CN117561806A - Organic electroluminescent element - Google Patents
Organic electroluminescent element Download PDFInfo
- Publication number
- CN117561806A CN117561806A CN202280044187.8A CN202280044187A CN117561806A CN 117561806 A CN117561806 A CN 117561806A CN 202280044187 A CN202280044187 A CN 202280044187A CN 117561806 A CN117561806 A CN 117561806A
- Authority
- CN
- China
- Prior art keywords
- group
- organic compound
- atom
- ring
- compound
- 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.)
- Pending
Links
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 310
- 239000000463 material Substances 0.000 claims abstract description 115
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 claims abstract description 85
- 230000003111 delayed effect Effects 0.000 claims abstract description 41
- 238000004020 luminiscence type Methods 0.000 claims abstract description 25
- 150000001875 compounds Chemical class 0.000 claims description 326
- 239000010410 layer Substances 0.000 claims description 249
- 125000001424 substituent group Chemical group 0.000 claims description 206
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 163
- 239000000126 substance Substances 0.000 claims description 156
- 229910052805 deuterium Inorganic materials 0.000 claims description 91
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 91
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 91
- 125000003118 aryl group Chemical group 0.000 claims description 86
- 229910052757 nitrogen Inorganic materials 0.000 claims description 84
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 56
- 229910052796 boron Inorganic materials 0.000 claims description 50
- -1 carbazol-5-yl group Chemical group 0.000 claims description 49
- 125000001072 heteroaryl group Chemical group 0.000 claims description 49
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 31
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical group C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 claims description 20
- 125000000168 pyrrolyl group Chemical group 0.000 claims description 15
- 239000012044 organic layer Substances 0.000 claims description 13
- 125000005842 heteroatom Chemical group 0.000 claims description 8
- 125000004431 deuterium atom Chemical group 0.000 claims description 7
- 230000000694 effects Effects 0.000 claims description 7
- 125000004556 carbazol-9-yl group Chemical group C1=CC=CC=2C3=CC=CC=C3N(C12)* 0.000 claims description 6
- 230000001747 exhibiting effect Effects 0.000 claims description 3
- 150000001975 deuterium Chemical group 0.000 description 87
- 125000004432 carbon atom Chemical group C* 0.000 description 69
- 125000000217 alkyl group Chemical group 0.000 description 64
- 239000010408 film Substances 0.000 description 61
- 125000004430 oxygen atom Chemical group O* 0.000 description 59
- 229910052799 carbon Inorganic materials 0.000 description 57
- 125000004429 atom Chemical group 0.000 description 56
- 150000001721 carbon Chemical group 0.000 description 52
- 125000004434 sulfur atom Chemical group 0.000 description 51
- 125000004122 cyclic group Chemical group 0.000 description 44
- 229910052717 sulfur Inorganic materials 0.000 description 44
- 239000000758 substrate Substances 0.000 description 42
- 230000000903 blocking effect Effects 0.000 description 39
- 125000005647 linker group Chemical group 0.000 description 31
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 30
- 230000004888 barrier function Effects 0.000 description 27
- 239000000203 mixture Substances 0.000 description 26
- 229910052727 yttrium Inorganic materials 0.000 description 26
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical group C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 24
- 125000003545 alkoxy group Chemical group 0.000 description 20
- 229910052751 metal Inorganic materials 0.000 description 19
- 239000002184 metal Substances 0.000 description 19
- 238000002347 injection Methods 0.000 description 17
- 239000007924 injection Substances 0.000 description 17
- 230000005525 hole transport Effects 0.000 description 16
- 125000001153 fluoro group Chemical group F* 0.000 description 15
- 238000004770 highest occupied molecular orbital Methods 0.000 description 15
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 14
- 125000003277 amino group Chemical group 0.000 description 14
- 229910052731 fluorine Inorganic materials 0.000 description 14
- 125000004104 aryloxy group Chemical group 0.000 description 13
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000007740 vapor deposition Methods 0.000 description 12
- 125000003342 alkenyl group Chemical group 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 125000004986 diarylamino group Chemical group 0.000 description 11
- 238000005538 encapsulation Methods 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- 238000006467 substitution reaction Methods 0.000 description 10
- 239000010409 thin film Substances 0.000 description 10
- 125000000732 arylene group Chemical group 0.000 description 9
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 9
- 239000004642 Polyimide Substances 0.000 description 8
- 125000001769 aryl amino group Chemical group 0.000 description 8
- 229920001721 polyimide Polymers 0.000 description 8
- 238000005259 measurement Methods 0.000 description 7
- 125000003373 pyrazinyl group Chemical group 0.000 description 7
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 239000000470 constituent Substances 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 6
- 230000008020 evaporation Effects 0.000 description 6
- 125000005843 halogen group Chemical group 0.000 description 6
- 238000001296 phosphorescence spectrum Methods 0.000 description 6
- 125000000714 pyrimidinyl group Chemical group 0.000 description 6
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 5
- FLBAYUMRQUHISI-UHFFFAOYSA-N 1,8-naphthyridine Chemical group N1=CC=CC2=CC=CN=C21 FLBAYUMRQUHISI-UHFFFAOYSA-N 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 5
- 238000005520 cutting process Methods 0.000 description 5
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 5
- 238000004146 energy storage Methods 0.000 description 5
- 238000005530 etching Methods 0.000 description 5
- 125000005549 heteroarylene group Chemical group 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 125000001624 naphthyl group Chemical group 0.000 description 5
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 5
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 4
- 238000010549 co-Evaporation Methods 0.000 description 4
- 239000003086 colorant Substances 0.000 description 4
- 150000001907 coumarones Chemical class 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- 230000005284 excitation Effects 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 125000002883 imidazolyl group Chemical group 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 238000002161 passivation Methods 0.000 description 4
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 4
- 238000005215 recombination Methods 0.000 description 4
- 230000006798 recombination Effects 0.000 description 4
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 3
- GWYPDXLJACEENP-UHFFFAOYSA-N 1,3-cycloheptadiene Chemical group C1CC=CC=CC1 GWYPDXLJACEENP-UHFFFAOYSA-N 0.000 description 3
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical group C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 125000001309 chloro group Chemical group Cl* 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- CHVJITGCYZJHLR-UHFFFAOYSA-N cyclohepta-1,3,5-triene Chemical group C1C=CC=CC=C1 CHVJITGCYZJHLR-UHFFFAOYSA-N 0.000 description 3
- 125000001162 cycloheptenyl group Chemical group C1(=CCCCCC1)* 0.000 description 3
- MGNZXYYWBUKAII-UHFFFAOYSA-N cyclohexa-1,3-diene Chemical group C1CC=CC=C1 MGNZXYYWBUKAII-UHFFFAOYSA-N 0.000 description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 125000002636 imidazolinyl group Chemical group 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 3
- ZLTPDFXIESTBQG-UHFFFAOYSA-N isothiazole Chemical group C=1C=NSC=1 ZLTPDFXIESTBQG-UHFFFAOYSA-N 0.000 description 3
- 125000000842 isoxazolyl group Chemical group 0.000 description 3
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 3
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 3
- 125000002971 oxazolyl group Chemical group 0.000 description 3
- 238000000206 photolithography Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 125000003226 pyrazolyl group Chemical group 0.000 description 3
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical group C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- MNCMBBIFTVWHIP-UHFFFAOYSA-N 1-anthracen-9-yl-2,2,2-trifluoroethanone Chemical group C1=CC=C2C(C(=O)C(F)(F)F)=C(C=CC=C3)C3=CC2=C1 MNCMBBIFTVWHIP-UHFFFAOYSA-N 0.000 description 2
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 2
- 125000003229 2-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 2
- 125000004105 2-pyridyl group Chemical group N1=C([*])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- 125000003349 3-pyridyl group Chemical group N1=C([H])C([*])=C([H])C([H])=C1[H] 0.000 description 2
- 125000000339 4-pyridyl group Chemical group N1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 2
- JHYLKGDXMUDNEO-UHFFFAOYSA-N [Mg].[In] Chemical compound [Mg].[In] JHYLKGDXMUDNEO-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 2
- 125000003282 alkyl amino group Chemical group 0.000 description 2
- 125000004414 alkyl thio group Chemical group 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 125000000304 alkynyl group Chemical group 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
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 2
- 125000002078 anthracen-1-yl 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 2
- 125000000748 anthracen-2-yl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C([H])=C([*])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 2
- 125000005577 anthracene group Chemical group 0.000 description 2
- 125000005161 aryl oxy carbonyl group Chemical group 0.000 description 2
- 125000005110 aryl thio group Chemical group 0.000 description 2
- RFRXIWQYSOIBDI-UHFFFAOYSA-N benzarone Chemical compound CCC=1OC2=CC=CC=C2C=1C(=O)C1=CC=C(O)C=C1 RFRXIWQYSOIBDI-UHFFFAOYSA-N 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 229940125782 compound 2 Drugs 0.000 description 2
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical group C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 125000005553 heteroaryloxy group Chemical group 0.000 description 2
- 125000005226 heteroaryloxycarbonyl group Chemical group 0.000 description 2
- 125000005368 heteroarylthio group Chemical group 0.000 description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 2
- 125000001041 indolyl group Chemical group 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- SJCKRGFTWFGHGZ-UHFFFAOYSA-N magnesium silver Chemical compound [Mg].[Ag] SJCKRGFTWFGHGZ-UHFFFAOYSA-N 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 125000004370 n-butenyl group Chemical group [H]\C([H])=C(/[H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 150000004866 oxadiazoles Chemical class 0.000 description 2
- 238000000059 patterning Methods 0.000 description 2
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 2
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical group C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 125000001792 phenanthrenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C=CC12)* 0.000 description 2
- 238000001420 photoelectron spectroscopy Methods 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 125000002294 quinazolinyl group Chemical group N1=C(N=CC2=CC=CC=C12)* 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 2
- 239000012780 transparent material Substances 0.000 description 2
- 125000004665 trialkylsilyl group Chemical group 0.000 description 2
- 125000005580 triphenylene group Chemical group 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 238000003631 wet chemical etching Methods 0.000 description 2
- UWRZIZXBOLBCON-VOTSOKGWSA-N (e)-2-phenylethenamine Chemical class N\C=C\C1=CC=CC=C1 UWRZIZXBOLBCON-VOTSOKGWSA-N 0.000 description 1
- OZXIZRZFGJZWBF-UHFFFAOYSA-N 1,3,5-trimethyl-2-(2,4,6-trimethylphenoxy)benzene Chemical group CC1=CC(C)=CC(C)=C1OC1=C(C)C=C(C)C=C1C OZXIZRZFGJZWBF-UHFFFAOYSA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- VERMWGQSKPXSPZ-BUHFOSPRSA-N 1-[(e)-2-phenylethenyl]anthracene Chemical class C=1C=CC2=CC3=CC=CC=C3C=C2C=1\C=C\C1=CC=CC=C1 VERMWGQSKPXSPZ-BUHFOSPRSA-N 0.000 description 1
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 1
- TVEXGJYMHHTVKP-UHFFFAOYSA-N 6-oxabicyclo[3.2.1]oct-3-en-7-one Chemical compound C1C2C(=O)OC1C=CC2 TVEXGJYMHHTVKP-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910000799 K alloy Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 1
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 1
- OWXLRKWPEIAGAT-UHFFFAOYSA-N [Mg].[Cu] Chemical compound [Mg].[Cu] OWXLRKWPEIAGAT-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- HAQFCILFQVZOJC-UHFFFAOYSA-N anthracene-9,10-dione;methane Chemical compound C.C.C1=CC=C2C(=O)C3=CC=CC=C3C(=O)C2=C1 HAQFCILFQVZOJC-UHFFFAOYSA-N 0.000 description 1
- 150000008425 anthrones Chemical class 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
- 150000007980 azole derivatives Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- BHXFKXOIODIUJO-UHFFFAOYSA-N benzene-1,4-dicarbonitrile Chemical compound N#CC1=CC=C(C#N)C=C1 BHXFKXOIODIUJO-UHFFFAOYSA-N 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000000609 electron-beam lithography Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 150000008376 fluorenones Chemical class 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 238000001506 fluorescence spectroscopy Methods 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 150000007857 hydrazones Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002460 imidazoles Chemical class 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
- VVVPGLRKXQSQSZ-UHFFFAOYSA-N indolo[3,2-c]carbazole Chemical class C1=CC=CC2=NC3=C4C5=CC=CC=C5N=C4C=CC3=C21 VVVPGLRKXQSQSZ-UHFFFAOYSA-N 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229940079865 intestinal antiinfectives imidazole derivative Drugs 0.000 description 1
- LAQPNDIUHRHNCV-UHFFFAOYSA-N isophthalonitrile Chemical compound N#CC1=CC=CC(C#N)=C1 LAQPNDIUHRHNCV-UHFFFAOYSA-N 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 125000002183 isoquinolinyl group Chemical group C1(=NC=CC2=CC=CC=C12)* 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000001748 luminescence spectrum Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- SHOJXDKTYKFBRD-UHFFFAOYSA-N mesityl oxide Natural products CC(C)=CC(C)=O SHOJXDKTYKFBRD-UHFFFAOYSA-N 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000006606 n-butoxy group Chemical group 0.000 description 1
- 125000003506 n-propoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000004893 oxazines Chemical class 0.000 description 1
- 150000007978 oxazole derivatives Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 150000004986 phenylenediamines Chemical class 0.000 description 1
- 108091008695 photoreceptors Proteins 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 description 1
- XOFYZVNMUHMLCC-ZPOLXVRWSA-N prednisone Chemical compound O=C1C=C[C@]2(C)[C@H]3C(=O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 XOFYZVNMUHMLCC-ZPOLXVRWSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 150000003219 pyrazolines Chemical class 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 229940042055 systemic antimycotics triazole derivative Drugs 0.000 description 1
- 150000004867 thiadiazoles Chemical class 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- IBBLKSWSCDAPIF-UHFFFAOYSA-N thiopyran Chemical compound S1C=CC=C=C1 IBBLKSWSCDAPIF-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 125000004306 triazinyl group Chemical group 0.000 description 1
- 150000003852 triazoles Chemical group 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
Landscapes
- Electroluminescent Light Sources (AREA)
Abstract
The present invention provides an organic electroluminescent element capable of obtaining high luminous efficiency even in the case where the LUMO level of a fluorescent material is lower than that of a delayed fluorescent material. An organic electroluminescent element comprising a 1 st organic compound, a 2 nd organic compound as a delayed fluorescent material, and a 3 rd organic compound which emits fluorescence, wherein the energy of LUMO of the 2 nd organic compound is higher than that of the 3 rd organic compound, the maximum component of luminescence from the element is fluorescence from the 3 rd organic compound, and the orientation value of the 3 rd organic compound in the light-emitting layer is-0.3 or less.
Description
Technical Field
The present invention relates to an organic electroluminescent device having high luminous efficiency.
Background
Research is actively being conducted to improve the light emission efficiency of an organic electroluminescent element (organic EL element). In particular, various studies have been made on the use of the material composition of the light-emitting layer of an organic electroluminescent element to convert the energy of the excited triplet state, which causes the non-radiative deactivation at room temperature, to the lowest excited singlet state energy for light emission.
For example, patent document 1 proposes a 3-component organic electroluminescent device in which a light-emitting layer is composed of a host material, a delayed fluorescent material, and a fluorescent material. In the light-emitting layer, the excited triplet energy from the host material to the delayed fluorescent material and the excited triplet energy generated by the delayed fluorescent material are converted to the excited singlet energy by the intersystem crossing from the triplet state to the singlet state in the delayed fluorescent material, and are moved into the fluorescent material and act as fluorescent radiation. Thus, the triplet excitation energy generated by the light-emitting layer is effectively used for light emission of the fluorescent material, and high light emission efficiency can be obtained.
Technical literature of the prior art
Patent literature
Patent document 1: japanese patent laid-open No. 2015-179809
Disclosure of Invention
Technical problem to be solved by the invention
Various fluorescent materials are being developed in which the emission wavelength depends on the energy gap between HOMO-LUMO and stokes shift, and these energy values are different. Therefore, in the above-described 3-component light-emitting layer, the energy of the LUMO of the fluorescent material may be higher than that of the LUMO of the delayed fluorescent material by the fluorescent material used, and may be lower (deeper) than that. In this case, the inventors have found that when the energy of LUMO of the fluorescent material is lower than that of LUMO of the delayed fluorescent material, the light-emitting efficiency is lowered and cannot be sufficiently improved by increasing the concentration of the fluorescent material, as a result of forming the light-emitting layer by combining various delayed fluorescent materials and fluorescent materials with the host material.
Accordingly, the present inventors have made intensive studies with a view to providing an organic electroluminescent element comprising a host material, a delayed fluorescent material, and a fluorescent material in a light-emitting layer, wherein a high light-emitting efficiency can be obtained even when the energy of the LUMO of the fluorescent material is lower than that of the delayed fluorescent material.
Means for solving the technical problems
As a result of intensive studies, the present inventors have found that even when the energy of LUMO of a fluorescent material is lower than that of LUMO of a delayed fluorescent material, if the orientation value S of organic compound molecules used as the fluorescent material is-0.3 or less, the concentration of the fluorescent material can be increased to improve the luminous efficiency.
The present invention has been made in view of such an insight, and specifically has the following structure.
An organic electroluminescent element having an anode, a cathode, and at least one organic layer including a light-emitting layer between the anode and the cathode, wherein,
the light-emitting layer comprises a 1 st organic compound, a 2 nd organic compound and a 3 rd organic compound, and satisfies the following formula (a) and the following formula (b),
the 2 nd organic compound is a delayed fluorescent material,
the maximum component of luminescence from the element is fluorescence from the 3 rd organic compound.
[ number 1]
E LUMO (2)＞E LUMO (3) (a)
S is less than or equal to 0.3 type (b)
[ wherein,
E LUMO (2) Represents the energy of LUMO of the 2 nd organic compound,
E LUMO (3) Represents the energy of LUMO of the 3 rd organic compound,
s represents an orientation value of the 3 rd organic compound in the light emitting layer. ]
[2] The organic electroluminescent element according to [1], wherein,
the concentration of the 3 rd organic compound in the light emitting layer is greater than 0.3 wt%.
[3] The organic electroluminescent element according to [1] or [2], wherein,
the 3 rd organic compound is a compound which contains a boron atom and a nitrogen atom exhibiting a multiple resonance effect and has a condensed ring structure having four or more ring numbers.
[4] The organic electroluminescent element as described in any one of [1] to [3], wherein,
the 3 rd organic compound has a structure in which a hetero 6-membered ring containing a boron atom and a nitrogen atom is condensed with a pyrrole ring sharing a nitrogen atom and two benzene rings.
[5] The organic electroluminescent element as described in any one of [1] to [4], wherein,
the 3 rd organic compound is a compound represented by the following general formula (16).
General formula (16)
[ chemical formula 1]
[ in the general formula (16), X 1 X is X 2 One of which is a nitrogen atom and the other is a boron atom.
R 1 ～R 26 、A 1 、A 2 Each independently represents a hydrogen atom, a deuterium atom or a substituent. R is R 1 And R is 2 、R 2 And R is 3 、R 3 And R is 4 、R 4 And R is 5 、R 5 And R is 6 、R 6 And R is 7 、R 7 And R is 8 、R 8 And R is 9 、R 9 And R is 10 、R 10 And R is 11 、R 11 And R is 12 、R 13 And R is 14 、R 14 And R is 15 、R 15 And R is 16 、R 16 And R is 17 、R 17 And R is 18 、R 18 And R is 19 、R 19 And R is 20 、R 20 And R is 21 、R 21 And R is 22 、R 22 And R is 23 、R 23 And R is 24 、R 24 And R is 25 、R 25 And R is 26 Can be bonded to each other to form a ring structure. Wherein when X is 1 R is a nitrogen atom 17 And R is 18 Are bonded to each other as a single bond and form a pyrrole ring. When X is 2 R is a nitrogen atom 21 And R is 22 Are bonded to each other as a single bond and form a pyrrole ring. Wherein X is 1 Is a nitrogen atom, and R 7 And R is 8 R is R 21 And R is 22 Bonded via nitrogen atoms to form a 6-membered ring when R 17 And R is 18 R when bonded to each other to form a single bond 1 ～R 6 At least one of which is substituted or unsubstituted aryl, or R 1 And R is 2 、R 2 And R is 3 、R 3 And R is 4 、R 4 And R is 5 、R 5 And R is 6 Any one of them is bonded to each other to form an aromatic ring or a heteroaromatic ring.]
[6] The organic electroluminescent element as described in any one of [1] to [5], wherein,
the concentration of the 2 nd organic compound in the light-emitting layer is 25 wt% or more.
[7] The organic electroluminescent element as described in any one of [1] to [6], wherein,
the 2 nd organic compound has a structure in which 1 to 2 cyano groups and at least one donor group are bonded to a benzene ring.
[8] The organic electroluminescent element according to [7], wherein,
the donor group has a structure in which a benzene ring constituting a carbazol-9-yl group is condensed with a substituted or unsubstituted benzofuran ring.
[9] The organic electroluminescent element according to [8], wherein,
the donor group is a substituted or unsubstituted 5H-benzofuran [3,2-c ] carbazol-5-yl group.
[10] The organic electroluminescent element as described in any one of [7] to [9], wherein,
the benzene ring is bonded to the donor group by three or more groups.
[11] The organic electroluminescent element as described in any one of [1] to [10], wherein,
the 1 st organic compound, the 2 nd organic compound, and the 3 rd organic compound satisfy the following formula (a 1).
E LUMO (1)＞E LUMO (2)＞E LUMO (3) (a 1)
Wherein,
[E LUMO (1) Represents the energy of LUMO of the 1 st organic compound,
E LUMO (2) Represents the energy of LUMO of the 2 nd organic compound,
E LUMO (3) L representing the 3 rd organic compoundThe energy of UMO is provided to the heat exchanger,
s represents an orientation value of the 3 rd organic compound in the light emitting layer. ]
Effects of the invention
According to the present invention, in an organic electroluminescent element including a1 st organic compound, a 2 nd organic compound as a delayed fluorescent material, and a 3 rd organic compound that emits fluorescence in a light-emitting layer, even in a case where the energy of LUMO of the 3 rd organic compound is lower than that of LUMO of the 2 nd organic compound, the light-emitting efficiency can be improved by increasing the concentration of the 3 rd organic compound.
Detailed Description
Hereinafter, the present invention will be described in detail. The following description of the constituent elements is sometimes made on the basis of representative embodiments or embodiments of the present invention, but the present invention is not limited to such embodiments or embodiments. In this context, the use of the numerical range indicated by "to" means a range including the numerical values described before and after "to" as the lower limit value and the upper limit value. In this context, "consisting of" means that the composition described above consists of "only," and does not include other contents. In addition, part or all of hydrogen atoms present in the molecule of the compound used in the present invention may be replaced with deuterium atoms [ (] 2 H. Deuterium D). In the chemical structural formulae herein, a hydrogen atom is represented by H or its representation is omitted. For example, when an atom bonded to a carbon atom constituting the ring skeleton of the benzene ring is omitted, it is assumed that the atom is bonded to the carbon atom constituting the ring skeleton at the omitted position H. In this context, the term "substituent" means an atom or group of atoms other than a hydrogen atom and a deuterium atom. On the other hand, the expression "substituted or unsubstituted" "" may be substituted "means that the hydrogen atom may be substituted with a deuterium atom or a substituent. In the present invention, "transparent" means that the transmittance of visible light is 50% or more, preferably 80% or more, more preferably 90% or more, and still more preferably 99% or more. Regarding the transmittance of visible light, measurement can be performed by an ultraviolet-visible spectrophotometer.
The organic electroluminescent element of the present invention has an anode, a cathode, and at least one organic layer including a light-emitting layer between the anode and the cathode. The organic layer may be composed of only the light-emitting layer, or may include an organic layer other than the light-emitting layer. For example, an organic layer may or may not be present between the anode and the light-emitting layer, and between the light-emitting layer and the cathode, respectively. In other words, the anode and the light-emitting layer may be stacked in direct contact or may not be stacked in direct contact. The light-emitting layer and the cathode may be stacked in direct contact or may not be stacked in direct contact. The light-emitting layer is preferably located between the anode and the cathode, and the entire light-emitting layer is preferably arranged in a non-protruding state in a region between the anode and the cathode.
The organic electroluminescent element of the present invention may have a substrate supporting at least one organic layer including an anode, a cathode, and a light-emitting layer. In this case, the substrate may be disposed on the side opposite to the light-emitting layer of the anode or on the side opposite to the light-emitting layer of the cathode. The organic electroluminescent element of the present invention may be a top emission type element in which most of the light is emitted from the side opposite to the substrate, or a bottom emission type element in which most of the light is emitted from the substrate side. The term "most of the light" means that the amount of light emitted from the element is 60% or more.
The organic electroluminescent element of the present invention comprises the 1 st organic compound, the 2 nd organic compound and the 3 rd organic compound in the light-emitting layer. Wherein the 2 nd organic compound is a delayed fluorescent material. The 3 rd organic compound is a compound that emits fluorescence. In the organic electroluminescent element of the present invention, the maximum component of the luminescence from the element is the fluorescence from the 3 rd organic compound.
The 2 nd organic compound and the 3 rd organic compound contained in the light-emitting layer satisfy the following formulas (a) and (b).
E LUMO (2)＞E LUMO (3) (a)
S is less than or equal to-0.3 type (b)
In one aspect of the present invention, the 1 st organic compound, the 2 nd organic compound, and the 3 rd organic compound contained in the light-emitting layer satisfy the following formulas (a 1) and (b).
E LUMO (1)＞E LUMO (2)＞E LUMO (3) (a 1)
S is less than or equal to-0.3 type (b)
E in the formula (a) and the formula (a 1) LUMO (1) Represents the energy, E, of the LUMO of the 1 st organic compound LUMO (2) Represents the energy, E, of the LUMO of the 2 nd organic compound LUMO (3) Represents the energy of LUMO of the 3 rd organic compound. LUMO is an abbreviation for Lowest Unoccupied Molecular Orbital (lowest unoccupied molecular orbital) and can be found by atmospheric photoelectron spectroscopy (RIKEN KEIKI co., ltd. AC-3, etc.).
The present invention satisfies the relation of formula (a), and therefore the energy of LUMO of the 2 nd organic compound contained in the light-emitting layer is higher than that of LUMO of the 3 rd organic compound. When the relation of the formula (a 1) is satisfied, the energy of LUMO of the 1 st organic compound is highest, the 2 nd organic compound is next highest, and then the 3 rd organic compound is lowest among the 1 st organic compound, the 2 nd organic compound, and the 3 rd organic compound contained in the light-emitting layer. Energy difference of LUMO [ E LUMO (1)-E LUMO (2)]For example, the energy storage device can be set in a range of 0.1eV or more, in a range of 0.5eV or more, in a range of 0.8eV or more, or in a range of 1.0eV or more, and can be set in a range of 2.0eV or less, in a range of 1.5eV or less, in a range of 1.3eV or less, or in a range of 1.1eV or less. Energy difference of LUMO [ E LUMO (2)-E LUMO (3)]For example, the energy storage device can be set in a range of 0.01eV or more, in a range of 0.05eV or more, in a range of 0.1eV or more, in a range of 0.15eV or more, or in a range of 0.2eV or more, and can be set in a range of 0.7eV or less, in a range of 0.5eV or less, in a range of 0.4eV or less, or in a range of 0.3eV or less. In an aspect of the present invention, a compound having an energy of LUMO in the range of-2.0 to-5.0 eV or a compound in the range of-2.5 to-4.0 eV can be employed as the 1 st organic compound. In one aspect of the invention, the energy of the LUMO can be used inAs the 2 nd organic compound, a compound in the range of-2.0 to-5.0 eV or a compound in the range of-2.5 to-4.0 eV is used. In addition, in one aspect of the present invention, a compound having an energy of LUMO in the range of-2.0 to-5.0 eV or a compound having an energy in the range of-2.5 to-4.0 eV can be used as the 3 rd organic compound.
The HOMO energy relationship of the 1 st organic compound, the 2 nd organic compound, and the 3 rd organic compound is not particularly limited. For example, the energy of the HOMO of the 2 nd organic compound may be greater than or less than the energy of the HOMO of the 1 st organic compound, or may be the same as the energy of the HOMO of the 1 st organic compound. The energy of HOMO of the 3 rd organic compound may be larger or smaller than the energy of HOMO of the 2 nd organic compound, or may be the same as the energy of HOMO of the 2 nd organic compound. HOMO is an abbreviation for Highest occupied Molecular Orbital (highest occupied molecular orbital) and can be determined by atmospheric photoelectron spectroscopy (RIKEN KEIKI co., ltd. AC-3, etc.). In one aspect of the present invention, a compound having an energy of HOMO in the range of-4.0 to-6.5 eV or a compound in the range of-5.5 to-6.2 eV can be used as the 1 st organic compound. In one aspect of the present invention, a compound having an energy of HOMO in the range of-4.0 to-6.5 eV or a compound in the range of-5.5 to-6.2 eV can be used as the 2 nd organic compound. In addition, in one aspect of the present invention, a compound having an energy of HOMO in the range of-4.0 to-6.5 eV or a compound having an energy of-5.0 to-6.0 eV can be used as the 3 rd organic compound.
S in the formula (b) represents an orientation value of the 3 rd organic compound in the light emitting layer. The present invention satisfies the formula (b), and thus the orientation value of the 3 rd organic compound in the light-emitting layer is-0.3 or less. The orientation value is also referred to as an S value, and is an index indicating the degree of orientation of the 3 rd organic compound in the light-emitting layer. The larger the negative value (smaller the value), the higher the orientation. The orientation value (S value) can be determined by the method described in Scientific Reports 2017,7,8405. In the organic electroluminescent element of the present invention, the 3 rd organic compound has an orientation value of-0.3 or less, whereby a high external quantum yield can be achieved while satisfying the LUMO energy relationship of the formula (a). That is, in the conventional organic electroluminescent element in which the orientation value of the fluorescent material is not considered, when the energy of the LUMO of the fluorescent material is lower than the energy of the LUMO of the delayed fluorescent material, if the concentration of the fluorescent material is increased, there is a problem that the light emission efficiency is lowered. In contrast, in the organic electroluminescent element of the present invention, the energy of LUMO of the 3 rd organic compound that emits fluorescence is set to be lower than the energy of LUMO of the 2 nd organic compound that is a delayed fluorescent material, but by setting the orientation value of the 3 rd organic compound in the light-emitting layer to-0.3 or less, it is possible to achieve an improvement in light-emitting efficiency while increasing the concentration of the 3 rd organic compound. Further, the 3 rd organic compound having an orientation value of-0.3 or less achieves an effect of high stability and improving the element lifetime by using it as a light-emitting material. The orientation value of the 3 rd organic compound in the light-emitting layer is preferably-0.38 or less, more preferably-0.40 or less, further preferably-0.41 or less, and further preferably-0.42 or less.
The 1 st organic compound, the 2 nd organic compound, and the 3 rd organic compound contained in the light-emitting layer preferably satisfy the following formula (c).
E S1 (1)＞E S1 (2)＞E S1 (3) (c)
E in formula (c) S1 (1) Represents the lowest excited singlet energy, E, of the 1 st organic compound S1 (2) Represents the lowest excited singlet energy, E, of the 2 nd organic compound S1 (3) Represents the lowest excited singlet energy of the 3 rd organic compound. Herein, eV is taken as a unit. Regarding the lowest excited singlet energy, it is possible to obtain a compound of interest by preparing a thin film of the compound of interest or toluene solution (concentration 10 -5 mol/L) and measured by fluorescence spectroscopy at normal temperature (300K) (for details, refer to the measurement method of the lowest excited singlet energy in the column for description of the 2 nd organic compound).
As shown in formula (c), it is preferable that the lowest excited singlet energy of the 1 st organic compound is largest, the 2 nd organic compound is the second largest, and then the 3 rd organic compound is the smallest among the 1 st organic compound, the 2 nd organic compound, and the 3 rd organic compound contained in the light emitting layer. E (E) S1 (1)-E S1 (2) For example, the energy storage device can be set in a range of 0.20eV or more, in a range of 0.40eV or more, or in a range of 0.60eV or more, and can be set in a range of 1.50eV or less, in a range of 1.20eV or less, or in a range of 0.80eV or less. E (E) S1 (2)-E S1 (3) For example, the energy storage device can be set in a range of 0.05eV or more, in a range of 0.10eV or more, or in a range of 0.15eV or more, and can be set in a range of 0.50eV or less, in a range of 0.30eV or less, or in a range of 0.20eV or less. E (E) S1 (1)-E S1 (3) For example, the energy storage device can be set in a range of 0.25eV or more, in a range of 0.45eV or more, or in a range of 0.65eV or more, and can be set in a range of 2.00eV or less, in a range of 1.70eV or less, or in a range of 1.30eV or less.
In the organic electroluminescent element of the present invention, the maximum component of luminescence from the element is fluorescence from the 3 rd organic compound. The term "light emission from the element" in the present invention means light emitted from the element when the element is driven at 20 ℃. In the light emission from the organic electroluminescent element of the present invention, the maximum component of the light emission from the element may include phosphorescence from the 3 rd organic compound, luminescence from the 1 st organic compound and luminescence from the 2 nd organic compound, as long as the component is fluorescence from the 3 rd organic compound, but these luminescence are preferably less than the luminescence from the 3 rd organic compound. In the present invention, 70% or more of the luminescence from the element may be fluorescence from the 3 rd organic compound, 90% or more may be fluorescence from the 3 rd organic compound, and 99% or more may be fluorescence from the 3 rd organic compound.
The concentration of the 3 rd organic compound in the light-emitting layer of the organic electroluminescent element of the present invention is preferably more than 0.3 wt%. The concentration of the 3 rd organic compound in the light-emitting layer may be in the range of 0.35 wt% or more, in the range of 0.5 wt% or more, in the range of 1 wt% or more, or in the range of 2 wt% or more. The concentration of the 3 rd organic compound in the light-emitting layer can be set in a range of 10 wt% or less, in a range of 5 wt% or less, or in a range of 3 wt% or less.
Further, when the concentrations of the 1 st organic compound, the 2 nd organic compound, and the 3 rd organic compound in the light-emitting layer of the organic electroluminescent element of the present invention are respectively represented by Conc (1), conc (2), and Conc (3), it is preferable that the relationship of the following formula (d) be satisfied.
Conc (1) > Conc (2) > Conc (3) formula (d)
The Conc (1) is preferably 30 wt% or more, can be set in a range of 50 wt% or more or in a range of 60 wt% or more, and can be set in a range of 99 wt% or less, in a range of 85 wt% or less, or in a range of 70 wt% or less.
The Conc (2) is preferably 5 wt% or more, can be set in a range of 15 wt% or more, 25 wt% or more, or 30 wt% or more, and can be set in a range of 45 wt% or less, 40 wt% or less, or 35 wt% or less. In a preferred aspect of the invention, conc (2) is 25 to 45% by weight.
Regarding the preferable range of Conc (3), the description of the concentration of the 3 rd organic compound in the light-emitting layer can be referred to.
The Conc (1)/Conc (3) may be set in a range of 10 or more, 50 or more, or 90 or more, and may be set in a range of 10000 or less, 1000 or less, or 200 or less.
The Conc (2)/Conc (3) may be set in a range of 10 or more, 50 or more, or 90 or more, and may be set in a range of 10000 or less, 1000 or less, or 200 or less.
The light-emitting layer of the organic electroluminescent element of the present invention preferably does not contain a metal element other than boron. Further, a light-emitting layer containing no boron-containing metal element can be used. For example, the light-emitting layer can be composed of only a compound composed of an atom selected from the group consisting of a carbon atom, a hydrogen atom, a nitrogen atom, an oxygen atom, a sulfur atom, a fluorine atom, and a boron atom. For example, the light-emitting layer can be composed of only a compound composed of an atom selected from the group consisting of a carbon atom, a hydrogen atom, a nitrogen atom, an oxygen atom, a sulfur atom, a fluorine atom, and a boron atom. For example, the light-emitting layer can be composed of only a compound composed of an atom selected from the group consisting of a carbon atom, a hydrogen atom, a nitrogen atom, an oxygen atom, and a sulfur atom. For example, the light-emitting layer can be composed of only a compound composed of an atom selected from the group consisting of a carbon atom, a hydrogen atom, a nitrogen atom, and an oxygen atom.
(1 st organic Compound)
The 1 st organic compound used for the light-emitting layer of the organic electroluminescent element of the present invention is selected from compounds having lower energy than the 2 nd organic compound and the 3 rd organic compound in LUMO. The 1 st organic compound is preferably selected from compounds having a higher energy of LUMO than the 2 nd organic compound and the 3 rd organic compound and having a higher minimum excited singlet energy than the 2 nd organic compound and the 3 rd organic compound. The 1 st organic compound preferably has a function in the form of a host material responsible for the transport carrier. The 1 st organic compound preferably has a function of confining the energy of the 3 rd organic compound to the compound. Thus, the 3 rd organic compound can efficiently convert energy generated by recombination of holes and electrons in the molecule and energy received from the 1 st organic compound and the 2 nd organic compound into luminescence.
The 1 st organic compound is preferably an organic compound having a hole transporting ability and an electron transporting ability, preventing a longer wavelength of light emission, and having a high glass transition temperature. Also, in a preferred aspect of the present invention, the 1 st organic compound is selected from compounds that do not radiate delayed fluorescence. The light emission from the 1 st organic compound is preferably less than 1% of the light emission from the organic electroluminescent element of the present invention, more preferably less than 0.1%, and for example, may be less than 0.01% and less than the detection limit.
The 1 st organic compound preferably does not contain a metal atom. For example, as the 1 st organic compound, a compound composed of an atom selected from the group consisting of a carbon atom, a hydrogen atom, a nitrogen atom, an oxygen atom, and a sulfur atom can be selected. For example, as the 1 st organic compound, a compound composed of an atom selected from the group consisting of a carbon atom, a hydrogen atom, a nitrogen atom, and an oxygen atom can be selected. For example, as the 1 st organic compound, a compound composed of a carbon atom, a hydrogen atom, and a nitrogen atom can be selected.
Hereinafter, preferred compounds that can be used as the 1 st organic compound are exemplified.
[ chemical formula 2-1]
[ chemical formula 2-2]
[ chemical formulas 2-3]
[ chemical formulas 2-4]
(2 nd organic Compound)
The 2 nd organic compound used in the light-emitting layer of the organic electroluminescent element of the present invention is a delayed fluorescent material having lower energy than the 1 st organic compound and higher energy than the 3 rd organic compound. The 2 nd organic compound is preferably a delayed fluorescent material having a LUMO of lower energy than the 1 st organic compound, a LUMO of higher energy than the 3 rd organic compound, and a lowest excited singlet energy smaller than the 1 st organic compound and larger than the 3 rd organic compound. The "delayed fluorescent material" in the present invention is an organic compound that generates an intersystem crossing from an excited triplet state to an excited singlet state in an excited state and radiates fluorescence (delayed fluorescence) when returning from the excited singlet state to a ground state. In the present invention, when the luminescence lifetime is measured by a fluorescence lifetime measurement system (Hamamatsu Photonics k.k. Stripe camera system, etc.), a material in which fluorescence having a luminescence lifetime of 100ns (nanosecond) or more is observed is referred to as a delayed fluorescence material. The 2 nd organic compound is a material capable of radiating delayed fluorescence, but when used in the organic electroluminescent element of the present invention, it is not necessary to radiate delayed fluorescence from the 2 nd organic compound. The light emission from the 2 nd organic compound is preferably less than 10% of the light emission from the organic electroluminescent element of the present invention, and may be, for example, less than 1%, less than 0.1%, less than 0.01% and less than the detection limit.
In the organic electroluminescent element of the present invention, the 2 nd organic compound receives energy from the 1 st organic compound in an excited singlet state and transits to the excited singlet state. Further, the 2 nd organic compound may receive energy from the 1 st organic compound in the excited triplet state and transit to the excited triplet state. Difference between excited singlet energy and excited triplet energy of the 2 nd organic compound (ΔE ST ) Small, so that the 2 nd organic compound in the excited triplet state easily reverses intersystem crossing to the 2 nd organic compound in the excited singlet state. The 2 nd organic compound of the excited singlet state generated through these paths provides energy to the 3 rd organic compound to transition the 3 rd organic compound to the excited singlet state.
The difference ΔE between the lowest excited singlet energy of the 2 nd organic compound and the lowest excited triplet energy of 77K ST Preferably 0.3eV or less, more preferably 0.25eV or less, more preferably 0.2eV or less, more preferably 0.15eV or less, more preferably 0.1eV or less, more preferably 0.07eV or less, still more preferably 0.05eV or less, still more preferably 0.03eV or less, and particularly preferably 0.01eV or less.
If delta E ST Since the organic compound 2 is easily transferred from the excited singlet-reverse system to the excited triplet state due to the absorption of thermal energy, the organic compound functions as a thermally activated delayed fluorescent material . The thermally activated delayed fluorescent material absorbs heat emitted from the device and relatively easily crosses from the excited triplet inversion system to the excited singlet state, thereby enabling the excited triplet state to be energy-efficiently contributing to light emission.
The lowest excited singlet energy (E) of the compounds of the present invention S1 ) And the lowest excited triplet energy (E T1 ) The value obtained by the following procedure was used. ΔE ST To calculate E S1 -E T1 And the obtained value.
(1) Minimum excited singlet energy (E S1 )
Preparation of thin film of Compound to be measured or toluene solution (concentration 10 -5 mol/L) was used as a sample. The fluorescence spectrum of the sample was measured at room temperature (300K). In the fluorescence spectrum, the vertical axis represents luminescence, and the horizontal axis represents wavelength. A tangential line is drawn with respect to the rise of the short wavelength side of the light emission spectrum, and the wavelength value λedge [ nm ] of the intersection of the tangential line and the horizontal axis is obtained]. The value obtained by converting the wavelength value into an energy value by the following conversion equation is set as E S1 。
Conversion formula: e (E) S1 [eV]＝1239.85/λedge
As for measurement of the luminescence spectrum in the later-described examples, an LED light source (Thorlabs, inc., M300L 4) was used as an excitation light source, and was performed by a detector (Hamamatsu Photonics k.k., PMA-12 multichannel spectrometer C10027-01).
(2) Minimum excited triplet energy (E) T1 )
Will be aligned with the energy of the lowest excited singlet state (E S1 ) The same sample used in the measurement of (C) was cooled to 77[ K ]]Excitation light (300 nm) was irradiated onto a sample for phosphorescence measurement, and phosphorescence was measured using a detector. The luminescence 100 milliseconds after the irradiation of the excitation light was used as a phosphorescence spectrum. A tangential line is drawn with respect to the rise of the phosphorescence spectrum on the short wavelength side, and the wavelength value λedge [ nm ] of the intersection point of the tangential line and the transverse axis is obtained]. The value obtained by converting the wavelength value into an energy value by the following conversion equation is set as E T1 。
Conversion formula: e (E) T1 [eV]＝1239.85/λedge
The tangent to the rise on the short wavelength side of the phosphorescence spectrum is drawn as follows. Consider a case where, from the short wavelength side of the phosphorescence spectrum, the spectrum curve moves to the maximum on the shortest wavelength side of the maximum values of the spectrum, toward the tangent line at each point on the curve on the long wavelength side. The tangent line increases in slope as the curve rises (i.e., as the longitudinal axis increases). The tangential line drawn at the point where the slope value takes the maximum value is defined as the tangential line rising toward the short wavelength side of the phosphorescence spectrum.
The maximum point of the peak intensity having 10% or less of the maximum peak intensity of the spectrum does not include the maximum value on the shortest wavelength side, and a tangential line drawn at a point closest to the maximum value on the shortest wavelength side and having a maximum value of the slope is defined as a tangential line rising on the short wavelength side of the phosphorescence spectrum.
The 2 nd organic compound preferably does not contain a metal atom. For example, as the 2 nd organic compound, a compound composed of an atom selected from the group consisting of a carbon atom, a hydrogen atom, a nitrogen atom, an oxygen atom, and a sulfur atom can be selected. For example, as the 2 nd organic compound, a compound composed of an atom selected from the group consisting of a carbon atom, a hydrogen atom, a nitrogen atom, and an oxygen atom can be selected. For example, as the 2 nd organic compound, a compound composed of a carbon atom, a hydrogen atom, and a nitrogen atom can be selected.
Typical 2 nd organic compounds include compounds having a structure in which 1 to 2 cyano groups and at least one donor group are bonded to a benzene ring. As the donor group, for example, a substituted or unsubstituted carbazol-9-yl group can be preferably exemplified. For example, a compound in which three or more substituted or unsubstituted carbazole-9-yl groups are bonded to the benzene ring, a substituted or unsubstituted benzofuran ring, a substituted or unsubstituted benzothiophene ring, a substituted or unsubstituted indole ring, a substituted or unsubstituted indene ring, a compound in which each 5-membered ring portion of a substituted or unsubstituted indene ring is condensed with at least one of two benzene rings constituting carbazole-9-yl groups, or the like can be exemplified. Specific examples of the group having a structure in which a benzene ring constituting the carbazole-9-yl group is condensed with a substituted or unsubstituted benzofuran ring include substituted or unsubstituted 5H-benzofuran [3,2-c ] carbazol-5-yl.
As the 2 nd organic compound, a compound which is represented by the following general formula (1) and which delays fluorescence by radiation can be particularly preferably used.
General formula (1)
[ chemical formula 3]
In the general formula (1), X 1 ～X 5 Represents N or C-R. R represents a hydrogen atom, a deuterium atom or a substituent. When X is 1 ～X 5 When two or more of these groups represent C-R, these C-R groups may be the same as or different from each other. Wherein X is 1 ～X 5 At least one of which is C-D (D as described herein represents a donor group). When X is 1 ～X 5 In the case of C-R, Z represents an acceptor group.
Among the compounds represented by the general formula (1), a compound represented by the following general formula (2) is particularly preferable.
General formula (2)
[ chemical formula 4]
In the general formula (2), X 1 ～X 5 Represents N or C-R. R represents a hydrogen atom, a deuterium atom or a substituent. When X is 1 ～X 5 When two or more of these groups represent C-R, these C-R groups may be the same as or different from each other. Wherein X is 1 ～X 5 At least one of which is C-D (D as described herein represents a donor group).
In a preferred aspect of the invention, X 1 ～X 5 Neither is a C-CN. That is, it is a compound having a structure in which 1 to 2 cyano groups and at least one donor group are bonded to a benzene ring. In another preferred aspect of the inventionIn which only X 2 Represents C-CN, X 1 、X 3 ～X 5 Not the C-CN. That is, the compound has a structure in which at least one donor group is bonded to the benzene ring of isophthalonitrile. In another aspect of the invention, only X 3 Represents C-CN, X 1 、X 2 、X 4 、X 5 Not the C-CN. That is, the compound has a structure in which at least one donor group is bonded to the benzene ring of terephthalonitrile.
The acceptor group represented by Z in the general formula (1) is a group having a property of supplying electrons to the ring bonded to Z, and can be selected from, for example, groups having positive σp values of hamite. The donor group represented by D of the general formulae (1) and (2) is a group having an electron-attracting property with respect to the ring bonded to D, and can be selected from, for example, groups having a negative σp value of hamite. In the following, the acceptor group is sometimes referred to as a.
Here, the "hamite σp value" is a value proposed by l.p. hammett, which is a value for quantifying the influence of a substituent on the reaction rate or balance of a para-substituted benzene derivative. Specifically, the following formula holds between the substituent in the para-substituted benzene derivative and the reaction rate constant or equilibrium constant:
log(k/k 0 )＝ρσp
or (b)
log(K/K 0 )＝ρσp
A constant (σp) specific to the substituent in (a). In the above formula, k represents a velocity constant, k, of a benzene derivative having no substituent 0 Represents the rate constant of the benzene derivative substituted with a substituent, K represents the equilibrium constant of the benzene derivative having no substituent, K 0 The equilibrium constant of the benzene derivative substituted with the substituent is represented by ρ, and the reaction constant is determined by the type and condition of the reaction. For the description about "the σp value of Hammett" and the numerical value of each substituent in the present invention, reference can be made to the description about the σp value of Hansch, C.et al, chem.Rev.,91,165-195 (1991).
As specific examples of the acceptor group, a cyano group or an acceptor group preferable as A in the following general formulae (12) to (14) can be cited. Further, as a specific example of the donor group, a donor group preferable as D in the following general formulae (12) to (14) can be referred to.
In the general formula (1) and the general formula (2), X 1 ～X 5 Represents N or C-R, but at least one is C-D. X is X 1 ～X 5 The number of N in the formula (I) is 0 to 4, and X is exemplified as 1 And X 3 And X 5 、X 1 And X 3 、X 1 And X 4 、X 2 And X 3 、X 1 And X 5 、X 2 And X 4 X only 1 X only 2 X only 3 N. X is X 1 ～X 5 The number of C-D is 1 to 5, preferably 2 to 5. For example, X may be exemplified 1 And X 2 And X 3 And X 4 And X 5 、X 1 And X 2 And X 4 And X 5 、X 1 And X 2 And X 3 And X 4 、X 1 And X 3 And X 4 And X 5 、X 1 And X 3 And X 5 、X 1 And X 2 And X 5 、X 1 And X 2 And X 4 、X 1 And X 3 And X 4 、X 1 And X 3 、X 1 And X 4 、X 2 And X 3 、X 1 And X 5 、X 2 And X 4 X only 1 X only 2 X only 3 In the case of C-D. X is X 1 ～X 5 At least one of which may be C-se:Sub>A. A as described herein represents an acceptor group. X is X 1 ～X 5 The number of C-A in (2) is preferably 0 to 2, more preferably 0 or 1. Preferred examples of A of C-A include heterocyclic aromatic groups having se:Sub>A cyano group and an unsaturated nitrogen atom. And X is 1 ～X 5 May each independently be C-D or C-A.
When X is 1 ～X 5 When adjacent ones of (2) represent C-R, two R may be bonded to each other to form a cyclic structure. The cyclic structure formed by bonding may be an aromatic ring or an alicyclic ringThe fused ring may have a condensed ring having 2 or more rings. The heteroatom described herein is preferably an atom selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom. Examples of the cyclic structure include a benzene ring, a naphthalene ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a pyrrole ring, an imidazole ring, a pyrazole ring, an imidazoline ring, an oxazole ring, an isoxazole ring, a thiazole ring, an isothiazole ring, a cyclohexadiene ring, a cyclohexene ring, a cyclopentadiene ring, a cycloheptatriene ring, a cycloheptadiene ring, a cycloheptene ring, a furan ring, a thiophene ring, a naphthyridine ring, a quinoxaline ring, and a quinoline ring. For example, a ring may be formed in which a plurality of rings such as phenanthrene rings or polytrimethylene rings are condensed.
The donor group D in the general formulae (1) and (2) is preferably a group represented by the following general formula (3), for example.
General formula (3)
[ chemical formula 5]
In the general formula (3), R 11 And R is 12 Each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. R is R 11 And R is 12 Can be bonded to each other to form a ring structure. L represents a single bond, a substituted or unsubstituted arylene group, or a substituted or unsubstituted heteroarylene group. The substituent capable of being introduced into the arylene or heteroarylene group of L may be a group represented by the general formula (1) or the general formula (2), or may be a group represented by the following general formulae (3) to (6). The groups represented by (1) to (6) may be introduced into the maximum number of substituents which can be introduced into L. When a plurality of groups represented by the general formulae (1) to (6) are introduced, these substituents may be the same or different from each other. * Represents a bonding position to a carbon atom (C) constituting a ring skeleton of the ring in the general formula (1) or the general formula (2).
As used herein, "alkyl" may be any of linear, branched, and cyclic. Further, 2 or more kinds of the linear part, the cyclic part, and the branched part may be mixed. The number of carbon atoms of the alkyl group can be 1 or more, 2 or more, or 4 or more, for example. The number of carbon atoms may be 30 or less, 20 or less, 10 or less, 6 or less, or 4 or less. Specific examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, 2-ethylhexyl, n-heptyl, isoheptyl, n-octyl, isooctyl, n-nonyl, isononyl, n-decyl, isodecyl, cyclopentyl, cyclohexyl and cycloheptyl. The alkyl group as a substituent may be further substituted with an aryl group.
The "alkenyl" may be any of straight-chain, branched, and cyclic. Further, 2 or more kinds of the linear part, the cyclic part, and the branched part may be mixed. The number of carbon atoms of the alkenyl group can be, for example, 2 or more and 4 or more. The number of carbon atoms may be 30 or less, 20 or less, 10 or less, 6 or less, or 4 or less. Specific examples of the alkenyl group include vinyl group, n-propenyl group, isopropenyl group, n-butenyl group, isobutenyl group, n-pentenyl group, isopentenyl group, n-hexenyl group, cyclohexenyl group and 2-ethylhexyl group. Alkenyl groups as substituents may be further substituted with substituents.
The "aryl" and "heteroaryl" may be a single ring or a condensed ring formed by condensing two or more rings. In the case of condensed rings, the number of condensed rings is preferably 2 to 6, and can be selected from 2 to 4, for example. Specific examples of the ring include benzene ring, pyridine ring, pyrimidine ring, triazine ring, naphthalene ring, anthracene ring, phenanthrene ring, triphenylene ring, quinoline ring, pyrazine ring, quinoxaline ring, and naphthyridine ring. Specific examples of the aryl or heteroaryl group include phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 2-pyridyl, 3-pyridyl and 4-pyridyl. "arylene" and "heteroaryl" can be groups in which the valences in the description of aryl and heteroaryl are replaced by 1 to 2.
Substituents mean groups that can be substituted with 1 valency of a hydrogen atom, rather than the concept of containing a fused group. Regarding the description and preferable ranges of the substituents, reference can be made to the description and preferable ranges of the substituents of the following general formula (7).
The compound represented by the general formula (3) is preferably a compound represented by any one of the following general formulae (4) to (6).
General formula (4)
[ chemical formula 6]
General formula (5)
[ chemical formula 7]
General formula (6)
[ chemical formula 8]
In the general formulae (4) to (6), R 51 ～R 60 、R 61 ～R 68 、R 71 ～R 78 Each independently represents a hydrogen atom, a deuterium atom or a substituent. Regarding the description and preferable ranges of the substituents described herein, reference can be made to the description and preferable ranges of the substituents in the following general formula (7). R is R 51 ～R 60 、R 61 ～R 68 、R 71 ～R 78 It is also preferable that each of the groups represented by any one of the above general formulae (4) to (6) is independently a group. The number of substituents in the general formulae (4) to (6) is not particularly limited. It is also preferable that all are unsubstituted (i.e., hydrogen or deuterium atoms). In the case where two or more substituents are present in each of the general formulae (4) to (6), these substituents may be the same or different. When substituents are present in formulae (4) to (6), the substituents are preferably R in the case of formula (4) 52 ～R 59 Any one ofIn the case of the general formula (5), the substituent is preferably R 62 ～R 67 Any of the substituents represented by the general formula (6) is preferably R 72 ～R 77 Any one of them.
In the general formula (6), X represents an oxygen atom, a sulfur atom, a substituted or unsubstituted nitrogen atom, a substituted or unsubstituted carbon atom, a substituted or unsubstituted silicon atom, a carbonyl group, or a substituted or unsubstituted ethylene group, a substituted or unsubstituted vinylidene group, a substituted or unsubstituted o-arylene group, or a substituted or unsubstituted o-heteroarylene group, each having a 2-valent chain length of 1 atom, bonded thereto. Specific examples and preferable ranges of the substituents can be referred to the description of the substituents in the above general formulae (1) and (2).
In the general formulae (4) to (6), L 12 ～L 14 Represents a single bond, a substituted or unsubstituted arylene group or a substituted or unsubstituted heteroarylene group. Regarding L 12 ～L 14 Reference can be made to the description and preferred ranges of arylene or heteroarylene groups represented by L. L (L) 12 ～L 14 Preferably a single bond, a substituted or unsubstituted arylene group. The substituent of the arylene or heteroarylene group described herein may be a group represented by the general formulae (1) to (6). The groups represented by the general formulae (1) to (6) may be introduced into L 11 ～L 14 The maximum number of substituents of (a). When a plurality of groups represented by the general formulae (1) to (6) are introduced, these substituents may be the same or different from each other. * Represents a bonding position to a carbon atom (C) constituting a ring skeleton of the ring in the general formula (1) or the general formula (2).
In the general formulae (4) to (6), R 51 And R is 52 、R 52 And R is 53 、R 53 And R is 54 、R 54 And R is 55 、R 55 And R is 56 、R 56 And R is 57 、R 57 And R is 58 、R 58 And R is 59 、R 59 And R is 60 、R 61 And R is 62 、R 62 And R is 63 、R 63 And R is 64 、R 65 And R is 66 、R 66 And R is 67 、R 67 And R is 68 、R 71 And R is 72 、R 72 And R is 73 、R 73 And R is 74 、R 75 And R is 76 、R 76 And R is 77 、R 77 And R is 78 Can be bonded to each other to form a ring structure. For the description and preferred examples of the cyclic structure, reference can be made to X of the above general formulae (1) and (2) 1 ～X 5 The description and preferred examples of the ring structure in (a).
Among the cyclic structures, preferred is a structure in which a substituted or unsubstituted benzofuran ring, a substituted or unsubstituted benzothiophene ring, a substituted or unsubstituted indole ring, a substituted or unsubstituted indene ring, a substituted or unsubstituted silane indene ring is condensed with at least one benzene ring in the general formulae (4) to (6). More preferably, the group represented by the following general formulae (5 a) to (5 f) is condensed with the general formula (5).
[ chemical formula 9]
In the general formulae (5 a) to (5 f), L 11 L and L 21 ～L 26 Represents a single bond or a 2-valent linking group. Regarding L 11 L and L 21 ～L 26 Can be referred to the above L 2 Is described and preferred.
In the general formulae (5 a) to (5 f), R 41 ～R 110 Each independently represents a hydrogen atom or a substituent. R is R 41 And R is 42 、R 42 And R is 43 、R 43 And R is 44 、R 44 And R is 45 、R 45 And R is 46 、R 46 And R is 47 、R 47 And R is 48 、R 51 And R is 52 、R 52 And R is 53 、R 53 And R is 54 、R 54 And R is 55 、R 55 And R is 56 、R 56 And R is 57 、R 57 And R is 58 、R 58 And R is 59 、R 59 And R is 60 、R 61 And R is 62 、R 62 And R is 63 、R 63 And R is 64 、R 65 And R is 66 、R 66 And R is 67 、R 67 And R is 68 、R 68 And R is 69 、R 69 And R is 70 、R 72 And R is 73 、R 73 And R is 74 、R 74 And R is 75 、R 75 And R is 76 、R 76 And R is 77 、R 77 And R is 78 、R 78 And R is 79 、R 79 And R is 80 、R 81 And R is 82 、R 82 And R is 83 、R 83 And R is 84 、R 84 And R is 85 、R 86 And R is 87 、R 87 And R is 88 、R 88 And R is 89 、R 89 And R is 90 、R 91 And R is 92 、R 93 And R is 94 、R 94 And R is 95 、R 95 And R is 96 、R 96 And R is 97 、R 97 And R is 98 、R 99 And R is 100 、R 101 And R is 102 、R 102 And R is 103 、R 103 And R is 104 、R 104 And R is 105 、R 105 And R is 106 、R 107 And R is 108 、R 108 And R is 109 、R 109 And R is 110 Can be bonded to each other to form a ring structure. The cyclic structure formed by bonding may be an aromatic ring or an aliphatic ring, may contain a hetero atom, and may be a condensed ring of 2 or more rings. The heteroatom described herein is preferably an atom selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom. Examples of the cyclic structure include benzene ring, naphthalene ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, pyrrole ring, imidazole ring, pyrazole ring, imidazoline ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, cyclohexadiene ring, cyclohexene ring, cyclopentadiene ring, cycloheptatriene ring, imidazole ring, and the like,Cycloheptadiene ring, cycloheptene ring, furan ring, thiophene ring, naphthyridine ring, quinoxaline ring, quinoline ring, and the like. For example, a ring may be formed in which a plurality of rings such as phenanthrene rings or polytrimethylene rings are condensed. The number of rings included in the group represented by the general formula (6) may be selected in the range of 3 to 5 or 5 to 7. The number of rings included in the groups represented by the general formulae (5 a) to (5 f) may be selected in the range of 5 to 7, or may be 5.
As R 41 ～R 110 The substituent which may be used is preferably an unsubstituted alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms which is substituted with an unsubstituted alkyl group having 1 to 10 carbon atoms. In a preferred aspect of the invention, R 41 ～R 110 Is a hydrogen atom or an unsubstituted alkyl group having 1 to 10 carbon atoms. In a preferred aspect of the invention, R 41 ～R 110 Is a hydrogen atom or an unsubstituted aryl group having 6 to 10 carbon atoms. In a preferred aspect of the invention, R 41 ～R 110 Are all hydrogen atoms.
R in the general formulae (5 a) to (5 f) 41 ～R 110 The bonded carbon atoms (the ring skeleton constituting the carbon atoms) may each be independently substituted with a nitrogen atom. That is, C-R in the general formulae (5 a) to (5 f) 41 ～C-R 110 Each independently substituted with N. The number of nitrogen atoms to be substituted is preferably 0 to 4, more preferably 1 to 2, of the groups represented by the general formulae (5 a) to (5 f). In one aspect of the invention, the number of substitution to nitrogen atoms is 0. Further, when two or more of the substituents are nitrogen atoms, it is preferable that the number of nitrogen atoms substituted in one ring is one.
In the general formulae (5 a) to (5 f), X 1 ～X 6 Represents an oxygen atom, a sulfur atom or N-R. In one aspect of the invention, X 1 ～X 6 Is an oxygen atom. In one aspect of the invention, X 1 ～X 6 Is a sulfur atom. In one aspect of the invention, X 1 ～X 6 Is N-R. R represents a hydrogen atom or a substituent, preferablyAnd (3) a substituent. As the substituent, a substituent selected from the above substituent group a can be exemplified. For example, an unsubstituted phenyl group and a phenyl group substituted with one group selected from the group consisting of an alkyl group and an aryl group or a combination of two or more groups may be preferably employed.
In the general formulae (5 a) to (5 f), the bonding position is represented.
In the present invention, a compound which is represented by the following general formula (7) and which radiates delayed fluorescence can be particularly preferably used as the delayed fluorescence material. In a preferred embodiment of the present invention, as the 2 nd organic compound, a compound represented by the general formula (7) may be used.
General formula (7)
[ chemical formula 10]
In the general formula (7), R 1 ～R 5 Wherein 0 to 4 of them represent cyano groups, R 1 ～R 5 At least one of which represents a substituted amino group, the remainder of R 1 ～R 5 Represents a hydrogen atom, a deuterium atom or a substituent other than cyano and substituted amino.
The substituted amino group described herein is preferably a substituted or unsubstituted diarylamino group, and two aryl groups constituting the substituted or unsubstituted diarylamino group may be linked to each other. The linking may be performed by a single bond (in this case, carbazole ring is formed), or may be performed by-O-, -S-, -N (R) 6 )-、-C(R 7 )(R 8 )-、-Si(R 9 )(R 10 ) -an alike linking group. Wherein R is 6 ～R 10 Represents a hydrogen atom, a deuterium atom or a substituent, R 7 And R is 8 、R 9 And R is 10 May be connected to each other to form a ring structure, respectively.
The substituted amino group may be R 1 ～R 5 Any one of them may, for example, be R 1 And R is 2 、R 1 And R is 3 、R 1 And R is 4 、R 1 And R is 5 、R 2 And R is 3 、R 2 And R is 4 、R 1 And R is 2 And R is 3 、R 1 And R is 2 And R is 4 、R 1 And R is 2 And R is 5 、R 1 And R is 3 And R is 4 、R 1 And R is 3 And R is 5 、R 2 And R is 3 And R is 4 、R 1 And R is 2 And R is 3 And R is 4 、R 1 And R is 2 And R is 3 And R is 5 、R 1 And R is 2 And R is 4 And R is 5 、R 1 And R is 2 And R is 3 And R is 4 And R is 5 Substituted amino groups, and the like. Cyano can also be R 1 ～R 5 Any one of them may, for example, be R 1 、R 2 、R 3 、R 1 And R is 2 、R 1 And R is 3 、R 1 And R is 4 、R 1 And R is 5 、R 2 And R is 3 、R 2 And R is 4 、R 1 And R is 2 And R is 3 、R 1 And R is 2 And R is 4 、R 1 And R is 2 And R is 5 、R 1 And R is 3 And R is 4 、R 1 And R is 3 And R is 5 、R 2 And R is 3 And R is 4 Cyano, etc.
R being neither cyano nor substituted amino 1 ～R 5 Represents a hydrogen atom, a deuterium atom or a substituent. Examples of the substituent described herein include a hydroxyl group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an alkyl group (for example, a carbon atom of 1 to 40), an alkoxy group (for example, a carbon atom of 1 to 40), an alkylthio group (for example, a carbon atom of 1 to 40), an aryl group (for example, a carbon atom of 6 to 30), an aryloxy group (for example, a carbon atom of 6 to 30), an arylthio group (for example, a carbon atom of 6 to 30), a heteroaryl group (for example, a ring skeleton constituting a carbon atom of 5 to 30), a heteroaryloxy group (for example, a ring skeleton constituting a carbon atom of 5 to 30), a heteroarylthio group (for example, a ring skeleton constituting a carbon atom of 5 to 30), an acyl group (for example, a carbon atom of 1 to 40), an alkenyl group (for example, a carbon atom of 1 to 40), an alkynyl group (for example, a carbon atom of 1 to 30) 40 An alkoxycarbonyl group (for example, a carbon number of 1 to 40), an aryloxycarbonyl group (for example, a carbon number of 1 to 40), a heteroaryloxycarbonyl group (for example, a carbon number of 1 to 40), a silyl group (for example, a trialkylsilyl group having a carbon number of 1 to 40), a nitro group, a substituent group a formed by a group as exemplified herein being further substituted with one or more groups as exemplified herein. Preferable examples of the substituent when the aryl group of the diarylamino group is substituted include the substituent of the substituent group a, and further include cyano groups and substituted amino groups.
Specific examples of the group of compounds and the compound contained in the general formula (7) include paragraphs 0008 to 0048 of WO2013/154064, paragraphs 0009 to 0030 of WO2015/080183, paragraphs 0006 to 0019 of WO2015/129715, paragraphs 0013 to 0025 of japanese patent application laid-open No. 2017-119663, and paragraphs 0013 to 0026 of japanese patent application laid-open No. 2017-119664, which are incorporated herein by reference.
In addition, a compound which is represented by the following general formula (8) and which radiates delayed fluorescence can also be particularly preferably used as the delayed fluorescence material of the present invention. In a preferred embodiment of the present invention, as the 2 nd organic compound, a compound represented by the general formula (8) may be used.
General formula (8)
[ chemical formula 11]
In the general formula (8), Y 1 、Y 2 Y and Y 3 Any two of them represent a nitrogen atom and the remaining one represents a methine group or Y 1 、Y 2 Y and Y 3 All of which represent nitrogen atoms. Z is Z 1 Z is as follows 2 Each independently represents a hydrogen atom, a deuterium atom or a substituent. R is R 11 ～R 18 Preferably each independently represents a hydrogen atom, a deuterium atom or a substituent, R 11 ～R 18 At least one of which is a substituted or unsubstituted arylamino group or a substituted or unsubstituted carbazolyl group. Benzene ring and structure constituting the arylamino groupThe benzene rings forming the carbazolyl groups can be respectively combined with R 11 ～R 18 Together forming a single bond or a linking group. The compound represented by the general formula (8) contains at least two carbazole structures in the molecule. As Z 1 、Z 2 Examples of the substituent that may be used include the substituent of the substituent group a described above. And, regarding R 11 ～R 18 Specific examples of the substituent which may be used for the arylamino group and the carbazolyl group include a substituent of the substituent group A, a cyano group, a substituted arylamino group and a substituted alkylamino group. In addition, R 11 And R is 12 、R 12 And R is 13 、R 13 And R is 14 、R 15 And R is 16 、R 16 And R is 17 、R 17 And R is 18 Can be bonded to each other to form a ring structure.
Among the compounds represented by the general formula (8), the compounds represented by the general formula (9) are particularly useful.
General formula (9)
[ chemical formula 12]
In the general formula (9), Y 1 、Y 2 Y and Y 3 Any two of them represent a nitrogen atom and the remaining one represents a methine group or Y 1 、Y 2 Y and Y 3 All of which represent nitrogen atoms. Z is Z 2 Represents a hydrogen atom, a deuterium atom or a substituent. R is R 11 ～R 18 R is R 21 ～R 28 Each independently represents a hydrogen atom, a deuterium atom or a substituent. R is R 11 ～R 18 At least one of and/or R 21 ～R 28 Preferably represents a substituted or unsubstituted arylamino group or a substituted or unsubstituted carbazolyl group. The benzene rings constituting the arylamino group and the benzene rings constituting the carbazolyl group may be each independently selected from R 11 ～R 18 Or R is 21 ～R 28 Together forming a single bond or a linking group. As Z 2 Examples of the substituent which may be used include the above substituentsSubstituents of group a. And, regarding R 11 ～R 18 、R 21 ～R 28 Specific examples of the substituent which may be used for the arylamino group and the carbazolyl group include a substituent of the substituent group A, a cyano group, a substituted arylamino group and a substituted alkylamino group. In addition, R 11 And R is 12 、R 12 And R is 13 、R 13 And R is 14 、R 15 And R is 16 、R 16 And R is 17 、R 17 And R is 18 、R 21 And R is 22 、R 22 And R is 23 、R 23 And R is 24 、R 25 And R is 26 、R 26 And R is 27 、R 27 And R is 28 Can be bonded to each other to form a ring structure.
Specific examples of the group of compounds and the compound contained in the general formula (9) include those described in paragraphs 0020 to 0062 or appl.Phys.let,98, 083302 (2011) of WO2013/081088, which is incorporated herein by reference.
In addition, a compound which is represented by the following general formula (10) and which radiates delayed fluorescence can also be particularly preferably used as the delayed fluorescence material of the present invention.
General formula (10)
[ chemical formula 13]
In the general formula (10), R 91 ～R 96 Each independently represents a hydrogen atom, a deuterium atom, a donor group or an acceptor group, at least one of which is the donor group, and at least two of which are the acceptor groups. The substitution positions of at least two acceptor groups are not particularly limited, but are preferably two acceptor groups containing a relationship with each other in meta position. For example, when R 91 When a donor group is used, at least R can be preferably exemplified 92 And R is 94 Is the structure of the acceptor group and at least R 92 And R is 96 Is the structure of the acceptor group. Acceptor groups present within the molecule may beAll of which may be identical or different from each other, for example, all of which may be identical in structure. The number of acceptor groups is preferably 2 to 3, for example 2 can be selected. Further, two or more donor groups may be present, and the donor groups may be the same or different from each other. The number of donor groups is preferably 1 to 3, and may be, for example, only one or two. In addition, as for the description and preferable ranges of the donor group and the acceptor group, reference can be made to the description and preferable ranges of D and Z of the general formula (1). In particular, in the general formula (10), the donor group is preferably represented by the general formula (3), and the acceptor group is preferably represented by a cyano group or the following general formula (11).
General formula (11)
[ chemical formula 14]
In the general formula (11), Y 4 ～Y 6 Represents a nitrogen atom or a methine group, but at least one is a nitrogen atom, preferably both represent nitrogen atoms. R is R 101 ～R 110 Each independently represents a hydrogen atom, a deuterium atom or a substituent, but at least one is preferably an alkyl group. Regarding the description and preferred ranges of the substituents described herein, reference can be made to the description and preferred ranges of the substituents in the general formula (7). L (L) 15 Represents a single bond or a linking group, and reference can be made to the description and preferred ranges of L in the general formula (3). In a preferred aspect of the present invention, L in formula (11) 15 Is a single bond. * Represents the bonding position to the carbon atom (C) constituting the ring skeleton of the ring in the general formula (10).
In another preferred embodiment of the present invention, as the 2 nd organic compound, a compound represented by the general formula (12) may be used. The compound represented by the general formula (12) includes a compound represented by the general formula (12 a).
General formula (12)
[ chemical formula 15]
General formula (12 a)
[ chemical formula 16]
Particularly preferred compounds among the compounds represented by the general formula (12) are compounds represented by the following general formula (13) or compounds represented by the general formula (14).
General formula (13)
[ chemical formula 17]
General formula (14)
[ chemical formula 18]
In another preferred embodiment of the present invention, as the 2 nd organic compound, a compound represented by the general formula (15) may be used.
[ chemical formula 19]
General formula (15)
In the general formulae (12) to (15), D represents a donor group, a represents an acceptor group, and R represents a hydrogen atom, a deuterium atom or a substituent. The two D's in the general formula (15) may be the same or different. For the description and preferred ranges of the donor group and the acceptor group, reference can be made to the corresponding description and preferred ranges of the aforementioned general formula (1). Examples of the substituent for R include an alkyl group and an aryl group which may be substituted with one group selected from the group consisting of an alkyl group and an aryl group, or a combination of two or more groups.
Specific examples of the preferred donor groups are given below as D in the general formulae (12) to (15). In the following embodiments, x represents a bonding position, and "D" represents a deuterium atom. In the following specific examples, the hydrogen atom may be substituted with an alkyl group, for example. And, the substituted or unsubstituted benzene ring may be further condensed.
[ chemical formula 20-1]
[ chemical formula 20-2]
Specific examples of the preferred acceptor group are given below as a in the general formulae (12) to (14). In the following embodiments, x represents a bonding position, and "D" represents deuterium.
[ chemical formula 21-1]
[ chemical formula 21-2]
In the following, R in the general formulae (12) to (15) is preferably exemplified. In the following embodiments, x represents a bonding position, and "D" represents deuterium.
[ chemical formula 22]
Particularly preferred compounds among the compounds represented by the general formula (15) are compounds represented by the following general formula (15 a).
General formula (15 a)
[ chemical formula 23]
In the general formula (15 a), R 201 ～R 221 Each independently represents a hydrogen atom or a substituent, and preferably represents a hydrogen atom, an alkyl group, an aryl group, or a group in which an alkyl group and an aryl group are bonded. R is R 201 And R is 202 、R 202 And R is 203 、R 203 And R is 204 、R 205 And R is 206 、R 206 And R is 207 、R 207 And R is 208 、R 214 And R is 215 、R 215 And R is 216 、R 216 And R is 217 、R 218 And R is 219 、R 219 And R is 220 、R 220 And R is 221 Is bonded to each other to form a benzofuran structure or a benzothiophene structure. Preferably, R 201 And R is 202 、R 202 And R is 203 、R 203 And R is 204 、R 205 And R is 206 、R 206 And R is 207 、R 207 And R is 208 Group 1 or 2 of (B) and R 214 And R is 215 、R 215 And R is 216 、R 216 And R is 217 、R 218 And R is 219 、R 219 And R is 220 、R 220 And R is 221 The groups 1 or 2 of (a) are bonded to each other to form a benzofuran structure or a benzothiophene structure. Further preferably R 203 And R is 204 Are bonded to each other to form a benzofuran structure or a benzothiophene structure, more preferably R 203 And R is 204 、R 216 And R is 217 Bonded to each other to form a benzofuran structure or a benzothiophene structure. Particularly preferably, R 203 And R is 204 、R 216 And R is 217 Are bonded to each other to form a benzofuran structure or a benzothiophene structure, R 206 And R is 219 Is a substituted or unsubstituted aryl group (preferably a substituted or unsubstituted phenyl group, more preferably an unsubstituted phenyl group)。
Some or all of the hydrogen atoms of the general formula (15 a) may be substituted with deuterium atoms. For example, part or all of the hydrogen atoms of two phenyl groups bonded to a triazinyl group may be substituted with deuterium atoms. Also, part or all of the hydrogen atoms bonded to the two carbazolyl groups may be substituted with deuterium atoms. And R is 209 ～R 213 And may be a deuterium atom.
Hereinafter, preferred compounds that can be used as the 2 nd organic compound are exemplified. In the structural formulae of the exemplary compounds below, t-Bu represents tert-butyl.
[ chemical formula 24-1]
[ chemical formula 24-2]
[ chemical formula 24-3]
[ chemical formula 24-4]
[ chemical formula 24-5]
[ chemical formula 24-6]
[ chemical formula 24-7]
[ chemical formula 24-8]
[ chemical formula 24-9]
[ chemical formula 24-10]
[ chemical formula 24-11]
[ chemical formula 24-12]
[ chemical formulas 24-13]
[ chemical formula 24-14]
In addition to the above, the known delayed fluorescence material may be used in combination with the 2 nd organic compound. And, even an unknown delayed fluorescent material can be used. In particular, as a part of the present document, a compound represented by the general formula (1) described in paragraphs 0013 to 0042 of the specification of Japanese patent application No. 2021-188860 cited herein may be preferably used, and a compound described in paragraphs 0043 to 0048 may be particularly preferably used.
As a preferred delayed fluorescent material, examples thereof include paragraphs 0008 to 0048 and 0095 to 0133 of WO2013/154064, paragraphs 0007 to 0047 and 0073 to 0085 of WO 2013/01954, paragraphs 0007 to 0033 and 0059 to 0066 of WO 2013/0110855, paragraphs 0008 to 0071 and 0118 to 0133 of WO2013/081088, paragraphs 0009 to 0046 and 0093 to 0134 of Japanese patent application publication 2013-256490, paragraphs 0008 to 0020 and 0038 to 0040 of Japanese patent application publication 2013-116975, paragraphs 0007 to 0032 and 0079 to 0084 of WO2013/133359, paragraphs 0008 to 0054 and 0101 to 0121 of WO2013/161437, and further, the like the compounds contained in the general formulae described in paragraphs 0007 to 0041 and 0060 to 0069 of Japanese patent application laid-open No. 2014-9252, paragraphs 0008 to 0048 and 0067 to 0076 of Japanese patent application laid-open No. 2017-119663, paragraphs 0013 to 0025 of Japanese patent application laid-open No. 2017-119664, paragraphs 0012 to 0025 of Japanese patent application laid-open No. 2017-222623, paragraphs 0010 to 0050 of Japanese patent application laid-open No. 2017-226838, paragraphs 0012 to 0043 of Japanese patent application laid-open No. 2018-100411, and paragraphs 0016 to 0044 of WO2018/047853, are particularly exemplified compounds and can delay fluorescence by radiation. And, in addition, the processing unit, the light-emitting materials of the WO 2013-253121, WO2013/133359, WO2014/034535, WO2014/115743, WO2014/122895, WO2014/126200, WO2014/136758, WO2014/133121, WO2014/136860, WO2014/196585, WO2014/189122, WO 2014/1681101, WO2015/008580, WO2014/203840, WO2015/002213, WO2015/016200, WO2015/019725, WO 201470/072213, WO2015/108049, WO2015/080182, WO2015/072537, WO 2015/136240, WO2014/196585, WO2014/189122, WO2014/168101, WO 2012012015/12945, WO 2012015/129714, WO 2015/12913720, WO 2015/12914, WO 13720, WO2015/129, and WO 137-137202 may be used. In addition, the above-mentioned publications described in this paragraph are incorporated herein by reference as part of this document.
(3 rd organic Compound)
The 3 rd organic compound used in the light-emitting layer of the organic electroluminescent element of the present invention is a compound that emits fluorescence, and is a compound that has lower LUMO energy than the 1 st organic compound or the 2 nd organic compound. The 3 rd organic compound is preferably a compound which radiates fluorescence and has lower LUMO energy than the 1 st organic compound and the 2 nd organic compound, and has lower lowest excited singlet energy than the 1 st organic compound and the 2 nd organic compound. In the organic electroluminescent element of the present invention, the substitution value of the 3 rd organic compound in the light-emitting layer is-0.3 or less. In the organic electroluminescent element of the present invention, fluorescence from the 3 rd organic compound is emitted. Luminescence from the 3 rd organic compound typically comprises delayed fluorescence. The largest component of luminescence from the element is fluorescence from the 3 rd organic compound. That is, the amount of luminescence of fluorescence from the 3 rd organic compound is largest in luminescence from the organic electroluminescent element of the present invention.
In a preferred aspect of the present invention, the 3 rd organic compound receives energy from the 1 st organic compound in an excited singlet state, the 2 nd organic compound in an excited singlet state, and the 2 nd organic compound in an excited triplet state, which is converted by intersystem crossing from the excited triplet state, and transits to the excited singlet state. In a more preferred embodiment of the present invention, the 3 rd organic compound is energy-receiving from the 2 nd organic compound in the excited singlet state and from the 2 nd organic compound in the excited triplet state, and is transited to the excited singlet state by the 2 nd organic compound in the excited singlet state through the reverse intersystem crossing. The excited singlet state of the 3 rd organic compound produced radiates fluorescence when returned to the base state afterwards.
The 3 rd organic compound is not particularly limited as long as it is a fluorescent material (a fluorescent compound) satisfying a predetermined condition. Herein, "fluorescent material" means a material in which fluorescence having a luminescence lifetime of less than 100ns (nanoseconds) is observed when the luminescence lifetime is measured by a fluorescence lifetime measurement system (Hamamatsu Photonics k.k. Fringe photographing system, etc.). Delayed fluorescence or phosphorescence may be included in the luminescence from the 3 rd organic compound, but the largest component of the luminescence from the 3 rd organic compound is fluorescence. In one aspect of the present invention, the organic electroluminescent element does not emit phosphorescence or emits phosphorescence in an amount of 1% or less of fluorescence.
If the conditions of the present invention are satisfied, two or more 3 rd organic compounds may be used. For example, a desired color can be emitted by simultaneously using two or more 3 rd organic compounds different in emission color. Further, single color light emission from the 3 rd organic compound may be performed using one 3 rd organic compound.
In the present invention, the maximum emission wavelength of the compound that can be used as the 3 rd organic compound is not particularly limited. Therefore, a light-emitting material having a maximum light-emitting wavelength in the visible region (380 to 780 nm), a light-emitting material having a maximum light-emitting wavelength in the infrared region (780 to 1 mm), a compound having a maximum light-emitting wavelength in the ultraviolet region (280 to 380 nm), or the like can be appropriately selected and used. Fluorescent materials having a maximum emission wavelength in the visible region are preferred. For example, a light-emitting material having a maximum light-emitting wavelength in the range of 380 to 570nm in the region of 380 to 780nm, a light-emitting material having a maximum light-emitting wavelength in the range of 570 to 650nm, a light-emitting material having a maximum light-emitting wavelength in the range of 650 to 700nm, or a light-emitting material having a maximum light-emitting wavelength in the range of 700 to 780nm may be selected.
In a preferred aspect of the present invention, the compounds are selected and combined such that there is overlap between the emission wavelength region of the 2 nd organic compound and the absorption wavelength region of the 3 rd organic compound. In particular, it is preferable that the edge on the short wavelength side of the emission spectrum of the 2 nd organic compound overlaps with the edge on the long wavelength side of the absorption spectrum of the 3 rd organic compound.
The 3 rd organic compound preferably contains no metal atom other than boron atom. For example, the 3 rd organic compound may be a compound containing both a boron atom and a fluorine atom. Further, the compound may contain a boron atom but not a fluorine atom. Further, the metal atom may not be contained at all. For example, as the 3 rd organic compound, a compound composed of an atom selected from the group consisting of a carbon atom, a hydrogen atom, a deuterium atom, a nitrogen atom, an oxygen atom, a sulfur atom, a fluorine atom, and a boron atom can be selected. For example, as the 3 rd organic compound, a compound composed of an atom selected from the group consisting of a carbon atom, a hydrogen atom, a deuterium atom, a nitrogen atom, an oxygen atom, a fluorine atom, and a boron atom can be selected. For example, as the 3 rd organic compound, a compound composed of an atom selected from the group consisting of a carbon atom, a hydrogen atom, a deuterium atom, a nitrogen atom, an oxygen atom, a sulfur atom, and a boron atom can be selected. For example, as the 3 rd organic compound, a compound composed of an atom selected from the group consisting of a carbon atom, a hydrogen atom, a deuterium atom, a nitrogen atom, and a boron atom can be selected. For example, as the 3 rd organic compound, a compound composed of an atom selected from the group consisting of a carbon atom, a hydrogen atom, a deuterium atom, a nitrogen atom, an oxygen atom, and a sulfur atom can be selected. For example, as the 3 rd organic compound, a compound composed of an atom selected from the group consisting of a carbon atom, a hydrogen atom, a deuterium atom, a nitrogen atom, and an oxygen atom can be selected. For example, as the 3 rd organic compound, a compound composed of carbon atoms and hydrogen atoms can be selected.
The 3 rd organic compound may be a compound having a multiple resonance effect of a boron atom and a nitrogen atom, or a compound containing a condensed aromatic ring structure such as anthracene, pyrene, perylene, or the like. As the 3 rd organic compound, a compound having a condensed ring structure including a boron atom and a nitrogen atom exhibiting a multiple resonance effect and having four or more rings can be exemplified. Further, as the 3 rd organic compound, a compound in which a hetero 6-membered ring containing a boron atom and a nitrogen atom is condensed with a pyrrole ring sharing a nitrogen atom and two benzene rings can also be exemplified.
In a preferred aspect of the present invention, a compound represented by the following general formula (16) is used as the 3 rd organic compound.
General formula (16)
[ chemical formula 25]
In the general formula (16), X 1 X is X 2 One of which is a nitrogen atom and the other is a boron atom. In one aspect of the invention, X 1 Is a nitrogen atom, X 2 Is a boron atom. At this time, R 17 And R is 18 Are bonded to each other as a single bond and form a pyrrole ring. In another aspect of the invention, X 1 Is a boron atom, X 2 Is a nitrogen atom. At this time, R 21 And R is 22 Are bonded to each other as a single bond and form a pyrrole ring.
In the general formula (16), R 1 ～R 26 、A 1 、A 2 Each independently represents a hydrogen atom, a deuterium atom or a substituent.
R 1 And R is 2 、R 2 And R is 3 、R 3 And R is 4 、R 4 And R is 5 、R 5 And R is 6 、R 6 And R is 7 、R 7 And R is 8 、R 8 And R is 9 、R 9 And R is 10 、R 10 And R is 11 、R 11 And R is 12 、R 13 And R is 14 、R 14 And R is 15 、R 15 And R is 16 、R 16 And R is 17 、R 17 And R is 18 、R 18 And R is 19 、R 19 And R is 20 、R 20 And R is 21 、R 21 And R is 22 、R 22 And R is 23 、R 23 And R is 24 、R 24 And R is 25 、R 25 And R is 26 Can be bonded to each other to form a ring structure.
R 7 And R is 8 The bonded cyclic structure contains a boron atom and four carbon atoms as ring skeleton constituent atoms. R is R 17 And R is 18 In the bonded cyclic structure, when X 1 In the case of boron atoms, boron atoms and four carbon atoms may be contained as ring skeleton constituting atoms. When X is 1 In the case of a nitrogen atom, the cyclic structure is limited to the pyrrole ring. R is R 21 And R is 22 In the bonded cyclic structure, when X 2 In the case of boron atoms, the ring skeleton contains boron atoms and four carbon atoms. When X is 2 In the case of a nitrogen atom, the cyclic structure is limited to the pyrrole ring. When R is 7 And R is 8 、R 17 And R is 18 、R 21 And R is 22 When bonded to each other to form a cyclic structure containing a boron atom, the cyclic structure is preferably a 5-to 7-membered ring, more preferably a 5-or 6-membered ring, and still more preferably a 6-membered ring. When R is 7 And R is 8 、R 17 And R is 18 、R 21 And R is 22 When bonded to each other, preferably bonded to each other to form a single bond, -O-, -S-, -N (R) 27 )-、-C(R 28 )(R 29 )-、-Si(R 30 )(R 31 )-、-B(R 32 ) -, -CO-, -CS-, more preferably-O-, -S-or-N (R) 27 ) -, further preferably form-N (R 27 ) -. Wherein R is 27 ～R 32 Each independently represents a hydrogen atom, a deuterium atom or a substituent. As the substituent, a group selected from any one of substituent groups A to E described below may be used, but is preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, particularly preferably R 27 Is a substituted or unsubstituted aryl group. When R is 27 ～R 32 R is substituent when it is substituent 7 And R is 8 R in the ring formed by bonding to each other 27 ～R 32 Can be combined with R 6 R is R 9 At least one of them is bonded to further form a cyclic structure, R 17 And R is 18 R in the ring formed by bonding to each other 27 ～R 32 Can be combined with R 16 R is R 19 At least one of them is bonded to further form a cyclic structure, R 21 And R is 22 Are bonded to each otherR in the ring formed by closing 27 ～R 32 Can be combined with R 20 R is R 23 At least one of them is bonded to further form a ring structure. In one aspect of the invention, R 7 And R is 8 、R 17 And R is 18 、R 21 And R is 22 Is bonded to each other in only 1 group. In one aspect of the invention, R 7 And R is 8 、R 17 And R is 18 、R 21 And R is 22 Is bonded to each other. In one aspect of the invention, R 7 And R is 8 、R 17 And R is 18 、R 21 And R is 22 Is bonded to each other.
R 1 And R is 2 、R 2 And R is 3 、R 3 And R is 4 、R 4 And R is 5 、R 5 And R is 6 、R 6 And R is 7 、R 8 And R is 9 、R 9 And R is 10 、R 10 And R is 11 、R 11 And R is 12 、R 13 And R is 14 、R 14 And R is 15 、R 15 And R is 16 、R 16 And R is 17 、R 18 And R is 19 、R 19 And R is 20 、R 20 And R is 21 、R 22 And R is 23 、R 23 And R is 24 、R 24 And R is 25 、R 25 And R is 26 The cyclic structure formed by bonding may be an aromatic ring or an aliphatic ring, and may contain a hetero atom, and other rings may be further condensed to 1 ring or more. The heteroatom described herein is preferably an atom selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom. Examples of the cyclic structure to be formed include a benzene ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a pyrrole ring, an imidazole ring, a pyrazole ring, a triazole ring, an imidazoline ring, a furan ring, a thiophene ring, an oxazole ring, an isoxazole ring, a thiazole ring, an isothiazole ring, a cyclohexadiene ring, a cyclohexene ring, a cyclopentene ring, a cycloheptatriene ring, a cycloheptadiene ring, a cycloheptene ring, and a ring obtained by further fusing one or more rings selected from the group consisting of these rings. At the book In a preferred aspect of the invention, the cyclic structure may be a substituted or unsubstituted benzene ring (the ring may be further condensed), for example, a benzene ring substituted with an alkyl group or an aryl group. In a preferred aspect of the invention, the cyclic structure is a substituted or unsubstituted heteroaromatic ring, preferably a furan ring of a benzofuran, a thiophene ring of a benzothiophene. R is R 1 And R is 2 、R 2 And R is 3 、R 3 And R is 4 、R 4 And R is 5 、R 5 And R is 6 、R 6 And R is 7 、R 8 And R is 9 、R 9 And R is 10 、R 10 And R is 11 、R 11 And R is 12 、R 13 And R is 14 、R 14 And R is 15 、R 15 And R is 16 、R 16 And R is 17 、R 18 And R is 19 、R 19 And R is 20 、R 20 And R is 21 、R 22 And R is 23 、R 23 And R is 24 、R 24 And R is 25 、R 25 And R is 26 The number of combinations of the above groups bonded to each other to form a ring structure may be 0, for example, any one of 1 to 6. For example, 1 to 4 may be selected, and 1, 2, or 3 or 4 may be selected. In one aspect of the invention, R is selected from 1 And R is 2 、R 2 And R is 3 、R 3 And R is 4 Is bonded to each other to form a ring structure. In one aspect of the invention, R 5 And R is 6 Bonded to each other to form a ring structure. In one aspect of the invention, R is selected from 9 And R is 10 、R 10 And R is 11 、R 11 And R is 12 Is bonded to each other to form a ring structure. In one aspect of the invention, R 1 And R is 2 、R 13 And R is 14 Any one of them is bonded to each other to form a ring structure. In one aspect of the invention, R is selected from 1 And R is 2 、R 2 And R is 3 、R 3 And R is 4 1 group of (C) are bonded to each other to form a cyclic structure, and R 5 And R is 6 Bonded to each other to form a ring structure. At the bookIn one aspect of the invention, R 5 And R is 6 、R 19 And R is 20 Any one of them is bonded to each other to form a ring structure.
Not adjacent R n (n=1 to 26) R bonded to each other 1 ～R 26 Is a hydrogen atom, a deuterium atom or a substituent. As the substituent, a group selected from any one of substituent groups a to E described later may be used.
R 1 ～R 26 Preferred substituents that may be employed are substituted or unsubstituted alkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, for example, substituents may be substituted or unsubstituted aryl, for example, substituents may be substituted or unsubstituted alkyl. The substituents of the alkyl group, the aryl group and the heteroaryl group described herein may be any one selected from the substituent groups a to E, but are preferably 1 or more selected from the group consisting of an alkyl group, an aryl group and a heteroaryl group, more preferably a substituent group E, and may be unsubstituted. In a preferred aspect of the invention, R 1 ～R 6 At least one of which is a substituent, preferably a group of substituents E. For example, R 1 ～R 6 At least one of them is a substituent, and more preferably a group of substituents E. For example, R 5 R is R 6 At least one of them is a substituent, and more preferably a group of substituents E. In a preferred aspect of the invention, R 3 R is R 6 At least one of them is a substituent, more preferably both are substituents, and still more preferably a group of substituents E. In a preferred aspect of the invention, when X 1 R is a nitrogen atom 15 R is R 20 At least one of them is a substituent, more preferably both are substituents, and still more preferably a group of substituents E. At this time, R 16 And R is 17 Bonded to each other to form a single bond. In a preferred aspect of the invention, when X 2 R is a nitrogen atom 19 R is R 24 At least one of them is a substituent, more preferably both are substituents, and still more preferably a group of substituents E. At this time, R 21 And R is 22 Bonded to each other to form a single bond. In one aspect of the invention, R 8 R is R 12 At least one of them is a substituent, preferably both are substituents. In one aspect of the invention, R 8 、R 10 R is R 12 Is a substituent. As R 8 ～R 12 Preferably an unsubstituted alkyl group. When X is 1 When boron atom, R 13 R is R 17 At least one of them is a substituent, preferably both are substituents. In one aspect of the invention, when X 1 When boron atom, R 13 、R 15 R is R 17 Is a substituent. When X is 1 When boron is an atom, R is as 13 ～R 17 Preferably an unsubstituted alkyl group. When X is 2 When boron atom, R 22 R is R 26 At least one of them is a substituent, preferably both are substituents. In one aspect of the invention, when X 2 When boron atom, R 22 、R 24 R is R 26 Is a substituent. When X is 2 When boron is an atom, R is as 22 ～R 26 Preferably an unsubstituted alkyl group.
A 1 A is a 2 Is a hydrogen atom, a deuterium atom or a substituent. As the substituent, a group selected from any one of substituent groups a to E described later may be used.
A 1 A is a 2 Preferred substituents that may be employed are acceptor groups. The acceptor group is a group with a positive sigma p value of Hammett. Here, the "hamite σp value" is a value proposed by l.p. hammett, which is a value for quantifying the influence of a substituent on the reaction rate or balance of a para-substituted benzene derivative. Specifically, the following formula holds between the substituent in the para-substituted benzene derivative and the reaction rate constant or equilibrium constant:
log(k/k 0 )＝ρσp
or (b)
log(K/K 0 )＝ρσp
A constant (σp) specific to the substituent in (a). In the above formula, k 0 Represents the velocity constant of benzene derivatives having no substituent, k represents substitutedVelocity constant, K of the radical-substituted benzene derivatives 0 The equilibrium constant of the benzene derivative having no substituent is represented by K, the equilibrium constant of the benzene derivative substituted with a substituent is represented by ρ, and the reaction constant is determined by the type and condition of the reaction. For the description about "the σp value of Hammett" and the numerical value of each substituent in the present invention, reference can be made to the description about the σp value of Hansch, C.et al, chem.Rev.,91,165-195 (1991).
A 1 A is a 2 More preferably, the acceptor groups that may be employed are those having a sigma p value of Hammett greater than 0.2. Examples of the group having a σp value of Hammett of more than 0.2 include a cyano group, an aryl group substituted with at least a cyano group, a group containing a fluorine atom, and a substituted or unsubstituted heteroaryl group containing a nitrogen atom as a ring skeleton constituting atom. The aryl group substituted at least with cyano group described herein may be substituted with a substituent other than cyano group (e.g., alkyl or aryl group), but may also be aryl group substituted only with cyano group. Aryl substituted with at least cyano is preferably phenyl substituted with at least cyano. The number of substitution of the cyano group is preferably 1 or 2, and may be 1 or 2, for example. Examples of the group containing a fluorine atom include a fluorine atom, a fluorinated alkyl group, a fluorine atom, or an aryl group substituted at least with a fluorinated alkyl group. The fluorinated alkyl group is preferably a perfluoroalkyl group, and the number of carbon atoms is preferably 1 to 6, more preferably 1 to 3. The heteroaryl group containing a nitrogen atom as a ring skeleton constituting atom may be a single ring or a condensed ring formed by condensing two or more rings. In the case of a condensed ring, the number of rings after the condensed ring is preferably 2 to 6, and for example, 2 to 4 rings can be selected or 2 rings can be used. Specific examples of the ring constituting the heteroaryl group include a pyridine ring, a pyrimidine ring, a pyrazine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a quinazoline ring, a quinoxaline ring, and naphthyridine rings other than the quinazoline ring and the quinoxaline ring. The ring constituting the heteroaryl group may be substituted with a deuterium atom or a substituent, and examples of the substituent include one group or two or more groups selected from the group consisting of an alkyl group, an aryl group and a heteroaryl group. As A 1 A is a 2 Acceptor groups which may be employed are particularly preferably cyano groups.
In one aspect of the invention, A 1 A is a 2 Each independently a hydrogen atom or a deuterium atom. In one aspect of the invention, A 1 A is a 2 At least one of which is an acceptor group. In one aspect of the invention, A 1 A is a 2 Both are acceptor groups. In one aspect of the invention, A 1 A is a 2 Is cyano. In one aspect of the invention, A 1 A is a 2 Halogen atoms, for example bromine atoms.
In the following, specific examples of acceptor groups that can be used in the present invention are shown. Among them, the acceptor groups that can be used in the present invention are not to be interpreted in a limiting manner by the following specific examples. Herein, the representation of methyl is omitted. Thus, for example, if A15 is used, it represents a group comprising two 4-tolyl groups. And, "D" represents a deuterium atom. * Indicating the bonding location.
[ chemical formula 26-1]
[ chemical formula 26-2]
In addition, when X 1 Is a nitrogen atom, R 7 And R is 8 Bonded via nitrogen atom to form a 6-membered ring, R 21 And R is 22 Bonded via nitrogen atom to form a 6-membered ring, R 17 And R is 18 R when bonded to each other to form a single bond 1 ～R 6 At least one of which is substituted or unsubstituted aryl, or R 1 And R is 2 、R 2 And R is 3 、R 3 And R is 4 、R 4 And R is 5 、R 5 And R is 6 Any one of which is bonded to each other to form an aromatic ring (a substituted or unsubstituted benzene ring which may be condensed) or a heteroaromatic ring (preferably a furan ring which may be condensed, a substituted or unsubstituted benzofuran, a heterocyclic ring which may be condensed) Thiophene rings with fused substituted or unsubstituted benzothiophenes).
When X of the general formula (16) 1 In the case of a nitrogen atom, the compound of the present invention has the following skeleton (16 a). When X of the general formula (16) 2 In the case of a nitrogen atom, the compound of the present invention has the following skeleton (16 b).
[ chemical formula 27]
Each hydrogen atom in the backbones (16 a) and (16 b) may be substituted with a deuterium atom or a substituent. Further, a cyclic structure may be formed by substitution with a linking group together with an adjacent hydrogen atom. For details, reference can be made to the corresponding R of the general formula (16) 1 ～R 26 、A 1 、A 2 The description of (2). Examples of the skeletons (16 a) and (16 b) include compounds in which the phenyl groups bonded to the boron atoms are each substituted with mesityl oxide, 2, 6-diisopropylphenyl group, or 2,4, 6-triisopropylphenyl group. In one aspect of the present invention, each hydrogen atom in the backbones (16 a) and (16 b) may be substituted with a linking group together with an adjacent hydrogen atom to form a cyclic structure.
As a preferred group of compounds having a skeleton (16 a), compounds represented by the following general formula (16 a) can be exemplified.
General formula (16 a)
[ chemical formula 28]
Ar in the general formula (16 a) 1 ～Ar 4 Each independently represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. R is R 41 R is R 42 Each independently represents a substituted or unsubstituted alkyl group. m1 and m2 each independently represent an integer of 0 to 5, n1 and n3 each independently represent an integer of 0 to 4, and n2 and n4 each independently represent an integer of 0 to 3. A is that 1 A is a 2 Respectively are provided withIndependently represents a hydrogen atom, a deuterium atom or a substituent.
In one aspect of the present invention, n1 to n4 represent integers each independently representing 0 to 2. In a preferred aspect of the present invention, at least one of n1 to n4 is 1 or more, preferably at least one of n1 and n2 is 1 or more and at least one of n3 and n4 is 1 or more. In one aspect of the invention, n1 and n3 are each independently 1 or 2, and n2 and n4 are 0. In one aspect of the invention, n2 and n4 are each independently 1 or 2, and n1 and n3 are 0. In one aspect of the invention, n1 to n4 are each independently 1 or 2. In one aspect of the invention, n1 is equal to n3 and n2 is equal to n 4. In one aspect of the invention, n1 and n3 are 1 and n2 and n4 are 0. In one aspect of the invention, n1 and n3 are 0 and n2 and n4 are 1. In one aspect of the invention, n1 to n4 are each 1.Ar (Ar) 1 ～Ar 4 The bonding position of (a) may be at least one of 3 and 6 positions, or at least one of 2 and 7 positions, or at least one of 1 and 8 positions, or at least one of 4 and 5 positions of the carbazole ring. Ar (Ar) 1 ～Ar 4 The bonding position of (a) may be either 3 or 6 or 2 or 7, or 1 or 8 or 4 or 5 of the carbazole ring. For example, at least one of the 3, 6 bits can be preferably selected or both of the 3, 6 bits can be further preferably selected. In a preferred aspect of the invention Ar 1 ～Ar 4 Are all identical groups. In a preferred aspect of the invention Ar 1 ～Ar 4 Each independently is a substituted or unsubstituted aryl group, more preferably a substituted or unsubstituted phenyl or naphthyl group, and still more preferably a substituted or unsubstituted phenyl group. The substituent may be any one selected from the substituent groups a to E described below, but an unsubstituted phenyl group is also preferable. As Ar 1 ～Ar 4 Specific examples of (a) include phenyl, o-biphenyl, m-biphenyl, p-biphenyl, and terphenyl.
In one aspect of the invention, m1 and m2 are each independently 0. In one aspect of the present invention, m1 and m2 are each independently an integer of any one of 1 to 5. In the present inventionIn one aspect, m1 and m2 are equal. In one aspect of the invention, R 41 R is R 42 The alkyl group having 1 to 6 carbon atoms may be selected from alkyl groups having 1 to 3 carbon atoms or methyl groups. Regarding the substitution position of the alkyl group, the carbon atom bonded to the boron atom may be exemplified as the 1-position, and it is only 2-position, only 3-position, only 4-position, 3-position and 5-position, 2-position and 4-position, 2-position and 6-position, 2-position and 4-position and 6-position, etc., preferably at least 2-position, more preferably at least 2-position and 6-position.
With respect to A 1 A is a 2 Reference can be made to the corresponding description of the general formula (16) for the description and preferred ranges thereof.
In the following, specific examples of the compound represented by the general formula (16 a) are given. The compounds of the general formula (16 a) which can be used in the present invention are not to be interpreted in a limiting manner by the following specific examples.
[ chemical formula 29-1]
[ chemical formula 29-2]
[ chemical formula 29-3]
[ chemical formula 29-4]
[ chemical formula 29-5]
[ chemical formula 29-6]
[ chemical formulas 29-7]
As a preferable group of compounds having a skeleton (16 b), compounds represented by the following general formula (16 b) can be exemplified.
General formula (16 b)
[ chemical formula 30]
Ar in the general formula (16 b) 5 ～Ar 8 Each independently represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. R is R 43 R is R 44 Each independently represents a substituted or unsubstituted alkyl group. m3 and m4 each independently represent an integer of 0 to 5, n6 and n8 each independently represent an integer of 0 to 3, and n5 and n7 each independently represent an integer of 0 to 4. A is that 1 A is a 2 Each independently represents a hydrogen atom, a deuterium atom or a substituent. With respect to Ar 5 ～Ar 8 、R 43 R is R 44 M3, m4, n5 to n8, A 1 、A 2 For details of (a), reference can be made to Ar of the general formula (16 a) 1 ～Ar 4 、R 41 R is R 42 M1, m2, n1 to n4, A 1 、A 2 The description of (2).
In the following, specific examples of the compound represented by the general formula (16 b) are given. The compounds of the general formula (16 b) which can be used in the present invention are not to be interpreted in a limiting manner by the following specific examples.
[ chemical formula 31]
When R of the general formula (16) 7 And R is 8 When bonded to each other to form N-Ph, the compound X of the present invention 1 When the compound is a nitrogen atom, for example, the compound has the following skeleton (17 a), when X 2 When the nitrogen atom is a nitrogen atom, the following skeleton (17 b) is provided. Ph is phenyl.
[ chemical formula 32]
Each hydrogen atom in the backbones (17 a) and (17 b) may be substituted with a deuterium atom or a substituent. Further, a cyclic structure may be formed by substitution with a linking group together with an adjacent hydrogen atom. For details, reference can be made to the corresponding R of the general formula (16) 1 ～R 26 、A 1 、A 2 The description of (2). At least one hydrogen atom in a benzene ring constituting a carbazole moiety structure included in the skeleton (17 a) is substituted with a substituted or unsubstituted aryl group. In one aspect of the present invention, each hydrogen atom in the backbones (17 a) and (17 b) may be substituted with a linking group together with an adjacent hydrogen atom without forming a cyclic structure.
As a preferred group of compounds having a skeleton (17 a), compounds represented by the following general formula (17 a) can be exemplified.
General formula (17 a)
[ chemical formula 33]
Ar in the general formula (17 a) 9 ～Ar 14 Each independently represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. n9, n11, n12, n14 each independently represent an integer of 0 to 4, and n10 and n13 each independently represent an integer of 0 to 2. Wherein at least one of n9, n10, n12, n13 is 1 or more. A is that 1 A is a 2 Each independently represents a hydrogen atom, a deuterium atom or a substituent.
In one aspect of the present invention, n9 to n14 each independently represents an integer of 0 to 2. In one aspect of the present invention, at least one of n9 to n14 is 1 or more, and for example, n9 and n12 may be 1 or more or n10 and n13 may be 1 or more. In a preferred aspect of the present invention, at least one of n9, n10, n12, n13 is 1 or more. In one aspect of the invention, n9 and n12 are each independently 1 or 2, n10, n11, n13, n14 are 0. In one aspect of the invention, n10 and n13 are each independently 1 or 2, n9, n11, n12, n14 are 0. In one aspect of the invention, n9 and n12 are each independently 1 or 2, n10 and n13 are each independently 1 or 2, and n11 and n14 are 0. In one aspect of the invention, n9 to n14 are each 1.Ar (Ar) 9 ～Ar 14 The bonding position of (a) may be set to 3, 6 or other positions of the carbazole ring. In a preferred aspect of the invention Ar 9 ～Ar 14 Are all identical groups. With respect to Ar 9 ～Ar 14 Can be referred to Ar 1 ～Ar 4 Corresponding to the above. With respect to A 1 A is a 2 Reference can be made to the corresponding description of the general formula (16) for the description and preferred ranges thereof.
In the following, specific examples of the compound represented by the general formula (17 a) are given. The compounds of the general formula (17 a) which can be used in the present invention are not to be interpreted in a limiting manner by the following specific examples.
[ chemical formula 34]
As a preferable group of compounds having a skeleton (17 b), compounds represented by the following general formula (17 b) can be exemplified.
General formula (17 b)
[ chemical formula 35]
Ar in the general formula (17 b) 15 ～Ar 20 Each independently represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. n15, n17, n18, n20 each independently represent an integer of 0 to 4, and n16 and n19 each independently represent an integer of 0 to 2. A is that 1 A is a 2 Each independently represents a hydrogen atom, a deuterium atom or a substituent. With respect to Ar 15 ～Ar 20 、n15～n20、A 1 、A 2 In detail, ar of the general formula (17 a) can be referred to in sequence 9 ～Ar 14 、n9～n14、A 1 、A 2 The description of (2).
In the following, specific examples of the compound represented by the general formula (17 b) are given. The compounds of the general formula (17 b) which can be used in the present invention are not to be interpreted in a limiting manner by the following specific examples.
[ chemical formula 36]
When R of the general formula (16) 7 And R is 8 When bonded to each other to form a single bond, the compounds of the invention are represented by X 1 When the compound is a nitrogen atom, for example, the compound has the following skeleton (18 a), when X 2 When the nitrogen atom is a nitrogen atom, the following skeleton (18 b) is provided.
[ chemical formula 37]
Each hydrogen atom in the backbones (18 a) and (18 b) may be substituted with a deuterium atom or a substituent. Further, a cyclic structure may be formed by substitution with a linking group together with an adjacent hydrogen atom. For details, reference can be made to the corresponding R of the general formula (16) 1 ～R 26 、A 1 、A 2 The description of (2). In one aspect of the present invention, each hydrogen atom in the backbones (18 a) and (18 b) may be substituted with a linking group together with an adjacent hydrogen atom without forming a cyclic structure.
As a preferred group of compounds having a skeleton (18 a), compounds represented by the following general formula (18 a) can be exemplified.
General formula (18 a)
[ chemical formula 38]
Ar in the general formula (18 a) 21 ～Ar 26 Each independently represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. n21, n23, n24, n26 each independently represent an integer of 0 to 4, and n22 and n25 each independently represent an integer of 0 to 2. A is that 1 A is a 2 Each independently represents a hydrogen atom, a deuterium atom or a substituent. With respect to Ar 21 ～Ar 25 For details of n21 to n25, reference can be made to Ar of the general formula (17 a) 9 ～Ar 14 、n9～n14、A 1 、A 2 The description of (2).
Specific examples of the compound represented by the general formula (18 a) are given below. The compounds of the general formula (18 a) which can be used in the present invention are not to be interpreted in a limiting manner by the following specific examples.
[ chemical formula 39]
As a preferred group of compounds having a skeleton (18 b), compounds represented by the following general formula (18 b) can be exemplified.
General formula (18 b)
[ chemical formula 40]
Ar in the general formula (18 b) 27 ～Ar 32 Each independently represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. n27, n29, n30, n32 each independently represent an integer of 0 to 4, and n28 and n31 each independently represent 0 to zero An integer of 2. A is that 1 A is a 2 Each independently represents a hydrogen atom, a deuterium atom or a substituent. With respect to Ar 27 ～Ar 32 、n27～n32、A 1 、A 2 In detail, ar of the general formula (17 b) can be referred to in sequence 15 ～Ar 20 、n15～n20、A 1 、A 2 The description of (2).
In the following, specific examples of the compound represented by the general formula (18 b) are given. The compounds of the general formula (18 b) which can be used in the present invention are not to be interpreted in a limiting manner by the following specific examples.
[ chemical formula 41]
In a preferred aspect of the present invention, a compound in which two benzene rings constituting the carbazole moiety structure present in the general formula (16) are condensed with other rings is selected. Among them, a compound in which benzofuran rings are condensed, a compound in which benzothiophene rings are condensed, and a compound in which benzene rings are condensed can be particularly preferably selected. In the following, specific examples will be described of compounds in which these rings are condensed.
The compound is preferably a compound in which a benzene ring, in which a boron atom is not directly bonded to a benzofuran ring or benzothiophene ring, among two benzene rings constituting the carbazole moiety structure existing in the general formula (16), is condensed. Examples of such a compound include a compound having the following skeleton (19 a) and a compound having the following skeleton (19 b).
[ chemical formula 42]
In the skeletons (19 a) and (19 b), Y 1 ～Y 4 Each independently represents two hydrogen atoms, a single bond or N (R) 27 ). The two hydrogen atoms described herein represent a state in which two benzene rings bonded to a boron atom are not connected to each other. Preferably Y 1 And Y 2 Identical and Y 3 And Y 4 The same as the first embodiment, but may be different from the second embodiment. In one aspect of the invention, Y 1 ～Y 4 Is a single bond. In one aspect of the invention, Y 1 ～Y 4 Is N (R) 27 )。R 27 Represents a hydrogen atom, a deuterium atom or a substituent.
Z 1 ～Z 4 Each independently represents an oxygen atom or a sulfur atom. Preferably Z 1 And Z 2 Identical and Z 3 And Z 4 The same as the first embodiment, but may be different from the second embodiment. In one aspect of the invention, Z 1 ～Z 4 Is an oxygen atom. In this case, the furan ring of the benzofuran is condensed with the benzene ring constituting the carbazole moiety structure in (19 a) and (19 b). The orientation of the fused furan ring is not limited. In one aspect of the invention, Z 1 ～Z 4 Is a sulfur atom. At this time, the thiophene ring of benzothiophene is condensed with the benzene ring constituting the carbazole moiety structure in (19 a) and (19 b). The orientation of the fused thiophene ring is not limited.
Each hydrogen atom in the backbones (19 a) and (19 b) may be substituted with a deuterium atom or a substituent. Further, a cyclic structure may be formed by substitution with a linking group together with an adjacent hydrogen atom. For details, reference can be made to the corresponding R of the general formula (16) 1 ～R 26 、A 1 、A 2 The description of (2). In one aspect of the present invention, each hydrogen atom in the backbones (19 a) and (19 b) may be substituted with a linking group together with an adjacent hydrogen atom without forming a cyclic structure.
As a preferred group of compounds having a skeleton (19 a), compounds represented by the following general formula (19 a) can be exemplified. In specific examples, X is an oxygen atom or a sulfur atom, and a compound in which X is an oxygen atom and a compound in which X is a sulfur atom are disclosed, respectively. X in the specific examples of the compounds represented by the following other general formulae also represents the same meaning.
General formula (19 a)
[ chemical formula 43]
Ar in the general formula (19 a) 51 Ar and Ar 52 Each independently represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. R is R 51 R is R 52 Each independently represents a substituted or unsubstituted alkyl group. m51 and m52 each independently represent an integer of 0 to 4. n51 and n52 each independently represent an integer of 0 to 2. Y is Y 1 ～Y 4 Each independently represents two hydrogen atoms, a single bond or N (R) 27 )。R 27 Represents a hydrogen atom, a deuterium atom or a substituent. Z is Z 1 ～Z 4 Each independently represents an oxygen atom or a sulfur atom. A is that 1 A is a 2 Each independently represents a hydrogen atom, a deuterium atom or a substituent.
In one aspect of the invention, n51 and n52 may be the same number. For example, n51 and n52 may be 0, and n51 and n52 may be 1. In one aspect of the invention, m51 and m52 may be the same number. In one aspect of the invention, m51 and m52 are integers from 0 to 3. For example, m51 and m52 may be 0, m51 and m52 may be 1, m51 and m52 may be 2, and m51 and m52 may be 3. With respect to Ar 51 、Ar 52 、R 51 、R 52 、A 1 、A 2 Can be referred to Ar of the general formula (16 a) 1 ～Ar 4 、R 41 ～R 42 、A 1 、A 2 Corresponding to the above.
In the following, specific examples of the compound represented by the general formula (19 a) are given. The compounds of the general formula (19 a) which can be used in the present invention are not to be interpreted in a limiting manner by the following specific examples. As specific examples containing X, a compound in which all X in the molecule are oxygen atoms and a compound in which all X in the molecule are sulfur atoms are disclosed, respectively. Compounds in which part of X in the molecule is an oxygen atom and the other is a sulfur atom may be used.
[ chemical formula 44-1]
/>
[ chemical formula 44-2]
[ chemical formula 44-3]
[ chemical formula 44-4]
[ chemical formula 44-5]
[ chemical formula 44-6]
[ chemical formula 44-7]
[ chemical formula 44-8]
As a preferable group of compounds having a skeleton (19 b), compounds represented by the following general formula (19 b) can be exemplified.
General formula (19 b)
[ chemical formula 45]
Ar in the general formula (19 b) 53 Ar and Ar 54 Each independently represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. R is R 53 R is R 54 Each independently represents a substituted or unsubstituted alkyl group. m53 and m54 each independently represent an integer of 0 to 4. n53 and n54 each independently represent an integer of 0 to 2. Y is Y 3 Y and Y 4 Each independently represents two hydrogen atoms, a single bond or N (R) 27 )。R 27 Represents a hydrogen atom, a deuterium atom or a substituent. Z is Z 3 Z is as follows 4 Each independently represents an oxygen atom or a sulfur atom. A is that 1 A is a 2 Each independently represents a hydrogen atom, a deuterium atom or a substituent. With respect to Ar 53 、Ar 54 、R 53 、R 54 、m53、m54、n53、n54、A 1 、A 2 For details of (a), reference can be made to Ar of the general formula (19 a) 51 、Ar 52 、R 51 、R 52 、m51、m52、n51、n52、A 1 、A 2 The description of (2).
In the following, specific examples of the compound represented by the general formula (19 b) are given. The compounds of the general formula (19 b) which can be used in the present invention are not to be interpreted in a limiting manner by the following specific examples. As specific examples containing X, a compound in which all X in the molecule are oxygen atoms and a compound in which all X in the molecule are sulfur atoms are disclosed, respectively. Compounds in which part of X in the molecule is an oxygen atom and the other is a sulfur atom may be used.
[ chemical formula 46]
The compound is preferably one in which a benzene ring directly bonded to a boron atom in two benzene rings constituting the carbazole moiety structure existing in the general formula (16) is condensed with a benzofuran ring or a benzothiophene ring. Examples of such a compound include a compound having the following skeleton (20 a) and a compound having the following skeleton (20 b).
[ chemical formula 47]
In the skeletons (20 a) and (20 b), Y 5 ～Y 8 Each independently represents two hydrogen atoms, a single bond or N (R) 27 )。Z 5 ～Z 8 Each independently represents an oxygen atom or a sulfur atom. With respect to Y 5 ～Y 8 、Z 5 ～Z 8 For details of (a), the corresponding descriptions of the skeletons (19 a) and (19 b) can be referred to. In one aspect of the present invention, each hydrogen atom in the backbones (20 a) and (20 b) may be substituted with a linking group together with an adjacent hydrogen atom without forming a cyclic structure.
As a preferable group of compounds of the skeleton (20 a), compounds represented by the following general formula (20 a) can be exemplified.
General formula (20 a)
[ chemical formula 48]
Ar in the general formula (20 a) 55 Ar and Ar 56 Each independently represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. R is R 55 R is R 56 Each independently represents a substituted or unsubstituted alkyl group. m55 and m56 each independently represent an integer of 0 to 4. n55 and n56 each independently represent an integer of 0 to 4. Y is Y 5 Y and Y 6 Each independently represents two hydrogen atoms, a single bond or N (R) 27 )。R 27 Represents a hydrogen atom, a deuterium atom or a substituent. Z is Z 5 Z is as follows 6 Each independently represents an oxygen atom or a sulfur atom. A is that 1 A is a 2 Each independently represents a hydrogen atom, a deuterium atom or a substituent.
In one aspect of the invention, n55 and n56 are integers from 0 to 2. For example, n55 and n56 may be 0, and n55 and n56 may be 1. In one aspect of the invention, m51 and m52 may be The same numbers. For details of m55 and m56, reference can be made to the descriptions of m51 and m52 of the general formula (19 a). With respect to Ar 55 、Ar 56 、R 55 、R 56 、A 1 、A 2 Can be referred to Ar of the general formula (16 a) 1 、Ar 3 、R 41 、R 42 、A 1 、A 2 Corresponding to the above.
In the following, specific examples of the compound represented by the general formula (20 a) are given. The compounds of the general formula (20 a) which can be used in the present invention are not to be interpreted in a limiting manner by the following specific examples. As specific examples containing X, a compound in which all X in the molecule are oxygen atoms and a compound in which all X in the molecule are sulfur atoms are disclosed, respectively. Compounds in which part of X in the molecule is an oxygen atom and the other is a sulfur atom may be used.
[ chemical formula 49-1]
[ chemical formula 49-2]
[ chemical formula 49-3]
[ chemistry 49-4]
[ chemistry 49-5]
As a preferred group of compounds having a skeleton (20 b), compounds represented by the following general formula (20 b) can be exemplified.
General formula (20 b)
[ chemical formula 50]
Ar in the general formula (20 b) 57 Ar and Ar 58 Each independently represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. R is R 57 R is R 58 Each independently represents a substituted or unsubstituted alkyl group. m57 and m58 each independently represent an integer of 0 to 4. n57 and n58 each independently represent an integer of 0 to 4. Y is Y 7 Y and Y 8 Each independently represents two hydrogen atoms, a single bond or N (R) 27 )。R 27 Represents a hydrogen atom, a deuterium atom or a substituent. Z is Z 7 Z is as follows 8 Each independently represents an oxygen atom or a sulfur atom. A is that 1 A is a 2 Each independently represents a hydrogen atom, a deuterium atom or a substituent. With respect to Ar 57 、Ar 58 、R 57 、R 58 、m57、m58、n57、n58、A 1 、A 2 For details of (a), reference can be made to Ar of the general formula (20 a) 55 、Ar 56 、R 55 、R 56 、m55、m56、n55、n56、A 1 、A 2 The description of (2).
In the following, specific examples of the compound represented by the general formula (20 b) are given. The compounds of the general formula (20 b) which can be used in the present invention are not to be interpreted in a limiting manner by the following specific examples. As specific examples containing X, a compound in which all X in the molecule are oxygen atoms and a compound in which all X in the molecule are sulfur atoms are disclosed, respectively. Compounds in which part of X in the molecule is an oxygen atom and the other is a sulfur atom may be used.
[ chemical formula 51]
Preferably, a compound in which both of the two benzene rings constituting the carbazole moiety structure existing in the general formula (16) are condensed with a benzofuran ring or a benzothiophene ring is exemplified. Examples of such a compound include a compound having the following skeleton (21 a) and a compound having the following skeleton (21 b).
[ chemical formula 52]
In the skeletons (21 a) and (21 b), Y 9 ～Y 12 Each independently represents two hydrogen atoms, a single bond or N (R) 27 )。Z 9 ～Z 16 Each independently represents an oxygen atom or a sulfur atom. Z is Z 9 ～Z 16 Preferably the same but may be different. In one aspect of the invention, Z 9 ～Z 16 Is an oxygen atom. In one aspect of the invention, Z 9 ～Z 16 Is a sulfur atom. With respect to Y 9 ～Y 12 For details of (a), the corresponding descriptions of the skeletons (19 a) and (19 b) can be referred to. In one aspect of the present invention, each hydrogen atom in the backbones (21 a) and (21 b) may be substituted with a linking group together with an adjacent hydrogen atom without forming a cyclic structure.
As a preferred group of compounds having a skeleton (21 a), compounds represented by the following general formula (21 a) can be exemplified.
General formula (21 a)
[ chemical formula 53]
In the general formula (21 a), R 59 R is R 60 Each independently represents a substituted or unsubstituted alkyl group. m59 and m60 each independently represent an integer of 0 to 4. Y is Y 9 Y and Y 10 Each independently represents two hydrogen atoms, a single bond or N (R) 27 )。R 27 Represents a hydrogen atom, a deuterium atom or a substituent. Z is Z 9 ～Z 12 Each independently represents an oxygen atom or a sulfur atom. A is that 1 A is a 2 Each independently represents a hydrogen atom, a deuterium atom or a substituent. With respect to R 59 、R 60 、m59、m60、Z 9 ～Z 12 、A 1 、A 2 For details of (a), reference can be made to R of the general formula (20 a) 55 、R 56 、m55、m56、A 1 、A 2 And Z in the skeleton (21 a) 9 ～Z 12 The description of (2).
In the following, specific examples of the compound represented by the general formula (21 a) are given. The compounds of the general formula (21 a) which can be used in the present invention are not to be interpreted in a limiting manner by the following specific examples. As specific examples containing X, a compound in which all X in the molecule are oxygen atoms and a compound in which all X in the molecule are sulfur atoms are disclosed, respectively. Compounds in which part of X in the molecule is an oxygen atom and the other is a sulfur atom may be used.
[ chemical formula 54-1]
[ chemical formula 54-2]
[ chemical formula 54-3]
[ chemical formula 54-4]
[ chemical formula 54-5]
As a preferred group of compounds having a skeleton (21 b), compounds represented by the following general formula (21 b) can be exemplified.
General formula (21 b)
[ chemical formula 55]
In the general formula (21 b), R 61 R is R 62 Each independently represents a substituted or unsubstituted alkyl group, and m61 and m60 each independently represent an integer of 0 to 4. Y is Y 11 Y and Y 12 Each independently represents two hydrogen atoms, a single bond or N (R) 27 )。R 27 Represents a hydrogen atom, a deuterium atom or a substituent. Z is Z 13 ～Z 16 Each independently represents an oxygen atom or a sulfur atom. A is that 1 A is a 2 Each independently represents a hydrogen atom, a deuterium atom or a substituent. With respect to R 61 、R 62 、m61、m62、Z 13 ～Z 16 、A 1 、A 2 For details of (a), reference can be made to R of the general formula (21 a) 59 、R 60 、m59、m60、A 1 、A 2 And Z in the skeleton (21 b) 13 ～Z 16 The description of (2).
In the following, specific examples of the compound represented by the general formula (21 b) are given. The compounds of the general formula (21 b) which can be used in the present invention are not to be interpreted in a limiting manner by the following specific examples. As specific examples containing X, a compound in which all X in the molecule are oxygen atoms and a compound in which all X in the molecule are sulfur atoms are disclosed, respectively. Compounds in which part of X in the molecule is an oxygen atom and the other is a sulfur atom may be used.
[ chemical formula 56-1]
[ chemical formula 56-2]
[ chemical formula 56-3]
The compound is preferably a compound in which a benzene ring in which a boron atom is not directly bonded to a benzene ring is condensed with the benzene ring among two benzene rings constituting the carbazole moiety structure existing in the general formula (16). Examples of such a compound include a compound having the following skeleton (22 a) and a compound having the following skeleton (22 b).
[ chemical formula 57]
In the skeletons (22 a) and (22 b), Y 21 ～Y 24 Each independently represents two hydrogen atoms, a single bond or N (R) 27 ). With respect to Y 21 ～Y 24 Can refer to Y of the skeletons (19 a) and (19 b) 1 ～Y 4 The description of (2). In one aspect of the present invention, each hydrogen atom in the backbones (22 a) and (22 b) may be substituted with a linking group together with an adjacent hydrogen atom without forming a cyclic structure.
As a preferred group of compounds having a skeleton (22 a), compounds represented by the following general formula (22 a) can be exemplified.
General formula (22 a)
[ chemical formula 58]
Ar in the general formula (22 a) 71 ～Ar 74 Each independently represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. n71 and n73 each independently represent an integer of 0 to 2. n72 and n74 minutesEach independently represents an integer of 0 to 4. Y is Y 21 Y and Y 22 Each independently represents two hydrogen atoms, a single bond or N (R) 27 )。R 27 Represents a hydrogen atom, a deuterium atom or a substituent. A is that 1 A is a 2 Each independently represents a hydrogen atom, a deuterium atom or a substituent.
In one aspect of the invention, n71 to n74 are integers from 0 to 2. In one aspect of the invention, n71 and n73 are the same number and n72 and n74 are the same number. n71 to n74 may be the same number. For example, n 71-n 74 may be 0. n71 to n74 may be 1. Also, for example, n71 and n73 may be 0, and n72 and n74 may be 1.
With respect to Ar 71 ～Ar 74 、A 1 、A 2 Can be referred to Ar of the general formula (16 a) 1 ～Ar 4 、A 1 、A 2 Corresponding to the above.
Specific examples of the compound represented by the general formula (22 a) are given below. The compounds of the general formula (22 a) which can be used in the present invention are not to be interpreted in a limiting manner by the following specific examples.
[ chemical formula 59]
As a preferred group of compounds having a skeleton (22 b), compounds represented by the following general formula (22 b) can be exemplified.
General formula (22 b)
[ chemical formula 60]
Ar in the general formula (22 b) 75 ～Ar 78 Each independently represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. n75 and n77 each independently represent an integer of 0 to 2. n76 and n78 each independently represent an integer of 0 to 4. Y is Y 23 Y and Y 24 Respectively independent earth's surface Shows two hydrogen atoms, a single bond or N (R) 27 )。R 27 Represents a hydrogen atom, a deuterium atom or a substituent. For the detailed description of n75 to n78, the description of n71 to n74 of the general formula (22 a) can be referred to in order. With respect to Ar 75 ～Ar 78 Can be referred to Ar of the general formula (16 a) 1 ～Ar 4 Corresponding to the above.
In the following, specific examples of the compound represented by the general formula (22 b) are given. The compounds of the general formula (22 b) which can be used in the present invention are not to be interpreted in a limiting manner by the following specific examples.
[ chemical formula 61]
The compound is preferably one in which a benzene ring directly bonded to a boron atom in two benzene rings constituting the carbazole moiety structure existing in the general formula (16) is condensed with a benzene ring. Examples of such a compound include a compound having the following skeleton (23 a) and a compound having the following skeleton (23 b).
[ chemical formula 62]
In the skeletons (23 a) and (23 b), Y 25 ～Y 28 Each independently represents two hydrogen atoms, a single bond or N (R) 27 ). With respect to Y 25 ～Y 28 For details of (a), the corresponding descriptions of the skeletons (19 a) and (19 b) can be referred to. In one aspect of the present invention, each hydrogen atom in the backbones (23 a) and (23 b) may be substituted with a linking group together with an adjacent hydrogen atom without forming a cyclic structure.
As a preferable group of compounds having a skeleton (23 a), compounds represented by the following general formula (23 a) can be exemplified.
General formula (23 a)
[ chemical formula 63]
Ar in the general formula (23 a) 79 Ar and Ar 80 Each independently represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. R is R 71 R is R 72 Each independently represents a substituted or unsubstituted alkyl group. m71 and m72 each independently represent an integer of 0 to 4. n79 and n80 each independently represent an integer of 0 to 4. Y is Y 25 Y and Y 26 Each independently represents two hydrogen atoms, a single bond or N (R) 27 )。R 27 Represents a hydrogen atom, a deuterium atom or a substituent. A is that 1 A is a 2 Each independently represents a hydrogen atom, a deuterium atom or a substituent.
In one aspect of the invention, n79 and n80 are integers from 0 to 2. In one aspect of the present invention, n79 and n80 are the same number, and may be, for example, 0 or 1. In one aspect of the invention, m71 and m72 are integers from 0 to 2. In one aspect of the present invention, m71 and m72 are the same number, and may be, for example, 0 or 1. With respect to Ar 79 、Ar 80 、R 71 、R 72 、A 1 、A 2 Can be referred to Ar of the general formula (16 a) 1 、Ar 3 、R 41 、R 42 、A 1 、A 2 Corresponding to the above.
In the following, specific examples of the compound represented by the general formula (23 a) are given. The compounds of the general formula (23 a) which can be used in the present invention are not to be interpreted in a limiting manner by the following specific examples.
[ chemical formula 64]
As a preferable group of compounds having a skeleton (23 b), compounds represented by the following general formula (23 b) can be exemplified.
General formula (23 b)
[ chemical formula 65]
/>
Ar in the general formula (23 b) 81 Ar and Ar 82 Each independently represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. R is R 73 R is R 74 Each independently represents a substituted or unsubstituted alkyl group. m73 and m74 each independently represent an integer of 0 to 4. n81 and n82 each independently represent an integer of 0 to 4. Y is Y 27 Y and Y 28 Each independently represents two hydrogen atoms, a single bond or N (R) 27 )。R 27 Represents a hydrogen atom, a deuterium atom or a substituent. A is that 1 A is a 2 Each independently represents a hydrogen atom, a deuterium atom or a substituent.
For a detailed description of m73, m74, n81, n82, reference can be made to the descriptions of m71, m72, n79, n80 of the general formula (23 a). With respect to Ar 81 、Ar 82 、R 73 、R 74 、A 1 、A 2 Can be referred to Ar of the general formula (16 a) 1 、Ar 3 、R 41 、R 42 、A 1 、A 2 Corresponding to the above.
In the following, specific examples of the compound represented by the general formula (23 b) are given. The compounds of the general formula (23 b) which can be used in the present invention are not to be interpreted in a limiting manner by the following specific examples.
[ chemical formula 66]
Preferably, a compound in which both of the two benzene rings constituting the carbazole moiety structure existing in the general formula (16) are condensed with benzene rings is exemplified. Examples of such a compound include a compound having the following skeleton (24 a) and a compound having the following skeleton (24 b).
[ chemical formula 67]
In the skeletons (24 a) and (24 b), Y 29 ～Y 32 Each independently represents two hydrogen atoms, a single bond or N (R) 27 ). With respect to Y 29 ～Y 32 For details of (a), the corresponding descriptions of the skeletons (19 a) and (19 b) can be referred to. In one aspect of the present invention, each hydrogen atom in the backbones (24 a) and (24 b) may be substituted with a linking group together with an adjacent hydrogen atom without forming a cyclic structure.
As a preferred group of compounds having a skeleton (24 a), compounds represented by the following general formula (24 a) can be exemplified.
General formula (24 a)
[ chemical formula 68]
In the general formula (24 a), R 75 R is R 76 Each independently represents a substituted or unsubstituted alkyl group, and m75 and m76 each independently represent an integer of 0 to 4. Y is Y 29 Y and Y 30 Each independently represents two hydrogen atoms, a single bond or N (R) 27 )。R 27 Represents a hydrogen atom, a deuterium atom or a substituent. A is that 1 A is a 2 Each independently represents a hydrogen atom, a deuterium atom or a substituent. With respect to R 75 、R 76 、m75、m76、A 1 、A 2 For details of (a), reference can be made to R of the general formula (23 a) 71 、R 72 、m71、m72、A 1 、A 2 The description of (2).
In the following, specific examples of the compound represented by the general formula (24 a) are given. The compounds of the general formula (24 a) which can be used in the present invention are not to be interpreted in a limiting manner by the following specific examples.
[ chemical formula 69-1]
[ chemical formula 69-2]
As a preferred group of compounds having a skeleton (24 b), compounds represented by the following general formula (24 b) can be exemplified.
General formula (24 b)
[ chemical formula 70]
In the general formula (24 b), R 77 R is R 78 Each independently represents a substituted or unsubstituted alkyl group, and m77 and m78 each independently represent an integer of 0 to 4. Y is Y 31 Y and Y 32 Each independently represents two hydrogen atoms, a single bond or N (R) 27 )。R 27 Represents a hydrogen atom, a deuterium atom or a substituent. A is that 1 A is a 2 Each independently represents a hydrogen atom, a deuterium atom or a substituent. With respect to R 77 、R 78 、m77、m78、A 1 、A 2 For details of (a), reference can be made to R of the general formula (23 a) 71 、R 72 、m71、m72、A 1 、A 2 The description of (2).
In the following, specific examples of the compound represented by the general formula (24 b) are given. The compounds of the general formula (24 b) which can be used in the present invention are not to be interpreted in a limiting manner by the following specific examples.
[ chemical formula 71]
/>
As the compound represented by the general formula (16), a compound having a structure including four or more carbazole moieties in the molecule is also preferable. Examples of such a compound include the following skeleton (25).
Skeleton (25)
[ chemical formula 72]
Each hydrogen atom in the skeleton (25) may be substituted with a deuterium atom or a substituent. Further, a cyclic structure may be formed by substitution with a linking group together with an adjacent hydrogen atom. For details, reference can be made to the corresponding R of the general formula (16) 1 ～R 26 、A 1 、A 2 The description of (2). At least one hydrogen atom in a benzene ring constituting a carbazole moiety structure included in the skeleton (25) is substituted with a substituted or unsubstituted aryl group. In one aspect of the invention, each hydrogen atom in the backbone (25) may be replaced with a linking group along with an adjacent hydrogen atom without forming a cyclic structure.
As a preferred group of compounds having a skeleton (25), compounds represented by the following general formula (25) can be exemplified.
General formula (25)
[ chemical formula 73]
Ar in the general formula (25) 91 ～Ar 94 Each independently represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. n91 and n93 each independently represent an integer of 0 to 4, and n92 and n94 each independently represent an integer of 0 to 3. The alpha, beta, gamma, delta rings may be substituted, at least one ring being substituted with a substituted or unsubstituted aryl group, fused with a benzene ring which may be substituted, or fused with a furan ring of a substituted or unsubstituted benzofuran or a thiophene ring of a substituted or unsubstituted benzothiophene. A is that 1 A is a 2 Each independently represents a hydrogen atom, a deuterium atom or a substituent.
In one aspect of the invention, n91 to n94 are integers from 0 to 2. In one aspect of the invention, n91 and n93 are the same number, and n92 and n94 are Are the same number. n91 to n94 may be the same number, and may be, for example, 0 or 1. With respect to Ar 91 ～Ar 94 Can be referred to Ar of the general formula (16 a) 1 ～Ar 4 Corresponding to the above. In one aspect of the invention, the alpha and gamma rings have the same substituent or have the same condensed structure, and the beta and delta rings have the same substituent or have the same condensed structure. In one aspect of the invention, the β and δ rings are substituted simultaneously with a substituted or unsubstituted aryl, fused with a benzene ring that may be substituted, or fused with a furan ring of a substituted or unsubstituted benzofuran or a thiophene ring of a substituted or unsubstituted benzothiophene. In one aspect of the invention, the alpha and gamma rings are simultaneously substituted with a substituted or unsubstituted aryl group, fused with a benzene ring which may be substituted, or a furan ring of a substituted or unsubstituted benzofuran or a thiophene ring of a substituted or unsubstituted benzothiophene. In one aspect of the invention, the alpha, beta, gamma, delta rings are each substituted with a substituted or unsubstituted aryl group, a benzene ring which may be substituted, or a thiophene ring fused with a furan ring of a substituted or unsubstituted benzofuran or a substituted or unsubstituted benzothiophene. With respect to A 1 A is a 2 Reference can be made to the corresponding description of the general formula (16) for the description and preferred ranges thereof.
In the following, specific examples of the compound represented by the general formula (25) are given. The compounds of the general formula (25) which can be used in the present invention are not to be interpreted in a limiting manner by the following specific examples.
[ chemical formula 74-1]
[ chemical formula 74-2]
[ chemical formula 74-3]
In one aspect of the present invention, the backbones (16 a) to (25) are backbones which are not fused with other rings. In one aspect of the present invention, the skeletons (16 a) to (25) are skeletons condensed with other rings. For other rings as described herein, reference can be made to R as described above 1 And R is 2 、R 2 And R is 3 、R 3 And R is 4 、R 4 And R is 5 、R 5 And R is 6 、R 6 And R is 7 、R 8 And R is 9 、R 9 And R is 10 、R 10 And R is 11 、R 11 And R is 12 、R 13 And R is 14 、R 14 And R is 15 、R 15 And R is 16 、R 16 And R is 17 、R 18 And R is 19 、R 19 And R is 20 、R 20 And R is 21 、R 22 And R is 23 、R 23 And R is 24 、R 24 And R is 25 、R 25 And R is 26 And a ring structure formed by bonding them together.
In one aspect of the invention, A of formula (16) 1 And A 2 Is an acceptor group. For example, may include A 1 And A 2 A compound having any one of the skeletons (16 a) to (25) at the acceptor group. For description and specific examples of acceptor groups, reference can be made to A of the above-mentioned formula (16) 1 And A 2 Description and specific examples of acceptor groups.
Hereinafter, A is exemplified as 1 And A 2 Specific examples of compounds that are acceptor groups. A which can be used in the invention 1 And A 2 The compounds which are acceptor groups are not to be interpreted in a limiting manner by the following specific examples. In the following specific examples, A 1 And A 2 Meanwhile, the structure of each compound is specified by specifying "a" alone, while having a structure as "a".
[ chemical formula 75-1]
[ chemical formula 75-2]
[ chemical formula 75-3]
[ chemical formula 75-4]
[ chemical formulas 75-5]
[ chemical formulas 75-6]
[ chemical formulas 75-7]
[ chemical formulas 75-8]
[ chemical formulas 75-9]
In one aspect of the present invention, a compound having a rotationally symmetrical structure is selected as the compound represented by the general formula (16). In one aspect of the present invention, a compound having a line-symmetrical structure is selected as the compound represented by the general formula (16). In one aspect of the present invention, a compound having an asymmetric structure is selected as the compound represented by the general formula (16).
Specific examples of the compound having an asymmetric skeleton are given below. The compound having an asymmetric skeleton and the compound having an asymmetric structure that can be used in the present invention are not to be interpreted in a limiting manner by the following specific examples. As specific examples containing X, a compound in which all X in the molecule are oxygen atoms and a compound in which all X in the molecule are sulfur atoms are disclosed, respectively. Compounds in which part of X in the molecule is an oxygen atom and the other is a sulfur atom may be used.
[ chemical formula 76-1]
[ chemical formula 76-2]
In a particularly preferred aspect of the present invention, as the 3 rd organic compound, a compound in which at least one of a tert-butyl group and a phenyl group is introduced into the following skeleton (26 a) or skeleton (26 b) is selected.
[ chemical formula 77]
In the following, specific examples of the compound having at least one of a tert-butyl group and a phenyl group introduced into the skeleton (26 a) or the skeleton (26 b) are given. The compounds of the general formula (16) which can be used in the present invention are not to be interpreted in a limiting manner by the following specific examples.
[ chemical formula 78-1]
[ chemical formula 78-2]
[ chemical formula 78-3]
[ chemical formula 78-4]
[ chemical formula 78-5]
The molecular weight of the compound represented by the general formula (16) is preferably 1500 or less, more preferably 1200 or less, even more preferably 1000 or less, and even more preferably 900 or less, when the compound represented by the general formula (16) is used by, for example, attempting to form a film on an organic layer containing the compound represented by the general formula (16) by vapor deposition. The lower limit of the molecular weight is the molecular weight of the smallest compound of the group of compounds represented by the general formula (16). Preferably 624 or more.
The compound represented by the general formula (16) can be formed into a film by a coating method regardless of the molecular weight. When the coating method is used, a film can be formed even with a compound having a relatively large molecular weight. The compound represented by the general formula (16) has an advantage of being easily dissolved in an organic solvent. Therefore, the compound represented by the general formula (16) can be easily applied to a coating method, and can be easily purified to improve the purity.
It is also possible to consider that the present invention is applied to use a compound containing a plurality of structures represented by the general formula (16) in the molecule as a light-emitting material.
For example, a polymer obtained by pre-existing a polymerizable group in a structure represented by the general formula (16) and polymerizing the polymerizable group can be considered as a light-emitting material. Specifically, it is conceivable to prepare a monomer containing a polymerizable functional group in any one of the structures represented by the general formula (16), polymerize it alone or copolymerize it with other monomers to obtain a polymer having a repeating unit, and use the polymer as a light-emitting material. Alternatively, it is also conceivable to obtain a dimer or trimer by coupling the compounds represented by the general formula (16) to each other, and use these as a light-emitting material.
Examples of the polymer including a repeating unit having a structure represented by the general formula (16) include polymers having a structure represented by the following general formula.
[ chemical formula 79]
In the above formula, Q represents a group comprising the structure represented by the formula (16), L 1 L and L 2 Representing a linking group. The number of carbon atoms of the linking group is preferably 0 to 20, more preferably 1 to 15, and still more preferably 2 to 10. The linking group preferably has the formula-X 11 -L 11 -a linking group of the represented structure. Here, X is 11 Represents an oxygen atom or a sulfur atom, preferably an oxygen atom. L (L) 11 Represents a linking group, preferably a substituted or unsubstituted alkylene group or a substituted or unsubstituted arylene group, more preferably a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms or a substituted or unsubstituted phenylene group.
R 101 、R 102 、R 103 R is R 104 Each independently represents a substituent. Preferably substituted or unsubstituted, having 1 to 6 carbon atomsAlkyl group, alkoxy group having 1 to 6 carbon atoms which may be substituted or unsubstituted, halogen atom, more preferably alkyl group having 1 to 3 carbon atoms which may be unsubstituted, alkoxy group having 1 to 3 carbon atoms which may be unsubstituted, fluorine atom, chlorine atom, still more preferably alkyl group having 1 to 3 carbon atoms which may be unsubstituted, alkoxy group having 1 to 3 carbon atoms which may be unsubstituted.
L 1 L and L 2 The linking group represented may be bonded at any position in the structure represented by the general formula (16) constituting Q. More than two linking groups may be linked to one Q to form a cross-linked structure or a network.
Specific examples of the structure of the repeating unit may include a structure represented by the following formula.
[ chemical formula 80]
Polymers having repeating units comprising these formulae can be synthesized by: hydroxyl groups are introduced into any position in the structure represented by the general formula (16) in advance, and the compound described below is reacted as a linking group to introduce a polymerizable group, and the polymerizable group is polymerized.
[ chemical formula 81]
The polymer having the structure represented by the general formula (16) in the molecule may be a polymer composed of only the repeating unit having the structure represented by the general formula (16), or may be a polymer having a repeating unit having another structure. The repeating unit having the structure represented by the general formula (16) contained in the polymer may be one kind or 2 or more kinds. The repeating unit not having the structure represented by the general formula (16) may include a repeating unit derived from a monomer commonly used for copolymerization. For example, a repeating unit derived from a monomer having an ethylenic unsaturated bond such as ethylene, styrene, or the like may be included.
The compound represented by the general formula (16) preferably contains no metal atom. The metal atoms described herein do not contain boron atoms. For example, as the compound represented by the general formula (16), a compound composed of an atom selected from the group consisting of a carbon atom, a hydrogen atom, a deuterium atom, a nitrogen atom, an oxygen atom, a sulfur atom and a boron atom can be selected. For example, as the compound represented by the general formula (16), a compound composed of an atom selected from the group consisting of a carbon atom, a hydrogen atom, a deuterium atom, a nitrogen atom, an oxygen atom, and a boron atom can be selected. For example, as the compound represented by the general formula (16), a compound composed of an atom selected from the group consisting of a carbon atom, a hydrogen atom, a deuterium atom, a nitrogen atom, a sulfur atom and a boron atom can be selected. For example, as the compound represented by the general formula (16), a compound composed of an atom selected from the group consisting of a carbon atom, a hydrogen atom, a deuterium atom, a nitrogen atom and a boron atom can be selected. For example, as the compound represented by the general formula (16), a compound composed of an atom selected from the group consisting of a carbon atom, a hydrogen atom, a nitrogen atom, an oxygen atom, a sulfur atom, and a boron atom can be selected.
As used herein, "alkyl" may be any of linear, branched, and cyclic. Further, 2 or more kinds of the linear part, the cyclic part, and the branched part may be mixed. The number of carbon atoms of the alkyl group can be 1 or more, 2 or more, or 4 or more, for example. The number of carbon atoms may be 30 or less, 20 or less, 10 or less, 6 or less, or 4 or less. Specific examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, 2-ethylhexyl, n-heptyl, isoheptyl, n-octyl, isooctyl, n-nonyl, isononyl, n-decyl, isodecyl, cyclopentyl, cyclohexyl and cycloheptyl. The alkyl group as a substituent may be further substituted with an aryl group.
The "alkenyl" may be any of straight-chain, branched, and cyclic. Further, 2 or more kinds of the linear part, the cyclic part, and the branched part may be mixed. The number of carbon atoms of the alkenyl group can be, for example, 2 or more and 4 or more. The number of carbon atoms may be 30 or less, 20 or less, 10 or less, 6 or less, or 4 or less. Specific examples of the alkenyl group include vinyl group, n-propenyl group, isopropenyl group, n-butenyl group, isobutenyl group, n-pentenyl group, isopentenyl group, n-hexenyl group, cyclohexenyl group and 2-ethylhexyl group. Alkenyl groups as substituents may be further substituted with substituents.
The "aryl" and "heteroaryl" may be a single ring or a condensed ring formed by condensing two or more rings. In the case of condensed rings, the number of condensed rings is preferably 2 to 6, and can be selected from 2 to 4, for example. Specific examples of the ring include a benzene ring, a pyrazinyl ring, a pyrimidine ring, a triazine ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a triphenylene ring, a quinoline ring, a pyrazine ring, a quinoxaline ring, and a naphthyridine ring, and these rings may be condensed. Specific examples of the aryl or heteroaryl group include phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 2-pyridyl, 3-pyridyl and 4-pyridyl. The number of ring skeleton constituting atoms of the aryl group is preferably 6 to 40, more preferably 6 to 20, and may be selected in the range of 6 to 14 or in the range of 6 to 10. The number of the ring skeleton constituting the heteroaryl group is preferably 4 to 40, more preferably 5 to 20, and may be selected in the range of 5 to 14 or in the range of 5 to 10. "arylene" and "heteroaryl" can be groups in which the valences in the description of aryl and heteroaryl are replaced by 1 to 2.
As used herein, "substituent group A" means a nitro group selected from one or two groups selected from the group consisting of a hydroxyl group, a halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, iodine atom), an alkyl group (e.g., 1 to 40 carbon atoms), an alkoxy group (e.g., 1 to 40 carbon atoms), an alkylthio group (e.g., 1 to 40 carbon atoms), an aryl group (e.g., 6 to 30 carbon atoms), an aryloxy group (e.g., 6 to 30 carbon atoms), an arylthio group (e.g., 6 to 30 carbon atoms), a heteroaryl group (e.g., 5 to 30 ring skeleton members), a heteroarylthio group (e.g., 5 to 30 ring skeleton members), an acyl group (e.g., 1 to 40 carbon atoms), an alkenyl group (e.g., 1 to 40 carbon atoms), an alkynyl group (e.g., 1 to 40 carbon atoms), an alkoxycarbonyl group (e.g., 1 to 40 carbon atoms), an aryloxycarbonyl group (e.g., 1 to 40 carbon atoms), a heteroaryloxycarbonyl group (e.g., 1 to 40 carbon atoms), a silyl group (e.g., 1 to 40 carbon atoms), and a trialkylsilyl group.
The "substituent group B" herein means one group or a combination of two or more groups selected from the group consisting of an alkyl group (for example, 1 to 40 carbon atoms), an alkoxy group (for example, 1 to 40 carbon atoms), an aryl group (for example, 6 to 30 carbon atoms), an aryloxy group (for example, 6 to 30 carbon atoms), a heteroaryl group (for example, 5 to 30 ring skeleton constituent atoms), a heteroaryloxy group (for example, 5 to 30 ring skeleton constituent atoms), and a diarylamino group (for example, 0 to 20 carbon atoms).
The "substituent group C" herein means one group or a combination of two or more groups selected from the group consisting of an alkyl group (for example, 1 to 20 carbon atoms), an aryl group (for example, 6 to 22 carbon atoms), a heteroaryl group (for example, 5 to 20 ring skeleton constituent atoms), and a diarylamino group (for example, 12 to 20 carbon atoms).
The "substituent group D" herein means one group or a combination of two or more groups selected from the group consisting of an alkyl group (for example, 1 to 20 carbon atoms), an aryl group (for example, 6 to 22 carbon atoms), and a heteroaryl group (for example, 5 to 20 ring skeleton constituent atoms).
The "substituent group E" herein means one group or a combination of two or more groups selected from the group consisting of an alkyl group (for example, having 1 to 20 carbon atoms) and an aryl group (for example, having 6 to 22 carbon atoms).
Substituents described herein as "substituents" or "substituted or unsubstituted" may be selected, for example, from substituent group a, from substituent group B, from substituent group C, from substituent group D, or from substituent group E.
As the 3 rd organic compound, the following compounds can also be used.
In a preferred aspect of the present invention, a compound represented by the following general formula (27) is used as the 3 rd organic compound.
General formula (27)
[ chemical formula 82]
In the above general formula (27), ar 1 ～Ar 3 Each independently is an aromatic or heteroaromatic ring, at least one hydrogen atom of which may be substituted, and the rings may be fused. When the hydrogen atom is substituted, it is preferably substituted with one group selected from the group consisting of deuterium atom, aryl group, heteroaryl group and alkyl group, or a combination of two or more groups. And, when the rings are condensed, it is preferable that a benzene ring or a heteroaromatic ring (for example, furan ring, thiophene ring, pyrrole ring, etc.) is condensed. R is R a R is R a ' each independently represents a substituent, preferably one group selected from the group consisting of deuterium atoms, aryl groups, heteroaryl groups, and alkyl groups, or a combination of two or more groups. R is R a And Ar is a group 1 、Ar 1 And Ar is a group 2 、Ar 2 And R is a ’、R a ' and Ar 3 、Ar 3 And R is a Can be bonded to each other to form a ring structure.
The compound represented by the general formula (27) preferably contains at least one carbazole structure. For example, one benzene ring constituting the carbazole structure may be Ar 1 The ring represented may be Ar as one of the benzene rings constituting the carbazole structure 2 The ring represented may be Ar as one of the benzene rings constituting the carbazole structure 3 Represented ring. And the carbazolyl group may be substituted with Ar 1 ～Ar 3 Any one or more of the bonds. For example, substituted or unsubstituted carbazol-9-yl may be substituted with Ar 3 The indicated ring bonds.
Thick anthracene, pyrene, perylene, etcThe aromatic ring structure may be bonded to Ar 1 ～Ar 3 And (5) bonding. And Ar is 1 ～Ar 3 The ring represented may be one ring constituting a condensed aromatic ring structure. In addition, R a R is R a At least one of' may be a group having a fused aromatic ring structure.
The skeleton represented by the general formula (27) may be present in plural numbers in the compound. For example, the skeletons represented by the general formula (27) may have a structure in which the skeletons are bonded to each other via a single bond or a linking group. In addition, a structure that exhibits a multiple resonance effect in which benzene rings are connected to each other by a boron atom, a nitrogen atom, an oxygen atom, and a sulfur atom may be further added to the skeleton represented by the general formula (27).
In a preferred aspect of the present invention, a compound comprising a BODIPY (4, 4-difluoro-4-bora-3a,4a-diaza-s-indacene:4, 4-difluoro-4-boron-3 a,4 a-diaza-s-indene) structure is used as the 3 rd organic compound. For example, a compound represented by the following general formula (28) is used.
General formula (28)
[ chemical formula 83]
In the general formula (28), R 1 ～R 7 Each independently is a hydrogen atom, a deuterium atom or a substituent. R is R 1 ～R 7 At least one of them is preferably a group represented by the following general formula (29).
General formula (29)
[ chemical formula 84]
In the general formula (29), R 11 ～R 15 Each independently represents a hydrogen atom, a deuterium atom or a substituent, and represents a bonding position.
The group represented by the general formula (29) may be R of the general formula (28) 1 ～R 7 In (a) and (b)One, two or three may be used. Further, at least four, for example, four or five may be provided. In a preferred aspect of the invention, R 1 ～R 7 One of them is a group represented by the general formula (29). In a preferred aspect of the invention, at least R 1 、R 3 、R 5 、R 7 Is a group represented by the general formula (29). In a preferred aspect of the invention, R is only 1 、R 3 、R 4 、R 5 、R 7 Is a group represented by the general formula (29). In a preferred aspect of the invention, R 1 、R 3 、R 4 、R 5 、R 7 Is a group represented by the general formula (29), R 2 R is R 4 Is a hydrogen atom, a deuterium atom, an unsubstituted alkyl group (for example, having 1 to 10 carbon atoms) or an unsubstituted aryl group (for example, having 6 to 14 carbon atoms). In one aspect of the invention, R 1 ～R 7 Are all groups represented by the general formula (29).
In a preferred aspect of the invention, R 1 And R is 7 The same applies. In a preferred aspect of the invention, R 3 And R is 5 The same applies. In a preferred aspect of the invention, R 2 And R is 6 The same applies. In a preferred aspect of the invention, R 1 And R is 7 Identical, R 3 And R is 5 Identical, and R is 1 And R is 3 Different from each other. In a preferred aspect of the invention, R 1 、R 3 、R 5 、R 7 The same applies. In a preferred aspect of the invention, R 1 And R is 4 And R is 7 Identical, R 3 And R is 5 Different. In a preferred aspect of the invention, R 3 And R is 4 And R is 5 Identical, R 1 And R is 7 Different. In a preferred aspect of the invention, R 1 、R 3 、R 5 、R 7 Are all with R 4 Different.
R as the general formula (29) 11 ～R 15 Substituents which can be used are, for example, the groups of the abovementioned substituent groups A. R is R 11 ～R 15 Substituents which may be usedPreferably, the compound is one group or a combination of two or more groups selected from the group consisting of a substituted or unsubstituted alkyl group (for example, 1 to 40 carbon atoms), a substituted or unsubstituted alkoxy group (for example, 1 to 40 carbon atoms), a substituted or unsubstituted aryl group (for example, 6 to 30 carbon atoms), a substituted or unsubstituted aryloxy group (for example, 6 to 30 carbon atoms), a substituted or unsubstituted amino group (for example, 0 to 20 carbon atoms) (hereinafter, these groups are referred to as "groups of substituent group C"). In the substituent group C, an unsubstituted alkyl group having 1 to 20 carbon atoms, an unsubstituted alkoxy group having 1 to 20 carbon atoms, an unsubstituted aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, or a ring skeleton is preferably selected to constitute an unsubstituted diarylamino group having 5 to 20 carbon atoms (hereinafter, these groups will be referred to as "groups of the substituent group D"). The substituted amino group described herein is preferably a di-substituted amino group, and the two substituents for the amino group are preferably each independently a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, or a substituted or unsubstituted alkyl group, and particularly preferably a substituted or unsubstituted aryl group (diarylamino group). As the substituents which can be used for the two aryl groups of the diarylamino group, the group of the substituent group a, the group of the substituent group B or the group of the substituent group C can be selected. The two aryl groups of the diarylamino group may be bonded to each other via a single bond or a linking group, for which reference can be made to R as described herein 33 And R is 34 Description of the linking group in (a). As a specific example of the diarylamino group, for example, a substituted or unsubstituted carbazol-9-yl group may be used. As the substituted or unsubstituted carbazol-9-yl group, for example, L of the above general formula (6) may be included 11 A group which is a single bond.
In a preferred aspect of the invention, R alone of formula (29) 13 R is a substituent, R 11 、R 12 、R 14 、R 15 Is a hydrogen atom. In a preferred aspect of the invention, R alone of formula (29) 11 R is a substituent, R 12 、R 13 、R 14 、R 15 Is a hydrogen atom. In a preferred aspect of the invention, R alone of formula (29) 11 And R is 13 R is a substituent, R 12 、R 14 、R 15 Is a hydrogen atom.
R in the general formula (28) 1 ～R 7 May contain R of the formula (29) 11 ～R 15 Groups each being a hydrogen atom (that is, phenyl). For example, R 2 、R 4 、R 6 May be phenyl.
In the general formula (28), R 8 R is R 9 Preferably, each independently is one group selected from the group consisting of a hydrogen atom, a deuterium atom, a halogen atom, an alkyl group (for example, having 1 to 40 carbon atoms), an alkoxy group (for example, having 1 to 40 carbon atoms), an aryloxy group (for example, having 6 to 30 carbon atoms), and a cyano group, or a group formed by combining two or more groups. In a preferred embodiment of the invention, R 8 And R is 9 The same applies. In a preferred embodiment of the invention, R 8 And R is 9 Halogen atoms, particularly preferably fluorine atoms.
In one aspect of the invention, R is present in formula (28) 1 ～R 9 The total of the number of the substituted or unsubstituted alkoxy groups, the substituted or unsubstituted aryloxy groups, and the substituted or unsubstituted amino groups is preferably three or more, and for example, three compounds or four compounds can be used. More preferably, R is present in formula (28) 1 ～R 7 The total of the number of the substituted or unsubstituted alkoxy groups, the substituted or unsubstituted aryloxy groups, and the substituted or unsubstituted amino groups is preferably three or more, and for example, a compound of three or a compound of four can be used. At this time, at R 8 And R is 9 Alkoxy, aryloxy, amino groups may not be present. More preferably, R present in formula (28) 1 、R 3 、R 4 、R 5 、R 7 The total number of the substituted or unsubstituted alkoxy groups, the substituted or unsubstituted aryloxy groups, the substituted or unsubstituted amino groups in (a) is preferably three or more, and for example, three can be usedOr four compounds can be used. At this time, at R 2 、R 6 、R 8 、R 9 Alkoxy, aryloxy, amino groups may not be present. In a preferred aspect of the present invention, there are more than three substituted or unsubstituted alkoxy groups. In a preferred aspect of the present invention, there are more than four substituted or unsubstituted alkoxy groups. In a preferred aspect of the present invention, more than one substituted or unsubstituted alkoxy group is present and more than two substituted or unsubstituted aryloxy groups are present. In a preferred aspect of the present invention, two or more substituted or unsubstituted alkoxy groups are present and one or more substituted or unsubstituted amino groups are present. In a preferred aspect of the invention, in R 1 、R 4 、R 7 Respectively, there are substituted or unsubstituted alkoxy groups or substituted or unsubstituted aryloxy groups. In a preferred aspect of the invention, in R 1 、R 4 、R 7 Respectively, have a substituted or unsubstituted alkoxy group.
In one aspect of the invention, R is present in formula (28) 1 ～R 9 The sum of substituents having a sigma p value of Hammett of less than-0.2 is three or more. Examples of the substituent having a sigma p value of Hammett of less than-0.2 include methoxy group (-0.27), ethoxy group (-0.24), n-propoxy group (-0.25), isopropoxy group (-0.45) and n-butoxy group (-0.32). On the other hand, fluorine atom (0.06), methyl group (-0.17), ethyl group (-0.15), tert-butyl group (-0.20), n-hexyl group (-0.15), cyclohexyl group (-0.15) and the like are substituents having a sigma p value of less than-0.2 other than Hammett.
In one aspect of the invention, R present in formula (28) can be employed 1 ～R 9 The number of substituents having a sigma p value of less than-0.2 in hamite is three, or four can be used. More preferably, R is present in formula (28) 1 ～R 7 The number of substituents having a sigma p value of less than-0.2 in Hammett is preferably 3 or more, and for example, a number of 3 compounds or a number of 4 compounds may be used. At this time, at R 8 And R is 9 May not be present inSubstituents having a sigma p value of Hammett less than-0.2. More preferably, R present in formula (28) 1 、R 3 、R 4 、R 5 、R 7 The number of substituents having a sigma p value of less than-0.2 in Hammett is preferably 3 or more, and for example, a number of 3 compounds or a number of 4 compounds may be used. At this time, at R 2 、R 6 、R 8 、R 9 Substituents having a sigma p value of Hammett less than-0.2 may be absent. In a preferred aspect of the invention, in R 1 、R 4 、R 7 Substituents having a sigma p value of Hammett of less than-0.2, respectively.
Hereinafter, preferred compounds that can be used as the 3 rd organic compound are exemplified. In the structural formulae of the exemplary compounds below, t-Bu represents tert-butyl.
[ chemical formula 85-1]
[ chemical formula 85-2]
[ chemical formula 85-3]
[ chemical formula 85-4]
The derivative of the above-mentioned exemplary compound includes a compound in which at least one hydrogen atom is substituted with a deuterium atom, an alkyl group, an aryl group, a heteroaryl group, or a diarylamino group.
Furthermore, the 3 rd organic compound of the present invention may be particularly preferably used as the compound described in paragraphs 0220 to 0239 of WO2015/022974, paragraphs 0066 and 0117 of WO2019/111971, and paragraphs 0196 to 0255 of WO 2021/015177.
(light-emitting layer)
The light-emitting layer of the organic electroluminescent element of the present invention comprises the 1 st organic compound, the 2 nd organic compound and the 3 rd organic compound satisfying the conditions (a) and (b). In a preferred aspect of the present invention, the compound T132 is used as the 2 nd organic compound, and the compound selected from the group consisting of the compounds F101 to F128 is used as the 3 rd organic compound. The light-emitting layer can have the following structure: the organic compound 1, the organic compound 2, and the organic compound 3 do not contain a compound that transfers electric charges or energy or a metal element other than boron. The light-emitting layer may be composed of only a compound composed of an atom selected from the group consisting of a carbon atom, a hydrogen atom, a deuterium atom, a nitrogen atom, a boron atom, an oxygen atom, and a sulfur atom. For example, the light-emitting layer can be composed of only a compound composed of an atom selected from the group consisting of a carbon atom, a hydrogen atom, a deuterium atom, a nitrogen atom, a boron atom, and an oxygen atom. For example, the light-emitting layer can be composed of only a compound composed of an atom selected from the group consisting of a carbon atom, a hydrogen atom, a deuterium atom, a nitrogen atom, a boron atom, and a sulfur atom. For example, the light-emitting layer can be composed of only a compound composed of an atom selected from the group consisting of a carbon atom, a hydrogen atom, a deuterium atom, a nitrogen atom, and a boron atom. For example, the light-emitting layer can be composed of only a compound composed of an atom selected from the group consisting of a carbon atom, a hydrogen atom, a deuterium atom, a nitrogen atom, an oxygen atom, and a sulfur atom. For example, the light-emitting layer can be composed of only a compound composed of an atom selected from the group consisting of a carbon atom, a hydrogen atom, a deuterium atom, and a nitrogen atom. The light-emitting layer may include a 1 st organic compound composed of an atom selected from the group consisting of a carbon atom, a hydrogen atom, a nitrogen atom, and an oxygen atom, a 2 nd organic compound composed of an atom selected from the group consisting of a carbon atom, a hydrogen atom, a deuterium atom, a nitrogen atom, an oxygen atom, and a sulfur atom, and a 3 rd organic compound composed of an atom selected from the group consisting of a carbon atom, a hydrogen atom, a deuterium atom, a nitrogen atom, a boron atom, an oxygen atom, and a sulfur atom. The light-emitting layer may contain a 1 st organic compound composed of an atom selected from the group consisting of a carbon atom, a hydrogen atom, a nitrogen atom, and an oxygen atom, a 2 nd organic compound composed of an atom selected from the group consisting of a carbon atom, a hydrogen atom, a deuterium atom, and a nitrogen atom, and a 3 rd organic compound composed of an atom selected from the group consisting of a carbon atom, a hydrogen atom, a deuterium atom, a nitrogen atom, and a boron atom.
The light-emitting layer may be formed by co-evaporation of the 1 st organic compound, the 2 nd organic compound, and the 3 rd organic compound, or may be formed by a coating method using a solution obtained by dissolving the 1 st organic compound, the 2 nd organic compound, and the 3 rd organic compound. When the light-emitting layer is formed by co-evaporation, 2 or more of the 1 st organic compound, the 2 nd organic compound, and the 3 rd organic compound may be mixed in advance and added to a crucible or the like as a vapor deposition source, and co-evaporation may be performed using the vapor deposition source, thereby forming the light-emitting layer. For example, the 1 st organic compound and the 2 nd organic compound may be mixed in advance to prepare one vapor deposition source, and co-vapor deposition may be performed using the vapor deposition source and the vapor deposition source of the 3 rd organic compound, thereby forming the light-emitting layer.
The components of the organic electroluminescent element and the layers other than the light-emitting layer will be described below.
A substrate:
in some embodiments, the organic electroluminescent element of the present invention is supported by a substrate, wherein the substrate is not particularly limited and may be any of those substrates that have been commonly used in organic electroluminescent elements, such as those formed of glass, transparent plastic, quartz, and silicon.
Anode:
in some embodiments, the anode of the organic electroluminescent device is made of a metal, an alloy, a conductive compound, or a combination thereof. In some embodiments, the metal, alloy, or conductive compound has a large work function (4 eV toUpper). In some embodiments, the metal is Au. In some embodiments, the conductive transparent material may be selected from CuI, indium Tin Oxide (ITO), snO 2 And selecting ZnO. In some embodiments, amorphous materials capable of forming transparent conductive films such as IDIXO (In 2 O 3 -ZnO) and the like. In some embodiments, the anode is a thin film. In some embodiments, the thin film is made by evaporation or sputtering. In some embodiments, the film is patterned by photolithography. In some embodiments, when a pattern may not require high precision (e.g., above about 100 μm), the pattern may be formed with a mask having a desired shape upon evaporation or sputtering of the electrode material. In some embodiments, when a material (e.g., an organic conductive compound) can be coated, wet film forming methods, such as printing and coating methods, are used. In some embodiments, the transmittance of the anode is greater than 10% and the sheet resistance of the anode is less than hundreds of ohms per square as the radiated light passes through the anode. In some embodiments, the anode has a thickness of 10 to 1,000nm. In some embodiments, the anode has a thickness of 10 to 200nm. In some embodiments, the thickness of the anode varies depending on the material used.
And (3) cathode:
in some embodiments, the cathode is fabricated from a metal (4 eV or less) with a small work function of the electrode material (referred to as an electron injecting metal), an alloy, a conductive compound, or a combination thereof. In some embodiments, the electrode material is selected from sodium, sodium-potassium alloy, magnesium, lithium, magnesium-copper mixture, magnesium-silver mixture, magnesium-aluminum mixture, magnesium-indium mixture, aluminum-aluminum oxide (Al 2 O 3 ) The mixture, indium, lithium-aluminum mixture and rare earth metal are selected. In some embodiments, a mixture of an electron injection metal and a 2 nd metal is used, the 2 nd metal being a stable metal having a work function greater than the electron injection metal. In some embodiments, the mixture is selected from the group consisting of magnesium-silver mixtures, magnesium-aluminum mixtures, magnesium-indium mixtures, aluminum-aluminum oxide (Al 2 O 3 ) The mixture, lithium-aluminum mixture and aluminum are selected.In some embodiments, the mixture increases electron injection characteristics and durability against oxidation. In some embodiments, the cathode is fabricated by forming the electrode material into a thin film by evaporation or sputtering. In some embodiments, the cathode has a sheet resistance of less than several hundred ohms per square. In some embodiments, the cathode has a thickness in the range of 10nm to 5 μm. In some embodiments, the cathode has a thickness in the range of 50 to 200 nm. In some embodiments, any one of the anode and the cathode of the organic electroluminescent element is transparent or translucent in order to transmit the radiated light. In some embodiments, the transparent or translucent electroluminescent element enhances the brightness of the emitted light.
In some embodiments, the cathode is formed with a conductive transparent material as described for the anode to form a transparent or translucent cathode. In some embodiments, the element comprises an anode and a cathode that are both transparent or translucent.
And (2) an injection layer:
the injection layer is a layer between the electrode and the organic layer. In some embodiments, the injection layer reduces a driving voltage and enhances light emission luminance. In some embodiments, the injection layer includes a hole injection layer and an electron injection layer. The injection layer may be disposed between the anode and the light emitting layer or the hole transporting layer, and between the cathode and the light emitting layer or the electron transporting layer. In some embodiments, an injection layer is present. In some embodiments, no implanted layer is present.
Hereinafter, examples of preferable compounds that can be used as the hole injecting material are given.
[ chemical formula 86]
MoO3.
Next, a preferable compound which can be used as an electron injection material is exemplified.
[ chemical formula 87]
i F，Cs F
Barrier layer:
the blocking layer is a layer capable of suppressing diffusion of charges (electrons or holes) and/or excitons existing in the light emitting layer to the outside of the light emitting layer. In some embodiments, an electron blocking layer is present between the light emitting layer and the hole transporting layer, and inhibits electrons from passing through the light emitting layer toward the hole transporting layer. In some embodiments, a hole blocking layer is present between the light emitting layer and the electron transport layer, and inhibits holes from passing through the light emitting layer toward the electron transport layer. In some embodiments, the blocking layer inhibits excitons from diffusing outside the light emitting layer. In some embodiments, the electron blocking layer and the hole blocking layer constitute an exciton blocking layer. The term "electron blocking layer" or "exciton blocking layer" as used herein includes a layer having the function of both an electron blocking layer and an exciton blocking layer.
Hole blocking layer:
the hole blocking layer functions as an electron transport layer. In some embodiments, the hole blocking layer inhibits holes from reaching the electron transport layer while transporting electrons. In some embodiments, the hole blocking layer enhances the probability of recombination of electrons and holes in the light emitting layer. The material for the hole blocking layer may be the same material as described for the electron transport layer.
Hereinafter, examples of preferable compounds that can be used for the hole blocking layer are given.
[ chemical formula 88]
Electron blocking layer:
holes are transported by the electron blocking layer. In some embodiments, the electron blocking layer inhibits electrons from reaching the hole transport layer while transporting holes. In some embodiments, the electron blocking layer enhances the probability of recombination of electrons and holes in the light emitting layer. The material for the electron blocking layer may be the same material as described for the hole transport layer.
Specific examples of preferred compounds that can be used as an electron blocking material are given below.
[ chemical formula 89]
Exciton blocking layer:
the exciton blocking layer inhibits diffusion of excitons generated via recombination of holes and electrons in the light emitting layer to the electron transport layer. In some embodiments, the exciton blocking layer enables efficient confinement of excitons in the light emitting layer. In some embodiments, the luminous efficiency of the device is enhanced. In some embodiments, the exciton blocking layer is adjacent to the light emitting layer on either of the anode side and the cathode side and on both sides thereof. In some embodiments, when an exciton blocking layer is present on the anode side, the layer may be present between and adjacent to the hole transport layer and the light emitting layer. In some embodiments, when an exciton blocking layer is present on the cathode side, the layer may be present between and adjacent to the light emitting layer and the cathode. In some embodiments, a hole injection layer, an electron blocking layer, or the same layer is present between the anode and an exciton blocking layer adjacent to the light emitting layer on the anode side. In some embodiments, a hole injection layer, an electron blocking layer, a hole blocking layer, or the same layer is present between the cathode and an exciton blocking layer adjacent to the light emitting layer on the cathode side. In some embodiments, the exciton blocking layer comprises an excited singlet state energy and an excited triplet state energy, at least one of which is higher than the excited singlet state energy and the excited triplet state energy, respectively, of the light emitting material.
Hole transport layer:
the hole transport layer comprises a hole transport material. In some embodiments, the hole transport layer is a single layer. In some embodiments, the hole transport layer has multiple layers.
In some embodiments, the hole transport material has one of an injection or transport property of holes and a blocking property of electrons. In some embodiments, the hole transport material is an organic material. In some embodiments, the hole transport material is an inorganic material. As examples of known hole transport materials that can be used in the present invention, there can be mentioned, but are not limited to, triazole derivatives, oxadiazole derivatives, imidazole derivatives, carbazole derivatives, indolocarbazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, dihydropyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene (stillene) derivatives, silazane derivatives, aniline copolymers and conductive polymer oligomers (particularly thiophene oligomers), or combinations thereof. In some embodiments, the hole transporting material is selected from the group consisting of porphyrin compounds, aromatic tertiary amine compounds, and styrylamine compounds. In some embodiments, the hole transport material is an aromatic tertiary amine compound. Specific examples of preferred compounds that can be used as the hole transport material are given below.
[ chemical formula 90]
Electron transport layer:
the electron transport layer comprises an electron transport material. In some embodiments, the electron transport layer is a single layer. In some embodiments, the electron transport layer has multiple layers.
In some embodiments, the electron transport material need only have a function of transporting electrons, which are injected from the cathode into the light emitting layer. In some embodiments, the electron transport material also functions as a hole blocking material. Examples of the electron transport layer that can be used in the present invention include, but are not limited to, a fluorene derivative substituted with a nitro group, a dibenzoquinone derivative, a thiopyran dioxide derivative, a carbodiimide, a fluorenylmethane derivative, an anthraquinone dimethane, an anthrone derivative, an oxadiazole derivative, an azole derivative, an oxazine derivative, or a combination thereof, or a polymer thereof. In some embodiments, the electron transport material is a thiadiazole derivative or a quinoxaline derivative. In some embodiments, the electron transport material is a polymeric material. Specific examples of preferred compounds that can be used as an electron transport material are given below.
[ chemical formula 91]
Examples of the material that can be added to each organic layer include preferable compounds. For example, addition as a stabilizing material or the like can be considered.
[ chemical formula 92]
Preferred materials that can be used for the organic electroluminescent element are specifically exemplified, but the materials that can be used in the present invention are not limitedly explained by the exemplified compounds below. Further, even a compound exemplified as a material having a specific function can be used as a material having another function.
The device comprises:
in some embodiments, the light emitting layer is incorporated into a device. For example, devices include, but are not limited to, OLED bulbs, OLED lamps, television screens, computer monitors, mobile phones, and tablet computers.
In some embodiments, an electronic device includes an OLED having an anode, a cathode, and at least one organic layer including a light emitting layer between the anode and the cathode.
In some embodiments, the compositions described herein may be incorporated into a variety of photosensitive or photoactivated devices, such as OLED or photovoltaic devices. In some embodiments, the compositions may be suitable for facilitating charge transfer or energy transfer within a device and/or for use as hole transport materials. Examples of the device include an Organic Light Emitting Diode (OLED), an Organic Integrated Circuit (OIC), an organic field effect transistor (O-FET), an organic thin film transistor (O-TFT), an organic light emitting transistor (O-LET), an organic solar cell (O-SC), an organic photodetector, an organic photoreceptor, an organic field-quench device (O-FQD), a light emitting electrochemical cell (LEC), and an organic laser diode (O-laser).
Bulb or lamp:
in some embodiments, an electronic device comprises an OLED comprising an anode, a cathode, and at least one organic layer comprising a light emitting layer between the anode and the cathode.
In some embodiments, the device comprises OLEDs of different colors. In some embodiments, the device comprises an array comprising OLED combinations. In some embodiments, the combination of OLEDs is a combination of three colors (e.g., RGB). In some embodiments, the combination of OLEDs is a combination of colors that are not red, green, or blue (e.g., orange and yellow-green). In some embodiments, the combination of OLEDs is a combination of two, four, or more colors.
In some embodiments, the device is an OLED lamp, the OLED lamp having:
a circuit board having a 1 st surface having a mounting surface and a 2 nd surface opposite thereto, and defining at least one opening;
at least one OLED disposed on the mounting surface and having a structure in which the at least one OLED includes an anode, a cathode, and at least one organic layer including a light emitting layer between the anode and the cathode and emits light;
A housing for a circuit substrate; and
At least one connector is disposed at an end of the housing, and the housing and the connector define a package adapted to be mounted to a lighting device.
In some embodiments, an OLED lamp includes a plurality of OLEDs mounted on a circuit board such that light is emitted in multiple directions. In some embodiments, a portion of the light emitted in the 1 st direction is deflected to emit in the 2 nd direction. In some embodiments, the reflector is used to deflect light emitted in the 1 st direction.
A display or screen:
in some embodiments, the light emitting layer of the present invention may be used in a screen or display. In some embodiments, methods including, but not limited to, vacuum evaporation, deposition, evaporation, or Chemical Vapor Deposition (CVD) are used to deposit the compounds of the present invention onto a substrate. In some embodiments, the substrate is a photo negative (photo plate) structure suitable for double sided etching, providing unique aspect ratio pixels. The screen (which may also be referred to as a mask) is used in a method of manufacturing an OLED display. The corresponding artwork design allows for the promotion of extremely steep and narrow tie-bars between pixels in the vertical direction, as well as the configuration of a wide range of bevel openings in the horizontal direction. Thereby allowing for the pixel tight patterning required for high definition displays while optimizing vapor deposition onto TFT backplanes.
The internal patterning of the pixels allows the construction of 3-dimensional pixel openings with aspect ratio variations in the horizontal and vertical directions. Furthermore, the use of imaged "stripes" or halftone circles within the pixel regions inhibits etching in certain areas until such time as these certain patterns are undercut and leave the substrate. At this time, all pixel regions are processed at the same etching rate, but the depth varies depending on the halftone pattern. Changing the size and spacing of the halftone patterns allows etching to be suppressed at different rates within the pixel, allowing localized deeper etching required to form steep vertical bevel angles.
A preferred material for the vapor deposition mask is constant-volume steel (innor). Constant-gauge steel is a metal alloy that is cold rolled into long sheets in a steelworks. Constant-gauge steel cannot be electrodeposited onto a spinning mandrel as a nickel mask. A suitable and low cost method for forming the opening region in the evaporation mask is a wet chemical etching-based method.
In some embodiments, the screen or display pattern is a matrix of pixels on a substrate. In some embodiments, the screen or display pattern is fabricated using photolithography (e.g., photolithography) and e-beam lithography. In some embodiments, the screen or display pattern is fabricated using wet chemical etching. In further embodiments, the screen or display pattern is fabricated using plasma etching.
The manufacturing method of the device comprises the following steps:
OLED displays are typically manufactured by forming a larger motherboard and then cutting the motherboard into unit panels. In general, each cell board on the motherboard is formed by: a Thin Film Transistor (TFT) including an active layer and source/drain electrodes is formed on a base substrate, a planarization film is coated on the TFT, and a pixel electrode, a light emitting layer, a counter electrode, and an encapsulation layer are sequentially formed and cut from the mother substrate.
In another aspect of the present invention, there is provided a method of manufacturing an Organic Light Emitting Diode (OLED) display, the method including:
forming a barrier layer on a base substrate of a motherboard;
forming a plurality of display units from a unit of a unit panel on the barrier layer;
forming an encapsulation layer on each of the display units of the unit panels; and
And a step of coating an organic film on an interface portion between the unit plates.
In some embodiments, the barrier layer is an inorganic film formed of, for example, siNx, and an edge portion of the barrier layer is covered with an organic film formed of polyimide or acryl. In some embodiments, the organic film aids in gently cutting the master into unit panels.
In some embodiments, a Thin Film Transistor (TFT) layer has a light emitting layer, a gate electrode, and source/drain electrodes. Each of the plurality of display units may include a Thin Film Transistor (TFT) layer, a planarization film formed on the TFT layer, and a light emitting unit formed on the planarization film, wherein the organic film coated on the interface portion is formed of the same material as that of the planarization film and is formed at the same time as the planarization film is formed. In some embodiments, the light emitting unit is connected to the TFT layer with a passivation layer, a planarization film, and an encapsulation layer therebetween, and the encapsulation layer covers and protects the light emitting unit. In some embodiments of the method of manufacture, the organic film contacts neither the display unit nor the encapsulation layer.
Each of the organic film and the planarization film may include any one of polyimide and acryl. In some embodiments, the barrier layer may be an inorganic film. In some embodiments, the base substrate may be formed of polyimide. The method may further include, before forming the barrier layer on one surface of the base substrate formed of polyimide, mounting a carrier substrate formed of a glass material on the other surface of the base substrate, and separating the carrier substrate from the base substrate before cutting along the interface portion. In some embodiments, the OLED display is a flexible display.
In some implementations, the passivation layer is an organic film disposed on the TFT layer to cover the TFT layer. In some embodiments, the planarization film is an organic film formed on the passivation layer. In some embodiments, the planarization film is formed of polyimide or acryl, as is an organic film formed on an edge portion of the barrier layer. In some embodiments, the planarization film and the organic film are formed simultaneously when the OLED display is manufactured. In some embodiments, the organic film may be formed on an edge portion of the barrier layer such that a portion of the organic film directly contacts the base substrate and the remaining portion of the organic film contacts the barrier layer while surrounding the edge portion of the barrier layer.
In some embodiments, the light emitting layer has a pixel electrode, an opposite electrode, and an organic light emitting layer disposed between the pixel electrode and the opposite electrode. In some embodiments, the pixel electrode is connected to a source/drain electrode of the TFT layer.
In some embodiments, when a voltage is applied to the pixel electrode via the TFT layer, an appropriate voltage is formed between the pixel electrode and the opposite electrode, whereby the organic light emitting layer emits light, thereby forming an image. Hereinafter, an image forming unit having a TFT layer and a light emitting unit is referred to as a display unit.
In some embodiments, the encapsulation layer that covers the display unit and prevents external moisture from penetrating may be formed to have a thin film encapsulation structure in which organic films and inorganic films are alternately laminated. In some embodiments, the encapsulation layer has a film encapsulation structure in which a plurality of films are laminated. In some embodiments, the organic film coated on the interface portion is spaced apart from each of the plurality of display units. In some embodiments, the organic film is formed such that a portion of the organic film directly contacts the base substrate, and a remaining portion of the organic film contacts the barrier layer while surrounding an edge portion of the barrier layer.
In one embodiment, the OLED display is flexible and uses a soft base substrate formed of polyimide. In some embodiments, the base substrate is formed on a carrier substrate formed of a glass material, and then the carrier substrate is separated.
In some embodiments, a barrier layer is formed on a surface of the base substrate on a side opposite the carrier substrate. In one embodiment, the barrier layer is patterned according to the size of each cell plate. For example, a barrier layer is formed according to the size of each cell plate while a base substrate is formed over the entire surface of the motherboard, thereby forming a groove at an interface portion between the cell plate barrier layers. Each cell plate may be cut along the grooves.
In some embodiments, the method of manufacturing further comprises a step of cutting along the interface portion, wherein a groove is formed in the barrier layer, wherein at least a portion of the organic film is formed in the groove, and the groove does not penetrate into the base substrate. In some embodiments, a TFT layer of each unit plate is formed, and a passivation layer (i.e., an inorganic film) and a planarization film (i.e., an organic film) are disposed on the TFT layer to cover the TFT layer. The grooves at the interface portion are covered with an organic film formed of, for example, polyimide or acryl, while forming a planarization film formed of, for example, polyimide or acryl. This is when cracking is prevented from occurring by allowing the organic film to absorb an impact that is generated when each unit plate is cut along the groove at the interface portion. That is, if the entire barrier layer is completely exposed without the organic film, an impact generated when each unit plate is cut along the groove at the interface portion is transferred to the barrier layer, thereby increasing the risk of cracking. However, in one embodiment, the grooves at the interface portion between the barrier layers are covered with an organic film, which if not present absorbs the impact that may be transferred to the barrier layers, so each cell plate may be gently cut and cracks may be prevented from occurring in the barrier layers. In one embodiment, the organic film and the planarizing film covering the recess at the interface portion are spaced apart from each other. For example, if an organic film and a planarization film are connected to each other as a single layer, the organic film and the planarization film are spaced apart from each other so that the organic film is spaced apart from the display unit because external moisture may penetrate into the display unit via the planarization film and a portion of the remaining organic film.
In some embodiments, a display unit is formed by forming a light emitting unit, and an encapsulation layer is disposed on the display unit to cover the display unit. Thereby, after the motherboard is completely manufactured, the carrier substrate supporting the base substrate is separated from the base substrate. In some embodiments, when the laser beam is irradiated toward the carrier substrate, the carrier substrate is separated from the base substrate due to a difference in thermal expansion coefficient between the carrier substrate and the base substrate.
In some embodiments, the motherboard is cut into unit boards. In some embodiments, the motherboard is cut along the interface portion between the unit boards by using a cutter. In some embodiments, since the grooves at the interface portion along which the motherboard is cut are covered with an organic film, the organic film absorbs impact during cutting. In some embodiments, cracking may be prevented from occurring in the barrier layer during dicing.
In some embodiments, the method reduces the defect rate of the product and stabilizes its quality.
Another aspect is an OLED display having: a barrier layer formed on the base substrate; a display unit formed on the barrier layer; an encapsulation layer formed on the display unit; and an organic film coated on an edge portion of the barrier layer.
Examples
The features of the present invention will be further specifically described below by way of examples. The materials, processing contents, processing steps, and the like described below can be appropriately modified as long as they do not depart from the gist of the present invention. Therefore, the scope of the present invention should not be construed in a limited manner by the following examples. The evaluation of the luminescence performance was performed using a source meter (TEKTRONIX, INC.: 2400 series), a semiconductor parameter-analyzer (Agilent Technologies Japan, ltd.: E5273A), an optical power meter measuring device (Newport Corporation: 1930C), an optical spectrometer (Ocean photonics.: USB 2000), a spectroradiometer (TOPCON CORPORATION: SR-3) and a streak camera (Hamamatsu Photonics K.K. C4334 type), and the measurement of the orientation value was performed using a molecular orientation characteristic measuring device (Hamamatsu Photonics K.K. C14234-01).
< 1 st to 3 rd organic Compounds used in examples and comparative examples >
The 1 st to 3 rd organic compounds used in the following examples and comparative examples are shown below.
[ chemical formula 93-1]
1 st organic compound
2 nd organic compound (delayed fluorescent material)
3 rd organic compound (fluorescent material)
[ chemical formula 93-2]
Energy E of HOMO of the above-mentioned Compound HOMO Energy E of LUMO LUMO Shown in table 1 below. And also shows the lowest excited singlet energy E measured for a portion of the compounds S1 And the lowest excited triplet energy E T1 。
TABLE 1
/>
(Unit eV)
Examples 1 to 10 and comparative examples 5 to 7, 9, 10 and 12
Vacuum deposition was performed on a glass substrate having a thickness of 2mm and formed with an anode made of Indium Tin Oxide (ITO) having a thickness of 50nm, at a vacuum level of 1X 10 -6 Pa each film was laminated. First, a hole injection layer was formed by vapor deposition of HATCN to a thickness of 5nm on ITO, and a hole transport layer was formed by vapor deposition of NPD to a thickness of 60nm thereon. Subsequently, EB1 was vapor deposited to a thickness of 5nm to form an electron blocking layer. Next, the 1 st organic compound, the 2 nd organic compound, and the 3 rd organic compound were co-deposited from different vapor deposition sources so as to have the compositions shown in table 2 or table 3, and a light-emitting layer having a thickness of 40nm was formed. Next, HB1 was vapor deposited to a thickness of 10nm to form a hole blocking layer, and ET1 was vapor deposited to a thickness of 30nm to formAn electron transport layer is provided. Further, liq was evaporated to a thickness of 2nm to form an electron injection layer, and then aluminum (Al) was evaporated to a thickness of 100nm to form a cathode. Thus, an organic electroluminescent element was produced. It was confirmed that the elements produced herein all satisfy the formula (a) and that the maximum component of luminescence is fluorescence from the 3 rd organic compound.
Comparative examples 1 to 4, 8 and 11
An organic electroluminescent device was produced in the same manner as in example 1, except that the light-emitting layer having the composition shown in table 2 was formed by co-evaporation of the 1 st organic compound and the 2 nd organic compound without using the evaporation source of the 3 rd organic compound.
(composition of light-emitting layer and evaluation result)
Table 2 shows the compositions of the light-emitting layers, the external quantum efficiencies EQE, and the maximum wavelength of light emission of the respective elements fabricated in examples 1 to 6 and comparative examples 1 to 10. The composition ratio of the 3 rd organic compound in examples 1 to 4 and comparative examples 5 to 7, 9 and 10 in the composition of the light-emitting layer is represented by a ratio (wt%) with respect to the total weight of the 1 st organic compound and the 2 nd organic compound, and the composition ratio of the other organic compounds is represented by a ratio (wt%) with respect to the total weight of the organic compounds constituting the light-emitting layer. In table 2, "-" indicates that no 3 rd organic compound was added.
TABLE 2
As shown in table 2, the elements of examples 1 to 6 in which the orientation value S of the 3 rd organic compound was-0.3 or less exhibited higher external quantum efficiency than the elements of comparative examples 1 to 3 in which the 3 rd organic compound was not included in the light-emitting layer. The elements of examples 2, 4 and 6 in which the concentration of the 3 rd organic compound was high obtained higher external quantum efficiency than the elements of examples 1, 3 and 5. In contrast, the elements of comparative examples 5 to 7, 9 to 10, and 12 in which the orientation value S of the 3 rd organic compound was greater than-0.3 contained the 3 rd organic compound in the light-emitting layer, respectively, and the external quantum efficiency was lower than that of the elements of comparative examples 4, 8, and 11 having the same structure. From the results of comparative examples 5 to 7 and comparative examples 9 to 10, it is evident that the higher the concentration of the 3 rd organic compound, the lower the external quantum efficiency. From the above results, it was confirmed that even in the element in which the energy of LUMO of the 3 rd organic compound is lower than that of LUMO of the 2 nd organic compound, if the orientation value S of the 3 rd organic compound is-0.3 or less, the concentration of the 3 rd organic compound is increased to achieve an improvement in external quantum efficiency.
Table 3 shows the composition and durability evaluation results of the light-emitting layers of the respective elements manufactured in examples 7 to 10. "LT95%" in Table 3 means that each element was set at 12.6mA/cm 2 The time (T95%) until the luminance reached 95% of the initial luminance was measured by continuous driving of the current density of (a) and the value of T95% was divided by the relative value calculated by T95% of the element fabricated in example 7. This means that the larger the LT95% value is, the more excellent the durability is.
TABLE 3
The elements of examples 7 to 10 were equivalent in that the concentration of the 2 nd organic compound in the light-emitting layer was changed, the maximum wavelength of light emission was 529nm, and the external quantum efficiency was about 22%. Further, it can be seen from table 3 that durability of the element is sometimes improved by increasing the concentration of the 2 nd organic compound.
[ chemical formula 94]
Industrial applicability
According to the present invention, in an organic electroluminescent element including a 1 st organic compound, a 2 nd organic compound as a delayed fluorescent material, and a 3 rd organic compound that emits fluorescence in a light-emitting layer, even in the case where the energy of LUMO of the 1 st organic compound is lower than that of LUMO of the 2 nd organic compound, an improvement in external quantum efficiency can be achieved by increasing the concentration of the 2 nd organic compound. This can expand the range of selection of LUMO energy of the 3 rd organic compound, and thus can improve the degree of freedom in designing the material of the organic electroluminescent element. Therefore, the industrial applicability of the present invention is high.
Claims (11)
1. An organic electroluminescent element having an anode, a cathode, and at least one organic layer including a light-emitting layer between the anode and the cathode, wherein,
the light-emitting layer comprises a 1 st organic compound, a 2 nd organic compound and a 3 rd organic compound, and satisfies the following formula (a) and the following formula (b),
the 2 nd organic compound is a delayed fluorescent material,
the maximum component of luminescence from the element is fluorescence from the 3 rd organic compound,
[ number 1]
E LUMO (2)>E LUMO (3) (a)
S is less than or equal to 0.3 type (b)
Wherein,
E LUMO (2) Represents the energy of LUMO of the 2 nd organic compound,
E LUMO (3) Represents the energy of LUMO of the 3 rd organic compound,
s represents an orientation value of the 3 rd organic compound in the light emitting layer.
2. The organic electroluminescent element according to claim 1, wherein,
the concentration of the 3 rd organic compound in the light emitting layer is greater than 0.3 wt%.
3. The organic electroluminescent element as claimed in claim 1 or 2, wherein,
the 3 rd organic compound is a compound which contains a boron atom and a nitrogen atom exhibiting a multiple resonance effect and has a condensed ring structure having four or more ring numbers.
4. The organic electroluminescent element as claimed in any one of claims 1 to 3, wherein,
The 3 rd organic compound has a structure in which a hetero 6-membered ring containing a boron atom and a nitrogen atom is condensed with a pyrrole ring sharing a nitrogen atom and two benzene rings.
5. The organic electroluminescent element as claimed in any one of claims 1 to 4, wherein,
the 3 rd organic compound is a compound represented by the following general formula (16),
general formula (16)
[ chemical formula 1]
In the general formula (16), X 1 X is X 2 One of which is a nitrogen atom and the other is a boron atom, R 1 ～R 26 、A 1 、A 2 Each independently represents a hydrogen atom, a deuterium atom or a substituent, R 1 And R is 2 、R 2 And R is 3 、R 3 And R is 4 、R 4 And R is 5 、R 5 And R is 6 、R 6 And R is 7 、R 7 And R is 8 、R 8 And R is 9 、R 9 And R is 10 、R 10 And R is 11 、R 11 And R is 12 、R 13 And R is 14 、R 14 And R is 15 、R 15 And R is 16 、R 16 And R is 17 、R 17 And R is 18 、R 18 And R is 19 、R 19 And R is 20 、R 20 And R is 21 、R 21 And R is 22 、R 22 And R is 23 、R 23 And R is 24 、R 24 And R is 25 、R 25 And R is 26 Can be bonded to each other to form a ring structure, wherein, when X 1 R is a nitrogen atom 17 And R is 18 Bonded to each other to form a single bond and form a pyrrole ring, when X 2 R is a nitrogen atom 21 And R is 22 Are bonded to each other to form a single bond and form a pyrrole ring, wherein X 1 Is a nitrogen atom, and R 7 And R is 8 R is R 21 And R is 22 Bonded via nitrogen atoms to form a 6-membered ring when R 17 And R is 18 R when bonded to each other to form a single bond 1 ～R 6 At least one of which is substituted or unsubstituted aryl, or R 1 And R is 2 、R 2 And R is 3 、R 3 And R is 4 、R 4 And R is 5 、R 5 And R is 6 Any one of them is bonded to each other to form an aromatic ring or a heteroaromatic ring.
6. The organic electroluminescent element as claimed in any one of claims 1 to 5, wherein,
the concentration of the 2 nd organic compound in the light-emitting layer is 25 wt% or more.
7. The organic electroluminescent element as claimed in any one of claims 1 to 6, wherein,
the 2 nd organic compound has a structure in which 1 to 2 cyano groups and at least one donor group are bonded to a benzene ring.
8. The organic electroluminescent element according to claim 7, wherein,
the donor group has a structure in which a benzene ring constituting a carbazol-9-yl group is condensed with a substituted or unsubstituted benzofuran ring.
9. The organic electroluminescent element according to claim 8, wherein,
the donor group is a substituted or unsubstituted 5H-benzofuran [3,2-c ] carbazol-5-yl group.
10. The organic electroluminescent element as claimed in any one of claims 7 to 9, wherein,
the benzene ring is bonded to the donor group by three or more groups.
11. The organic electroluminescent element as claimed in any one of claims 1 to 10, wherein,
the 1 st organic compound, the 2 nd organic compound, and the 3 rd organic compound satisfy the following formula (a 1),
E LUMO (1)＞E LUMO (2)＞E LUMO (3) (a 1)
Wherein,
E LUMO (1) Represents the energy of LUMO of the 1 st organic compound,
E LUMO (2) Represents the energy of LUMO of the 2 nd organic compound,
E LUMO (3) Represents the energy of LUMO of the 3 rd organic compound,
s represents an orientation value of the 3 rd organic compound in the light emitting layer.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2021-103702 | 2021-06-23 | ||
| JP2021-151805 | 2021-09-17 | ||
| JP2021-188860 | 2021-11-19 | ||
| JP2021-204983 | 2021-12-17 | ||
| JP2021204983 | 2021-12-17 | ||
| PCT/JP2022/015888 WO2022270113A1 (en) | 2021-06-23 | 2022-03-30 | Organic electroluminescent element |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117561806A true CN117561806A (en) | 2024-02-13 |
Family
ID=89823800
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202280044187.8A Pending CN117561806A (en) | 2021-06-23 | 2022-03-30 | Organic electroluminescent element |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117561806A (en) |
-
2022
- 2022-03-30 CN CN202280044187.8A patent/CN117561806A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113169286A (en) | Organic light emitting element | |
| CN115280535A (en) | Host material, composition and organic light-emitting element | |
| KR20230035234A (en) | organic light emitting device | |
| WO2023282224A1 (en) | Organic light-emitting element and design method therefor | |
| KR20240025546A (en) | Organic electroluminescence device | |
| WO2022168825A1 (en) | Organic electroluminescence element, method for designing luminous composition, and program | |
| JP7152805B1 (en) | Compounds, compositions, host materials, electron barrier materials and organic light-emitting devices | |
| KR20230035534A (en) | organic light emitting device | |
| CN117561806A (en) | Organic electroluminescent element | |
| JP7461095B1 (en) | Organic light-emitting device, design method thereof and program | |
| WO2022249750A1 (en) | Top-emission-type organic electroluminescent element, and method for designing same | |
| WO2022230573A1 (en) | Organic light-emitting device and method for making same | |
| WO2022270591A1 (en) | Compound, composition, host material, electron barrier material and organic light emitting element | |
| WO2022264857A1 (en) | Organic light emitting element and method for producing same | |
| WO2022244503A1 (en) | Organic light emitting element | |
| CN117546634A (en) | Electron blocking material, organic semiconductor element, and compound | |
| CN117651705A (en) | Compound, light-emitting material, and organic light-emitting element | |
| CN117546630A (en) | Organic light-emitting element and film | |
| WO2022270592A1 (en) | Electron barrier material, organic semiconductor element and compound | |
| CN117397389A (en) | Top emission organic electroluminescent device and method for designing the same | |
| KR20240026147A (en) | Organic light emitting devices and membranes | |
| CN116458278A (en) | Organic electroluminescent element, method for designing light-emitting composition, and program | |
| KR20240023051A (en) | Compounds, light-emitting materials, and organic light-emitting devices | |
| KR20240026148A (en) | Organic light emitting devices and membranes | |
| WO2023120062A1 (en) | Electronic barrier material and organic semiconductor element |
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 |