JP3158600B2 - Organic electroluminescent device - Google Patents
Organic electroluminescent deviceInfo
- Publication number
- JP3158600B2 JP3158600B2 JP02849392A JP2849392A JP3158600B2 JP 3158600 B2 JP3158600 B2 JP 3158600B2 JP 02849392 A JP02849392 A JP 02849392A JP 2849392 A JP2849392 A JP 2849392A JP 3158600 B2 JP3158600 B2 JP 3158600B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- organic
- substituent
- electroluminescent device
- transport layer
- 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.)
- Expired - Lifetime
Links
- 150000001875 compounds Chemical class 0.000 claims description 43
- 239000000463 material Substances 0.000 claims description 32
- 125000001424 substituent group Chemical group 0.000 claims description 23
- 230000005525 hole transport Effects 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 11
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 4
- 125000000623 heterocyclic group Chemical group 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000003368 amide group Chemical group 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 125000004185 ester group Chemical group 0.000 claims description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical group [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 229910052711 selenium Inorganic materials 0.000 claims description 2
- 125000004434 sulfur atom Chemical group 0.000 claims description 2
- 150000004696 coordination complex Chemical class 0.000 claims 1
- -1 coumarin compound Chemical class 0.000 description 27
- 230000032258 transport Effects 0.000 description 20
- 239000000758 substrate Substances 0.000 description 16
- 239000007850 fluorescent dye Substances 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 239000011230 binding agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 6
- 239000010408 film Substances 0.000 description 6
- 229910052709 silver Inorganic materials 0.000 description 6
- 239000004332 silver Substances 0.000 description 6
- 238000001771 vacuum deposition Methods 0.000 description 6
- 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
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000010409 thin film Substances 0.000 description 5
- 239000005725 8-Hydroxyquinoline Substances 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 230000005684 electric field Effects 0.000 description 4
- 230000007774 longterm Effects 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 229960003540 oxyquinoline Drugs 0.000 description 4
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N benzo-alpha-pyrone Natural products C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 125000001624 naphthyl group Chemical group 0.000 description 3
- 229920000515 polycarbonate Polymers 0.000 description 3
- 239000004417 polycarbonate Substances 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
- QENGPZGAWFQWCZ-UHFFFAOYSA-N 3-Methylthiophene Chemical compound CC=1C=CSC=1 QENGPZGAWFQWCZ-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy 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
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 2
- 229960000956 coumarin Drugs 0.000 description 2
- 235000001671 coumarin Nutrition 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000011521 glass 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
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 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
- 239000000203 mixture Substances 0.000 description 2
- 150000004866 oxadiazoles Chemical class 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
- 125000001792 phenanthrenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C=CC12)* 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920000728 polyester Polymers 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
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 230000001846 repelling effect Effects 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 125000000547 substituted alkyl group Chemical group 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- 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
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical group C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 1
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical group C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-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
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 1
- 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 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 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
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical group C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000005452 alkenyloxyalkyl group Chemical group 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000005081 alkoxyalkoxyalkyl group Chemical group 0.000 description 1
- 125000005138 alkoxysulfonyl group Chemical group 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000005160 aryl oxy alkyl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000006297 carbonyl amino group Chemical group [H]N([*:2])C([*:1])=O 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 150000004775 coumarins Chemical class 0.000 description 1
- 125000004966 cyanoalkyl group Chemical group 0.000 description 1
- 125000001316 cycloalkyl alkyl group Chemical group 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 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 1
- 125000004210 cyclohexylmethyl group Chemical group [H]C([H])(*)C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical class C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 1
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 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
- 239000011888 foil Substances 0.000 description 1
- 239000007789 gas 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
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 125000001041 indolyl group Chemical group 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 1
- 239000003550 marker Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- CELAVSIYCCQNGG-UHFFFAOYSA-N n-(4-cyclohexylphenyl)-4-methyl-n-(4-methylphenyl)aniline Chemical compound C1=CC(C)=CC=C1N(C=1C=CC(=CC=1)C1CCCCC1)C1=CC=C(C)C=C1 CELAVSIYCCQNGG-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000006503 p-nitrobenzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1[N+]([O-])=O)C([H])([H])* 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 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 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
- 229920006255 plastic film 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
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000193 polymethacrylate Polymers 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
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 125000003748 selenium group Chemical group *[Se]* 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
- 239000007787 solid Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 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
- 125000003718 tetrahydrofuranyl group Chemical group 0.000 description 1
- IBBLKSWSCDAPIF-UHFFFAOYSA-N thiopyran Chemical compound S1C=CC=C=C1 IBBLKSWSCDAPIF-UHFFFAOYSA-N 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical compound [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Electroluminescent Light Sources (AREA)
- Luminescent Compositions (AREA)
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、有機化合物から成る正孔輸
送層と発光層との組合せによって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 particularly, to a thin film type device which emits light by applying an electric field by a combination of a hole transporting layer composed of an organic compound and a light emitting layer. Things.
【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 compound semiconductors of inorganic materials
In S, SrS, etc., Mn as a luminescence center and rare earth elements (E
u, Ce, Tb, Sm, etc.) are generally used. However, electroluminescent devices made from the above inorganic materials require: 1) AC drive (50 to 1000 Hz); 2) High drive voltage (Up to 200 V), 3) it is difficult to achieve full color (particularly, blue is a problem), and 4) the cost of peripheral driving circuits 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,
Electroluminescent devices using organic materials have been developed. As the light emitting layer material, in addition to anthracene and pyrene which have been known for a long time, a cyanine dye (J. Chem. S)
oc., Chem. Commun., 557, 1985), pyrazoline (Mol. Crys. Liq. Cryst., 135, 355,
1986), perylene (Jpn. J. Appl. Phys., 25).
Vol. L773, 1986) or a coumarin compound or tetraphenylbutadiene (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., の６５巻、３６１０頁、１９８９年）も行われて
いる。Further, in order to improve the efficiency of injecting carriers from the electrodes in order to increase the luminous efficiency, the type of the electrodes is optimized, and a device for providing a luminescent layer composed of a hole transport layer and an organic phosphor is disclosed (Japanese Patent Application Laid-open No. Sho. No. 57-51781, JP-A-59
194393, JP-A-63-29569, Appl. Phys. Lett., 51, 913, 1987.
Year). Further, for the purpose of improving the luminous efficiency of the device and changing the luminescent color, doping a fluorescent dye for laser such as coumarin using an aluminum complex of 8-hydroxyquinoline as a host material (J. Appl.
hys., 65, 3610, 1989).
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、これら
に開示されている有機電界発光素子では発光性能、特に
長期にわたる素子の安定性がまだ不十分であり、更なる
改良検討が望まれていた。本発明者等は、上記実状に鑑
み、安定に駆動させることができる有機電界発光素子を
提供することを目的として鋭意検討した結果、特定の化
合物が好適であることを見いだし、本発明を完成した。However, the organic electroluminescent devices disclosed in these publications still have insufficient light-emitting performance, especially long-term stability of the device, and further improvement has been desired. In view of the above situation, the present inventors have conducted intensive studies with the aim of providing an organic electroluminescent device that can be driven stably, and as a result, found that a specific compound was suitable, and completed the present invention. .
【０００６】[0006]
【課題を解決するための手段】すなわち、本発明の要旨
は、順次に、陽極、有機正孔輸送層、有機電子輸送層、
陰極が積層された有機電界発光素子において、有機正孔
輸送層中の有機正孔輸送材料および／または有機電子輸
送層中の有機電子輸送材料をホスト材料とし、該ホスト
材料に対して、下記一般式（Ｉ）で表される化合物がド
ープされていることを特徴とする有機電界発光素子。That is, the gist of the present invention is to provide an anode, an organic hole transport layer, an organic electron transport layer,
In an organic electroluminescent device having a cathode laminated, an organic hole transport material and / or an organic electron transport material in an organic hole transport layer are provided.
An organic electron transporting material in the transport layer as a host material;
A compound represented by the following general formula (I) is added to the material.
The organic electroluminescent device characterized by being over-flop.
【０００７】[0007]
【化２】 Embedded image
【０００８】（式中、Ｒ1、Ｒ2、Ｒ3およびＲ4はそれぞ
れ独立して置換基を有していてもよい芳香族炭化水素基
を示し、Ｘは置換基を有していてもよい窒素原子、置換
基を有していてもよい硫黄原子、置換基を有していても
よい酸素原子または置換基を有していてもよいセレン原
子を示し、Ｙは水素原子、シアノ基、カルボキシル基、
置換基を有していてもよいアミド基、置換基を有してい
てもよいエステル基、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芳香族炭化水素基また
は置換基を有していてもよい複素環基を示す。）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説明
する。(Wherein, R 1 , R 2 , R 3 and R 4 each independently represent an aromatic hydrocarbon group which may have a substituent, and X represents an aromatic hydrocarbon group which may have a substituent. A good nitrogen atom, a sulfur atom which may have a substituent, an oxygen atom which may have a substituent or a selenium atom which may have a substituent, Y is a hydrogen atom, a cyano group, Carboxyl group,
An amide group which may have a substituent, an ester group which may have a substituent, an alkyl group which may have a substituent, and an aromatic hydrocarbon group which may have a substituent Or a heterocyclic group which may have a substituent. )Less than,
The organic electroluminescent device of the present invention will be described with reference to the attached drawings.
【０００９】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は有機正孔輸送層、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。FIG. 1 is a sectional view schematically showing an example of the structure of an organic electroluminescent device of the present invention, wherein 1 is a substrate, 2a and 2b are conductive layers, 3 is an organic hole transport layer, and 4 is an organic electron transport. Each layer is represented. The substrate 1 serves as a support for the organic electroluminescent device of the present invention, and may be a quartz or glass plate, a metal plate or metal foil, a plastic film or sheet, or the like. Transparent synthetic resin substrates such as polymethacrylate, polycarbonate, and polysulfone are preferred.
【００１０】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、インジウムおよび
／また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界重合によ
り直接基板上に薄膜を形成することもできる。上記の導
電層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,
The conductive layer 2a is usually made of a metal such as aluminum, gold, silver, nickel, palladium, and tellurium, a metal oxide such as an oxide of indium and / or tin, copper iodide, carbon black, or poly (3-methylthiophene). )
And the like. The formation of the conductive layer 2a is usually performed 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,
In the case of a conductive resin fine powder or the like, it can also be formed by dispersing 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 formed directly on a substrate by electric field polymerization. The above conductive layer can be formed by stacking different substances.
【００１１】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. If transparency is required, the visible light transmittance is desirably 60% or more, preferably 80% or more. In this case, the thickness is usually 50 to 1000
0 °, preferably about 100 to 5000 °. If opaque, the conductive layer 2a may be the same as the substrate 1. Further, the conductive layer 2a can be stacked with a different material.
【００１２】図１の例では、導電層２ａは陽極（アノー
ド）として正孔注入の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。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 shown in FIG. 1, the conductive layer 2a functions as an anode (anode) for injecting holes. on the other hand,
The conductive layer 2b serves as a cathode (cathode) as the organic electron transport layer 4
Plays the role of injecting electrons into As the material used for the conductive layer 2b, the material for the conductive layer 2a can be used. However, for efficient electron injection, a metal having a low work function is preferable, and tin, magnesium,
A metal such as indium, aluminum, silver, or an alloy thereof is used. The thickness of the conductive layer 2b is generally the same as that of the conductive layer 2a, and can be formed by the same method as the conductive layer 2a.
【００１３】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 substrate 1 can be further provided on conductive layer 2b. However, as 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
The thickness is preferably 100 to 5000 °, and good transparency is desired.
【００１４】導電層２ａの上には有機正孔輸送層３が設
けられるが、有機正孔輸送層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。有機正孔輸送化合物としては、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。An organic hole transport layer 3 is provided on the conductive layer 2a. The organic hole transport layer 3 efficiently transports holes from the anode between the electrodes to which an electric field is applied. Formed from compounds that can be transported in the direction of The organic hole transport compound 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 this purpose, it is required that the compound has a small ionization potential, a large hole mobility, and a trap which is excellent in stability and positive and hardly occurs during production or use.
【００１５】このような正孔輸送化合物としては、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欄に記載
されているもの等が挙げられる。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
合物が挙げられる。これらの芳香族アミン化合物または
ヒドラゾン化合物は、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。Examples of such hole transport compounds include those described on pages 5 to 6 of JP-A-59-194393 and columns 13 and 14 of US Pat. No. 4,175,960. Can be Preferred specific examples of these compounds include N, N'-diphenyl-N, N'-
(3-methylphenyl) -1,1′-biphenyl-4,
Aromatic amine compounds such as 4'-diamine, 1,1'-bis (4-di-p-tolylaminophenyl) cyclohexane, and 4,4'-bis (diphenylamino) quadrophenyl. Other than the aromatic amine compounds,
Hydrazone compounds disclosed in JP-A-2-311591 can be mentioned. These aromatic amine compounds or hydrazone compounds may be used alone or, if necessary, as a mixture.
【００１６】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、レペ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、乾燥して有機性孔輸送層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 evaporation method. For example, in the case of a coating method, one or more organic hole transporting compounds are added and, if necessary, an additive such as a binder resin which does not trap holes and an additive such as a coating agent such as a repelling agent are dissolved. The applied coating solution is prepared, applied to the conductive layer 2a by a method such as spin coating, and dried to form the organic hole transporting layer 3. Examples of the binder resin include polycarbonate, polyacrylate, and polyester. Since a large amount of the binder resin decreases the hole mobility, a small amount is desirable, and the amount is preferably 50% by weight or less.
【００１７】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、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。有機
正孔輸送層３の膜厚は、通常、１００〜３０００Å、好
ましくは３００〜１０００Åである。この様に薄い膜を
一様に形成するためには、真空蒸着法がよく用いられ
る。In the case of the vacuum evaporation method, the organic hole transporting material is put in a crucible provided in a vacuum vessel, and the inside of the vacuum vessel is evacuated to 10 -6 Torr by a suitable vacuum pump. Is heated to evaporate the hole transport material and form a layer on the substrate placed opposite the crucible. The thickness of the organic hole transport layer 3 is usually 100 to 3000 °, preferably 300 to 1000 °. In order to uniformly form such a thin film, a vacuum deposition method is often used.
【００１８】有機正孔輸送層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有機正孔
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。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。An organic electron transporting layer 4 is provided on the organic hole transporting layer 3. The organic electron transporting layer 4 efficiently transfers electrons from a cathode between electrodes to which an electric field is applied. It is formed from a compound that can be transported in three directions. The organic electron transport compound needs to be a compound having high electron injection efficiency from the conductive layer 2b and capable of efficiently transporting injected electrons. For this purpose, it is required that the compound has a high electron affinity, a high electron mobility, a high stability, and hardly generates impurities serving as traps during production or use.
【００１９】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などの芳香族化合物（特開昭５
７−５１７８１号公報）、８−ヒドロキシキノリンのア
ルミニウム錯体などの金属錯体（特開昭５９−１９４３
９３号公報）、シクロペンタジエン誘導体（特開平２−
２８９６７５号公報）、ペリノン誘導体（特開平２−２
８９６７６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２−２２２４８
４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）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。Materials satisfying such conditions include aromatic compounds such as tetraphenylbutadiene (Japanese Patent Application Laid-Open No.
And metal complexes such as aluminum complexes of 8-hydroxyquinoline (JP-A-59-1943).
No. 93), cyclopentadiene derivatives (Japanese Unexamined Patent Publication No.
289675), perinone derivatives (JP-A 2-2)
No. 89676), oxadiazole derivatives (Japanese Patent Application Laid-Open No. 2-216991), and bisstyrylbenzene derivatives (Japanese Patent Application Laid-Open Nos. 1-245087 and 2-222448).
No. 4), perylene derivatives (JP-A-2-189890)
JP-A-3-7991), coumarin compounds (JP-A-2-191694 and JP-A-3-792), rare-earth complexes (JP-A-1-256584), and distyrylpyrazine derivatives (JP-A-Heisei 2). No. 252793). When these compounds are used, the organic electron transport layer 4 simultaneously plays the role of transporting electrons and the role of emitting light when holes and electrons recombine.
【００２０】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も有機正孔輸送層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、有機電子輸送層４の上に、図２に示すよう
に、さらに他の有機電子輸送層５を積層することもでき
る。この有機電子輸送層５に用いられる化合物は、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（Ｄ９）で表わされる化合物などの
ニトロ置換フルオレノン誘導体、下記構造式（Ｄ１０）
で表わされる化合物などのチオピランジオキシド誘導
体、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（Jp
n. 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 transporting layer 4 is usually 100
Å2000Å, preferably 300〜1000Å.
The organic electron transporting layer 4 can be formed in the same manner as the organic hole transporting layer 3, but usually, a vacuum evaporation method is used. Further, in order to further improve the luminous efficiency of the organic electroluminescent element, another organic electron transport layer 5 can be further laminated on the organic electron transport layer 4 as shown in FIG. The compound used for the organic electron transport layer 5 is required to be capable of easily injecting electrons from the cathode and to have a higher electron transport ability. Examples of such an organic electron transporting compound include nitro-substituted fluorenone derivatives such as a compound represented by the following structural formula (D9), and a compound represented by the following structural formula (D10)
Thiopyran dioxide derivative such as a compound represented by the following formula, diphenylquinone derivative such as a compound represented by the following structural formula (D11), perylene tetracarboxylic acid derivative such as a compound represented by the following structural formula (D12) (Jp
n. J. Appl. Phys. 27, L269, 1988
Oxadiazole derivatives such as compounds represented by the following structural formula (D13) (Appl. Phys. Lett. 55,
1489, 1989).
【００２１】[0021]
【化３】 Embedded image
【００２２】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、すなわち基板上に
導電層２ｂ、有機電子輸送層４、有機正孔輸送層３、導
電層２ａ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 as follows.
Usually 100 to 2000 °, preferably 300 to 100
0 °. In addition, it is also possible to stack the conductive layer 2b, the organic electron transport layer 4, the organic hole transport layer 3, and the conductive layer 2a in this order on the substrate, that is, at least as described above. It is also possible to provide the electroluminescent element of the present invention between two substrates, one of which is highly transparent. Also,
Similarly, the structure may be reversed from that of FIG.
【００２３】従来、有機発光素子の発光効率を向上させ
るとともに発光色を変化させる目的で、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、各種
の蛍光色素をドープすることが行われている（米国特許
４，７６９，２９２号）が、このドープによる方法の利
点としては、 高効率の蛍光色素により発光効率が向上、 蛍光色素の選択により発光波長が調べる、 濃度消光を起こす蛍光色素も使用可能、 薄膜性のわるい蛍光色素も使用可能、 等が挙げられる。Conventionally, various fluorescent dyes have been doped with an 8-hydroxyquinoline aluminum complex as a host material for the purpose of improving the luminous efficiency of an organic light emitting device and changing the luminescent color (US). Japanese Patent No. 4,769,292) has the advantages of this doping method that the luminous efficiency is improved by using a high-efficiency fluorescent dye, the emission wavelength is checked by selecting the fluorescent dye, and a fluorescent dye that causes concentration quenching can also be used. Fluorescent dyes having poor film properties can also be used.
【００２４】本発明においては、有機電子輸送層がその
役割を果たす場合、ホスト材料としては、前述の有機電
子輸送化合物が挙げられ、有機正孔輸送層がその役割を
果たす場合、ホスト材料としては、前述の芳香族アミン
化合物やヒドラゾン化合物が挙げられる。本発明におい
て、前記一般式（Ｉ）で表される化合物がドープされる
領域は、有機正孔輸送層３および／または有機電子輸送
層４の全体であっても、その一部分であってもよい。前
記一般式（Ｉ）で表される化合物が、ホスト材料に対し
てドープされる量は、１０-3〜１０モル％が好ましい。In the present invention, when the organic electron transporting layer plays a role, the host material includes the above-mentioned organic electron transporting compound. When the organic hole transporting layer plays a role, the host material serves as the host material. And the aforementioned aromatic amine compounds and hydrazone compounds. In the present invention, the region doped with the compound represented by the general formula (I) may be the whole or a part of the organic hole transport layer 3 and / or the organic electron transport layer 4. . The amount of the compound represented by the general formula (I) doped with respect to the host material is preferably 10 −3 to 10 mol%.
【００２５】前記一般式（Ｉ）で表される化合物は、固
体状態および溶液状態で強い蛍光を示し、前記の濃度消
光による問題がなく、ドープする濃度範囲に制限がな
い。また、それ自体が安定な非晶質膜を形成する能力を
有するため、ホスト材料にドープされた場合、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。The compound represented by the general formula (I) shows strong fluorescence in a solid state and a solution state, does not have the above-described problem of concentration quenching, and has no limitation on the concentration range of doping. In addition, since it itself has the ability to form a stable amorphous film, when doped into a host material, the thin film state of the host material can be structurally stabilized, and the organic electroluminescent device can be used for a long time. It is possible to provide stability.
【００２６】前記一般式（Ｉ）で表される化合物を、有
機正孔輸送層３および／または有機電子輸送層４にドー
プする方法としては、例えば、塗布法の場合は、有機正
孔輸送化合物または有機電子輸送化合物と、前記一般式
（Ｉ）で表される化合物、さらに必要により、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、レペ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、有機正孔輸送化合物または有機電子輸送化
合物を真空容器内に設置されたルツボに入れ、前記一般
式（Ｉ）で表される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。As a method of doping the compound represented by the general formula (I) into the organic hole transporting layer 3 and / or the organic electron transporting layer 4, for example, in the case of a coating method, an organic hole transporting compound is used. Alternatively, an organic electron transporting compound, a compound represented by the general formula (I), and if necessary, an additive such as a binder resin which does not trap holes or electrons as necessary, or a coating improver such as a repelling agent. The coating solution added and dissolved is adjusted, applied by a method such as spin coating, and dried to form a coating solution. Examples of the binder resin include polycarbonate, polyarylate, and polyester. If the amount of the binder resin is large, the mobility of holes or electrons is reduced. In the case of the vacuum evaporation method, an organic hole transporting compound or an organic electron transporting compound is put in a crucible placed in a vacuum vessel, and the compound represented by the general formula (I) is put in another crucible, After the inside is evacuated to about 10 -6 Torr by an appropriate vacuum pump, each crucible is heated and evaporated at the same time to form a layer on the substrate placed facing the crucible. As another method, a mixture of the above materials at a predetermined ratio may be evaporated using the same crucible.
【００２７】前記一般式（Ｉ）において、Ｒ1、Ｒ2、Ｒ
3およびＲ4は置換基を有していてもよい芳香族炭化水素
基を示し、好ましくはフェニル基、ナフチル基、フェナ
ンスレン基等から選ばれる。置換基としては、塩素原
子、臭素原子、ヨウ素原子等のハロゲン原子、メチル
基、エチル基等の炭素数１〜６のアルキル基；メトキシ
基、エトキシ基等の炭素数１〜６のアルコキシ基；メト
キシカルボニル基、エトキシカルボニル基等の炭素数１
〜６のアルコキシカルボニル基；メトキシスルホニル
基、エトキシスルホニル基等のアルコキシスルホニル
基；シアノ基、アミノ基、ジメチルアミノ基、ニトロ基
等が挙げられる。In the general formula (I), R 1 , R 2 , R
3 and R 4 represent an aromatic hydrocarbon group which may have a substituent, and is preferably selected from a phenyl group, a naphthyl group, a phenanthrene group and the like. Examples of the substituent include a halogen atom such as a chlorine atom, a bromine atom and an iodine atom; an alkyl group having 1 to 6 carbon atoms such as a methyl group and an ethyl group; an alkoxy group having 1 to 6 carbon atoms such as a methoxy group and an ethoxy group; 1 carbon atom such as methoxycarbonyl group and ethoxycarbonyl group
To 6; an alkoxysulfonyl group such as a methoxysulfonyl group and an ethoxysulfonyl group; a cyano group, an amino group, a dimethylamino group and a nitro group.
【００２８】Ｘは置換基を有していてもよい窒素原子、
硫黄原子、酸素原子、セレン原子を示す。置換基として
は、炭素数１〜２８のアルキル基等のアルキル基；メト
キシエチル基、エトキシエチル基等のアルコキシアルキ
ル基；メトキシエトキシエチル基、ｎ−ブトキシエトキ
シエチル基等のアルコキシアルコキシアルキル基；メト
キシエトキシエトキシエチル基、エトキシエトキシエト
キシエチル基等のアルコキシアルコキシアルコキシアル
キル基；フェニルオキシエチル基、ナフチルオキシエチ
ル基、ｐ−クロロフェニルオキシエチル基等のアリール
オキシアルキル基；ベンジル基、フェネチル基、ｐ−ク
ロロベンジル基、ｐ−ニトロベンジル基等のアリールア
ルキル基；シクロヘキシルメチル基、シクロヘキシルエ
チル基、シクロペンチルエチル基等のシクロアルキルア
ルキル基；アリルオキシエチル基、３−ブロモアリルオ
キシエチル基等のアルケニルオキシアルキル基；シアノ
エチル基、シアノメチル基等のシアノアルキル基；ヒド
ロキシエチル基、ヒドロキシメチル基等のヒドロキシア
ルキル基；テトラヒドロフリル基、テトラヒドロフリル
エチル基等のテトラヒドロフリルアルキル基等の置換ま
たは非置換のアルキル基、アリル基、２−クロロアリル
基等の置換または非置換のアルケニル基、フェニル基、
ｐ−メチルフェニル基、ナフチル基、ｍ−メトキシフェ
ニル基等の置換または非置換のアリール基、シクロヘキ
シル基、シクロペンチル基等のシクロアルキル基が挙げ
られる。X is a nitrogen atom which may have a substituent,
Indicate sulfur, oxygen and selenium atoms. Examples of the substituent include an alkyl group such as an alkyl group having 1 to 28 carbon atoms; an alkoxyalkyl group such as a methoxyethyl group and an ethoxyethyl group; an alkoxyalkoxyalkyl group such as a methoxyethoxyethyl group and an n-butoxyethoxyethyl group; Alkoxyalkoxyalkoxyalkyl groups such as ethoxyethoxyethyl group and ethoxyethoxyethoxyethyl group; aryloxyalkyl groups such as phenyloxyethyl group, naphthyloxyethyl group and p-chlorophenyloxyethyl group; benzyl group, phenethyl group and p-chloro Arylalkyl groups such as benzyl group and p-nitrobenzyl group; cycloalkylalkyl groups such as cyclohexylmethyl group, cyclohexylethyl group and cyclopentylethyl group; allyloxyethyl group and 3-bromoallyloxy Alkenyloxyalkyl groups such as tyl group; cyanoalkyl groups such as cyanoethyl group and cyanomethyl group; hydroxyalkyl groups such as hydroxyethyl group and hydroxymethyl group; substitution of tetrahydrofurylalkyl group such as tetrahydrofuryl group and tetrahydrofurylethyl group. Or an unsubstituted alkyl group, an allyl group, a substituted or unsubstituted alkenyl group such as a 2-chloroallyl group, a phenyl group,
Examples include a substituted or unsubstituted aryl group such as a p-methylphenyl group, a naphthyl group, and an m-methoxyphenyl group, and a cycloalkyl group such as a cyclohexyl group and a cyclopentyl group.
【００２９】Ｙは水素原子、シアノ基、、カルボキシル
基、アミド基；ＣＯＮＨ2 、ＣＯＮＨＲ、ＣＯＮＲＲ′
（式中、Ｒ、Ｒ′はフェニル基等の芳香族炭化水素基ま
たは置換されていてもよいアルキル基を示す）、エステ
ル基；ＣＯＯＲ″（式中、Ｒ″はフェニル基等の芳香族
炭化水素基または置換されていてもよいアルキル基を示
す）、置換されていてもよい１〜２８の炭素原子を有す
るアルキル基、置換されていてもよいフェニル基、ナフ
タレン基、フェナンスレン基等の芳香族炭化水素基；置
換されていてもよいチオフェン環基、ピロール環基、チ
アゾール環基、フラン環基、オキサゾール環基、ベンゾ
チオフェン環基、ベンゾフラン環基、インドール環基、
ピリジン環基等の複素環基等から選ばれる。Y is a hydrogen atom, a cyano group, a carboxyl group, an amide group; CONH 2 , CONHR, CONRR '
(Wherein R and R 'each represent an aromatic hydrocarbon group such as a phenyl group or an alkyl group which may be substituted); an ester group; COOR "(where R" represents an aromatic hydrocarbon group such as a phenyl group). A hydrogen group or an optionally substituted alkyl group), an optionally substituted alkyl group having 1 to 28 carbon atoms, an optionally substituted phenyl group, a naphthalene group, an aromatic group such as a phenanthrene group A hydrocarbon group; an optionally substituted thiophene ring group, a pyrrole ring group, a thiazole ring group, a furan ring group, an oxazole ring group, a benzothiophene ring group, a benzofuran ring group, an indole ring group,
It is selected from a heterocyclic group such as a pyridine ring group.
【００３０】これらの化合物の合成法は、又賀らによっ
て、J. Heterocyclic. Chem.の１８巻、１０７３頁（１
９８１年）；同２６巻、２１５頁（１９８９年）に示さ
れている。このようにして得られる上記化合物の具体例
を以下に例示する。The synthesis of these compounds is described by Magaga et al. In J. Heterocyclic. Chem.
981); 26: 215, 1989 (1989). Specific examples of the compound thus obtained are described below.
【００３１】[0031]
【化４】 Embedded image
【００３２】[0032]
【化５】 Embedded image
【００３３】[0033]
【作用】本発明においては、有機電子輸送層および／ま
たは有機正孔輸送層のドープ材料として、前記一般式
（Ｉ）で表わされる蛍光性化合物を用いることにより、
優れた発光特性と長期間にわたる安定性をもたらすこと
が可能となる。In the present invention, by using the fluorescent compound represented by the general formula (I) as a doping material for the organic electron transporting layer and / or the organic hole transporting layer,
Excellent light-emitting characteristics and long-term stability can be provided.
【００３４】[0034]
【実施例】次に、本発明を実施例によって更に具体的に
説明するが、本発明はその要旨を越えない限り、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１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, 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. 1 was produced by the following method.
【００３５】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堆積したものを水
洗、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２×１０-6Ｔ
ｏｒｒ以下になるまで油拡散ポンプを用いて排気した。
有機正孔輸送層材料として、下記構造式(XIX) および(X
X)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 on a glass substrate at 1200.degree. Was washed with water and ultrasonically washed with isopropyl alcohol, and then placed in a vacuum evaporation apparatus to reduce the degree of vacuum in the apparatus. 2 × 10 -6 T
The gas was exhausted using an oil diffusion pump until the pressure became orr or less.
As the organic hole transport layer material, the following structural formulas (XIX) and (X
X) is a hydrazone compound represented by the following formula:
And mixed.
【００３６】[0036]
【化６】 Embedded image
【００３７】これらセラミックるつぼに入れ、るつぼの
周囲のＴａ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１３０〜１５０℃の範囲で、蒸発時
の真空度は７×１０-7Ｔｏｒｒであった。有機正孔注入
輸送層をこのようにして５２０Åの膜厚で蒸着した。蒸
着時間は２分３０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These ceramic crucibles were put into a crucible and heated by a Ta wire heater around the crucible to evaporate in a vacuum vessel. The temperature of the crucible was in the range of 130 to 150 ° C., and the degree of vacuum during evaporation was 7 × 10 −7 Torr. An organic hole injecting and transporting layer was thus deposited to a thickness of 520 °. The deposition time was 2 minutes and 30 seconds. Next, an 8-hydroxyquinoline complex of aluminum represented by the following structural formula (E1) is used as a material for the organic electron transport layer.
【００３８】[0038]
【化７】 Embedded image
【００３９】およびドープする蛍光色素として前記の化
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２２
０〜２４０℃、化合物（１）に対しては１１０〜１２０
℃で制御した。蒸着時の真空度は６×１０-7Ｔｏｒｒ
で、蒸着時間は２分であった。結果として、膜厚５２５
Åで化合物（１）が４モル％ドープされた有機電子輸送
層が得られた。The compound (1) as a fluorescent dye to be doped was simultaneously heated and deposited in separate crucibles. At this time, the temperature of each crucible was set at 22 for the 8-hydroxyquinoline complex of aluminum.
0 to 240 ° C, 110 to 120 for compound (1)
Controlled at ° C. The degree of vacuum at the time of vapor deposition is 6 × 10 −7 Torr
The deposition time was 2 minutes. As a result, the film thickness 525
In Å, an organic electron transporting layer doped with 4 mol% of the compound (1) was obtained.
【００４０】最後にカソードとして、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１５００Åに
蒸着した。蒸着はモリブデンボートを用いて、真空度は
６×１０-6Ｔｏｒｒで、蒸着時間は８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
０：３の範囲であった。このようにして作製した有機電
界発光素子のＩＴＯ電極（アノード）にプラス、マグネ
シウム・銀電極（カソード）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以下の表１に示す。こ
の素子は、緑色の一様な発光を示した。Finally, as a cathode, an alloy electrode of magnesium and silver was deposited to a thickness of 1500 ° by a binary simultaneous vapor deposition method. The evaporation was performed using a molybdenum boat, the degree of vacuum was 6 × 10 −6 Torr, and the evaporation time was 8 minutes. A glossy film was obtained. The atomic ratio of magnesium to silver is 1
The range was 0: 3. The results of the 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 manufactured are shown in Table 1 below. This device emitted green uniform light.
【００４１】比較例１ 有機電子輸送層に化合物（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１に示す。この
素子は、緑色の一様な発光を示した。Comparative Example 1 An organic electroluminescent device was produced in the same manner as in Example 1 except that the organic electron transporting layer was not doped with the compound (1). Table 1 shows the measurement results of the light emission characteristics of this device. This device emitted green uniform light.
【００４２】[0042]
【表１】 [Table 1]
【００４３】実施例２および比較例２ 実施例１および比較例１で作製した各素子を真空中で保
存して、輝度が１００ｃｄ／ｍ2となる実用駆動電圧
（Ｖ100）の経時変化を測定した結果を図３に示す。実
施例１の素子は長期にわたる安定性を示したのに対し
て、比較例１の素子は３０日以上経つと駆動電圧の増加
が顕著になると同時に輝度が大きく低下した。Example 2 and Comparative Example 2 Each element produced in Example 1 and Comparative Example 1 was stored in a vacuum, and the change with time in the practical driving voltage (V 100 ) at which the luminance became 100 cd / m 2 was measured. The results obtained are shown in FIG. While the device of Example 1 exhibited long-term stability, the device of Comparative Example 1 showed a significant increase in driving voltage and a significant decrease in luminance after 30 days or more.
【００４４】[0044]
【発明の効果】本発明の有機電界発光素子は、陽極（ア
ノード）、有機正孔注入輸送層、有機電子注入輸送層お
よび陰極（カソード）が基板上に順次設けられており、
有機正孔注入輸送層および／または有機電子注入輸送
層、もしくはその一部分に特定の蛍光色素をドープして
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、かつ長期間保存した後も初期の発光特性を維持する
ことができる。According to the organic electroluminescent device of the present invention, an anode (anode), an organic hole injecting and transporting layer, an organic electron injecting and transporting layer, and a cathode (cathode) are sequentially provided on a substrate.
Since the organic hole injection transport layer and / or organic electron injection transport layer, or a part thereof is doped with a specific fluorescent dye, when a voltage is applied using both conductive layers as electrodes,
Light emission with practically sufficient luminance can be obtained at a low drive voltage, and the initial light emission characteristics can be maintained even after long-term storage.
【００４５】従って、本発明の電界発光素子はフラット
パネル・ディスプレイ（例えば壁掛けテレビ）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、その技術的
価値は大きいものである。Therefore, the electroluminescent device of the present invention can be used as a light source (for example, a light source of a copier, a backlight of a liquid crystal display or an instrument) utilizing the characteristics of a flat panel display (for example, a wall-mounted television) and a surface light emitting element. It can be applied to light sources, display boards, and marker lights, and its technical value is great.
【図１】本発明の有機電界発光素子の一実施例の断面図
である。FIG. 1 is a cross-sectional view of one embodiment of the organic electroluminescent device of the present invention.
【図２】本発明の有機電界発光素子のその他の実施例の
断面図である。FIG. 2 is a sectional view of another embodiment of the organic electroluminescent device of the present invention.
【図３】本発明の実施例および比較例で作製した有機電
界発光素子の実用駆動電圧の経時変化を測定した結果を
示す図である。FIG. 3 is a diagram showing the results of measuring the change over time of the practical driving voltage of the organic electroluminescent devices manufactured in Examples and Comparative Examples of the present invention.
１ 基板 ２ａ，２ｂ 導電層 ３ 有機正孔輸送層 ４ 有機電子輸送層 ５ ４とは異なる化合物で構成される有機電子輸送層 DESCRIPTION OF SYMBOLS 1 Substrate 2a, 2b Conductive layer 3 Organic hole transport layer 4 Organic electron transport layer 5 Organic electron transport layer comprised of a compound different from 4
フロントページの続き (56)参考文献 特開 平３−37293（ＪＰ，Ａ) 特開 昭63−264692（ＪＰ，Ａ) Ｊ．Ａｐｐｌ．Ｐｈｙｓ．65（９）, 1989，Ｐ．3610−3616 (58)調査した分野(Int.Cl.7，ＤＢ名) C09K 11/06 ＣＡ（ＳＴＮ) ＲＥＧＩＳＴＲＹ（ＳＴＮ)Continuation of front page (56) References JP-A-3-37293 (JP, A) JP-A-63-264692 (JP, A) Appl. Phys. 65 (9), 1989, p. 3610-3616 (58) Field surveyed (Int. Cl. 7 , DB name) C09K 11/06 CA (STN) REGISTRY (STN)
Claims (3)
子輸送層、陰極が積層された有機電界発光素子におい
て、 有機正孔輸送層中の有機正孔輸送材料および／または有
機電子輸送層中の有機電子輸送材料をホスト材料とし、 該ホスト材料に対して、下記一般式（Ｉ）で表される化
合物がドープされている ことを特徴とする有機電界発光
素子。 【化１】 （式中、Ｒ1、Ｒ2、Ｒ3およびＲ4はそれぞれ独立して置
換基を有していてもよい芳香族炭化水素基を示し、Ｘは
置換基を有していてもよい窒素原子、置換基を有してい
てもよい硫黄原子、置換基を有していてもよい酸素原子
または置換基を有していてもよいセレン原子を示し、Ｙ
は水素原子、シアノ基、カルボキシル基、置換基を有し
ていてもよいアミド基、置換基を有していてもよいエス
テル基、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芳香族炭化水素基または置換基を有
していてもよい複素環基を示す。）1. An organic electroluminescent device in which an anode, an organic hole transport layer, an organic electron transport layer, and a cathode are sequentially laminated, wherein an organic hole transport material and / or organic hole transport material in the organic hole transport layer is provided.
The organic electron transporting material in the organic electron transporting layer is used as a host material, and the host material is represented by the following general formula (I).
An organic electroluminescent device, wherein the compound is doped . Embedded image (Wherein, R 1 , R 2 , R 3 and R 4 each independently represent an aromatic hydrocarbon group which may have a substituent, and X represents a nitrogen atom which may have a substituent. Represents a sulfur atom which may have a substituent, an oxygen atom which may have a substituent or a selenium atom which may have a substituent,
Has a hydrogen atom, a cyano group, a carboxyl group, an amide group which may have a substituent, an ester group which may have a substituent, an alkyl group which may have a substituent, Represents an aromatic hydrocarbon group which may be substituted or a heterocyclic group which may have a substituent. )
表される化合物のドープ量が、ホスト材料に対して１０The doping amount of the represented compound is 10 to the host material.
-3-3 〜１０モル％であることを特徴とする有機電界発光素Organic electroluminescent element characterized by being 10 mol% to 10 mol%
子。Child.
子輸送材料である、請求項１または２記載の有機電界発
光素子。3. The organic electroluminescent device according to claim 1, wherein the host material is an organic electron transporting material comprising a metal complex.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02849392A JP3158600B2 (en) | 1992-02-14 | 1992-02-14 | Organic electroluminescent device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02849392A JP3158600B2 (en) | 1992-02-14 | 1992-02-14 | Organic electroluminescent device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05222360A JPH05222360A (en) | 1993-08-31 |
| JP3158600B2 true JP3158600B2 (en) | 2001-04-23 |
Family
ID=12250199
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP02849392A Expired - Lifetime JP3158600B2 (en) | 1992-02-14 | 1992-02-14 | Organic electroluminescent device |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3158600B2 (en) |
-
1992
- 1992-02-14 JP JP02849392A patent/JP3158600B2/en not_active Expired - Lifetime
Non-Patent Citations (1)
| Title |
|---|
| Ｊ．Ａｐｐｌ．Ｐｈｙｓ．６５（９），１９８９，Ｐ．３６１０−３６１６ |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05222360A (en) | 1993-08-31 |
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