selected from aromatic amine derivatives, styrylamine compounds, boron complexes, fluoranthene compounds, metal complexes, and the like.
The electron transport layer may function to facilitate electron transport. The electron transporting material is a material that advantageously receives electrons from the cathode and transports the electrons to the light emitting layer, preferably a material having high electron mobility. The electron transport layer may include at least one of an electron buffer layer, a hole blocking layer, an electron transport layer, and an electron injection layer, and preferably at least one of an electron transport layer and an electron injection layer. The electron transport layer material is a compound shown in a formula I.
The electron injection layer may function to promote electron injection. Has an ability to transport electrons, and prevents excitons generated in the light emitting layer from migrating to the hole injection layer. The material of the electron injection layer includes, but is not limited to, metal such as oxazole, oxadiazole, triazole, imidazole, perylene tetracarboxylic acid, fluorenylmethane, anthrone, their derivatives, magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, ytterbium, or their alloys, metal complexes, nitrogen-containing 5-membered ring derivatives, and the like.
The cathode is generally preferably of a material having a small work function so that electrons are smoothly injected into the organic material layer, which layer preferably has a layer thickness of between 0.5 and 5 nm. The cathode material is generally preferably a material having a small work function in order to facilitate injection of electrons into the organic layer. Specific examples of the cathode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, and alloys thereof: liF/A1 or LiO 2 And (3) multilayer structural materials such as (A1) and Mg/Ag.
There are no particular restrictions on the other layer materials in an OLED device, except that the electron transport layer disclosed herein comprises formula I. Existing hole injection materials, hole transport auxiliary materials, dopant materials, hole blocking layer materials, electron transport layer materials, and electron injection materials may be used.
An organic electroluminescent composition and an organic electroluminescent device provided in the present application are specifically described below with reference to specific application examples.
Application example 1: preparation of organic electroluminescent device
a. ITO anode: washing ITO (indium tin oxide) -Ag-ITO (indium tin oxide) glass substrate with the coating thickness of 150nm in distilled water for 2 times, washing with ultrasonic waves for 30min, washing with distilled water for 2 times repeatedly, washing with ultrasonic waves for 10min, baking with a vacuum oven at 220 ℃ for 2 hours after washing, and cooling after baking is finished, so that the glass substrate can be used. The substrate is used as an anode, a vapor deposition device process is performed by using a vapor deposition machine, and other functional layers are sequentially vapor deposited on the substrate.
b. HIL (hole injection layer): the hole injection layer materials HT and P-dopant were vacuum evaporated at an evaporation rate of 1 Å/s, the chemical formulas of which are shown below. The evaporation rate ratio of HT to P-dock is 95:5, the thickness is 10nm;
c. HTL (hole transport layer): vacuum evaporating 135nm HT as a hole transport layer on the hole injection layer at an evaporation rate of 1.5 Å/s;
d. prime (light-emitting auxiliary layer): vacuum evaporating prime of 5nm on the hole transmission layer as light-emitting auxiliary layer at evaporating rate of 0.5 Å/s;
e. EML (light emitting layer): then, a Host material (Host) and a Dopant material (Dopant) having a thickness of 30nm were vacuum-deposited as light-emitting layers on the above light-emitting auxiliary layer at a deposition rate of 1 Å/s, and the chemical formulas of Host and Dopant are as follows. Wherein the evaporation rate ratio of Host to Dopant is 95:5.
f. HB (hole blocking layer): a hole blocking layer having a thickness of 5.0nm was vacuum deposited at a deposition rate of 0.5. 0.5 Å/s.
g. ETL (electron transport layer): compound 1 and Liq having a thickness of 30nm were vacuum-deposited as electron transport layers at a deposition rate of 1 Å/s. Wherein the evaporation rate ratio of the compound 1 to the Liq is 50:50.
h. EIL (electron injection layer): an electron injection layer was formed by vapor deposition of 1.0nm on a Yb film layer at a vapor deposition rate of 0.5. 0.5 Å/s.
i. And (3) cathode: and evaporating magnesium and silver at a deposition rate ratio of 1 Å/s of 13nm, wherein the deposition rate ratio is 1:9, so as to obtain the OLED device.
j. Light extraction layer: CPL with a thickness of 60nm was vacuum deposited on the cathode at a deposition rate of 1 Å/s as a light extraction layer.
k. And packaging the substrate subjected to evaporation. Firstly, a gluing device is adopted to carry out a coating process on a cleaned cover plate by UV glue, then the coated cover plate is moved to a lamination working section, a substrate subjected to vapor deposition is placed at the upper end of the cover plate, and finally the substrate and the cover plate are bonded under the action of a bonding device, and meanwhile, the UV glue is cured by illumination.
Application examples 2-72: the organic electroluminescent devices of application examples 2 to 72 were prepared according to the above-described preparation method of the organic electroluminescent device, except that the compound 1 of application example 1 was replaced with the corresponding compound (as shown in table 2) to form an electron transport layer.
Comparative example 1-comparative example 9: an organic electroluminescent device was prepared according to the above-described preparation method of an organic electroluminescent device, except that compound 1 in application example 1 was replaced with comparative compound 1, comparative compound 2, comparative compound 3, comparative compound 4, comparative compound 5, comparative compound 6, comparative compound 7, comparative compound 8, and comparative compound 9, respectively, wherein the structural formulae of comparative compound 1-comparative compound 9 are as follows:
the organic electroluminescent devices obtained in the above device application examples 1 to 72 and device comparative examples 1 to 9 were characterized in terms of driving voltage, luminous efficiency, BI value and lifetime at a luminance of 1000 (nits), and the test results are shown in table 2 below:
/>
/>
as known to those skilled in the art, the blue-light organic electroluminescent device is affected by the microcavity effect, and the luminous efficiency is greatly affected by chromaticity, so that a BI value is introduced as the basis of the efficiency of the blue-light luminescent material, bi=luminous efficiency/CIEy. And the problems of short lifetime and low efficiency of blue light devices have been one of the problems that those skilled in the art are urgent to solve in the art. In general, the improvement of luminous efficiency is relatively difficult for those skilled in the art.
The compounds of the present application are composed of 3 major parts: triazine, cyano groups substituted on phenyl and R 1 ，R 2 The test results of Table 2 show that the organic electroluminescent device prepared by the above groups simultaneously connects 1,2 or 2,3 sites of naphthalene has a luminous efficiency of about 183.1-197.9cd/A, a driving voltage of about 3.6-3.74V, a lifetime of about 453-511h, a luminous efficiency of about 175.8-179.7cd/A, a driving voltage of about 3.84-3.9V, a lifetime of about 391-425h, and improved performance compared with the conventional organic electroluminescent device provided by comparative examples 1-9.
Compound 1 of the present application differs from comparative compound 1, compound 349 from comparative compound 2 mainly in that R is introduced simultaneously with the substitution of cyano group on the phenyl group of the present application 1 ，R 2 The method has the advantages that the strong electron withdrawing capability of the cyanide base is maintained, meanwhile, the rigidity and the flatness of molecules are guaranteed, the molecules and triazine or pyrimidine on the other side are combined to act together, the electron hole distribution is regulated, the electron withdrawing capability at two ends is balanced, the cyanide base has larger electron distribution characteristics, the electron mobility is improved, the luminous efficiency is further improved, and the driving voltage is reduced.
Compound 111 of the present application differs from comparative compound 3, compound 398 from comparative compound 5 in that benzene of the present applicationSubstituted cyano and R on the radical 1 ，R 2 And the positions of the connection on naphthalene are different, 1 on naphthalene , 2 bits or 2 , The 3-bit substitution can improve the triplet state energy level, so that electron holes can be quickly combined in the light-emitting layer to form excitons, and meanwhile, the exciton combination position is in the main body part, so that a large amount of exciton diffusion and non-radiation loss are avoided, and the service life of the OLED device is prolonged.
The above examples only represent a few embodiments of the present application, which are described in more detail and are not to be construed as limiting the scope of the present application. It should be noted that it would be apparent to those skilled in the art that various modifications and improvements could be made without departing from the spirit of the present application, which would be within the scope of the present application. Accordingly, the scope of protection of the present application is to be determined by the claims appended hereto.
Claims (10)
1. The organic electroluminescent material is characterized in that the structure of the organic electroluminescent material is shown as a formula I:
；
wherein,
L 1 ，L 2 the substitution positions on naphthalene are 1, 2-position combination or 2, 3-position combination;
L 1 ，L 2 each independently selected from a bond, a substituted or unsubstituted C6-C24 aryl, a substituted or unsubstituted C3-C24 heteroaryl, wherein the heteroatoms are selected from oxygen, nitrogen, sulfur;
Z 1 -Z 3 at least one N and the rest are C;
Ar 1 ，Ar 2 each independently selected from a bond, a substituted or unsubstituted C6-C24 aryl, a substituted or unsubstituted C3-C24 heteroaryl;
R 1 ，R 2 each independently selected from hydrogen, substituted or unsubstituted C6-C24 aryl, and R 1 And R is R 2 Are not hydrogen at the same time;
the 1,2 and 2,3 substitution positions on naphthalene are defined as follows:
。
2. the organic electroluminescent material according to claim 1, wherein the structure of the organic electroluminescent material is as shown in formulas I-a to I-c:
。
3. the organic electroluminescent material as claimed in claim 1 or 2, wherein,
Z 1 -Z 3 2 or 3N;
L 1 、L 2 each independently selected from a bond or a group substituted at a substitutable position:
。
4. the organic electroluminescent material as claimed in claim 1 or 2, wherein,
Ar 1 ，Ar 2 independently selected from the group consisting of substitution at a substitutable position:
。
5. the organic electroluminescent material as claimed in claim 1 or 2, wherein,
R 1 ，R 2 selected from hydrogen or a group R 1 -R 2 Not both hydrogen, substitution at substitutable positions:
。
6. the organic electroluminescent material according to claim 1 or 2, wherein the L 1 ，L 2 Selected from the group consisting of a bond, phenyl, naphthyl, biphenyl, terphenyl, phenanthryl, phenyl-substituted naphthyl.
7. The organic electroluminescent material according to claim 1 or 2, wherein the Ar 1 ，Ar 2 Selected from phenyl, naphthyl, biphenyl, terphenyl, phenyl-substituted naphthyl, methylphenyl, cyanophenyl, dimethylfluorenyl, dibenzofuranyl.
8. The organic electroluminescent material according to claim 1 or 2, wherein R 1 ，R 2 Selected from phenyl, naphthyl, biphenyl, terphenyl, phenyl-substituted naphthyl, phenanthryl.
9. The organic electroluminescent material according to claim 1, wherein the structure of the organic electroluminescent material is any one of the following structures:
/>
/>
/>
/>
/>
/>
/>
/>
。
10. an organic electroluminescent device, characterized in that the organic electroluminescent device comprises an electron transport layer comprising the organic electroluminescent material according to any one of claims 1-7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410216773.7A CN117777038B (en) | 2024-02-28 | Organic electroluminescent material, preparation method thereof and organic electroluminescent device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410216773.7A CN117777038B (en) | 2024-02-28 | Organic electroluminescent material, preparation method thereof and organic electroluminescent device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN117777038A true CN117777038A (en) | 2024-03-29 |
| CN117777038B CN117777038B (en) | 2024-05-28 |
Family
ID=
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115894491A (en) * | 2022-11-24 | 2023-04-04 | 吉林奥来德光电材料股份有限公司 | Electron transport material, preparation method thereof, light-emitting device and light-emitting device |
| CN116655611A (en) * | 2023-08-01 | 2023-08-29 | 吉林奥来德光电材料股份有限公司 | Electron transport material, preparation method and organic electroluminescent device |
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115894491A (en) * | 2022-11-24 | 2023-04-04 | 吉林奥来德光电材料股份有限公司 | Electron transport material, preparation method thereof, light-emitting device and light-emitting device |
| CN116655611A (en) * | 2023-08-01 | 2023-08-29 | 吉林奥来德光电材料股份有限公司 | Electron transport material, preparation method and organic electroluminescent device |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2015119186A (en) | Organoselenium material and use of the same in organic light emitting device | |
| CN115872959B (en) | Light-emitting auxiliary material, preparation method and application thereof, and light-emitting device | |
| CN115745977B (en) | Electron transport material, preparation method thereof and organic electroluminescent device | |
| CN114716330A (en) | Luminescent auxiliary material, preparation method and application thereof | |
| CN115991689B (en) | Light-emitting auxiliary material, preparation method thereof and organic electroluminescent device | |
| CN115557920B (en) | Light-emitting auxiliary material, preparation method thereof and organic electroluminescent device | |
| CN117024287B (en) | Light-emitting auxiliary material, preparation method thereof, organic electroluminescent device and organic electroluminescent device | |
| CN113402507A (en) | Triphenylene derivative, light-emitting device material, and light-emitting device | |
| CN116987060B (en) | Luminescent auxiliary material and preparation method and application thereof | |
| CN116514752B (en) | Light-emitting auxiliary material, preparation method and application thereof in organic electroluminescent device | |
| CN116375587B (en) | Luminescent auxiliary material, preparation method thereof and organic electroluminescent device | |
| CN113130771A (en) | Organic electroluminescent device based on iridium-containing organic complex as luminescent material | |
| CN114751888B (en) | Electron transport material, preparation method thereof, light-emitting device and light-emitting device | |
| CN116063293A (en) | Light-emitting auxiliary material, preparation method thereof and organic electroluminescent device | |
| CN115947706A (en) | Luminous auxiliary material and preparation method and application thereof | |
| CN116283982A (en) | Nitrogen-containing heterocyclic organic electroluminescent material and organic electroluminescent device comprising same | |
| CN117777038B (en) | Organic electroluminescent material, preparation method thereof and organic electroluminescent device | |
| CN117777038A (en) | Organic electroluminescent material, preparation method thereof and organic electroluminescent device | |
| CN116836136B (en) | Luminescent auxiliary material and preparation method and application thereof | |
| CN117003729B (en) | Light-emitting auxiliary material, preparation method thereof and organic electroluminescent device | |
| CN117285492B (en) | Light-emitting auxiliary material, preparation method thereof and organic electroluminescent device | |
| CN109535013A (en) | A kind of organic photoelectrical material and preparation method thereof and organic electroluminescence device comprising it | |
| CN115093335B (en) | Luminescent auxiliary material and preparation method and application thereof | |
| CN117024387B (en) | Light-emitting auxiliary material, preparation method thereof and organic electroluminescent device | |
| CN115745900B (en) | Spirofluorene electron transport organic electroluminescent compound and organic electroluminescent device comprising same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant |