JPH05311161A - Organic electroluminescent device - Google Patents
Organic electroluminescent deviceInfo
- Publication number
- JPH05311161A JPH05311161A JP4111818A JP11181892A JPH05311161A JP H05311161 A JPH05311161 A JP H05311161A JP 4111818 A JP4111818 A JP 4111818A JP 11181892 A JP11181892 A JP 11181892A JP H05311161 A JPH05311161 A JP H05311161A
- Authority
- JP
- Japan
- Prior art keywords
- group
- substituent
- transport layer
- optionally substituted
- organic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- -1 aromatic diamine compound Chemical class 0.000 claims abstract description 56
- 230000005525 hole transport Effects 0.000 claims abstract description 25
- 125000001424 substituent group Chemical group 0.000 claims description 96
- 125000003118 aryl group Chemical group 0.000 claims description 20
- 125000000217 alkyl group Chemical group 0.000 claims description 18
- 125000005843 halogen group Chemical group 0.000 claims description 17
- 125000003545 alkoxy group Chemical group 0.000 claims description 14
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 14
- 125000003342 alkenyl group Chemical group 0.000 claims description 13
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 12
- 125000004663 dialkyl amino group Chemical group 0.000 claims description 11
- 125000004986 diarylamino group Chemical group 0.000 claims description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 125000004104 aryloxy group Chemical group 0.000 claims description 6
- 229920006395 saturated elastomer Polymers 0.000 claims description 6
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 3
- 125000005415 substituted alkoxy group Chemical group 0.000 claims description 3
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 2
- 125000004429 atom Chemical group 0.000 claims 2
- 229910052739 hydrogen Inorganic materials 0.000 claims 2
- 239000001257 hydrogen Substances 0.000 claims 2
- 125000005017 substituted alkenyl group Chemical group 0.000 claims 1
- 125000005346 substituted cycloalkyl group Chemical group 0.000 claims 1
- DCZNSJVFOQPSRV-UHFFFAOYSA-N n,n-diphenyl-4-[4-(n-phenylanilino)phenyl]aniline Chemical group C1=CC=CC=C1N(C=1C=CC(=CC=1)C=1C=CC(=CC=1)N(C=1C=CC=CC=1)C=1C=CC=CC=1)C1=CC=CC=C1 DCZNSJVFOQPSRV-UHFFFAOYSA-N 0.000 abstract 1
- 230000032258 transport Effects 0.000 description 44
- 239000000463 material Substances 0.000 description 27
- 150000001875 compounds Chemical class 0.000 description 26
- 239000007924 injection Substances 0.000 description 24
- 238000002347 injection Methods 0.000 description 24
- 238000000034 method Methods 0.000 description 16
- 239000000758 substrate Substances 0.000 description 16
- 230000004888 barrier function Effects 0.000 description 12
- 239000010408 film Substances 0.000 description 12
- 229920005989 resin Polymers 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- 238000007740 vapor deposition Methods 0.000 description 10
- 238000000576 coating method Methods 0.000 description 8
- 150000002430 hydrocarbons Chemical group 0.000 description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 7
- 229910052749 magnesium Inorganic materials 0.000 description 7
- 239000011777 magnesium Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 229910052709 silver Inorganic materials 0.000 description 7
- 239000004332 silver Substances 0.000 description 7
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 6
- 125000003277 amino group Chemical group 0.000 description 6
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 6
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
- 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 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 6
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 125000001624 naphthyl group Chemical group 0.000 description 6
- 125000004923 naphthylmethyl group Chemical group C1(=CC=CC2=CC=CC=C12)C* 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
- 238000001771 vacuum deposition Methods 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000005684 electric field Effects 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 239000010409 thin film Substances 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000000969 carrier Substances 0.000 description 4
- 229910010272 inorganic material Inorganic materials 0.000 description 4
- 239000011147 inorganic material Substances 0.000 description 4
- 150000002894 organic compounds Chemical class 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- 239000005725 8-Hydroxyquinoline Substances 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 150000004984 aromatic diamines Chemical class 0.000 description 3
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 125000004956 cyclohexylene group Chemical group 0.000 description 3
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 3
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 3
- 229960003540 oxyquinoline Drugs 0.000 description 3
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 3
- 229920000515 polycarbonate Polymers 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- KLCLIOISYBHYDZ-UHFFFAOYSA-N 1,4,4-triphenylbuta-1,3-dienylbenzene Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)=CC=C(C=1C=CC=CC=1)C1=CC=CC=C1 KLCLIOISYBHYDZ-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- QENGPZGAWFQWCZ-UHFFFAOYSA-N 3-Methylthiophene Chemical compound CC=1C=CSC=1 QENGPZGAWFQWCZ-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910021417 amorphous silicon Inorganic materials 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 2
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 2
- 150000004775 coumarins Chemical class 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000005401 electroluminescence Methods 0.000 description 2
- 125000005678 ethenylene group Chemical group [H]C([*:1])=C([H])[*:2] 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 150000004866 oxadiazoles Chemical class 0.000 description 2
- DGBWPZSGHAXYGK-UHFFFAOYSA-N perinone Chemical class C12=NC3=CC=CC=C3N2C(=O)C2=CC=C3C4=C2C1=CC=C4C(=O)N1C2=CC=CC=C2N=C13 DGBWPZSGHAXYGK-UHFFFAOYSA-N 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
- 239000002985 plastic film Substances 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 2
- 125000006839 xylylene group Chemical group 0.000 description 2
- 229910052984 zinc sulfide Inorganic materials 0.000 description 2
- VIMMECPCYZXUCI-MIMFYIINSA-N (4s,6r)-6-[(1e)-4,4-bis(4-fluorophenyl)-3-(1-methyltetrazol-5-yl)buta-1,3-dienyl]-4-hydroxyoxan-2-one Chemical compound CN1N=NN=C1C(\C=C\[C@@H]1OC(=O)C[C@@H](O)C1)=C(C=1C=CC(F)=CC=1)C1=CC=C(F)C=C1 VIMMECPCYZXUCI-MIMFYIINSA-N 0.000 description 1
- QGKMIGUHVLGJBR-UHFFFAOYSA-M (4z)-1-(3-methylbutyl)-4-[[1-(3-methylbutyl)quinolin-1-ium-4-yl]methylidene]quinoline;iodide Chemical compound [I-].C12=CC=CC=C2N(CCC(C)C)C=CC1=CC1=CC=[N+](CCC(C)C)C2=CC=CC=C12 QGKMIGUHVLGJBR-UHFFFAOYSA-M 0.000 description 1
- PFNQVRZLDWYSCW-UHFFFAOYSA-N (fluoren-9-ylideneamino) n-naphthalen-1-ylcarbamate Chemical compound C12=CC=CC=C2C2=CC=CC=C2C1=NOC(=O)NC1=CC=CC2=CC=CC=C12 PFNQVRZLDWYSCW-UHFFFAOYSA-N 0.000 description 1
- SULWTXOWAFVWOY-PHEQNACWSA-N 2,3-bis[(E)-2-phenylethenyl]pyrazine Chemical class C=1C=CC=CC=1/C=C/C1=NC=CN=C1\C=C\C1=CC=CC=C1 SULWTXOWAFVWOY-PHEQNACWSA-N 0.000 description 1
- MVWPVABZQQJTPL-UHFFFAOYSA-N 2,3-diphenylcyclohexa-2,5-diene-1,4-dione Chemical class O=C1C=CC(=O)C(C=2C=CC=CC=2)=C1C1=CC=CC=C1 MVWPVABZQQJTPL-UHFFFAOYSA-N 0.000 description 1
- OAIASDHEWOTKFL-UHFFFAOYSA-N 3-methyl-n-[4-[4-(n-(4-methylphenyl)anilino)phenyl]phenyl]-n-phenylaniline Chemical compound C1=CC(C)=CC=C1N(C=1C=CC(=CC=1)C=1C=CC(=CC=1)N(C=1C=CC=CC=1)C=1C=C(C)C=CC=1)C1=CC=CC=C1 OAIASDHEWOTKFL-UHFFFAOYSA-N 0.000 description 1
- 150000004325 8-hydroxyquinolines Chemical class 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229940125907 SJ995973 Drugs 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- LUTSRLYCMSCGCS-BWOMAWGNSA-N [(3s,8r,9s,10r,13s)-10,13-dimethyl-17-oxo-1,2,3,4,7,8,9,11,12,16-decahydrocyclopenta[a]phenanthren-3-yl] acetate Chemical compound C([C@@H]12)C[C@]3(C)C(=O)CC=C3[C@@H]1CC=C1[C@]2(C)CC[C@H](OC(=O)C)C1 LUTSRLYCMSCGCS-BWOMAWGNSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000004450 alkenylene group Chemical group 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 125000000732 arylene group Chemical group 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229960000956 coumarin Drugs 0.000 description 1
- 235000001671 coumarin Nutrition 0.000 description 1
- 125000002993 cycloalkylene group Chemical group 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000005524 hole trap Effects 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910021424 microcrystalline silicon Inorganic materials 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- XZMHJYWMCRQSSI-UHFFFAOYSA-N n-[5-[2-(3-acetylanilino)-1,3-thiazol-4-yl]-4-methyl-1,3-thiazol-2-yl]benzamide Chemical compound CC(=O)C1=CC=CC(NC=2SC=C(N=2)C2=C(N=C(NC(=O)C=3C=CC=CC=3)S2)C)=C1 XZMHJYWMCRQSSI-UHFFFAOYSA-N 0.000 description 1
- 125000004957 naphthylene group Chemical group 0.000 description 1
- 150000005054 naphthyridines Chemical class 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- WSRHMJYUEZHUCM-UHFFFAOYSA-N perylene-1,2,3,4-tetracarboxylic acid Chemical class C=12C3=CC=CC2=CC=CC=1C1=C(C(O)=O)C(C(O)=O)=C(C(O)=O)C2=C1C3=CC=C2C(=O)O WSRHMJYUEZHUCM-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 125000001792 phenanthrenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C=CC12)* 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical group N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 1
- 229920000548 poly(silane) polymer Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 150000004032 porphyrins Chemical group 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- DNXIASIHZYFFRO-UHFFFAOYSA-N pyrazoline Chemical compound C1CN=NC1 DNXIASIHZYFFRO-UHFFFAOYSA-N 0.000 description 1
- 150000005255 pyrrolopyridines Chemical class 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 125000005156 substituted alkylene group Chemical group 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- QKTRRACPJVYJNU-UHFFFAOYSA-N thiadiazolo[5,4-b]pyridine Chemical class C1=CN=C2SN=NC2=C1 QKTRRACPJVYJNU-UHFFFAOYSA-N 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Electroluminescent Light Sources (AREA)
- Luminescent Compositions (AREA)
Abstract
(57)【要約】 （修正有）
【目的】 長期にわたって安定に駆動させることができ
る有機電界発光素子を提供する。
【構成】 順次に、陽極、正孔輸送層、有機電子輸送層
及び陰極が積層されてなる有機電界発光素子において、
有機電子輸送層が一般式Ｉの芳香族ジアミン化合物を含
有する。芳香族ジアミン化合物の具体例には４，４′−
ビス（ジフェニルアミノ）ビフェニルがある。
【効果】 低い駆動電圧で実用上十分な輝度の発光を得
ることができ、長期間安定した発光性能を示す。
(57) [Summary] (Modified) [Objective] To provide an organic electroluminescent device which can be stably driven for a long period of time. [Structure] An organic electroluminescent device comprising an anode, a hole transport layer, an organic electron transport layer and a cathode, which are sequentially laminated,
The organic electron transport layer contains an aromatic diamine compound of general formula I. Specific examples of the aromatic diamine compound include 4,4'-
There is bis (diphenylamino) biphenyl. [Effect] It is possible to obtain light emission with practically sufficient brightness at a low driving voltage, and exhibit stable light emission performance for a long period of time.
Description
【０００１】[0001]
【産業上の利用分野】本発明は、有機電界発光素子に関
するものであり、詳しくは、正孔輸送層と有機化合物か
ら成る電子輸送層との組合せにより、電界をかけて光を
放出する薄膜型デバイスに関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic electroluminescent device, and more specifically, it is a thin film type device which emits light by applying an electric field by a combination of a hole transporting layer and an electron transporting layer made of an organic compound. It is about devices.
【０００２】[0002]
【従来の技術】従来、薄膜型の電界発光素子としては、
無機材料のII−VI族化合物半導体であるＺｎＳ、Ｃａ
Ｓ、ＳｒＳ等に、発光中心であるＭｎや希土類元素（Ｅ
ｕ、Ｃｅ、Ｔｂ、Ｓｍ等）をドープしたものが一般的で
あるが、上記の無機材料から作製した電界発光素子は、 １）交流駆動が必要（５０〜１０００Ｈｚ）、 ２）駆動電圧が高い（〜２００Ｖ）、 ３）フルカラー化が困難（特に青色が問題）、 ４）周辺駆動回路のコストが高い、 という問題点を持っている。2. Description of the Related Art Conventionally, as a thin film type electroluminescent device,
ZnS, Ca which are II-VI group compound semiconductors of inorganic materials
In S, SrS, etc., Mn, which is the emission center, and rare earth elements (E
(u, Ce, Tb, Sm, etc.) is generally doped, but the electroluminescent device made of the above inorganic material is: 1) AC drive is required (50 to 1000 Hz), 2) High drive voltage (Up to 200 V), 3) full colorization is difficult (especially blue color is a problem), and 4) peripheral drive circuit cost is high.
【０００３】しかし、近年、上記問題点の改良のため、
有機材料を用いた電界発光素子の開発が行われるように
なった。発光層材料としては以前から知られていたアン
トラセンやピレン等の他に、シアニン色素（J. Chem. S
oc., Chem. Commun., ５５７頁、１９８５年）、ピラゾ
リン（Mol. Crys. Liq. Cryst., １３５巻、３５５頁、
１９８６年）、ペリレン（Jpn. J. Appl. Phys.,２５
巻、Ｌ７７３頁、１９８６年）あるいはクマリン系化合
物やテトラフェニルブタジエン（特開昭５７−５１７８
１号公報）などが報告されている。However, in recent years, in order to improve the above problems,
Development of electroluminescent devices using organic materials has started. In addition to the previously known anthracene and pyrene as the light emitting layer material, cyanine dyes (J. Chem. S
oc., Chem. Commun., 557, p. 1985, pyrazoline (Mol. Crys. Liq. Cryst., 135, 355,
1986), Perylene (Jpn. J. Appl. Phys., 25)
Vol., L773, 1986) or coumarin compounds and tetraphenyl butadiene (JP-A-57-5178).
No. 1) has been reported.
【０００４】また、発光効率を高めるために電極からの
キャリアーの注入効率の向上を目的として、電極種類の
最適化や、正孔輸送層と有機蛍光体からなる発光層を設
ける工夫（特開昭５７−５１７８１号公報、特開昭５９
−１９４３９３号公報、特開昭６３−２９５６９５号公
報、Appl. Phys. Lett.,５１巻、９１３頁、１９８７
年）等が行われている。さらに、素子の発光効率を向上
させるとともに発光色を変える目的で、８−ヒドロキシ
キノリンのアルミニウム錯体をホスト材料としてクマリ
ン等のレーザ用蛍光色素をドープすること（J. Appl. P
hys., ６５巻、３６１０頁、１９８９年）も行われてい
る。Further, in order to improve the efficiency of carrier injection from the electrode in order to increase the luminous efficiency, the kind of the electrode is optimized and a light emitting layer comprising a hole transport layer and an organic phosphor is provided. 57-51781, JP-A-59-59
-194393, JP-A-63-295695, Appl. Phys. Lett., 51, 913, 1987.
Years) etc. Furthermore, for the purpose of improving the light emission efficiency of the device and changing the light emission color, dope a fluorescent dye for laser such as coumarin using aluminum complex of 8-hydroxyquinoline as a host material (J. Appl. P.
hys., 65, 3610, 1989).
【０００５】[0005]
【発明が解決しようとする課題】上記のような有機電界
発光素子においては、電子輸送層に陰極から電子を注入
させるために仕事関数の低い電極材料、例えば特開平２
−１５５９５号公報に示されているマグネシウム系合金
が用いられているが、電子注入の効率がまだ十分ではな
い。In the organic electroluminescence device as described above, an electrode material having a low work function for injecting electrons from the cathode into the electron transport layer, for example, Japanese Patent Laid-Open No. HEI-2.
The magnesium-based alloy disclosed in Japanese Patent Publication No. -15595 is used, but the efficiency of electron injection is still insufficient.
【０００６】特開平２−２１３０８８号公報には、ポル
フィリン環あるいはフタロシアニン骨格を有する有機化
合物を有機電子輸送層として、これに電子供与性有機化
合物であるテトラチオフルバレン（ＴＴＦ）やテトラチ
オテトラセン（ＴＴＴ）などを５：１の割合で混合する
ことが開示されている。しかしながら、これらの化合物
はいずれも消光作用を有するために、発光層と接した場
合には発光輝度が大きく低下することが考えられる。ま
た、これらの化合物は、可視光領域大きな吸収を有する
ので発光スペクトル自体も変化してしまうと考えられ、
有機電界発光素子のフルカラー表示への応用を考えた場
合、上記の方法は好ましくない。In Japanese Unexamined Patent Publication No. 2-213088, an organic compound having a porphyrin ring or a phthalocyanine skeleton is used as an organic electron transport layer, and an electron-donating organic compound such as tetrathiofulvalene (TTF) or tetrathiotetracene ( It has been disclosed to mix TTT) and the like in a ratio of 5: 1. However, since all of these compounds have a quenching effect, it is conceivable that the emission brightness will be significantly reduced when they come into contact with the light emitting layer. Further, since these compounds have large absorption in the visible light region, it is considered that the emission spectrum itself is changed,
Considering the application of the organic electroluminescent device to full-color display, the above method is not preferable.
【０００７】また、特開平３−７９０号公報には、正孔
輸送機能を有する電子供与性化合物と電子輸送機能を有
する蛍光性有機化合物を混合することが開示されている
が、芳香族ジアミン化合物とペリノン誘導体を１：１で
混合した例では極めて低い発光効率しか得られていな
い。これまでに開示されている有機電界発光素子におい
ては、電界発光は注入された正孔及び電子の再結合によ
りもたらされる。しかしながら、一般にキャリアの注
入、例えば正孔の注入は陽極と有機正孔輸送層との界面
での注入障壁、電子の注入は陰極と発光層との界面での
注入障壁を乗り越えて行われなければならない。特に、
電子注入の障壁のために高電界が必要となり、結果とし
て素子の駆動電圧が高くなるため、発光性能、特に発光
効率が不十分となり、また界面の不安定性に起因する動
作の不安定性もみられ、更なる改良検討が望まれてい
る。Japanese Patent Laid-Open No. 3-790 discloses that an electron-donating compound having a hole-transporting function and a fluorescent organic compound having an electron-transporting function are mixed. In the example in which 1: 1 and the perinone derivative are mixed, extremely low luminous efficiency is obtained. In the organic electroluminescent devices disclosed so far, electroluminescence is brought about by the recombination of injected holes and electrons. However, in general, injection of carriers, for example, injection of holes must be carried out by overcoming the injection barrier at the interface between the anode and the organic hole transport layer, and injection of electrons by overcoming injection barrier at the interface between the cathode and the light emitting layer. I won't. In particular,
A high electric field is required due to the barrier of electron injection, and as a result, the driving voltage of the element becomes high, the light emission performance, especially the light emission efficiency becomes insufficient, and the instability of the operation due to the instability of the interface is also observed. Further improvement studies are desired.
【０００８】本発明者等は、上記実状に鑑み低電圧で駆
動させることができる有機電界発光素子を提供すること
を目的として鋭意検討した結果、有機電子輸送層が芳香
族ジアミン化合物を含有することが好適であることを見
い出し、本発明を完成した。In view of the above situation, the inventors of the present invention have conducted extensive studies for the purpose of providing an organic electroluminescent device which can be driven at a low voltage, and as a result, found that the organic electron transport layer contains an aromatic diamine compound. Was found to be suitable, and the present invention has been completed.
【０００９】[0009]
【課題を解決するための手段】本発明の有機電界発光素
子は、順次に、陽極、正孔輸送層、有機電子輸送層及び
陰極が積層されてなる有機電界発光素子において、有機
電子輸送層が芳香族ジアミン化合物を含有することを特
徴とする。なお、本発明において、有機電子輸送層は、
特に、下記一般式（Ｉ）で表される芳香族ジアミン化合
物The organic electroluminescent device of the present invention is an organic electroluminescent device in which an anode, a hole transporting layer, an organic electron transporting layer and a cathode are laminated in this order. It is characterized by containing an aromatic diamine compound. In the present invention, the organic electron transport layer is
In particular, an aromatic diamine compound represented by the following general formula (I)
【００１０】[0010]
【化４】 [Chemical 4]
【００１１】（一般式（Ｉ）中、Ｒ1、Ｒ2、Ｒ3及びＲ4
はそれぞれ独立して、置換基を有していてもよいアルキ
ル基、置換基を有していてもよいシクロアルキル基、置
換基を有していてもよいアルケニル基、置換基を有して
いてもよいアリール基、置換基を有していてもよいアラ
ルキル基を示し、Ｒ5及びＲ6はそれぞれ独立して、水素
原子、ハロゲン原子、水酸基、置換基を有していてもよ
いアルキル基、置換基を有していてもよいシクロアルキ
ル基、置換基を有していてもよいアルケニル基、置換基
を有していてもよいアリール基、置換基を有していても
よいアラルキル基、置換基を有していてもよいアルコキ
シ基、置換基を有していてもよいジアルキルアミノ基又
は置換基を有していてもよいジアリールアミノ基を示
し、Ａは置換基を有していてもよい２価の炭化水素残基
又は直接結合を示す。）又は下記一般式（II）で表され
る芳香族ジアミン化合物(In the general formula (I), R 1 , R 2 , R 3 and R 4
Are each independently an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an alkenyl group which may have a substituent, and a substituent which may have a substituent. Represents an optionally substituted aryl group or an optionally substituted aralkyl group, and R 5 and R 6 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, or an optionally substituted alkyl group, A cycloalkyl group which may have a substituent, an alkenyl group which may have a substituent, an aryl group which may have a substituent, an aralkyl group which may have a substituent, a substituent Shows an alkoxy group which may have a group, a dialkylamino group which may have a substituent or a diarylamino group which may have a substituent, and A may have a substituent Shows divalent hydrocarbon residue or direct bond .. ) Or an aromatic diamine compound represented by the following general formula (II)
【００１２】[0012]
【化５】 [Chemical 5]
【００１３】（一般式（II）中、Ｒ7、Ｒ8、Ｒ9及びＲ
10はそれぞれ独立して、置換基を有していてもよいアル
キル基、置換基を有していてもよいシクロアルキル基、
置換基を有していてもよいアルケニル基、置換基を有し
ていてもよいアリール基、置換基を有していてもよいア
ラルキル基を示し、Ｒ11及びＲ12はそれぞれ独立して、
水素原子、ハロゲン原子、水酸基、置換基を有していて
もよい飽和あるいは不飽和の脂肪族炭化水素基、置換基
を有していてもよい芳香族炭化水素基、置換基を有して
いてもよいアルコキシ基、置換基を有していてもよいア
リールオキシ基、置換基を有していてもよいジアルキル
アミノ基又は置換基を有していてもよいジアリールアミ
ノ基を示し、Ｘは置換基を有していてもよい２価の炭化
水素残基を示す。）又は下記一般式（III）で表される
芳香族ジアミン化合物(In the general formula (II), R 7 , R 8 , R 9 and R
10 are each independently an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent,
An alkenyl group which may have a substituent, an aryl group which may have a substituent and an aralkyl group which may have a substituent are shown, and R 11 and R 12 are each independently
Hydrogen atom, halogen atom, hydroxyl group, saturated or unsaturated aliphatic hydrocarbon group which may have a substituent, aromatic hydrocarbon group which may have a substituent, which has a substituent Represents an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, a dialkylamino group which may have a substituent or a diarylamino group which may have a substituent, and X represents a substituent Represents a divalent hydrocarbon residue which may have. ) Or an aromatic diamine compound represented by the following general formula (III)
【００１４】[0014]
【化６】 [Chemical 6]
【００１５】（一般式（III）中、Ｒ13、Ｒ14、Ｒ15及
びＲ16はそれぞれ独立して、置換基を有していてもよい
アルキル基、置換基を有していてもよいシクロアルキル
基、置換基を有していてもよいアルケニル基、置換基を
有していてもよいアリール基、置換基を有していてもよ
いアラルキル基を示し、Ｒ17及びＲ18はそれぞれ独立し
て、水素原子、ハロゲン原子、水酸基、置換基を有して
いてもよい飽和あるいは不飽和の脂肪族炭化水素基、置
換基を有していてもよい芳香族炭化水素基、置換基を有
していてもよいアルコキシ基、置換基を有していてもよ
いアリールオキシ基、置換基を有していてもよいジアル
キルアミノ基又は置換基を有していてもよいジアリール
アミノ基を示し、Ｙ及びＺは置換基を有していてもよい
２価の炭化水素残基又は直接結合を示し、これらは同一
であっても異なっていてもよい。）を含有することが好
ましい。(In the general formula (III), R 13 , R 14 , R 15 and R 16 are each independently an alkyl group which may have a substituent or a cyclo group which may have a substituent. An alkyl group, an alkenyl group which may have a substituent, an aryl group which may have a substituent, an aralkyl group which may have a substituent, and R 17 and R 18 are each independently A hydrogen atom, a halogen atom, a hydroxyl group, a saturated or unsaturated aliphatic hydrocarbon group which may have a substituent, an aromatic hydrocarbon group which may have a substituent, and a substituent An optionally substituted alkoxy group, an optionally substituted aryloxy group, an optionally substituted dialkylamino group or an optionally substituted diarylamino group, and Y and Z is a divalent hydrocarbon residue which may have a substituent. Or shows a direct bond, it preferably contains may.) To be different even for the same.
【００１６】以下、本発明の有機電界発光素子について
添付図面に従い詳細に説明する。図１は、本発明の有機
電界発光素子の構造例を模式的に示す断面図であり、１
は基板、２ａ、２ｂは導電層、３は正孔輸送層、４は有
機電子輸送層を各々表わす。基板１は、本発明の有機電
界発光素子の支持体となるものであり、石英やガラスの
板、金属板や金属箔、プラスチックフィルムやシート等
を用いることができるが、ガラス板や、ポリエステル、
ポリメタアクリレート、ポリカーボネート、ポリサルホ
ンなどの透明な合成樹脂基板が好ましい。Hereinafter, the organic electroluminescent device of the present invention will be described in detail with reference to the accompanying drawings. FIG. 1 is a cross-sectional view schematically showing a structural example of the organic electroluminescent element of the present invention.
Is a substrate, 2a and 2b are conductive layers, 3 is a hole transport layer, and 4 is an organic electron transport layer. The substrate 1 serves as a support for the organic electroluminescent element of the present invention, and a plate of quartz or glass, a metal plate or metal foil, a plastic film or sheet, or the like can be used, but a glass plate, polyester,
A transparent synthetic resin substrate such as polymethacrylate, polycarbonate or polysulfone is preferable.
【００１７】基板１上には導電層２ａが設けられるが、
この導電層２ａは、通常、アルミニウム、金、銀、ニッ
ケル、パラジウム、テルル等の金属、インジウム及び／
又はスズの酸化物などの金属酸化物やヨウ化銅、カーボ
ンブラックあるいはポリ（３−メチルチオフェン）等の
導電性樹脂などにより構成される。導電層２ａの形成は
通常、スパッタリング法、真空蒸着法などにより行われ
ることが多いが、銀などの金属微粒子あるいはヨウ化
銅、カーボンブラック、導電性の金属酸化物微粒子、導
電性樹脂微粉末等の場合には、適当なバインダー樹脂溶
液に分散し、基板上に塗布することにより形成すること
もできる。さらに、導電性樹脂の場合は電解重合により
直接基板上に薄膜を形成することもできる。導電層２ａ
は異なる物質を積層して形成することも可能である。A conductive layer 2a is provided on the substrate 1,
This conductive layer 2a is usually a metal such as aluminum, gold, silver, nickel, palladium, tellurium, indium and / or
Alternatively, a metal oxide such as tin oxide, a conductive resin such as copper iodide, carbon black, or poly (3-methylthiophene) is used. The conductive layer 2a is usually formed by a sputtering method, a vacuum deposition method or the like, but metal fine particles such as silver or copper iodide, carbon black, conductive metal oxide fine particles, conductive resin fine powder, etc. In this case, it can also be formed by dispersing it in an appropriate binder resin solution and applying it on a substrate. Further, in the case of a conductive resin, a thin film can be directly formed on the substrate by electrolytic polymerization. Conductive layer 2a
Can be formed by stacking different materials.
【００１８】導電層２ａの厚みは、必要とする透明性に
より異なるが、透明性が必要とされる場合は、可視光の
透過率が６０％以上、好ましくは８０％以上であること
が望ましく、この場合、厚みは、通常、５０〜１０００
０Å、好ましくは１００〜５０００Å程度である。不透
明でよい場合は導電層２ａは基板１と同一でもよい。ま
た、導電層２ａは異なる物質で積層することも可能であ
る。The thickness of the conductive layer 2a varies depending on the required transparency, but when transparency is required, it is desirable that the visible light transmittance is 60% or more, preferably 80% or more. In this case, the thickness is usually 50 to 1000.
It is 0Å, preferably about 100 to 5000Å. The conductive layer 2a may be the same as the substrate 1 if it is opaque. Further, the conductive layer 2a can be laminated with different materials.
【００１９】図１の例では、導電層２ａは陽極（アノー
ド）として正孔を注入する役割を果たすものである。一
方、導電層２ｂは陰極（カソード）として有機電子輸送
層４に電子を注入する役割を果たすものである。導電層
２ｂとして用いられる材料は、前記導電層２ａ用の材料
を用いることが可能であるが、効率よく電子注入を行う
には、仕事関数の低い値をもつ金属が好ましく、スズ、
マグネシウム、インジウム、アルミニウム、銀等の金属
またはそれらの合金が用いられる。導電層２ｂの膜厚
は、通常、導電層２ａと同程度であり、導電層２ａと同
様の方法で形成することができる。In the example of FIG. 1, the conductive layer 2a plays a role of injecting holes as an anode. On the other hand, the conductive layer 2b plays a role of injecting electrons into the organic electron transport layer 4 as a cathode. The material used for the conductive layer 2b can be the material for the conductive layer 2a, but a metal having a low work function is preferable for efficient electron injection, and tin,
Metals such as magnesium, indium, aluminum and silver or alloys thereof are used. The thickness of the conductive layer 2b is usually about the same as that of the conductive layer 2a, and the conductive layer 2b can be formed by the same method.
【００２０】また、図１には示してはいないが、導電層
２ｂの上にさらに基板１と同様の基板を設けることもで
きる。但し、電界発光素子としては導電層２ａと導電層
２ｂの少なくとも一方は透明性の良いことが必要であ
る。このことから、導電層２ａと導電層２ｂの一方は、
１００〜５０００Åの膜厚であることが好ましく、透明
性の良いことが望まれる。Although not shown in FIG. 1, a substrate similar to the substrate 1 may be further provided on the conductive layer 2b. However, in the electroluminescent element, at least one of the conductive layer 2a and the conductive layer 2b needs to have good transparency. From this, one of the conductive layers 2a and 2b is
A film thickness of 100 to 5000Å is preferable, and good transparency is desired.
【００２１】導電層２ａの上には正孔輸送層３が設けら
れるが、正孔輸送層３は、電界を与えられた電極間にお
いて陽極からの正孔を効率よく有機電子輸送層４の方向
に輸送することができる化合物より形成される。正孔輸
送材料としては、導電層２ａからの正孔注入効率が高
く、かつ注入された正孔を効率よく輸送することができ
る化合物であることが必要である。そのためには、イオ
ン化ポテンシャルが小さく、しかも正孔移動度が大き
く、さらに安定正にすぐれたトラップとなる不純物が製
造時や使用時に発生しにくい化合物であることが要求さ
れる。The hole transport layer 3 is provided on the conductive layer 2a. The hole transport layer 3 efficiently directs holes from the anode between the electrodes to which an electric field is applied to the organic electron transport layer 4. Formed from a compound that can be transported to. The hole transport material needs to be a compound having a high hole injection efficiency from the conductive layer 2a and capable of efficiently transporting the injected holes. For that purpose, it is required that the compound has a small ionization potential, a large hole mobility, and a stable and excellent trapping impurity that does not easily occur during manufacturing or use.
【００２２】このような正孔輸送材料としては、例え
ば、特開昭５９−１９４３９３号公報の第５〜６頁およ
び米国特許第４１７５９６０号の第１３〜１４欄等に記
載されている有機材料が挙げられる。これら化合物の好
ましい具体例としては、Ｎ，Ｎ′−ジフェニル−Ｎ，
Ｎ′−（３−メチルフェニル）−１，１′−ビフェニル
−４，４′−ジアミン、１，１′−ビス（４−ジ−ｐ−
トリルアミノフェニル）シクロヘキサン、４，４′−ビ
ス（ジフェニルアミノ）クワドロフェニル等の芳香族ア
ミン系化合物が挙げられる。芳香族アミン系化合物以外
では、特開平２−３１１５９１号公報に示されるヒドラ
ゾン化合物、米国特許第４９５０９５０号公報に示され
るシラザン化合物等が挙げられる。これらの化合物は、
単独で用いても、必要に応じて各々混合物として用いて
もよい。上記の化合物以外にはポリビニルカルバゾール
やAppl．Phys．Lett．５９巻、２７６０頁（１９９１
年）に示されるポリシラン等の高分子化合物が挙げられ
る。Examples of such hole-transporting materials include organic materials described in JP-A-59-194393, pages 5-6 and US Pat. No. 4,175,960, columns 13-14. Can be mentioned. Specific preferred examples of these compounds include N, N'-diphenyl-N,
N '-(3-methylphenyl) -1,1'-biphenyl-4,4'-diamine, 1,1'-bis (4-di-p-
Examples thereof include aromatic amine compounds such as tolylaminophenyl) cyclohexane and 4,4′-bis (diphenylamino) quadrophenyl. Other than aromatic amine compounds, hydrazone compounds disclosed in JP-A-2-311591, silazane compounds disclosed in US Pat. No. 4,950,950 and the like can be mentioned. These compounds are
They may be used alone or as a mixture as required. In addition to the above compounds, polyvinylcarbazole and Appl. Phys. Lett. Volume 59, page 2760 (1991)
Polymer compounds such as polysilanes shown in 1).
【００２３】有機正孔輸送層３は、塗布法あるいは真空
蒸着法により前記導電層２ａ上に積層することにより形
成される。例えば、塗布法の場合は、有機正孔輸送化合
物を１種または２種以上と必要により正孔のトラップに
ならないバインダー樹脂や、レベリング剤等の塗布性改
良剤などの添加剤を添加して溶解させた塗布溶液を調整
し、スピンコート法などの方法により導電層２ａ上に塗
布し、乾燥して有機正孔輸送層３を形成する。バインダ
ー樹脂としては、ポリカーボネート、ポリアクリレー
ト、ポリエステル等が挙げられる。バインダー樹脂は添
加量が多いと正孔移動度を低下させるので、少ない方が
望ましく、５０重量％以下が好ましい。The organic hole transport layer 3 is formed by laminating on the conductive layer 2a by a coating method or a vacuum deposition method. For example, in the case of a coating method, one or more organic hole transport compounds are added and dissolved by adding a binder resin that does not become a hole trap if necessary and an additive such as a coating property improving agent such as a leveling agent. The coating solution thus prepared is prepared, coated on the conductive layer 2a by a method such as spin coating, and dried to form the organic hole transport layer 3. Examples of the binder resin include polycarbonate, polyacrylate, polyester and the like. If the addition amount of the binder resin is large, the hole mobility is lowered.
【００２４】また、真空蒸着法の場合には、有機正孔輸
送材料を真空容器内に設置されたルツボに入れ、真空容
器内を適当な真空ポンプで１０-6Ｔｏｒｒにまで排気し
た後、ルツボを加熱して、有機正孔輸送材料を蒸発さ
せ、ルツボと向き合って置かれた基板上に層を形成す
る。また、正孔輸送材料として無機材料を使用すること
もできる。無機材料としては、ｐ型水素化非晶質シリコ
ン、ｐ型水素化非晶質炭化シリコン、ｐ型水素化微結晶
性炭化シリコン、ｐ型硫化亜鉛、ｐ型セレン化亜鉛等が
挙げられる。このような無機正孔輸送層３は、ＣＶＤ
法、プラズマＣＶＤ法、真空蒸着法、スパッタリング法
等により形成される。In the case of the vacuum deposition method, the organic hole transporting material is placed in a crucible installed in a vacuum container, the interior of the vacuum container is evacuated to 10 -6 Torr by an appropriate vacuum pump, and then the crucible is placed. Is heated to evaporate the organic hole transport material and form a layer on the substrate placed facing the crucible. An inorganic material can also be used as the hole transport material. Examples of the inorganic material include p-type hydrogenated amorphous silicon, p-type hydrogenated amorphous silicon carbide, p-type hydrogenated microcrystalline silicon carbide, p-type zinc sulfide, and p-type zinc selenide. Such an inorganic hole transport layer 3 is formed by CVD.
Method, plasma CVD method, vacuum deposition method, sputtering method, or the like.
【００２５】正孔輸送層３の膜厚は、通常、１００〜３
０００Å、好ましくは３００〜１０００Åである。この
ように薄い膜を一様に形成するためには、真空蒸着法が
よく用いられる。正孔輸送層３の上には有機電子輸送層
４が設けられるが、有機電子輸送層４は、電界を与えら
れた電極間において陰極からの電子を効率よく正孔輸送
層３の方向に輸送することができる化合物より形成され
る。The thickness of the hole transport layer 3 is usually 100-3.
It is 000Å, preferably 300 to 1000Å. In order to uniformly form such a thin film, the vacuum evaporation method is often used. An organic electron transport layer 4 is provided on the hole transport layer 3, and the organic electron transport layer 4 efficiently transports electrons from the cathode between the electrodes to which an electric field is applied in the direction of the hole transport layer 3. Is formed from a compound that can
【００２６】有機電子輸送化合物としては、導電層２ｂ
からの電子注入効率が高く、かつ、注入された電子を効
率よく輸送することができる化合物であることが必要で
ある。そのためには、電子親和力が大きく、しかも電子
移動度が大きく、さらに安定性にすぐれトラップとなる
不純物が製造時や使用時に発生しにくい化合物であるこ
とが要求される。As the organic electron transport compound, the conductive layer 2b is used.
It is necessary for the compound to have a high electron injection efficiency and to efficiently transport the injected electrons. For that purpose, it is required that the compound has a high electron affinity, a high electron mobility, excellent stability, and an impurity that becomes a trap and is unlikely to be generated at the time of production or use.
【００２７】このような条件を満たす材料としては、テ
トラフェニルブタジエン等の芳香族化合物（特開昭５７
−５１７８１号公報）、８−ヒドロキシキノリンのアル
ミニウム錯体等の金属錯体（特開昭５９−１９４３９３
号公報）、シクロペンタジエン誘導体（特開平２−２８
９６７５号公報）、ペリノン誘導体（特開平２−２８９
６７６号公報）、オキサジアゾール誘導体（特開平２−
２１６７９１号公報）、ビススチリルベンゼン誘導体
（特開平１−２４５０８７号公報、同２−２２２４８４
号公報）、ペリレン誘導体（特開平２−１８９８９０号
公報、同３−７９１号公報）、クマリン化合物（特開平
２−１９１６９４号公報、同３−７９２号公報）、希土
類錯体（特開平１−２５６５８４号公報）、ジスチリル
ピラジン誘導体（特開平２−２５２７９３号公報）、チ
アジアゾロピリジン誘導体（特開平３−３７２９２号公
報）、ピロロピリジン誘導体（特開平３−３７２９３号
公報）、ナフチリジン誘導体（特開平３−２０３９８２
号公報）等が挙げられる。これらの化合物を用いた場合
は、有機電子輸送層４は電子を輸送する役割と、正孔と
電子の再結合の際に発光をもたらす役割を同時に果た
す。As a material satisfying such a condition, an aromatic compound such as tetraphenyl butadiene (JP-A-57 / 1982) is used.
No. 51781), aluminum complexes of 8-hydroxyquinoline, and other metal complexes (JP-A-59-194393).
JP-A-2-28).
9675), perinone derivatives (JP-A-2-289)
676), an oxadiazole derivative (JP-A-2-
No. 216791), and bisstyrylbenzene derivatives (JP-A Nos. 1-245087 and 2-222484).
No.), perylene derivatives (JP-A-2-189890 and JP-A-3-791), coumarin compounds (JP-A-2-191694 and JP-A-3-792), and rare earth complexes (JP-A-1-256584). No.), a distyrylpyrazine derivative (JP-A-2-252793), a thiadiazolopyridine derivative (JP-A-3-37292), a pyrrolopyridine derivative (JP-A-3-37293), a naphthyridine derivative (special Kaihei 3-203982
Gazette) and the like. When these compounds are used, the organic electron transport layer 4 simultaneously plays a role of transporting electrons and a role of causing light emission upon recombination of holes and electrons.
【００２８】有機電子輸送層４の膜厚は、通常、１００
〜２０００Å、好ましくは３００〜１０００Åである。
有機電子輸送層４も正孔輸送層３と同様の方法で形成す
ることができるが、通常は、真空蒸着法が用いられる。
また、有機電界発光素子の発光効率をより向上させるた
めに、図３に示すように、陽極、正孔輸送層、有機発光
層、芳香族ジアミン化合物がドープされた有機電子輸送
層、陰極が積層された素子構造でもよい。この場合、有
機発光材料としては前記有機電子輸送材料が挙げられ、
芳香族ジアミン化合物がドープされた有機電子輸送材料
としては有機発光層とは異なる材料から選ばれ、前記有
機電子輸送材料の中から選択されるか、あるいは陰極か
らの電子注入が容易で、電子の輸送能力がさらに大きい
ことが要求される。このような有機電子輸送化合物とし
ては、下記構造式（Ｄ１１）で表わされる化合物などの
ジフェニルキノン誘導体、下記構造式（Ｄ１２）で表わ
される化合物などのペリレンテトラカルボン酸誘導体
（Jpn. J. Appl. Phys．２７巻、Ｌ２６９頁、１９８８
年）、下記構造式（Ｄ１３）で表わされる化合物などの
オキサジアゾール誘導体（Appl．Phys．Lett．５５巻、
１４８９頁、１９８９年）が挙げられる。The thickness of the organic electron transport layer 4 is usually 100.
˜2000 Å, preferably 300 to 1000 Å.
The organic electron transport layer 4 can also be formed by the same method as that of the hole transport layer 3, but a vacuum deposition method is usually used.
Further, in order to further improve the luminous efficiency of the organic electroluminescent device, as shown in FIG. 3, an anode, a hole transport layer, an organic light emitting layer, an organic electron transport layer doped with an aromatic diamine compound, and a cathode are laminated. It may be a device structure that has been formed. In this case, examples of the organic light emitting material include the organic electron transporting material,
The organic electron transporting material doped with an aromatic diamine compound is selected from materials different from the organic light emitting layer, and is selected from the above organic electron transporting materials, or electron injection from the cathode is easy, and Greater transport capacity is required. As such an organic electron transport compound, a diphenylquinone derivative such as a compound represented by the following structural formula (D11), a perylene tetracarboxylic acid derivative such as a compound represented by the following structural formula (D12) (Jpn. J. Appl. Phys. 27, L269, 1988.
), An oxadiazole derivative such as a compound represented by the following structural formula (D13) (Appl. Phys. Lett. 55,
1489, 1989).
【００２９】[0029]
【化７】 [Chemical 7]
【００３０】[0030]
【化８】 [Chemical 8]
【００３１】[0031]
【化９】 [Chemical 9]
【００３２】このような、有機電子輸送層５の膜厚は、
通常、１００〜２０００Å、好ましくは３００〜１００
０Åである。尚、図１とは逆の構造、即ち、基板上に導
電層２ｂ、有機電子輸送層４、正孔輸送層３、導電層２
ａの順に積層することも可能であり、既述したように少
なくとも一方が透明性の高い２枚の基板の間に本発明の
電界発光素子を設けることも可能である。また、同様
に、図２とは逆の構造にすることも可能である。The film thickness of the organic electron transport layer 5 is
Usually, 100 to 2000Å, preferably 300 to 100
It is 0Å. The structure opposite to that of FIG. 1, that is, the conductive layer 2b, the organic electron transport layer 4, the hole transport layer 3, and the conductive layer 2 are formed on the substrate.
It is also possible to stack in the order of a, and as described above, the electroluminescent element of the present invention can be provided between two substrates, at least one of which is highly transparent. Similarly, the structure opposite to that shown in FIG. 2 can be adopted.
【００３３】本発明において、芳香族ジアミン化合物が
ドープされる領域は、有機電子輸送層４の全体であって
も、その一部分であってもよい。芳香族ジアミン化合物
が、ホスト材料に対してドープされる量は、１０-3〜１
０モル％が好ましい。本発明で用いる芳香族ジアミン化
合物、特に前記一般式（Ｉ）、（II）又は（III）で表
される化合物は、分散状態で強い蛍光を示し、ホスト材
料にドープされた場合、素子の発光効率が向上する。さ
らに、ホスト材料の薄膜状態を構造的に安定化すること
ができ、有機電界発光素子に長期にわたる安定性を与え
ることが可能である。In the present invention, the region doped with the aromatic diamine compound may be the whole organic electron transport layer 4 or a part thereof. The amount of the aromatic diamine compound doped with respect to the host material is 10 −3 to 1
0 mol% is preferable. The aromatic diamine compound used in the present invention, particularly the compound represented by the general formula (I), (II) or (III), exhibits strong fluorescence in a dispersed state and emits light from a device when doped in a host material. Efficiency is improved. Furthermore, the thin film state of the host material can be structurally stabilized, and the organic electroluminescent device can be provided with long-term stability.
【００３４】芳香族ジアミン化合物を有機電子輸送層４
にドープする方法としては、例えば、塗布法の場合は、
有機電子輸送化合物と、芳香族ジアミン化合物、さらに
必要により正孔または電子のトラップにならないバイン
ダー樹脂や、レべリング剤等の塗布性改良剤などの添加
剤を添加して溶解させた塗布溶液を調整し、スピンコー
ト法などの方法により塗布し、乾燥して形成する。バイ
ンダー樹脂としては、ポリカーボネート、ポリアリレー
ト、ポリエステル等が挙げられる。バインダー樹脂は、
添加量が多いと正孔または電子の移動度を低下させるの
で少ない方が望ましく、５０重量％以下が好ましい。真
空蒸着法の場合には、有機電子輸送化合物を真空容器内
に設置されたルツボに入れ、芳香族ジアミン化合物を別
のルツボに入れ、真空容器内を適当な真空ポンプで１０
-6Ｔｏｒｒ程度にまで排気した後、各々のルツボを同時
に加熱して蒸発させ、ルツボと向き合って置かれた基板
上に層を形成する。また、別の方法としては、上記材料
を所定の割合で混合したものを同一のルツボを用いて蒸
発させてもよい。The aromatic diamine compound is added to the organic electron transport layer 4
As a method of doping into, for example, in the case of a coating method,
An organic electron transporting compound, an aromatic diamine compound, a binder resin that does not trap holes or electrons as necessary, and an additive such as a coating improver such as a leveling agent are dissolved to obtain a coating solution. It is formed by adjusting, coating by a method such as spin coating, and drying. Examples of the binder resin include polycarbonate, polyarylate, polyester and the like. The binder resin is
If the addition amount is large, the mobility of holes or electrons is lowered, so the addition amount is preferable, and 50% by weight or less is preferable. In the case of the vacuum vapor deposition method, the organic electron transport compound is put in a crucible installed in a vacuum container, the aromatic diamine compound is put in another crucible, and the inside of the vacuum container is adjusted by a suitable vacuum pump.
After evacuation to about -6 Torr, each crucible is simultaneously heated and evaporated to form a layer on the substrate facing the crucible. Further, as another method, a mixture of the above materials in a predetermined ratio may be evaporated using the same crucible.
【００３５】本発明の有機電界発光素子においては、有
機電子輸送層４が芳香族ジアミン化合物、好ましくは、
前記一般式（Ｉ）、（II）又は（III）で表される芳香
族ジアミン化合物を含有するものである。前記一般式
（Ｉ）において、Ｒ1、Ｒ2、Ｒ3及びＲ4はそれぞれ独立
して、置換基を有していてもよいメチル基、エチル基、
プロピル基、ブチル基、ヘキシル基等のアルキル基；置
換基を有していてもよいシクロヘキシル基等のシクロア
ルキル基；置換基を有していてもよいビニル基等のアル
ケニル基；アルキル基、アルコキシ基、ハロゲン原子、
アミノ基、アリール基等の置換基を有していてもよいフ
ェニル基、ナフチル基等のアリール基；置換基を有して
いてもよいベンジル基、ナフチルメチル基、フェネチル
基等のアラルキル基を示す。In the organic electroluminescent device of the present invention, the organic electron transport layer 4 is an aromatic diamine compound, preferably,
It contains an aromatic diamine compound represented by the general formula (I), (II) or (III). In the general formula (I), R 1 , R 2 , R 3 and R 4 are each independently a methyl group which may have a substituent, an ethyl group,
Alkyl group such as propyl group, butyl group and hexyl group; Cycloalkyl group such as cyclohexyl group which may have a substituent; alkenyl group such as vinyl group which may have a substituent; alkyl group, alkoxy Group, halogen atom,
An phenyl group which may have a substituent such as an amino group or an aryl group, an aryl group such as a naphthyl group; an aralkyl group which may have a substituent such as a benzyl group, a naphthylmethyl group or a phenethyl group ..
【００３６】Ｒ5及びＲ6はそれぞれ独立して、水素原
子、ハロゲン原子、水酸基、置換基を有していてもよい
メチル基、エチル基、プロピル基、ブチル基、ヘキシル
基等のアルキル基；置換基を有していてもよいシクロヘ
キシル基等のシクロアルキル基；置換基を有していても
よいビニル基等のアルケニル基；アルキル基、アルコキ
シ基、ハロゲン原子、アミノ基、アリール基等の置換基
を有していてもよいフェニル基、ナフチル基等のアリー
ル基；置換基を有していてもよいベンジル基、ナフチル
メチル基、フェネチル基等のアラルキル基；置換基を有
していてもよいメトキシ基、エトキシ基、ブトキシ基等
のアルコキシ基；置換基を有していてもよいジメチルア
ミノ基、ジエチルアミノ基等のジアルキルアミノ基；又
は置換基を有していてもよいジベンジルアミノ基、ジフ
ェニルアミノ基等のジアリールアミノ基を示す。R 5 and R 6 are each independently an alkyl group such as a hydrogen atom, a halogen atom, a hydroxyl group, an optionally substituted methyl group, an ethyl group, a propyl group, a butyl group or a hexyl group; Cycloalkyl group such as cyclohexyl group which may have a substituent; alkenyl group such as vinyl group which may have a substituent; substitution of alkyl group, alkoxy group, halogen atom, amino group, aryl group etc. A phenyl group which may have a group, an aryl group such as a naphthyl group; an aralkyl group which may have a substituent such as a benzyl group, a naphthylmethyl group and a phenethyl group; which may have a substituent An alkoxy group such as a methoxy group, an ethoxy group, a butoxy group; a dialkylamino group such as a dimethylamino group or a diethylamino group which may have a substituent; or a substituent And optionally represents a diarylamino group such as a dibenzylamino group and a diphenylamino group.
【００３７】また、Ａは、好ましくは、−ＣＨ2−、−
ＣＨ2−ＣＨ2−、−ＣＨ2ＣＨ2ＣＨ2−等の置換基を有
していてもよいアルキレン基；シクロヘキシレン基等の
シクロアルキレン基；−ＣＨ＝ＣＨ−、−Ｃ（ＣＨ3）
＝ＣＨ−、−ＣＨ2−ＣＨ＝ＣＨ−ＣＨ2−、−ＣＨ＝Ｃ
Ｈ−ＣＨ＝ＣＨ−等の置換基を有していてもよいアルケ
ニレン基；置換基を有していてもよいフェニレン基、ナ
フチレン基、フェナンスレン基等のアリーレン基等の２
価の炭化水素残基又は直接結合を示す。A is preferably --CH 2 -,-
CH 2 -CH 2 -, - CH 2 CH 2 CH 2 - optionally substituted alkylene group which may have a group such as, cycloalkylene groups such as cyclohexylene group; -CH = CH -, - C (CH 3)
= CH -, - CH 2 -CH = CH-CH 2 -, - CH = C
Alkenylene group which may have a substituent such as H-CH = CH-; 2 such as an arylene group which may have a substituent such as a phenylene group, a naphthylene group and a phenanthrene group
Indicates a valent hydrocarbon residue or a direct bond.
【００３８】前記一般式（Ｉ）で表される芳香族ジアミ
ン化合物の主な具体例を表−１に示すが、これらに限定
するものではない。Specific examples of the aromatic diamine compound represented by the general formula (I) are shown in Table 1, but not limited thereto.
【００３９】[0039]
【表１】 [Table 1]
【００４０】前記一般式（II）において、Ｒ7、Ｒ8、Ｒ
9及びＲ10はそれぞれ独立して、置換基を有していても
よいメチル基、エチル基、プロピル基、ブチル基、ヘキ
シル基等のアルキル基；置換基を有していてもよいシク
ロヘキシル基等のシクロアルキル基；置換基を有してい
てもよいアリル基等のアルケニル基；アルキル基、アル
コキシ基、ハロゲン原子、アミノ基、アリール基等の置
換基を有していてもよいフェニル基、ナフチル基等のア
リール基；置換基を有していてもよいベンジル基、ナフ
チルメチル基、フェネチル基等のアラルキル基を示す。In the general formula (II), R 7 , R 8 and R
9 and R 10 are each independently an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group or a hexyl group which may have a substituent; a cyclohexyl group which may have a substituent, etc. Cycloalkyl group; alkenyl group such as allyl group which may have a substituent; phenyl group which may have a substituent such as alkyl group, alkoxy group, halogen atom, amino group, aryl group, naphthyl An aryl group such as a group; and an aralkyl group which may have a substituent, such as a benzyl group, a naphthylmethyl group and a phenethyl group.
【００４１】Ｒ11及びＲ12はそれぞれ独立して、水素原
子、ハロゲン原子、水酸基、置換基を有していてもよい
メチル基、エチル基、プロピル基、ブチル基、ヘキシル
基等のアルキル基；置換基を有していてもよいシクロヘ
キシル基等のシクロアルキル基；置換基を有していても
よいビニル基等のアルケニル基；アルキル基、アルコキ
シ基、ハロゲン原子、アミノ基、アリール基等の置換基
を有していてもよいフェニル基、ナフチル基等のアリー
ル基；置換基を有していてもよいベンジル基、ナフチル
メチル基、フェネチル基等のアラルキル基；置換基を有
していてもよいメトキシ基、エトキシ基、ブトキシ基等
のアルコキシ基；置換基を有していてもよいジメチルア
ミノ基、ジエチルアミノ基等のジアルキルアミノ基；又
は置換基を有していてもよいジベンジルアミノ基、ジフ
ェニルアミノ基等のジアリールアミノ基を示す。R 11 and R 12 are each independently an alkyl group such as a hydrogen atom, a halogen atom, a hydroxyl group, an optionally substituted methyl group, an ethyl group, a propyl group, a butyl group or a hexyl group; Cycloalkyl group such as cyclohexyl group which may have a substituent; alkenyl group such as vinyl group which may have a substituent; substitution of alkyl group, alkoxy group, halogen atom, amino group, aryl group etc. A phenyl group which may have a group, an aryl group such as a naphthyl group; an aralkyl group which may have a substituent such as a benzyl group, a naphthylmethyl group and a phenethyl group; which may have a substituent An alkoxy group such as a methoxy group, an ethoxy group, a butoxy group; a dialkylamino group such as a dimethylamino group or a diethylamino group which may have a substituent; or a substituent Which may be dibenzylamino group, a diarylamino group such as diphenylamino group.
【００４２】また、Ｘは、好ましくは、メチレン基、プ
ロピレン基、キシリレン基、シクロヘキシレン基、ビニ
レン基、フェニレン基、カルボニル基等の２価の炭化水
素残基を示し、これらはハロゲン原子、水酸基、飽和あ
るいは不飽和の炭化水素基、アルコキシ基、アリールオ
キシ基、ジアルキルアミノ基、ジアリールアミノ基等の
置換基を有していてもよい。X is preferably a divalent hydrocarbon residue such as a methylene group, a propylene group, a xylylene group, a cyclohexylene group, a vinylene group, a phenylene group and a carbonyl group, and these are a halogen atom or a hydroxyl group. It may have a substituent such as a saturated or unsaturated hydrocarbon group, an alkoxy group, an aryloxy group, a dialkylamino group or a diarylamino group.
【００４３】前記一般式（II）で表される芳香族ジアミ
ン化合物の主な具体例を表−２に示すが、これらに限定
するものではない。Specific examples of the aromatic diamine compound represented by the general formula (II) are shown in Table 2, but not limited thereto.
【００４４】[0044]
【表２】 [Table 2]
【００４５】前記一般式（III）において、Ｒ13、
Ｒ14、Ｒ15及びＲ16はそれぞれ独立して、置換基を有し
ていてもよいメチル基、エチル基、プロピル基、ブチル
基、ヘキシル基等のアルキル基；置換基を有していても
よいシクロヘキシル基等のシクロアルキル基；置換基を
有していてもよいアリル基等のアルケニル基；アルキル
基、アルコキシ基、ハロゲン原子、アミノ基、アリール
基等の置換基を有していてもよいフェニル基、ナフチル
基等のアリール基；置換基を有していてもよいベンジル
基、ナフチルメチル基、フェネチル基等のアラルキル基
を示す。In the general formula (III), R 13 ,
R 14 , R 15 and R 16 are each independently an alkyl group which may have a substituent, such as a methyl group, an ethyl group, a propyl group, a butyl group or a hexyl group; Good cycloalkyl group such as cyclohexyl group; alkenyl group such as allyl group which may have a substituent; optionally substituted group such as alkyl group, alkoxy group, halogen atom, amino group and aryl group An aryl group such as a phenyl group and a naphthyl group; an aralkyl group such as a benzyl group, a naphthylmethyl group and a phenethyl group which may have a substituent are shown.
【００４６】Ｒ17及びＲ18はそれぞれ独立して、水素原
子、ハロゲン原子、水酸基、置換基を有していてもよい
メチル基、エチル基、プロピル基、ブチル基、ヘキシル
基等のアルキル基；置換基を有していてもよいシクロヘ
キシル基等のシクロアルキル基；置換基を有していても
よいビニル基等のアルケニル基；アルキル基、アルコキ
シ基、ハロゲン原子、アミノ基、アリール基等の置換基
を有していてもよいフェニル基、ナフチル基等のアリー
ル基；置換基を有していてもよいベンジル基、ナフチル
メチル基、フェネチル基等のアラルキル基；置換基を有
していてもよいメトキシ基、エトキシ基、ブトキシ基等
のアルコキシ基；置換基を有していてもよいジメチルア
ミノ基、ジエチルアミノ基等のジアルキルアミノ基；又
は置換基を有していてもよいジベジルアミノ基、ジフェ
ニルアミノ基等のジアリールアミノ基を示す。R 17 and R 18 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, or an optionally substituted alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group or a hexyl group; Cycloalkyl group such as cyclohexyl group which may have a substituent; alkenyl group such as vinyl group which may have a substituent; substitution of alkyl group, alkoxy group, halogen atom, amino group, aryl group etc. A phenyl group which may have a group, an aryl group such as a naphthyl group; an aralkyl group which may have a substituent such as a benzyl group, a naphthylmethyl group and a phenethyl group; which may have a substituent An alkoxy group such as a methoxy group, an ethoxy group, a butoxy group; a dialkylamino group such as a dimethylamino group or a diethylamino group which may have a substituent; or a substituent Which may be Jibejiruamino group, a diarylamino group such as diphenylamino group.
【００４７】また、Ｙ及びＺは、好ましくは、直接結合
又はメチレン基、プロピレン基、キシリレン基、シクロ
ヘキシレン基、ビニレン基、フェニレン基等の２価の炭
化水素残基を示し、これらはハロゲン原子、水酸基、飽
和あるいは不飽和の炭化水素基、アルコキシ基、アリー
ルオキシ基、ジアルキルアミノ基、ジアリールアミノ基
等の置換基を有していてもよい。Y and Z preferably represent a direct bond or a divalent hydrocarbon residue such as a methylene group, a propylene group, a xylylene group, a cyclohexylene group, a vinylene group and a phenylene group, which are halogen atoms. It may have a substituent such as a hydroxyl group, a saturated or unsaturated hydrocarbon group, an alkoxy group, an aryloxy group, a dialkylamino group and a diarylamino group.
【００４８】前記一般式（III）で表される芳香族ジア
ミン化合物の主な具体例を表−３に示すが、これらに限
定するものではない。Specific examples of the aromatic diamine compound represented by the above general formula (III) are shown in Table 3, but not limited thereto.
【００４９】[0049]
【表３】 [Table 3]
【００５０】前記表−１〜表−３に例示した芳香族ジア
ミン化合物を用いて作製した真空蒸着膜のイオン化ポテ
ンシャルの値を例示すると以下の通りである。The values of the ionization potential of the vacuum deposited film produced by using the aromatic diamine compounds exemplified in Tables 1 to 3 are shown below.
【００５１】[0051]
【表４】 本発明において、有機電子輸送層４にドープされる芳香
族ジアミン化合物のイオン化ポテンシャルの値は５．４
ｅＶ以下であることが好ましい。[Table 4] In the present invention, the value of the ionization potential of the aromatic diamine compound with which the organic electron transport layer 4 is doped is 5.4.
It is preferably eV or less.
【００５２】[0052]
【作用】通常、有機電子輸送材料は、電極からのキャリ
アの注入がなければそれ自体絶縁体であり、キャリアは
殆ど持たないと考えられる。一般に、導電層２ｂと有機
電子輸送層４との間には電子注入障壁が存在し、この注
入障壁は導電層２ｂの仕事関数と有機電子輸送層４の電
子親和力との差であると考えることができる。導電層２
ｂの材料としては仕事関数の低い電極材料、例えば特開
平２−１５５９５号公報に示されているマグネシウム系
合金が使用されるが、マグネシウムと銀の原子比が１
０：２である合金膜の仕事関数は３．６ｅＶである（仕
事関数の測定は理研計器（株）製の紫外線光電子分析装
置（ＡＣ−１型）で行った。）。In general, the organic electron transport material is an insulator itself without injection of carriers from the electrodes, and it is considered that it has almost no carriers. Generally, there is an electron injection barrier between the conductive layer 2b and the organic electron transport layer 4, and it is considered that this injection barrier is the difference between the work function of the conductive layer 2b and the electron affinity of the organic electron transport layer 4. You can Conductive layer 2
As the material of b, an electrode material having a low work function, for example, a magnesium-based alloy disclosed in JP-A-2-15595 is used, but the atomic ratio of magnesium to silver is 1
The work function of the alloy film of 0: 2 is 3.6 eV (the work function was measured by an ultraviolet photoelectron analyzer (AC-1 type) manufactured by Riken Keiki Co., Ltd.).
【００５３】一方、有機電子輸送層４としてよく用いら
れている８−ヒドロキノリンのアルミニウム錯体（J. P
hys. Lett., ５１巻、９１３頁、１９８７年）の還元電
位は−１．７８〜−１．７９ｅＶという値が報告されて
おり（米国特許４，７６９，２９２号、電気通信学会研
究報告ＯＭＥ９０−４１，１９９０年）、これらの酸化
電位の値から電子親和力を以下の式から求めると２．５
ｅＶとなる。On the other hand, 8-hydroquinoline aluminum complex (J.P.
Hys. Lett., 51, 913, 1987) has been reported to have a reduction potential of -1.78 to -1.79 eV (US Pat. No. 4,769,292, IEICE Research Report OME90). -41, 1990), the electron affinity is 2.5 from the value of these oxidation potentials.
It becomes eV.
【００５４】電子親和力＝還元電位＋４．３ （J. Simon and J. J, Andre、Moleculer Semiconducto
rs、Springer-Verlag、１９８５年、２４頁）上記のマ
グネシウム合金の仕事関数と８−ヒドロキノリンのアル
ミニウム錯体の電子親和力の値から、この場合導電層２
ｂ（陰極）と有機電子輸送層４との間に存在する電子注
入障壁は１．１ｅＶと見積もられる。Electron affinity = reduction potential + 4.3 (J. Simon and J. J, Andre, Moleculer Semiconducto
rs, Springer-Verlag, 1985, p. 24) From the work function of the above magnesium alloy and the electron affinity of the aluminum complex of 8-hydroquinoline, in this case, the conductive layer 2
The electron injection barrier existing between b (cathode) and the organic electron transport layer 4 is estimated to be 1.1 eV.
【００５５】同様にして導電層２ａと有機正孔輸送層３
との間には正孔注入障壁が存在し、この注入障壁は有機
正孔輸送層３のイオン化ポテンシャルと導電層２ａの仕
事関数の差であると考えることができる。導電層２ａに
はインジウム・スズ酸化物（以下「ＩＴＯ」と略す。）
が通常使われるが、市販されているＩＴＯガラス（ＨＯ
ＹＡ（株）製でガラスはＮＡ−４０、ＩＴＯ膜厚は１２
００Å）の仕事関数は４．７０ｅＶ程度である。Similarly, the conductive layer 2a and the organic hole transport layer 3 are formed.
There is a hole injection barrier between and, and this injection barrier can be considered to be the difference between the ionization potential of the organic hole transport layer 3 and the work function of the conductive layer 2a. Indium tin oxide (hereinafter abbreviated as "ITO") is used for the conductive layer 2a.
Is usually used, but commercially available ITO glass (HO
YA Co., Ltd., glass is NA-40, ITO film thickness is 12
The work function of 00Å) is about 4.70 eV.
【００５６】また、有機正孔輸送層として、例えば、従
来用いられた芳香族ジアミンである前記Ｎ，Ｎ’−ジフ
ェニル−Ｎ，Ｎ’−（３−メチルフェニル）−１，１’
−ビフェニル−４，４’−ジアミン（Jpn. J. Appl. Ph
ys., ２７巻、Ｌ２６９頁、１９８８年）を真空蒸着に
よって形成し、そのイオン化ポテンシャルをＡＣ−１で
同様にして測定したところ５．２３ｅＶであった。した
がって、この場合の正孔注入障壁は０．５３ｅＶと見積
られる。Further, as the organic hole transporting layer, for example, the above-mentioned N, N'-diphenyl-N, N '-(3-methylphenyl) -1,1' which is an aromatic diamine which has been conventionally used is used.
-Biphenyl-4,4'-diamine (Jpn. J. Appl. Ph
ys., 27, L269, 1988) was formed by vacuum vapor deposition, and its ionization potential was similarly measured with AC-1 and found to be 5.23 eV. Therefore, the hole injection barrier in this case is estimated to be 0.53 eV.
【００５７】以上の結果から導電層２ｂから有機電子輸
送層４への電子注入障壁は正孔注入障壁の２倍程度大き
く、そのために電子注入障壁を越えるのに高電界を要す
る。また、それに伴って電圧降下が陽極／有機電子輸送
層界面で生じるので、素子の駆動時にジュール発熱が上
記界面に集中し、素子の動作の不安定性や劣化の原因と
なる。From the above results, the electron injection barrier from the conductive layer 2b to the organic electron transport layer 4 is about twice as large as the hole injection barrier, and therefore a high electric field is required to cross the electron injection barrier. In addition, since a voltage drop occurs at the interface between the anode and the organic electron transport layer, Joule heat is concentrated on the interface when the device is driven, which causes instability and deterioration of the device operation.
【００５８】本発明においては、芳香族ジアミン化合
物、特に前記一般式（Ｉ）、（II）又は（III）で表さ
れる芳香族ジアミン化合物はイオン化ポテンシャルが小
さく、有機電子輸送層にドープされた場合、それ自体が
イオン化して電子を有機電子輸送物質に与えると考えら
れ、結果として陰極からの電子注入によらずにキャリア
としての電子生成が有機電子輸送層内で起こり、結果と
して優れた発光特性、特に発光効率の向上と駆動電圧の
低下を達成することができる。In the present invention, the aromatic diamine compound, particularly the aromatic diamine compound represented by the general formula (I), (II) or (III), has a small ionization potential and is doped in the organic electron transport layer. In this case, it is considered that the ions themselves are ionized to give electrons to the organic electron transporting material, and as a result, electron generation as carriers occurs in the organic electron transporting layer without depending on electron injection from the cathode, resulting in excellent light emission. It is possible to improve the characteristics, particularly the luminous efficiency and reduce the driving voltage.
【００５９】[0059]
【実施例】次に、実施例及び比較例を挙げて本発明を更
に具体的に説明するが、本発明はその要旨を超えない限
り、以下の実施例の記載に限定されるものではない。 実施例１ 図２に示す構造の有機電界発光素子を以下の方法で作製
した。EXAMPLES Next, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to the description of the following Examples unless it exceeds the gist. Example 1 An organic electroluminescent device having the structure shown in FIG. 2 was produced by the following method.
【００６０】ガラス基板上にインジウム・スズ酸化物
（ＩＴＯ）透明導電膜を１２００Å厚さに堆積したもの
を有機アルカリで超音波洗浄、水洗、さらにイソプロピ
ルアルコールで超音波洗浄した後、真空蒸着装置内に設
置して、装置内の真空度が２×１０-6Ｔｏｒｒ以下にな
るまで油拡散ポンプを用いて排気した。有機正孔注入層
材料として、下記構造式(Ｈ１) 及び(Ｈ２)で表わされ
るヒドラゾン化合物をモル比で１：０．３で混合した。A transparent conductive film of indium tin oxide (ITO) deposited to a thickness of 1200 Å on a glass substrate was ultrasonically washed with organic alkali, washed with water, and further with isopropyl alcohol, and then in a vacuum vapor deposition apparatus. And was evacuated using an oil diffusion pump until the degree of vacuum in the apparatus became 2 × 10 −6 Torr or less. As the organic hole injection layer material, hydrazone compounds represented by the following structural formulas (H1) and (H2) were mixed at a molar ratio of 1: 0.3.
【００６１】[0061]
【化１０】 [Chemical 10]
【００６２】これをセラミックるつぼに入れ、るつぼの
周囲のタンタル線ヒーターで加熱して真空容器中で蒸発
させた。るつぼの温度は１５０〜１５５℃の範囲で、蒸
発時の真空度は１〜２×１０-6Ｔｏｒｒであった。この
ようにして５２０Åの膜厚の有機正孔輸送層を形成し
た。蒸着時間は１分４０秒であった。次に、有機電子輸
送層の材料として、下記構造式（Ｅ１）で表わされるア
ルミニウムの８−ヒドロキシキノリン錯体This was placed in a ceramic crucible, heated by a tantalum wire heater around the crucible and evaporated in a vacuum vessel. The temperature of the crucible was in the range of 150 to 155 ° C., and the degree of vacuum during evaporation was 1 to 2 × 10 −6 Torr. Thus, an organic hole transport layer having a film thickness of 520Å was formed. The vapor deposition time was 1 minute and 40 seconds. Next, as a material for the organic electron transport layer, an aluminum 8-hydroxyquinoline complex represented by the following structural formula (E1)
【００６３】[0063]
【化１１】 [Chemical 11]
【００６４】を単独で有機正孔輸送層上に同様にして蒸
着を行った。この時のるつぼの温度は２００〜２４０℃
の範囲で制御した。蒸着時の真空度は６×１０-7Ｔｏｒ
ｒ、蒸着時間は１分、膜厚は３６０Åであった。この層
は、発光層としての役割を果たす。さらに、有機電子輸
送層の材料として、前記構造式（Ｅ１）で表わされるア
ルミニウムの８−ヒドロキシキノリン錯体及びドープす
る化合物として前記表−１に示した芳香族ジアミン化合
物（１）を、各々、別々のるつぼを用いて、同時に加熱
して蒸着を行った。この時の各るつぼの温度は、アルミ
ニウムの８−ヒドロキシキノリン錯体に対しては２００
〜２４０℃の範囲、芳香族ジアミン化合物（１）に対し
ては１００〜１１０℃の範囲で制御した。蒸着時の真空
度は６×１０ -7Ｔｏｒｒで、蒸着時間は１分であった。
結果として、芳香族ジアミン化合物（１）が上記錯体に
対して１．８モル％ドープされた膜厚４１０Åの有機電
子輸送層が得られた。Is independently vaporized on the organic hole transport layer in the same manner.
I put on my clothes. The temperature of the crucible at this time is 200-240 ℃
Controlled in the range of. Vacuum degree during deposition is 6 × 10-7Tor
r, the vapor deposition time was 1 minute, and the film thickness was 360Å. This layer
Serves as a light emitting layer. In addition, organic electronic transport
As the material for the layer to be transferred, the layer represented by the structural formula (E1) is used.
Luminium 8-hydroxyquinoline complex and dope
Compounds shown in Table 1 above as aromatic diamine compounds
Object (1) is heated simultaneously using separate crucibles.
Then, vapor deposition was performed. The temperature of each crucible at this time is
200 for 8-hydroxyquinoline complexes of nickel
~ 240 ° C, relative to aromatic diamine compound (1)
The temperature was controlled in the range of 100 to 110 ° C. Vacuum during vapor deposition
6 × 10 -7At Torr, the vapor deposition time was 1 minute.
As a result, the aromatic diamine compound (1) becomes the above complex.
In contrast, 1.8 mol% doped organic film with a film thickness of 410Å
A child transport layer was obtained.
【００６５】最後に陰極として、マグネシウムと銀の合
金電極を２元同時蒸着法によって膜厚１２００Åに蒸着
した。蒸着はモリブデンボートを用いて、真空度は７〜
８１×１０-6Ｔｏｒｒで、蒸着時間は５分であった。光
沢のある膜が得られた。マグネシウムと銀の原子比は１
０：２．４であった。このようにして作製した有機電界
発光素子のＩＴＯ電極（陽極）にプラス、マグネシウム
・銀電極（陰極）にマイナスの直流電圧を印加して測定
した発光特性の結果を表−４に示す。Finally, as a cathode, an alloy electrode of magnesium and silver was vapor-deposited with a film thickness of 1200 Å by a binary vapor deposition method. A molybdenum boat is used for vapor deposition, and the degree of vacuum is 7 to
The deposition time was 5 minutes at 81 × 10 −6 Torr. A glossy film was obtained. The atomic ratio of magnesium to silver is 1
It was 0: 2.4. Table 4 shows the results of the light emission characteristics measured by applying a positive DC voltage to the ITO electrode (anode) and a negative DC voltage to the magnesium / silver electrode (cathode) of the organic electroluminescent device thus produced.
【００６６】この素子は、黄緑色の一様な発光を示し、
発光のピーク波長は５６０ｎｍであった。この素子の発
光輝度と電圧特性との関係を図４に示す。 実施例２ 芳香族ジアミン化合物（１）の代わりに前記表−１に示
した芳香族ジアミン化合物（２）を有機電子輸送層の陰
極側にドープしたこと以外は実施例１と同様にして図２
に示す構造の有機電界発光素子を作製した。この時のド
ープ濃度は３．４モル％であった。This device shows a uniform emission of yellow-green color,
The peak wavelength of light emission was 560 nm. FIG. 4 shows the relationship between the light emission luminance and the voltage characteristic of this element. Example 2 In the same manner as in Example 1 except that the cathode side of the organic electron transport layer was doped with the aromatic diamine compound (2) shown in Table 1 in place of the aromatic diamine compound (1).
An organic electroluminescent device having the structure shown in was produced. The dope concentration at this time was 3.4 mol%.
【００６７】得られた素子の発光特性の測定結果を表−
４に示す。この素子は、緑色の一様な発光を示し、発光
のピーク波長は５６０ｎｍであった。 実施例３ 芳香族ジアミン化合物（１）の代わりに前記表−１に示
した芳香族ジアミン化合物（８）を有機電子輸送層の陰
極側にドープしたこと以外は実施例１と同様にして図２
に示す構造の有機電界発光素子を作製した。この時のド
ープ濃度は１．９モル％であった。The measurement results of the emission characteristics of the obtained device are shown in the table.
4 shows. This device showed uniform emission of green light, and the emission peak wavelength was 560 nm. Example 3 In the same manner as in Example 1 except that the cathode side of the organic electron transport layer was doped with the aromatic diamine compound (8) shown in Table 1 in place of the aromatic diamine compound (1).
An organic electroluminescent device having the structure shown in was produced. The dope concentration at this time was 1.9 mol%.
【００６８】得られた素子の発光特性の測定結果を表−
４に示す。この素子は、緑色の一様な発光を示し、発光
のピーク波長は５６０ｎｍであった。 比較例１ 有機電子輸送層に芳香族ジアミン化合物（１）をドープ
しなかったこと以外は実施例１と同様にして有機電界発
光素子を作製した。この素子の発光特性の測定結果を表
−４に示す。この素子は、５６０ｎｍに発光のピーク波
長を持ち、緑色の一様な発光を示した。また、この素子
の発光輝度と電圧特性との関係を図４に示す。The measurement results of the emission characteristics of the obtained device are shown in the table.
4 shows. This device showed uniform emission of green light, and the emission peak wavelength was 560 nm. Comparative Example 1 An organic electroluminescent device was produced in the same manner as in Example 1 except that the aromatic diamine compound (1) was not doped in the organic electron transport layer. Table 4 shows the measurement results of the light emission characteristics of this device. This device had a peak wavelength of light emission at 560 nm and showed uniform green light emission. Further, FIG. 4 shows the relationship between the light emission luminance of this element and the voltage characteristics.
【００６９】[0069]
【表５】 Ｖth：輝度が１cd/m2となる電圧 発光効率：実用輝度(100cd/m2)での値 実施例４ 実施例１で作製した素子を、真空中で３０日間保存した
後、発光特性を測定した。結果を表−５に示す。発光輝
度、発光効率の低下は実用上問題とならず、長期にわた
る安定性を示した。[Table 5] Vth: voltage at which luminance becomes 1 cd / m 2 Luminous efficiency: value at practical luminance (100 cd / m 2 ) Example 4 The device manufactured in Example 1 was stored in vacuum for 30 days, and then the luminescent characteristics were measured. did. The results are shown in Table-5. The decrease in light emission brightness and light emission efficiency did not pose any practical problems, and stability was exhibited for a long period of time.
【００７０】[0070]
【表６】 Ｖ100：輝度が100cd/m2となる実用駆動電圧 比較例２ 比較例１で作製した素子を、真空中で保存して発光特性
を測定した結果、３０日後、駆動電圧の増加が顕著にな
ると同時に輝度も大きく低下した。[Table 6] V 100 : Practical driving voltage at which brightness becomes 100 cd / m 2 Comparative Example 2 The device manufactured in Comparative Example 1 was stored in vacuum and the emission characteristics were measured. As a result, after 30 days, the increase in the driving voltage became remarkable. At the same time, the brightness was greatly reduced.
【００７１】[0071]
【発明の効果】本発明の有機電界発光素子は、導電層
（陽極）、正輸送層、有機電子輸送層、導電層（陰極）
が基板上に順次設けられ、しかも、有機電子輸送層に芳
香族ジアミン化合物をドープしているため、両導電層を
電極として電圧を印加した場合、低い駆動電圧で実用上
十分な輝度の発光を得ることができ、長期間安定した発
光性能を示す素子が得られる。The organic electroluminescent device of the present invention comprises a conductive layer (anode), a positive transport layer, an organic electron transport layer, and a conductive layer (cathode).
Are sequentially provided on the substrate, and since the organic electron transport layer is doped with an aromatic diamine compound, when a voltage is applied with both conductive layers as electrodes, light emission of practically sufficient brightness is achieved with a low driving voltage. An element that can be obtained and exhibits stable light emission performance for a long period of time can be obtained.
【００７２】本発明の有機電界発光素子はフラットパネ
ル・ディスプレイ（例えばＯＡコンピュータ用や壁掛け
テレビ）の分野や面発光体としての特徴を生かした光源
（例えば、複写機の光源、液晶ディスプレイや計器類の
バックライト光源）、表示板、標識灯への応用が考えら
れ、その工業的有用性は極めて大きい。The organic electroluminescent device of the present invention is a light source (for example, a light source of a copying machine, a liquid crystal display, and instruments) which makes the most of the field of flat panel displays (for OA computers and wall-mounted televisions) and its characteristics as a surface light emitter. Is considered to be industrially useful.
【図１】本発明の有機電界発光素子の一実施例の模式断
面図。FIG. 1 is a schematic cross-sectional view of an example of the organic electroluminescent element of the present invention.
【図２】本発明の有機電界発光素子の他の実施例の模式
断面図。FIG. 2 is a schematic cross-sectional view of another embodiment of the organic electroluminescent element of the present invention.
【図３】本発明の有機電界発光素子のその他の実施例の
模式断面図。FIG. 3 is a schematic cross-sectional view of another embodiment of the organic electroluminescent element of the present invention.
【図４】本発明の実施例１及び比較例１で作製した有機
電界発光素子の発光輝度と電圧特性との関係を示す図。FIG. 4 is a diagram showing the relationship between the light emission luminance and the voltage characteristics of the organic electroluminescent elements produced in Example 1 and Comparative Example 1 of the present invention.
１ 基板 ２ａ、２ｂ 導電層 ３ 正孔輸送層 ４、４ｂ 芳香族ジアミン化合物がドープされた有機
電子輸送層 ４ａ 芳香族ジアミン化合物がドープされていない有
機電子輸送層 ４ｃ 有機発光層 ５ ４とは異なる芳香族ジアミン化合物がドープされ
た有機電子輸送層1 Substrate 2a, 2b Conductive Layer 3 Hole Transport Layer 4, 4b Organic Electron Transport Layer Doped with Aromatic Diamine Compound 4a Organic Electron Transport Layer Not Doped with Aromatic Diamine Compound 4c Different from Organic Light Emitting Layer 5 4 Organic electron transport layer doped with aromatic diamine compound
Claims (4)
送層及び陰極が積層されてなる有機電界発光素子におい
て、有機電子輸送層が芳香族ジアミン化合物を含有する
ことを特徴とする有機電界発光素子。1. An organic electroluminescent device comprising an anode, a hole transport layer, an organic electron transport layer and a cathode, which are sequentially laminated, wherein the organic electron transport layer contains an aromatic diamine compound. Electroluminescent device.
表される芳香族ジアミン化合物を含有する請求項１記載
の有機電界発光素子。 【化１】 （一般式（Ｉ）中、Ｒ1、Ｒ2、Ｒ3及びＲ4はそれぞれ独
立して、置換基を有していてもよいアルキル基、置換基
を有していてもよいシクロアルキル基、置換基を有して
いてもよいアルケニル基、置換基を有していてもよいア
リール基、置換基を有していてもよいアラルキル基を示
し、Ｒ5及びＲ6はそれぞれ独立して、水素原子、ハロゲ
ン原子、水酸基、置換基を有していてもよいアルキル
基、置換基を有していてもよいシクロアルキル基、置換
基を有していてもよいアルケニル基、置換基を有してい
てもよいアリール基、置換基を有していてもよいアラル
キル基、置換基を有していてもよいアルコキシ基、置換
基を有していてもよいジアルキルアミノ基又は置換基を
有していてもよいジアリールアミノ基を示し、Ａは置換
基を有していてもよい２価の炭化水素残基又は直接結合
を示す。）2. The organic electroluminescent device according to claim 1, wherein the organic electron transport layer contains an aromatic diamine compound represented by the following general formula (I). [Chemical 1] (In the general formula (I), R 1 , R 2 , R 3 and R 4 are each independently an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, The alkenyl group which may have a substituent, the aryl group which may have a substituent, and the aralkyl group which may have a substituent are shown, and R 5 and R 6 are each independently hydrogen. Atom, halogen atom, hydroxyl group, optionally substituted alkyl group, optionally substituted cycloalkyl group, optionally substituted alkenyl group, optionally substituted Optionally an aryl group, optionally substituted aralkyl group, optionally substituted alkoxy group, optionally substituted dialkylamino group or optionally substituted Is a diarylamino group, wherein A has a substituent It indicates a divalent hydrocarbon residue or a direct bond good.)
表される芳香族ジアミン化合物を含有する請求項１記載
の有機電界発光素子。 【化２】 （一般式（II）中、Ｒ7、Ｒ8、Ｒ9及びＲ10はそれぞれ
独立して、置換基を有していてもよいアルキル基、置換
基を有していてもよいシクロアルキル基、置換基を有し
ていてもよいアルケニル基、置換基を有していてもよい
アリール基、置換基を有していてもよいアラルキル基を
示し、Ｒ11及びＲ12はそれぞれ独立して、水素原子、ハ
ロゲン原子、水酸基、置換基を有していてもよい飽和あ
るいは不飽和の脂肪族炭化水素基、置換基を有していて
もよい芳香族炭化水素基、置換基を有していてもよいア
ルコキシ基、置換基を有していてもよいアリールオキシ
基、置換基を有していてもよいジアルキルアミノ基又は
置換基を有していてもよいジアリールアミノ基を示し、
Ｘは置換基を有していてもよい２価の炭化水素残基を示
す。）3. The organic electroluminescent device according to claim 1, wherein the organic electron transport layer contains an aromatic diamine compound represented by the following general formula (II). [Chemical 2] (In the general formula (II), R 7 , R 8 , R 9 and R 10 are each independently an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, An alkenyl group which may have a substituent, an aryl group which may have a substituent, and an aralkyl group which may have a substituent, wherein R 11 and R 12 are each independently hydrogen. Atom, halogen atom, hydroxyl group, saturated or unsaturated aliphatic hydrocarbon group which may have a substituent, aromatic hydrocarbon group which may have a substituent, and which may have a substituent Good alkoxy group, an aryloxy group optionally having a substituent, a dialkylamino group optionally having a substituent or a diarylamino group optionally having a substituent,
X represents a divalent hydrocarbon residue which may have a substituent. )
で表される芳香族ジアミン化合物を含有する請求項１記
載の有機電界発光素子。 【化３】 （一般式（III）中、Ｒ13、Ｒ14、Ｒ15及びＲ16はそれ
ぞれ独立して、置換基を有していてもよいアルキル基、
置換基を有していてもよいシクロアルキル基、置換基を
有していてもよいアルケニル基、置換基を有していても
よいアリール基、置換基を有していてもよいアラルキル
基を示し、Ｒ17及びＲ18はそれぞれ独立して、水素原
子、ハロゲン原子、水酸基、置換基を有していてもよい
飽和あるいは不飽和の脂肪族炭化水素基、置換基を有し
ていてもよい芳香族炭化水素基、置換基を有していても
よいアルコキシ基、置換基を有していてもよいアリール
オキシ基、置換基を有していてもよいジアルキルアミノ
基又は置換基を有していてもよいジアリールアミノ基を
示し、Ｙ及びＺは置換基を有していてもよい２価の炭化
水素残基又は直接結合を示し、これらは同一であっても
異なっていてもよい。）4. The organic electron transport layer has the following general formula (III):
The organic electroluminescent element according to claim 1, which contains an aromatic diamine compound represented by: [Chemical 3] (In the general formula (III), R 13 , R 14 , R 15 and R 16 are each independently an alkyl group which may have a substituent,
It represents a cycloalkyl group which may have a substituent, an alkenyl group which may have a substituent, an aryl group which may have a substituent, and an aralkyl group which may have a substituent. , R 17 and R 18 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a saturated or unsaturated aliphatic hydrocarbon group which may have a substituent, and an aromatic group which may have a substituent. Group hydrocarbon group, optionally substituted alkoxy group, optionally substituted aryloxy group, optionally substituted dialkylamino group or optionally substituted Represents a diarylamino group, Y and Z represent a divalent hydrocarbon residue which may have a substituent or a direct bond, and these may be the same or different. )
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11181892A JP3189376B2 (en) | 1992-04-30 | 1992-04-30 | Organic electroluminescent device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11181892A JP3189376B2 (en) | 1992-04-30 | 1992-04-30 | Organic electroluminescent device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05311161A true JPH05311161A (en) | 1993-11-22 |
| JP3189376B2 JP3189376B2 (en) | 2001-07-16 |
Family
ID=14570935
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11181892A Expired - Lifetime JP3189376B2 (en) | 1992-04-30 | 1992-04-30 | Organic electroluminescent device |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3189376B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000164362A (en) * | 1998-05-19 | 2000-06-16 | Sanyo Electric Co Ltd | Organic electroluminescent element |
| JP2003077676A (en) * | 1998-05-19 | 2003-03-14 | Sanyo Electric Co Ltd | Organic electroluminescent element |
| JP2005085658A (en) * | 2003-09-10 | 2005-03-31 | Konica Minolta Holdings Inc | Organic electroluminescent element |
| US7727640B2 (en) | 2004-12-28 | 2010-06-01 | Fujifilm Corporation | Organic electroluminescent element |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102866465B1 (en) | 2020-07-20 | 2025-10-01 | 삼성디스플레이 주식회사 | Organic electroluminescence device and diamine compound for organic electroluminescence device |
-
1992
- 1992-04-30 JP JP11181892A patent/JP3189376B2/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000164362A (en) * | 1998-05-19 | 2000-06-16 | Sanyo Electric Co Ltd | Organic electroluminescent element |
| JP2003077676A (en) * | 1998-05-19 | 2003-03-14 | Sanyo Electric Co Ltd | Organic electroluminescent element |
| JP2005085658A (en) * | 2003-09-10 | 2005-03-31 | Konica Minolta Holdings Inc | Organic electroluminescent element |
| US7727640B2 (en) | 2004-12-28 | 2010-06-01 | Fujifilm Corporation | Organic electroluminescent element |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3189376B2 (en) | 2001-07-16 |
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