CN115304575B - 一种有机化合物和有机电致发光装置 - Google Patents
一种有机化合物和有机电致发光装置 Download PDFInfo
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- CN115304575B CN115304575B CN202210937845.8A CN202210937845A CN115304575B CN 115304575 B CN115304575 B CN 115304575B CN 202210937845 A CN202210937845 A CN 202210937845A CN 115304575 B CN115304575 B CN 115304575B
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- 150000002894 organic compounds Chemical class 0.000 title claims abstract description 53
- 239000000463 material Substances 0.000 claims abstract description 30
- 125000001424 substituent group Chemical group 0.000 claims abstract description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 27
- -1 spirofluorenyl Chemical group 0.000 claims description 20
- 125000001072 heteroaryl group Chemical group 0.000 claims description 11
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 10
- 125000001624 naphthyl group Chemical group 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 239000010409 thin film Substances 0.000 claims description 6
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 5
- 235000010290 biphenyl Nutrition 0.000 claims description 5
- 239000004305 biphenyl Substances 0.000 claims description 5
- 229910052805 deuterium Inorganic materials 0.000 claims description 5
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 5
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 4
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 claims description 4
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 4
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 4
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 4
- 125000001207 fluorophenyl group 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
- 125000005842 heteroatom Chemical group 0.000 claims description 3
- 125000002183 isoquinolinyl group Chemical group C1(=NC=CC2=CC=CC=C12)* 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000002950 monocyclic group Chemical group 0.000 claims description 3
- 125000002294 quinazolinyl group Chemical group N1=C(N=CC2=CC=CC=C12)* 0.000 claims description 3
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 claims description 3
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 claims description 3
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims description 2
- 125000004988 dibenzothienyl group Chemical group C1(=CC=CC=2SC3=C(C21)C=CC=C3)* 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000003784 fluoroethyl group Chemical group [H]C([H])(F)C([H])([H])* 0.000 claims description 2
- 125000002541 furyl group Chemical group 0.000 claims description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 claims description 2
- 125000001792 phenanthrenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C=CC12)* 0.000 claims description 2
- 125000004309 pyranyl group Chemical group O1C(C=CC=C1)* 0.000 claims description 2
- 125000003373 pyrazinyl group Chemical group 0.000 claims description 2
- 125000001725 pyrenyl group Chemical group 0.000 claims description 2
- 125000004076 pyridyl group Chemical group 0.000 claims description 2
- 125000000714 pyrimidinyl group Chemical group 0.000 claims description 2
- 125000000168 pyrrolyl group Chemical group 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 125000001544 thienyl group Chemical group 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 125000004306 triazinyl group Chemical group 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 abstract description 43
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthene Chemical compound C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 abstract description 4
- 238000005401 electroluminescence Methods 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 62
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 36
- 238000006243 chemical reaction Methods 0.000 description 28
- 238000002360 preparation method Methods 0.000 description 21
- 230000015572 biosynthetic process Effects 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 238000003786 synthesis reaction Methods 0.000 description 17
- 238000012360 testing method Methods 0.000 description 16
- 239000012074 organic phase Substances 0.000 description 15
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 14
- 239000000376 reactant Substances 0.000 description 13
- 239000002904 solvent Substances 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 230000005525 hole transport Effects 0.000 description 12
- 239000007788 liquid Substances 0.000 description 11
- 238000001816 cooling Methods 0.000 description 10
- 238000000921 elemental analysis Methods 0.000 description 10
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 7
- 230000000903 blocking effect Effects 0.000 description 7
- 238000001704 evaporation Methods 0.000 description 7
- 229910000027 potassium carbonate Inorganic materials 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000000741 silica gel Substances 0.000 description 6
- 229910002027 silica gel Inorganic materials 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- SJCKRGFTWFGHGZ-UHFFFAOYSA-N magnesium silver Chemical compound [Mg].[Ag] SJCKRGFTWFGHGZ-UHFFFAOYSA-N 0.000 description 5
- 238000004321 preservation Methods 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 229910052736 halogen Inorganic materials 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 229940098779 methanesulfonic acid Drugs 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 150000002367 halogens Chemical group 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 2
- QENGPZGAWFQWCZ-UHFFFAOYSA-N 3-Methylthiophene Chemical compound CC=1C=CSC=1 QENGPZGAWFQWCZ-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 125000005264 aryl amine group Chemical group 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- 238000007738 vacuum evaporation Methods 0.000 description 2
- 229910016036 BaF 2 Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 125000004216 fluoromethyl group Chemical group [H]C([H])(F)* 0.000 description 1
- 230000004927 fusion 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
- 230000005283 ground state Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 150000002907 osmium Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 150000003057 platinum Chemical class 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000006467 substitution reaction Methods 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
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 230000003313 weakening effect Effects 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/96—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings spiro-condensed with carbocyclic rings or ring systems
-
- 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
- C07D405/04—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 directly linked by a ring-member-to-ring-member bond
-
- 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
- C07D405/10—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 carbon chain containing aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
- C07D407/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings
- C07D407/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- 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
- C07D409/04—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 directly linked by a ring-member-to-ring-member bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
- C07D417/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
- C07D487/04—Ortho-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
- C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
- C07D491/04—Ortho-condensed systems
- C07D491/044—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring
- C07D491/048—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring the oxygen-containing ring being five-membered
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
- C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
- C07D491/06—Peri-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/04—Ortho-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
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Abstract
本发明提供了一种有机化合物,具有式Ⅰ所示结构。上述化合物以O杂大环结构为中心骨架,荧蒽以特定形式与O杂大环结构稠合,并通过取代基团的限定,可作为蓝光掺杂材料应用于有机光电装置中,可以降低器件的驱动电压,提高器件的发光效率和寿命,在电致发光技术领域中可得到较好的应用。
Description
技术领域
本发明涉及有机电致发光材料技术领域,尤其涉及一种有机化合物和有机电致发光装置。
背景技术
有机电致发光材料(OLED)作为新一代显示技术,具有超薄、自发光、视角宽、响应快、发光效率高、温度适应性好、生产工艺简单、驱动电压低、能耗低等优点,已广泛应用于平板显示、柔性显示、固态照明和车载显示等行业。
有机电致发光材料按发光机理可分为电致荧光和电致磷光两种,荧光是单重态激子的辐射衰减跃迁,磷光则是三重态激子辐射衰减到基态所发射的光。根据自旋量子统计理论,单重态激子和三重态激子的形成概率比例是1:3。荧光材料内量子效率不超过25%的限制,外量子效率普遍低于5%;电致磷光材料的内量子效率理论上达到100%,外量子效率可达20%。1998年,我国吉林大学的马於光教授和美国普林斯顿大学的Forrest教授分别报道了采用锇配合物和铂配合物作为染料掺杂入发光层,第一次成功得到并解释了磷光电致发光现象,并开创性的将所制备磷光材料应用于电致发光器件。
由于磷光重金属材料有较长的寿命(μs),在高电流密度下,可能导致三线态-三线态湮灭和浓度淬灭,造成器件性能衰减,因此通常将重金属磷光材料掺杂到合适的主体材料中,形成一种主客体掺杂体系,使得能量传递最优化,发光效率和寿命最大化。
现在使用的蓝光掺杂材料存在寿命不够长,效率不够高及驱动电压比较高的问题。
发明内容
有鉴于此,本发明要解决的技术问题在于提供一种有机化合物和有机电致发光装置,可以有效提高OLED器件效率、寿命,降低其驱动电压。
本发明提供了一种有机化合物,具有式Ⅰ所示结构:
其中,L1、L2、L3、L4独立的选自单键、取代或未取代的芳基;
R1、R2、R3、R4独立的选自取代或未取代的芳基、杂芳基或芳胺基;
n1、n2、n3、n4独立的选自0、1或2,且不同时为0。
本发明提供了上述有机化合物作为蓝光掺杂材料的应用。
本发明提供了一种有机发光器件,所述有机发光器件包括阳极、阴极,以及位于所述阳极和阴极之间的有机薄膜层,所述有机薄膜层包括发光层,所述发光层中含有至少一种上述有机化合物。
本发明提供了一种显示面板,包括上述有机发光器件。
与现有技术相比,本发明提供了一种有机化合物,具有式Ⅰ所示结构。上述化合物以O杂螺型大环结构为中心骨架,荧蒽以特定形式与O杂大环结构稠合,其具有相互交叉的构型,此结构刚性较强,空间位阻大,不易转动;LX-RX的引入增加了分子的不对称性,能够降低分子的结晶性和分子的平面性,阻止分子在平面上移动,使得本发明系列化合物的立体结构更加稳定;LX-RX的引入还可以提升材料的玻璃化转变温度、钝化活泼C-H键,提高材料的稳定性。通过调整取代基类型,可以调整分子的能级,使其可以作为蓝光掺杂材料应用于有机光电装置中,可以降低器件的驱动电压,提高器件的发光效率和寿命,在电致发光技术领域中可得到较好的应用。
附图说明
图1为本发明提供的有机发光器件的结构示意图。
具体实施方式
本发明提供了一种有机化合物,具有式Ⅰ所示结构:
其中,L1、L2、L3、L4独立的选自单键、取代或未取代的芳基;
R1、R2、R3、R4独立的选自取代或未取代的芳基、杂芳基或芳胺基;
n1、n2、n3、n4独立的选自0、1或2,且不同时为0。
可选的,所述L1、L2、L3、L4独立的选自单键,苯基,由2~3个苯基通过单键连接或稠合形成的基团。
可选的,所述L1、L2、L3、L4独立的选自单键、苯基、联苯基、萘基或蒽基。
可选的,所述R1、R2、R3、R4独立的选自取代或未取代的苯基、由2~5个苯基通过单键连接或稠合形成的稠芳香基团、单环杂芳基、由2~5个苯基和单环杂芳基稠合形成的稠环杂芳基、芴基、螺芴基、NR5R6;
所述单环杂芳基中的杂原子选自N、O、S、Si中的一种或多种;
所述R5、R6独立的选自苯基、由2~3个苯基通过单键连接或稠合形成的基团。
可选的,所述稠芳香基团由2、3、4或5个苯基通过单键连接或稠合形成。
可选的,所述稠环杂芳基由2、3、4或5个苯基和单环杂芳基稠合形成。
可选的,所述R5、R6独立的选自苯基、联苯基、萘基、蒽基、菲基。
可选的,所述R1、R2、R3、R4独立的选自取代或未取代的苯基、联苯基、萘基、蒽基、菲基、芘基、苝基、吡咯基、呋喃基、噻吩基、吡啶基、吡喃基、嘧啶基、吡嗪基、三嗪基、喹啉基、异喹啉基、喹喔啉基、喹唑啉基、咔唑基、二苯并呋喃基、二苯并噻吩基、苯并咔唑基、苯并菲基、硅杂芴基、螺硅芴基、苯并呋喃并咔唑基、苯并呋喃并菲基、芴基、螺芴基、N,N-二苯基胺基、N,N-二萘基胺基、式a-c所示任一结构:
X1、X2、X3、X4独立的选自C、N、O、S或Si;
X5为N。
所述R1、R2、R3、R4可通过其中的任意碳原子或杂原子与相应的L连接。
可选的,所述R1、R2、R3、R4独立的选自以下任一结构:
#表示连接位置。
可选的,所述R1、R2、R3、R4的取代基独立的选自氘、卤素、C1~C10烷基、卤素取代C1~C10烷基、三甲基硅基、五元或六元环烷基、芳基、烷基取代芳基、卤素取代芳基、杂芳基、烷基取代杂芳基、卤素取代杂芳基、芳胺基中的一种或多种。
可选的,所述R1、R2、R3、R4的取代基独立的选自氘、F、Cl、Br、C1~C6烷基、氟代C1~C6烷基、三甲基硅基、环戊基、环己基、苯基、萘基、C1~C6烷基取代苯基、氟代苯基、N,N-二苯基胺基、N,N-二萘基胺基。
可选的,所述R1、R2、R3、R4的取代基独立的选自氘、F、Cl、Br、甲基、氟代甲基、乙基、氟代乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、三甲基硅基、环戊基、环己基、苯基、萘基、甲基苯基、氟代苯基、N,N-二苯基胺基、N,N-二萘基胺基。
可选的,所述n1、n2、n3、n4中的任意1~3个为1,其余为0。
可选的,所述n1、n2、n3、n4中的任意1、2或3个为1,其余为0。
可选的,所述有机化合物,具有以下任一结构:
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上述结构式中的单键表示甲基。
本发明提供的上述蓝光掺杂材料具有良好的热稳定性和成膜性,适宜的玻璃化温度Tg,利于在热真空蒸镀过程中形成稳定、均一的薄膜,同时减少相分离,保持器件的稳定性。具有较高的载流子传输速率以及平衡的载流子传输性能,以利于器件中空穴和电子传输的平衡,同时获得较宽的载流子复合区域,提高发光效率。
基于此,本发明提供了上述有机化合物作为蓝光掺杂材料的应用。
本发明提供了一种有机发光器件,所述有机发光器件包括阳极、阴极,以及位于所述阳极和阴极之间的有机薄膜层,所述有机薄膜层包括发光层,所述发光层中含有至少一种上述有机化合物。
本发明提供了一种显示面板,包括上述有机发光器件。
本发明提供的有机发光器件可以为本领域技术人员熟知的有机发光器件,本发明可选的,所述有机发光器件包括基板、ITO阳极、第一空穴传输层、第二空穴传输层、电子阻挡层、发光层、第一电子传输层、第二电子传输层、阴极(镁银电极,镁银质量比为1:9)和盖帽层(CPL)。
本发明可选的,所述有机发光器件的阳极材料可选自金属-铜、金、银、铁、铬、镍、锰、钯、铂等及它们的合金;如金属氧化物-氧化铟、氧化锌、氧化铟锡(ITO)、氧化铟锌(IZO)等;如导电性聚合物-聚苯胺、聚吡咯、聚(3-甲基噻吩)等,除以上有助于空穴注入材料及其组合,还包括已知的适合做阳极的材料。
本发明可选的,所述有机发光器件的阴极材料可选自金属-铝、镁、银、铟、锡、钛等及它们的合金;如多层金属材料-LiF/Al、LiO2/Al、BaF2/Al等;除以上有助于电子注入的材料及其组合,还包括已知的适合做阴极的材料。
本发明可选的,所述有机光电装置,如有机发光器件中的有机薄膜层至少有一层发光层(EML),还可以包含其他功能层,包括空穴注入层(HIL)、空穴传输层(HTL)、电子阻挡层(EBL)、空穴阻挡层(HBL)、电子传输层(ETL)、电子注入层(EIL)。
本发明可选的,所述有机发光器件按照以下方法制备:
在透明或不透明的光滑的基板上形成阳极,在阳极上形成有机薄层,在有机薄层上形成阴极。
本发明可选的,形成有机薄层可采用如蒸镀、溅射、旋涂、浸渍、离子镀等已知的成膜方法。
本发明提供了一种显示装置,包括上述显示面板。
在本发明中,有机发光器件(OLED器件)可以用在显示装置中,其中有机发光显示装置可以是手机显示屏、电脑显示屏、电视显示屏、智能手表显示屏、智能汽车显示面板、VR或AR头盔显示屏、各种智能设备的显示屏等。
下面将结合本发明实施例的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
中间体制备
H51、H52、H56所示结构的有机化合物的中间体可以通过如下合成路线制备得到:
1)中间体1的制备:在1L三口瓶中,加入0.20mol反应物1,0.21mol反应物2,0.40mol碳酸钾,165.6g水,1.0mmol Pd(PPh3)4,400mL甲苯,100mL无水乙醇,N2保护,升温至回流,保温反应8小时,停反应,降温至25℃,分液,收集有机相,水洗至中性,有机相减压脱去溶剂,采用纯甲苯柱层析纯化,甲苯、无水乙醇重结晶,得到中间体1。
2)中间体2的制备:在1L三口瓶中,加入0.15mol中间体1,0.375mol氢氧化钠,400mL无水乙醇,N2保护,升温至回流,保温反应3小时,降温至25℃,滴加0.375mol 10%稀盐酸溶液搅拌0.5h,乙酸乙酯萃取,有机相过硅胶柱,减压脱除溶剂,得到粗品中间体2,甲苯、无水乙醇重结晶,得到精品中间体2。
3)中间体3的制备:在500mL三口瓶中,加入0.10mol中间体2,240g甲磺酸,N2保护,升温至70~75℃,保温反应6小时,降温至25℃,将反应液缓慢倒入250g碎冰中,搅拌,抽滤,50mL水淋洗,得到粗品中间体3,甲苯重结晶得到精品。
4)中间体4的制备:在500mL三口瓶中,加入0.05mol中间体3,0.50mol苯酚,100g甲磺酸,N2保护,升温至140~145℃,保温反应15小时,反应结束后搅拌降温至25℃,加入100g水、100g二氯甲烷,搅拌,分液,水洗,有机相过硅胶柱,减压脱除溶剂,得到粗品化合物4,乙酸乙酯重结晶,得到中间体4。
实施例1
H51的合成:
在500mL三口瓶中,加入5mmol中间体4-51,5mmol反应物G51,20mmol碳酸钾,0.25mmol Pd(PPh3)4,300mL二氯乙烷,N2保护,75~80℃保温反应6小时,停止反应,降温至25℃,加入150mL去离子水,搅拌分液,收集有机相,脱去溶剂,得到H51化合物。
MALDI-TOF:m/z:计算值:C53H32O:684.25,实测值:684.63。
化合物元素分析结果:计算值:C53H32O(%):C,92.95;H,4.71;O,2.34;测试值:C,92.97;H,4.70;O,2.33。
实施例2
H52的合成:
化合物H52的合成方法与H51的合成方法相似,区别在于,将反应中的G51替换为等摩尔量的G52。
MALDI-TOF:m/z:计算值:C47H29NO:623.22,实测值:623.45。
化合物元素分析结果:计算值:C47H29NO(%):C,90.50;H,4.69;N,2.25;O,2.57;测试值:C,90.49;H,4.68;N,2.26;O,2.57。
实施例3
H56的合成:
化合物H56的合成方法与H51的合成方法相似,区别在于,将反应中的中间体4-51、G51分别替换为等摩尔量的中间体4-56、G56。
MALDI-TOF:m/z:计算值:C53H31NO:697.24,实测值:697.47。
化合物元素分析结果:计算值:C53H31NO(%):C,91.22;H,4.48;N,2.01;O,2.29;测试值:C,91.23;H,4.47;N,2.02;O,2.29。
化合物H33、H65、H105所示结构的有机化合物的中间体可以通过如下合成路线制备得到:
1)中间体1’的制备:在1L三口瓶中,加入0.20mol反应物1,0.21mol反应物2’,0.40mol碳酸钾,165.6g水,1.0mmol Pd(PPh3)4,400mL甲苯,100mL无水乙醇,N2保护,升温至回流,保温反应8小时,停反应,降温至25℃,分液,收集有机相,水洗至中性,有机相减压脱去溶剂,采用纯甲苯柱层析纯化,甲苯、无水乙醇重结晶,得到中间体1’。
2)中间体2’的制备:在1L三口瓶中,加入0.15mol中间体1’,0.375mol氢氧化钠,400mL无水乙醇,N2保护,升温至回流,保温反应3小时,降温至25℃,滴加0.375mol 10%稀盐酸溶液搅拌0.5h,乙酸乙酯萃取,有机相过硅胶柱,减压脱除溶剂,得到粗品中间体2’,甲苯、无水乙醇重结晶,得到精品中间体2’。
3)中间体3’的制备:在500mL三口瓶中,加入0.10mol中间体2’,240g甲磺酸,N2保护,升温至70~75℃,保温反应6小时,降温至25℃,将反应液缓慢倒入250g碎冰中,搅拌,抽滤,50mL水淋洗,得到粗品中间体3’,甲苯重结晶得到精品。
4)中间体4’的制备:在500mL三口瓶中,加入0.05mol中间体3’,0.50mol苯酚,100g甲磺酸,N2保护,升温至140~145℃,保温反应15小时,反应结束后搅拌降温至25℃,加入100g水、100g二氯甲烷,搅拌,分液,水洗,有机相过硅胶柱,减压脱除溶剂,得到粗品化合物4’,乙酸乙酯重结晶,得到中间体4’。
实施例4
H33的合成:
在500mL三口瓶中,加入50mol中间体4’,300g二氯乙烷,冰水浴降温至0~5℃,缓慢滴加液溴,0~5℃保温反应8小时,加亚硫酸钠溶液淬灭反应,分液,水洗,有机相过硅胶柱,减压脱除溶剂,甲苯重结晶,得到中间体4’-1。
在500mL三口瓶中,加入5mmol中间体4’-1,5mmol反应物G33,20mmol碳酸钾,0.25mmol Pd(PPh3)4,300mL二氯乙烷,N2保护,75~80℃保温反应6小时,停反应,降温至25℃,加入150mL去离子水,搅拌分液,收集有机相,脱去溶剂,得到H33化合物。
MALDI-TOF:m/z:计算值:C45H32O:588.25,实测值:588.49。
化合物元素分析结果:计算值:C45H32O(%):C,91.80;H,5.48;O,2.72;测试值:C,91.81;H,5.47;O,2.72。
实施例5
H65的合成:
化合物H65的合成方法与H33的合成方法相似,区别在于,将反应中的G33替换为等摩尔量的G65。
MALDI-TOF:m/z:计算值:C50H32O:648.25,实测值:648.63。
化合物元素分析结果:计算值:C50H32O(%):C,92.56;H,4.97;O,2.47;测试值:C,92.57;H,4.96;O,2.47。
实施例6
H105的合成:
化合物H105的合成方法与H33的合成方法相似,区别在于,将反应中的G33替换为等摩尔量的G105。
MALDI-TOF:m/z:计算值:C59H34O:758.26,实测值:758.55。
化合物元素分析结果:计算值:C59H34O(%):C,93.38;H,4.52;O,2.11;测试值:C,93.36;H,4.53;O,2.11。
实施例7
H63的合成:
1)在500mL三口瓶中,加入5mmol中间体4-51,5mmol反应物G63,20mmol碳酸钾,0.25mmol Pd(PPh3)4,300mL二氯乙烷,N2保护,75~80℃保温反应6小时,停反应,降温至25℃,加入150mL去离子水,搅拌分液,收集有机相,脱去溶剂,得到H63-1化合物。
2)在500mL三口瓶中,加入50mol化合物H63-1,300g二氯乙烷,冰水浴降温至0~5℃,缓慢滴加液溴,0~5℃保温反应8小时,加亚硫酸钠溶液淬灭反应,分液,水洗,有机相过硅胶柱,减压脱除溶剂,甲苯重结晶,得到中间体H63-2。
3)在500mL三口瓶中,加入5mmol中间体H63-2,10mmol反应物G63-1,20mmol碳酸钾,0.25mmol Pd(PPh3)4,300mL二氯乙烷,N2保护,75~80℃保温反应6小时,停反应,降温至25℃,加入150mL去离子水,搅拌分液,收集有机相,脱去溶剂,得到H63化合物。
MALDI-TOF:m/z:计算值:C65H41NO:851.32,实测值:851.78。
化合物元素分析结果:计算值:C65H41NO(%):C,91.63;H,4.85;N,1.64;O,1.88;测试值:C,91.63;H,4.85;N,1.64;O,1.88。
化合物H120、H143、H186所示结构的有机化合物可以通过如下合成路线制备得到:
中间体4a的合成方法与中间体4的合成方法相似,区别在于,将反应1)中的反应物1、反应物2分别替换为等摩尔量的反应物1a、反应物2a。
实施例8
H120的合成:
在500mL三口瓶中,加入5mmol中间体4a,5mmol反应物G120,20mmol碳酸钾,0.25mmol Pd(PPh3)4,300mL二氯乙烷,N2保护,75~80℃保温反应6小时,停反应,降温至25℃,加入150mL去离子水,搅拌分液,收集有机相,脱去溶剂,得到H120化合物。
MALDI-TOF:m/z:计算值:C61H36N2O:812.28,实测值:812.63。
化合物元素分析结果:计算值:C61H36N2O(%):C,90.12;H,4.46;N,3.45;O,1.97;测试值:C,90.10;H,4.47;N,3.45;O,1.97。
实施例9
H143的合成:
化合物H143的合成方法与H120的合成方法相似,区别在于,将反应中的G120替换为等摩尔量的G143。
MALDI-TOF:m/z:计算值:C59H34OSi:786.24,实测值:786.24。
化合物元素分析结果:计算值:C59H34OSi(%):C,90.04;H,4.35;O,2.03;Si,3.57;测试值:C,90.06;H,4.34;O,2.03;Si,3.57。
实施例10
H186的合成
化合物H186的合成方法与H120的合成方法相似,区别在于,将反应中的G120替换为等摩尔量的G186。
MALDI-TOF:m/z:计算值:C57H31NO:745.24,实测值:745.69。
化合物元素分析结果:计算值:C57H31NO(%):C,91.79;H,4.19;N,1.88;O,2.15;测试值:C,91.77;H,4.19;N,1.88;O,2.15。
器件实施例1
本实施例提供了一种有机发光器件。如图1所示,有机发光器件包括:基板1、ITO阳极2、第一空穴传输层3、第二空穴传输层4、电子阻挡层5、发光层6、第一电子传输层7、第二电子传输层8、阴极9(镁银电极,镁银质量比为9:1)和盖帽层(CPL)10,其中ITO阳极2的厚度是15nm,第一空穴传输层3的厚度是10nm、第二空穴传输层4的厚度是95nm、电子阻挡层5的厚度是30nm、发光层6的厚度是30nm、第一电子传输层7的厚度是30nm、第二电子传输层8的厚度是5nm、镁银电极9的厚度是15nm和盖帽层(CPL)10的厚度是100nm。
OLED器件的制备步骤如下:
1)将玻璃基板1切成50mm×50mm×0.7mm的大小,分别在异丙醇和去离子水中超声处理30min,然后在臭氧下暴露约10分钟来进行清洁;将所得的具有ITO阳极2的玻璃基板安装到真空沉积设备上;
2)在ITO阳极2上,通过真空蒸镀方式蒸镀空穴缓冲层材料化合物a与化合物b,化合物a与化合物b的质量比例为2:98得到厚度为10nm的层,该层作为第一空穴传输层3;
3)在第一空穴传输层3上真空蒸镀第二空穴传输层4的材料化合物b,得到厚度为95nm的层,该层作为第二空穴传输层4;
4)在第二空穴传输层4上蒸镀材料化合物c,得到厚度为30nm的层,该层作为电子阻挡层5;
5)在电子阻挡层5上共沉积发光层6,其中用化合物d作为主体材料,本发明实施例1提供的有机化合物H51作为掺杂材料,有机化合物d和H51的质量比为97:3,厚度为30nm;;
6)在发光层6上真空蒸镀第一电子传输层7化合物e,得到厚度为30nm的第一电子传输层7;
7)在第一电子传输层7上真空蒸镀第二电子传输层8的材料LiF,得到厚度为5nm的第二电子传输层8;
8)在第二电子传输层8上真空蒸镀镁银,制得厚度为15nm的阴极9,其中,质量比Mg:Ag为9:1;
9)在阴极9上真空蒸镀高折射率的空穴型材料化合物f,厚度为100nm,作为阴极覆盖层(盖帽层或CPL)10使用。
上述步骤中提到的材料化合物a-f的结构式分别如下所示:
器件实施例2
本器件实施例与器件实施例1的区别仅在于,将步骤(5)中的有机化合物H51用等量的本发明提供的有机化合物H52替换;其它制备步骤均相同。
器件实施例3
本器件实施例与器件实施例1的区别仅在于,将步骤(5)中的有机化合物H51用等量的本发明提供的有机化合物H56替换;其它制备步骤均相同。
器件实施例4
本器件实施例与器件实施例1的区别仅在于,将步骤(5)中的有机化合物H51用等量的本发明提供的有机化合物H33替换;其它制备步骤均相同。
器件实施例5
本器件实施例与器件实施例1的区别仅在于,将步骤(5)中的有机化合物H51用等量的本发明提供的有机化合物H65替换;其它制备步骤均相同。
器件实施例6
本器件实施例与器件实施例1的区别仅在于,将步骤(5)中的有机化合物H51用等量的本发明提供的有机化合物H105替换;其它制备步骤均相同。
器件实施例7
本器件实施例与器件实施例1的区别仅在于,将步骤(5)中的有机化合物H51用等量的本发明提供的有机化合物H63替换;其它制备步骤均相同。
器件实施例8
本器件实施例与器件实施例1的区别仅在于,将步骤(5)中的有机化合物H51用等量的本发明提供的有机化合物H120替换;其它制备步骤均相同。
器件实施例9
本器件实施例与器件实施例1的区别仅在于,将步骤(5)中的有机化合物H51用等量的本发明提供的有机化合物H143替换;其它制备步骤均相同。
器件实施例10
本器件实施例与器件实施例1的区别仅在于,将步骤(5)中的有机化合物H51用等量的本发明提供的有机化合物H186替换;其它制备步骤均相同。
器件实施例11
本器件实施例与器件实施例1的区别仅在于,将步骤(5)中的有机化合物H51用等量的本发明提供的有机化合物H176替换;其它制备步骤均相同。
器件对比例1
本器件对比例与器件实施例1的区别仅在于,将步骤(5)中的有机化合物H51用等量的对比化合物HA替换;其它制备步骤均相同。
器件对比例2
本器件对比例与器件实施例1的区别仅在于,将步骤(5)中的有机化合物H51用等量的对比化合物HB替换;其它制备步骤均相同。
OLED器件的性能评价:
用Keithley 2365A数字纳伏表测试OLED器件在不同电压下的电流,然后用电流除以发光面积得到OLED器件在不同电压下的电流密度;用Konicaminolta CS-2000分光辐射亮度计测试OLED器件在不同电压下的亮度和辐射能流密度;根据OLED器件在不同电压下的电流密度和亮度,得到在相同电流密度下(10mA/cm2)的启亮电压和电流效率(CE,Cd/A),Von为亮度1Cd/m2下的启亮电压;通过测量OLED器件的亮度达到初始亮度的95%时的时间而获得寿命LT95(在50mA/cm2测试条件下)。
以器件对比例(REF)的启亮电压Von、电流效率CE和寿命LT95的测试数据为100%计,器件实施例1-5的Von、CE和LT95分别为各自的测试数据与对比例的测试数据的比值,即为与对比例1相比的相对值;具体数据如表1所示。
表1
从表1的数据可知,与器件对比例相比,使用本发明所述有机化合物的电致发光器件具有更低的启亮电压,启亮电压下降4%左右,因此可以降低器件的功耗;使用本发明所述有机化合物的器件具有更高的电流效率,相比于对比例约提升4%左右;使用本发明所述有机化合物的器件具有更长的寿命,相比于对比例器件寿命延长了5%左右。这可能是因为本发明化合物特殊的核心结构,具有较为立体的空间结构、具有较大的HOMO-LUMO间隙、较窄的半峰宽、较高的色纯度。且通过引入取代基可以有效地抑制分子之间的聚集,避免因聚集诱导导致荧光减弱,提高器件的发光效率,同时,可以有效地调控分子的三线态能级,有效提高器件的寿命。
申请人声明,本发明通过上述实施例来说明本发明的有机化合物及其应用,但本发明并不局限于上述实施例,即不意味着本发明必须依赖上述实施例才能实施。所属技术领域的技术人员应该明了,对本发明的任何改进,对本发明产品各原料的等效替换及辅助成分的添加、具体方式的选择等,均落在本发明的保护范围和公开范围之内。
Claims (10)
1.一种有机化合物,具有式Ⅰ所示结构:
其中,n1、n2、n3、n4独立的选自0、1或2,且不同时为0;
所述L1、L2、L3、L4独立的选自单键,苯基,由2~3个苯基通过单键连接或稠合形成的基团;
所述R1、R2、R3、R4独立的选自取代或未取代的苯基、由2~5个苯基通过单键连接或稠合形成的稠芳香基团、单环杂芳基、由2~5个苯基和单环杂芳基稠合形成的稠环杂芳基、芴基、螺芴基、喹啉基、异喹啉基、喹喔啉基、喹唑啉基、硅杂芴基、螺硅芴基、NR5R6;
所述单环杂芳基中的杂原子选自N、O、S、Si中的一种或多种;
所述R5、R6独立的选自苯基、由2~3个苯基通过单键连接或稠合形成的基团;
所述R1、R2、R3、R4的取代基独立的选自氘、F、Cl、Br、C1~C6烷基、氟代C1~C6烷基、三甲基硅基、环戊基、环己基、苯基、萘基、C1~C6烷基取代苯基、氟代苯基、N,N-二苯基胺基、N,N-二萘基胺基。
2.根据权利要求1所述的有机化合物,其特征在于,所述L1、L2、L3、L4独立的选自单键、苯基、联苯基、萘基或蒽基。
3.根据权利要求1所述的有机化合物,其特征在于,所述R1、R2、R3、R4独立的选自取代或未取代的苯基、联苯基、萘基、蒽基、菲基、芘基、苝基、吡咯基、呋喃基、噻吩基、吡啶基、吡喃基、嘧啶基、吡嗪基、三嗪基、喹啉基、异喹啉基、喹喔啉基、喹唑啉基、咔唑基、二苯并呋喃基、二苯并噻吩基、苯并咔唑基、苯并菲基、硅杂芴基、螺硅芴基、苯并呋喃并咔唑基、苯并呋喃并菲基、芴基、螺芴基、N,N-二苯基胺基、N,N-二萘基胺基、式a-c所示任一结构:
X1、X2、X3、X4独立的选自O或S;
X5选自N。
4.根据权利要求1所述的有机化合物,其特征在于,所述R1、R2、R3、R4独立的选自以下任一结构:
#表示连接位置。
5.根据权利要求1所述的有机化合物,其特征在于,所述R1、R2、R3、R4的取代基独立的选自氘、F、Cl、Br、甲基、氟代甲基、乙基、氟代乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、三甲基硅基、环戊基、环己基、苯基、萘基、甲基苯基、氟代苯基、N,N-二苯基胺基、N,N-二萘基胺基。
6.根据权利要求1所述的有机化合物,其特征在于,所述n1、n2、n3、n4中的任意1~3个为1,其余为0。
7.一种有机化合物,其特征在于,具有以下任一结构:
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8.权利要求1-7任一项所述的有机化合物作为蓝光掺杂材料的应用。
9.一种有机发光器件,所述有机发光器件包括阳极、阴极,以及位于所述阳极和阴极之间的有机薄膜层,所述有机薄膜层包括发光层,所述发光层中含有至少一种如权利要求1-7任一项所述的有机化合物。
10.一种显示面板,包括权利要求9所述的有机发光器件。
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