JPH0812967A - Organic electroluminescent element - Google Patents
Organic electroluminescent elementInfo
- Publication number
- JPH0812967A JPH0812967A JP6147730A JP14773094A JPH0812967A JP H0812967 A JPH0812967 A JP H0812967A JP 6147730 A JP6147730 A JP 6147730A JP 14773094 A JP14773094 A JP 14773094A JP H0812967 A JPH0812967 A JP H0812967A
- Authority
- JP
- Japan
- Prior art keywords
- organic
- group
- light emitting
- hole transport
- anode
- 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
- 125000003118 aryl group Chemical group 0.000 claims abstract description 7
- 125000006615 aromatic heterocyclic group Chemical group 0.000 claims abstract description 3
- 230000005525 hole transport Effects 0.000 claims description 35
- 239000000758 substrate Substances 0.000 claims description 19
- CASHWAGXBJSQDV-UHFFFAOYSA-N 2-(1,3,5-triazin-2-yl)-1,3,5-triazine Chemical compound C1=NC=NC(C=2N=CN=CN=2)=N1 CASHWAGXBJSQDV-UHFFFAOYSA-N 0.000 claims description 7
- 125000001424 substituent group Chemical group 0.000 claims description 4
- 125000006267 biphenyl group Chemical group 0.000 claims description 3
- 239000010409 thin film Substances 0.000 abstract description 13
- 238000000576 coating method Methods 0.000 abstract description 6
- 229910010272 inorganic material Inorganic materials 0.000 abstract description 6
- 239000011147 inorganic material Substances 0.000 abstract description 6
- 239000011248 coating agent Substances 0.000 abstract description 5
- 229910021417 amorphous silicon Inorganic materials 0.000 abstract description 4
- 238000000151 deposition Methods 0.000 abstract description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 abstract description 4
- 239000011521 glass Substances 0.000 abstract description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 abstract description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 abstract description 3
- 229920000728 polyester Polymers 0.000 abstract description 3
- 235000010290 biphenyl Nutrition 0.000 abstract description 2
- 239000004305 biphenyl Substances 0.000 abstract description 2
- VUCHLZJMRUTYJU-UHFFFAOYSA-N 4-[4-[2-[4-(triazin-4-yl)phenyl]ethenyl]phenyl]triazine Chemical class C=1C=C(C=2N=NN=CC=2)C=CC=1C=CC(C=C1)=CC=C1C1=CC=NN=N1 VUCHLZJMRUTYJU-UHFFFAOYSA-N 0.000 abstract 2
- 239000012789 electroconductive film Substances 0.000 abstract 1
- 229910003437 indium oxide Inorganic materials 0.000 abstract 1
- 239000011368 organic material Substances 0.000 abstract 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 abstract 1
- 229910001887 tin oxide Inorganic materials 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 74
- 239000000463 material Substances 0.000 description 25
- 150000001875 compounds Chemical class 0.000 description 23
- 239000010408 film Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- -1 poly (p-phenylene vinylene) Polymers 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 238000005401 electroluminescence Methods 0.000 description 8
- 238000007740 vapor deposition Methods 0.000 description 8
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 6
- 238000002347 injection Methods 0.000 description 6
- 239000007924 injection Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 235000021286 stilbenes Nutrition 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 238000001771 vacuum deposition Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 150000004984 aromatic diamines Chemical class 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 150000002894 organic compounds Chemical class 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 239000005083 Zinc sulfide Substances 0.000 description 3
- 229920001940 conductive polymer Polymers 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 230000005684 electric field Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 125000006617 triphenylamine group Chemical group 0.000 description 3
- 229910052984 zinc sulfide Inorganic materials 0.000 description 3
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 3
- 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 2
- QENGPZGAWFQWCZ-UHFFFAOYSA-N 3-Methylthiophene Chemical compound CC=1C=CSC=1 QENGPZGAWFQWCZ-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 241000284156 Clerodendrum quadriloculare Species 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
- 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
- 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
- 239000013078 crystal Substances 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000007850 fluorescent dye Substances 0.000 description 2
- 229910052738 indium Inorganic materials 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
- 150000002739 metals Chemical class 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000193 polymethacrylate Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- 150000003513 tertiary aromatic amines Chemical group 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical class C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 2
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 description 1
- CHBDXRNMDNRJJC-UHFFFAOYSA-N 1,2,3-triphenylbenzene Chemical class C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1C1=CC=CC=C1 CHBDXRNMDNRJJC-UHFFFAOYSA-N 0.000 description 1
- LHGFMZOQWYPJHE-UHFFFAOYSA-N 1-phenylphenanthridine-2,3-diamine Chemical class NC=1C(N)=CC2=NC=C3C=CC=CC3=C2C=1C1=CC=CC=C1 LHGFMZOQWYPJHE-UHFFFAOYSA-N 0.000 description 1
- GOLORTLGFDVFDW-UHFFFAOYSA-N 3-(1h-benzimidazol-2-yl)-7-(diethylamino)chromen-2-one Chemical compound C1=CC=C2NC(C3=CC4=CC=C(C=C4OC3=O)N(CC)CC)=NC2=C1 GOLORTLGFDVFDW-UHFFFAOYSA-N 0.000 description 1
- 125000004179 3-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(Cl)=C1[H] 0.000 description 1
- ZFXPBTZXYNIAJW-UHFFFAOYSA-N 4-[2-(2-phenylethenyl)phenyl]triazine Chemical class C=1C=CC=CC=1C=CC1=CC=CC=C1C1=CC=NN=N1 ZFXPBTZXYNIAJW-UHFFFAOYSA-N 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
- 239000005725 8-Hydroxyquinoline Substances 0.000 description 1
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical class C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 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
- 229910052693 Europium Inorganic materials 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
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical class N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 125000000051 benzyloxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])O* 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 125000004663 dialkyl amino group Chemical group 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
- 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
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229910003472 fullerene Inorganic materials 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
- PQTCMBYFWMFIGM-UHFFFAOYSA-N gold silver Chemical compound [Ag].[Au] PQTCMBYFWMFIGM-UHFFFAOYSA-N 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000005524 hole trap Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000003550 marker Substances 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
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 229910021424 microcrystalline silicon Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- VDQLDLGIMZTPQO-UHFFFAOYSA-N n-[4-(2,5-dimethylphenyl)phenyl]-4-methyl-n-(4-methylphenyl)aniline Chemical group C1=CC(C)=CC=C1N(C=1C=CC(=CC=1)C=1C(=CC=C(C)C=1)C)C1=CC=C(C)C=C1 VDQLDLGIMZTPQO-UHFFFAOYSA-N 0.000 description 1
- IBHBKWKFFTZAHE-UHFFFAOYSA-N n-[4-[4-(n-naphthalen-1-ylanilino)phenyl]phenyl]-n-phenylnaphthalen-1-amine Chemical group C1=CC=CC=C1N(C=1C2=CC=CC=C2C=CC=1)C1=CC=C(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C3=CC=CC=C3C=CC=2)C=C1 IBHBKWKFFTZAHE-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 150000004866 oxadiazoles Chemical class 0.000 description 1
- 229960003540 oxyquinoline Drugs 0.000 description 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 125000001644 phenoxazinyl group Chemical group C1(=CC=CC=2OC3=CC=CC=C3NC12)* 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000553 poly(phenylenevinylene) Polymers 0.000 description 1
- 229920002627 poly(phosphazenes) Polymers 0.000 description 1
- 229920000548 poly(silane) polymer Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000001725 pyrenyl group Chemical group 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical class [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 239000000126 substance Substances 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
- 125000001935 tetracenyl group Chemical class C1(=CC=CC2=CC3=CC4=CC=CC=C4C=C3C=C12)* 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- XDDVRYDDMGRFAZ-UHFFFAOYSA-N thiobenzophenone Chemical class C=1C=CC=CC=1C(=S)C1=CC=CC=C1 XDDVRYDDMGRFAZ-UHFFFAOYSA-N 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Electroluminescent Light Sources (AREA)
- Luminescent Compositions (AREA)
Abstract
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発光層に
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 electroluminescence device, and more particularly, to a thin film type device which emits light by applying an electric field to a light emitting layer made of an organic compound.
【0002】[0002]
【従来の技術】従来、薄膜型の電界発光(EL)素子と
しては、無機材料のII−VI族化合物半導体であるZn
S、CaS、SrS等に、発光中心であるMnや希土類
元素(Eu、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EL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、 という問題点を有している。2. Description of the Related Art Conventionally, as a thin film type electroluminescent (EL) element, Zn which is a II-VI group compound semiconductor of an inorganic material has been used.
It is general that S, CaS, SrS, etc. are doped with Mn or a rare earth element (Eu, Ce, Tb, Sm, etc.), which is the emission center, but the EL element made from 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 is a problem), and 4) peripheral drive circuit costs are high. ing.
【0003】しかし、近年、上記問題点の改良のため、
有機薄膜を用いたEL素子の開発が行われるようになっ
た。特に、発光効率を高めるために電極からのキャリア
ー注入の効率向上を目的とした電極種類の最適化を行
い、芳香族ジアミンから成る有機正孔輸送層と8−ヒド
ロキシキノリンのアルミニウム錯体から成る有機発光層
を設けた有機電界発光素子の開発(Appl.Phy
s.Lett.,51巻,913頁,1987年)によ
り、従来のアントラセン等の単結晶を用いた電界発光素
子と比較して発光効率の大幅な改善がなされ、実用特性
に近づいている。However, in recent years, in order to improve the above problems,
EL devices using organic thin films have been developed. In particular, the electrode type was optimized for the purpose of improving the efficiency of carrier injection from the electrode in order to increase the light emission efficiency, and the organic hole transport layer made of an aromatic diamine and the organic light emission made of an aluminum complex of 8-hydroxyquinoline. Of an organic electroluminescent device having a layer (Appl. Phy
s. Lett. , 51, p. 913, 1987), the luminous efficiency is greatly improved as compared with the conventional electroluminescent device using a single crystal such as anthracene, and is close to practical characteristics.
【0004】上記の様な低分子材料の他にも、有機発光
層の材料として、ポリ(p−フェニレンビニレン)(N
ature,347巻,539頁,1990年;App
l.Phys.Lett.,61巻,2793頁,19
92年)、ポリ[2−メトキシ,5−(2’−エチルヘ
キソキシ)−1,4−フェニレンビニレン](App
l.Phys.Lett.,58巻,1982頁,19
91年;ThinSolid Films,216巻,
96頁,1992年;Nature,357巻,477
頁,1992年)、ポリ(3−アルキルチオフェン)
(Jpn.J.Appl.Phys,30巻,L193
8頁,1991年;J.Appl.Phys.,72
巻,564頁,1992年)等の高分子材料の開発や、
ポリビニルカルバゾール等の高分子に低分子の発光材料
と電子移動材料を混合した素子(応用物理,61巻,1
044頁,1992年)の開発も行われている。In addition to the above low molecular weight materials, poly (p-phenylene vinylene) (N
ature, 347, 539, 1990; App.
l. Phys. Lett. , 61, 2793, 19
1992), poly [2-methoxy, 5- (2'-ethylhexoxy) -1,4-phenylenevinylene] (App
l. Phys. Lett. , 58, 1982, 19
1991; Thin Solid Films, Volume 216,
96, 1992; Nature, 357, 477.
P., 1992), poly (3-alkylthiophene)
(Jpn. J. Appl. Phys, 30 volumes, L193
8 pages, 1991; Appl. Phys. , 72
Vol., P. 564, 1992), etc.
A device in which a low molecular weight light emitting material and an electron transfer material are mixed with a polymer such as polyvinylcarbazole (Applied Physics, 61, 1)
044, 1992) is also being developed.
【0005】[0005]
【発明が解決しようとする課題】低分子材料を用いた有
機電界発光素子では、低分子薄膜層が経時的にあるいは
熱的に結晶化して、結果として薄膜形状の一様性が失わ
れ、最終的にはダークスポットと呼ばれる非発光部分が
発生したり、素子の短絡を招いたりすることが大きな問
題である。この結晶化問題の解決方法として、前述の高
分子を用いた有機電界発光素子が検討されているが、ス
ピンコート等の湿式法で発光層を形成するために、膜厚
の精密な制御が困難であり、また不純物の制御もむずか
しく、そのために発光効率が低分子型と比較して低く、
また駆動時の寿命も短い。In an organic electroluminescence device using a low molecular weight material, the low molecular weight thin film layer is crystallized with time or thermally, resulting in loss of uniformity of the thin film shape, and A major problem is that a non-light emitting portion called a dark spot is generated or an element is short-circuited. As a solution to this crystallization problem, an organic electroluminescence device using the above-mentioned polymer has been studied, but it is difficult to precisely control the film thickness because the light emitting layer is formed by a wet method such as spin coating. In addition, it is difficult to control impurities, so that the luminous efficiency is lower than that of the low molecular type,
In addition, the operating life is short.
【0006】上述の理由から、実用化の上で、有機電界
発光素子は、薄膜形状に起因する不安定性の問題を抱え
ているのが実状である。For the above-mentioned reason, the organic electroluminescence device actually has a problem of instability due to the shape of the thin film in practical use.
【0007】[0007]
【課題を解決するための手段】本発明者等は上記実状に
鑑み、長期間に亙って安定な発光特性を維持できる有機
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、有機発光層が4,4’−ビス−トリアジニルスチ
ルベン誘導体を含有することが好適であることを見い出
し、本発明を完成するに至った。SUMMARY OF THE INVENTION 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 capable of maintaining stable light emitting characteristics over a long period of time, and as a result, organic light emitting We have found that it is preferable for the layer to contain a 4,4'-bis-triazinyl stilbene derivative and have completed the invention.
【0008】すなわち、本発明の要旨は、基板上に、陽
極及び陰極により挟持された正孔輸送層および有機発光
層を少なくとも含む有機電界発光素子であって、有機発
光層が下記一般式(I)That is, the gist of the present invention is an organic electroluminescent device comprising at least a hole transport layer sandwiched by an anode and a cathode and an organic light emitting layer on a substrate, wherein the organic light emitting layer has the following general formula (I): )
【0009】[0009]
【化2】 Embedded image
【0010】(式中、Ar1 からAr4 は、各々独立して
置換基を有していてもよいアリール基、ビフェニル基ま
たは芳香族複素環基を示す)で表わされる4,4’−ビ
ス−トリアジニルスチルベン誘導体を含有することを特
徴とする有機電界発光素子に存する。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。 4 , wherein Ar 1 to Ar 4 each independently represent an aryl group, a biphenyl group or an aromatic heterocyclic group which may have a substituent. -An organic electroluminescent device characterized by containing a triazinyl stilbene derivative. Hereinafter, the organic electroluminescent device of the present invention will be described with reference to the accompanying drawings.
【0011】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、2は陽極、3
は正孔輸送層、4は有機発光層、5は陰極を各々表わ
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などが用いられるが、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 the organic electroluminescence device of the present invention, in which 1 is a substrate, 2 is an anode, and 3 is a substrate.
Represents a hole transport layer, 4 represents an organic light emitting layer, and 5 represents a cathode. The substrate 1 serves as a support for the organic electroluminescence device of the present invention, and a plate of quartz or glass, a metal plate or a metal foil, a plastic film or a sheet, and the like are used, and a glass plate, polyester, polymethacrylate. A transparent synthetic resin substrate such as polycarbonate, polysulfone, or the like is preferable.
【0012】基板1上には陽極2が設けられるが、この
陽極としては通常、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/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
導電性高分子などにより構成される。陽極の形成は通
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
高分子微粉末などの場合には、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、導電性高分子の場合は電解重合によ
り直接基板上に薄膜を形成したり、基板上に塗布して形
成することもできる(Appl.Phys.Let
t.,60巻,2711頁,1992年)。上記の陽極
は異なる物質で積層することも可能である。陽極2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%以上透過することが望ましく、この場合、厚
みは、通常、5〜1000nm、好ましくは10〜50
0nm程度である。An anode 2 is provided on the substrate 1, which is usually aluminum, gold, silver, nickel,
It is composed of a metal such as palladium or tellurium, a metal oxide such as an oxide of indium and / or tin, copper iodide, carbon black, or a conductive polymer such as poly (3-methylthiophene). The anode is usually formed by a sputtering method, a vacuum vapor deposition method or the like, but metal fine particles such as silver or copper iodide,
In the case of carbon black, conductive metal oxide fine particles, conductive polymer fine powder, etc., they can be formed by dispersing them in a suitable binder resin solution and applying them on a substrate. Further, in the case of a conductive polymer, a thin film can be directly formed on the substrate by electrolytic polymerization or can be formed by coating on the substrate (Appl. Phys. Let.
t. , 60, 2711, 1992). The above anodes can be laminated with different materials. The thickness of the anode 2 varies depending on the required transparency, but when the transparency is required, it is desirable that the visible light has a transmittance of 60% or more, preferably 80% or more. Is usually 5 to 1000 nm, preferably 10 to 50
It is about 0 nm.
【0013】不透明でよい場合は陽極2は基板1と同一
でもよい。また、さらには上記の陽極を異なる物質で積
層することも可能である。図1の例では、陽極2は正孔
注入の役割を果たすものである。一方、陰極5は有機発
光層4に電子を注入する役割を果たす。陰極5として用
いられる材料は、前記陽極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なうには、仕事関数の
低い金属が好ましく、スズ、マグネシウム、インジウ
ム、アルミニウム、銀等の適当な金属またはそれらの合
金が用いられる。陰極5の膜厚は通常、陽極2と同様で
ある。また、図1には示してはいないが、陰極5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、陽極2と陰極5の少なくとも一方は透明性の良いこ
とが有機電界発光素子としては必要である。このことか
ら、陽極2と陰極5の一方は、10〜500nm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。The anode 2 may be the same as the substrate 1 if it is opaque. Further, it is also possible to stack the above anodes with different materials. In the example of FIG. 1, the anode 2 plays a role of hole injection. On the other hand, the cathode 5 plays a role of injecting electrons into the organic light emitting layer 4. The material used for the cathode 5 may be the material for the anode, but a metal having a low work function is preferable for efficient electron injection, and tin, magnesium, indium, aluminum, silver or the like is preferable. Appropriate metals or their alloys are used. The film thickness of the cathode 5 is usually the same as that of the anode 2. Although not shown in FIG. 1, a substrate similar to the substrate 1 may be further provided on the cathode 5. However, it is necessary for at least one of the anode 2 and the cathode 5 to have good transparency as an organic electroluminescence device. From this, one of the anode 2 and the cathode 5 preferably has a film thickness of 10 to 500 nm, and is desired to have good transparency.
【0014】陽極2の上には正孔輸送層3が設けられる
が、正孔輸送層としては、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発光層の方向に輸送
することができる材料より形成される。通常、正孔輸送
層には有機正孔輸送材料が用いられる。有機正孔輸送材
料としては、陽極2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材料で
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
に発生しにくいことが要求される。このような有機正孔
輸送化合物としては、例えば、1,1−ビス(4−ジ−
p−トリルアミノフェニル)シクロヘキサン等の3級芳
香族アミンユニットを連結した芳香族ジアミン化合物
(特開昭59−194393号公報)、4,4’−ビス
[(N−1−ナフチル)−N−フェニルアミノ]ビフェ
ニルで代表される2個以上の3級アミンを含み2個以上
の縮合芳香族環が窒素原子に置換した芳香族アミン(特
開平5−234681号公報)、トリフェニルベンゼン
の誘導体でスターバースト構造を有する芳香族トリアミ
ン(米国特許第4,923,774号)、N,N’−ジ
フェニル−N,N’−ビス(3−メチルフェニル)−
(1,1’−ビフェニル)−4,4’−ジアミン等の芳
香族ジアミン(米国特許第4,764,625号)、
α,α,α’,α’−テトラメチル−α,α’−ビス
(4−ジ−p−トリルアミノフェニル)−p−キシレン
(特開平3−269084号公報)、分子全体として立
体的に非対称なトリフェニルアミン誘導体(特開平4−
129271号公報)、ピレニル基に芳香族ジアミノ基
が複数個置換した化合物(特開平4−175395号公
報)、エチレン基で3級芳香族アミンユニットを連結し
た芳香族ジアミン(特開平4−264189号公報)、
スチリル構造を有する芳香族ジアミン(特開平4−29
0851号公報)、チオフェン基で芳香族3級アミンユ
ニットを連結したもの(特開平4−304466号公
報)、スターバースト型芳香族トリアミン(特開平4−
308688号公報)、ベンジルフェニル化合物(特開
平4−364153号公報)、フルオレン基で3級アミ
ンを連結したもの(特開平5−25473号公報)、ト
リアミン化合物(特開平5−239455号公報)、ビ
スジピリジルアミノビフェニル(特開平5−32063
4号公報)、N,N,N−トリフェニルアミン誘導体
(特開平6−1972号公報)、フェノキサジン構造を
有する芳香族ジアミン(特願平5−290728号)、
ジアミノフェニルフェナントリジン誘導体(特願平6−
45669号)に示される芳香族アミン系化合物、ヒド
ラゾン化合物(特開平2−311591号公報)、シラ
ザン化合物(米国特許第4,950,950号公報)、
シラナミン誘導体(特開平6−49079号公報)、ホ
スファミン誘導体(特開平6−25659号公報)、キ
ナクリドン化合物等が挙げられる。これらの化合物は、
単独で用いるか、必要に応じて、各々、混合して用いて
もよい。A hole transport layer 3 is provided on the anode 2. As the hole transport layer, holes from the anode are efficiently transported between the electrodes to which an electric field is applied toward the organic light emitting layer. Formed of a material that can. Usually, an organic hole transport material is used for the hole transport layer. As the organic hole transport material, the hole injection efficiency from the anode 2 is high, and
It is necessary that the material is capable of efficiently transporting the injected holes. For that purpose, it is required that the ionization potential is small, the hole mobility is large, the stability is excellent, and impurities that serve as traps are hard to be generated during manufacturing or use. Examples of such an organic hole transport compound include 1,1-bis (4-di-).
Aromatic diamine compounds in which tertiary aromatic amine units such as p-tolylaminophenyl) cyclohexane are linked (JP-A-59-194393), 4,4'-bis [(N-1-naphthyl) -N- Aromatic amines containing two or more tertiary amines represented by phenylamino] biphenyl and having two or more condensed aromatic rings substituted by nitrogen atoms (Japanese Patent Laid-Open No. 234681/1993), a derivative of triphenylbenzene. Aromatic triamines having a starburst structure (U.S. Pat. No. 4,923,774), N, N'-diphenyl-N, N'-bis (3-methylphenyl)-
Aromatic diamines such as (1,1′-biphenyl) -4,4′-diamine (US Pat. No. 4,764,625),
α, α, α ′, α′-tetramethyl-α, α′-bis (4-di-p-tolylaminophenyl) -p-xylene (JP-A-3-269084), the molecule as a whole is three-dimensionally Asymmetric triphenylamine derivative
No. 129,271), a compound in which a pyrenyl group is substituted with a plurality of aromatic diamino groups (JP-A-4-175395), and an aromatic diamine in which a tertiary aromatic amine unit is linked with an ethylene group (JP-A-4-264189). Gazette),
Aromatic diamine having styryl structure (JP-A-4-29)
No. 0851), one in which an aromatic tertiary amine unit is linked by a thiophene group (JP-A-4-304466), and a starburst type aromatic triamine (JP-A-4-304).
308688), a benzylphenyl compound (JP-A-4-364153), a compound in which a tertiary amine is linked by a fluorene group (JP-A-5-25473), a triamine compound (JP-A-5-239455), Bisdipyridylaminobiphenyl (JP-A-5-32063)
4), N, N, N-triphenylamine derivatives (JP-A-6-1972), aromatic diamines having a phenoxazine structure (Japanese Patent Application No. 5-290728),
Diaminophenylphenanthridine derivative (Japanese Patent Application No. 6-
45669), hydrazone compounds (JP-A-2-311591), silazane compounds (US Pat. No. 4,950,950),
Examples thereof include silanamine derivatives (JP-A-6-49079), phosphamine derivatives (JP-A-6-25659), and quinacridone compounds. These compounds are
They may be used alone or, if necessary, may be mixed and used.
【0015】上記の化合物以外に、正孔輸送性の高分子
である、ポリビニルカルバゾールやポリシラン(App
l.Phys.Lett.,59巻,2760頁,19
9等が挙げられる年)、ポリフォスファゼン(特開平5
−310949号公報)、ポリアミド(特開平5−31
0949号公報)、ポリビニルトリフェニルアミン(特
願平5−205377)、トリフェニルアミン骨格を有
する高分子(特開平4−133065号公報)、トリフ
ェニルアミン単位をメチレン基等で連結した高分子(S
ynthetic Metals,55−57巻,41
63頁,1993年)、芳香族アミンを含有するポリメ
タクリレート(J.Polym.Sci.,Poly
m.Chem.Ed.,21巻,969頁,1983
年)等の高分子材料が挙げられる。In addition to the above compounds, polyvinyl carbazole and polysilane (App, which are hole-transporting polymers).
l. Phys. Lett. , 59, 2760, 19
9 etc.), polyphosphazene (Japanese Patent Laid-Open No. Hei 5)
-310949), polyamide (JP-A-5-31)
No. 0949), polyvinyl triphenylamine (Japanese Patent Application No. 5-205377), a polymer having a triphenylamine skeleton (Japanese Patent Laid-Open No. 4-133065), a polymer in which triphenylamine units are linked by a methylene group or the like ( S
ynthetic Metals, 55-57, 41
63, 1993), polymethacrylates containing aromatic amines (J. Polym. Sci., Poly.
m. Chem. Ed. , 21: 969, 1983
Years) and other polymeric materials.
【0016】上記の有機正孔輸送材料は塗布法あるいは
真空蒸着法により前記陽極2上に積層することにより正
孔輸送層3を形成する。塗布の場合は、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溶解した塗布溶液を調整
し、スピンコート法などの方法により陽極2上に塗布
し、乾燥して正孔輸送層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 above organic hole transport material is laminated on the anode 2 by a coating method or a vacuum deposition method to form a hole transport layer 3. In the case of coating, a coating solution prepared by adding one or more organic hole-transporting compounds and 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, is dissolved. It is adjusted, coated on the anode 2 by a method such as spin coating, and dried to form the hole transport layer 3. Examples of the binder resin include polycarbonate, polyarylate, polyester and the like. If the binder resin is added in a large amount, it lowers the hole mobility, so a smaller amount is desirable,
It is preferably 50% by weight or less.
【0017】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。上記有機正
孔輸送層を形成する場合、さらに、アクセプタとして、
芳香族カルボン酸の金属錯体及び/または金属塩(特開
平4−320484号公報)、ベンゾフェノン誘導体お
よびチオベンゾフェノン誘導体(特開平5−29536
1号公報)、フラーレン類(特開平5−331458号
公報)を10-3から10重量%の濃度でドープして、フ
リーキャリアとしての正孔を生成させ、低電圧駆動とす
ることが可能である。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,
The crucible is heated to evaporate the hole transport material and form a layer on the substrate placed facing the crucible. When forming the organic hole transport layer, further as an acceptor,
Aromatic carboxylic acid metal complexes and / or metal salts (JP-A-4-320484), benzophenone derivatives and thiobenzophenone derivatives (JP-A-5-29536).
No. 1) and fullerenes (Japanese Patent Laid-Open No. 5-331458) at a concentration of 10 −3 to 10% by weight to generate holes as free carriers and low voltage driving is possible. is there.
【0018】正孔輸送層3の膜厚は、通常、10〜30
0nm、好ましくは30〜100nm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。正孔輸送層3の材料としてはの有機化合物の
代わりに無機材料を使用することも可能である。無機材
料に要求される条件は、有機正孔輸送材料と同じであ
る。正孔輸送層3に用いられ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、あるいは、p型
硫化亜鉛、p型セレン化亜鉛等が挙げられる。これらの
無機正孔輸送層はCVD法、プラズマCVD法、真空蒸
着法、スパッタ法等により形成される。The thickness of the hole transport layer 3 is usually 10 to 30.
It is 0 nm, preferably 30 to 100 nm. In order to uniformly form such a thin film, the vacuum evaporation method is often used. As the material of the hole transport layer 3, an inorganic material can be used instead of the organic compound. The conditions required for the inorganic material are the same as those for the organic hole transport material. Examples of the inorganic material used for the hole transport layer 3 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 sulfide. Examples include type zinc selenide. These inorganic hole transport layers are formed by a CVD method, a plasma CVD method, a vacuum deposition method, a sputtering method, or the like.
【0019】無機正孔輸送層の膜厚も有機正孔輸送層と
同様に、通常、10〜300nm、好ましくは30〜1
00nmである。正孔輸送層3の上には有機発光層4が
設けられるが、有機発光層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 inorganic hole transport layer is usually 10 to 300 nm, preferably 30 to 1 as in the organic hole transport layer.
00 nm. The organic light emitting layer 4 is provided on the hole transport layer 3, and the organic light emitting layer 4 can efficiently transport the electrons from the cathode in the direction of the hole transport layer between the electrodes to which an electric field is applied. It is formed from a compound that can.
【0020】有機発光層4に用いられる化合物は、陰極
5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。また、正孔と電子の再結合の際に青色発光をもた
らす役割も求られる。The compound used for the organic light-emitting layer 4 is required to have high electron injection efficiency from the cathode 5 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 less likely to be generated at the time of production or use. It is also required to play a role of emitting blue light when the holes and the electrons are recombined.
【0021】有機発光層に用いられる化合物に要求され
る、さらに重要な条件として、安定な非晶質薄膜を形成
することが挙げられる。このことは、有機電界発光素子
における膜欠陥の発生を抑制するために、さらには、有
機電界発光素子が長期にわたって安定に動作するために
必要な条件である。本発明者が有機電界発光素子の劣化
について検討した結果、一つの大きな原因として、有機
発光層が時間とともに均一な膜状態から島状の不均一な
状態に変化していることを見い出した。A more important condition required for the compound used for the organic light emitting layer is to form a stable amorphous thin film. This is a condition necessary for suppressing the occurrence of film defects in the organic electroluminescent device and for operating the organic electroluminescent device stably for a long period of time. As a result of examining the deterioration of the organic electroluminescent device, the present inventor has found that one of the major causes is that the organic light emitting layer changes from a uniform film state to an island-like non-uniform state with time.
【0022】上記の例の様に、多くの有機化合物は固体
状態では分子性結晶であるために、薄膜化した直後は非
晶質状態であったとしても、時間の経過とともに結晶化
していくことはよくみられる現象である。この様な結晶
化が起きるかどうかはガラス転移温度に大きく依存して
おり、ガラス転移温度が高い材料から成る薄膜は結晶化
しにくい傾向がある。一般に、ガラス転移温度と融点の
間にはよい相関関係が成立するので、高い融点を有する
有機化合物はは高いガラス転移温度を示すと考えてよ
い。本発明者が、この薄膜の結晶化を防ぐために鋭意検
討した結果、4,4’−ビス−トリアジニルスチルベン
誘導体が300℃以上と非常に高い融点を示し、均一な
非晶質薄膜を与え、結晶化しにくく熱的にも安定で、素
子の安定性にも好影響を与えることを見い出した。As in the above example, since many organic compounds are molecular crystals in the solid state, even if they are in the amorphous state immediately after thinning, they should be crystallized with the passage of time. Is a common phenomenon. Whether such crystallization occurs depends largely on the glass transition temperature, and a thin film made of a material having a high glass transition temperature tends to be difficult to crystallize. Generally, since a good correlation is established between the glass transition temperature and the melting point, it can be considered that an organic compound having a high melting point exhibits a high glass transition temperature. As a result of diligent studies for preventing the crystallization of the thin film, the present inventor has found that the 4,4′-bis-triazinyl stilbene derivative has a very high melting point of 300 ° C. or higher and gives a uniform amorphous thin film. It was found that it is hard to crystallize, is thermally stable, and has a favorable effect on the stability of the device.
【0023】本発明においては、有機電界発光素子の有
機発光層として、前記一般式(I)で表される4,4’
−ビス−トリアジニルスチルベン誘導体を用いることに
より長期にわたって安定した素子特性が得られる。前記
一般式(I)において、好ましくは、Ar1 、Ar2 、A
r3 およびAr4 は、各々独立して、置換基を有していて
もよいフェニル基、ナフチル基、アントリル基、ビフェ
ニル基、ピリジル基、チエニル基を示し、前記置換基と
してはハロゲン原子;メチル基、エチル基等の炭素数1
〜6のアルキル基;ビニル基等のアルケニル基;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;メトキシ基、エトキシ基
等の炭素数1〜6のアルコキシ基;フェノキシ基、ベン
ジルオキシ基などのアリールオキシ基;アミノ基、ジメ
チルアミノ基、ジイソプロピルアミノ基等のジアルキル
アミノ基、シアノ基、水酸基である。In the present invention, 4,4 'represented by the above general formula (I) is used as the organic light emitting layer of the organic electroluminescent device.
By using the -bis-triazinyl stilbene derivative, stable device characteristics can be obtained for a long period of time. In the general formula (I), Ar 1 , Ar 2 and A are preferred.
r 3 and Ar 4 each independently represent a phenyl group which may have a substituent, a naphthyl group, an anthryl group, a biphenyl group, a pyridyl group or a thienyl group, wherein the substituent is a halogen atom; methyl. Carbon number such as group and ethyl group
~ 6 alkyl groups; alkenyl groups such as vinyl groups; methoxycarbonyl groups, ethoxycarbonyl groups and other carbon atoms 1 to 6
6 alkoxycarbonyl group; C1-6 alkoxy group such as methoxy group and ethoxy group; aryloxy group such as phenoxy group and benzyloxy group; dialkylamino group such as amino group, dimethylamino group and diisopropylamino group; A cyano group and a hydroxyl group.
【0024】特に好ましくは、Ar1 、Ar2 、Ar3 お
よびAr4 は、各々独立に、フェニル基、p−メチルフ
ェニル基、m−メチルフェニル基、p−クロロフェニル
基、m−クロロフェニル基、p−メトキシフェニル基、
p−t−ブチルフェニル基から選ばれる。前記一般式
(I)で表される4,4’−ビス−トリアジニルスチル
ベン誘導体は、例えば、スイス特許第472,416号
に開示される方法により合成することができる。Particularly preferably, Ar 1 , Ar 2 , Ar 3 and Ar 4 are each independently phenyl group, p-methylphenyl group, m-methylphenyl group, p-chlorophenyl group, m-chlorophenyl group, p. -Methoxyphenyl group,
It is selected from the pt-butylphenyl group. The 4,4'-bis-triazinyl stilbene derivative represented by the general formula (I) can be synthesized, for example, by the method disclosed in Swiss Patent No. 472,416.
【0025】前記一般式(I)で表される4,4’−ビ
ス−トリアジニルスチルベン誘導体の好ましい具体例を
下記の表1に示すが、これらに限定されるものではな
い。Specific preferred examples of the 4,4'-bis-triazinyl stilbene derivative represented by the general formula (I) are shown in Table 1 below, but the invention is not limited thereto.
【0026】[0026]
【表1】 [Table 1]
【0027】[0027]
【表2】 [Table 2]
【0028】[0028]
【表3】 [Table 3]
【0029】上記の表1〜3に示した例示化合物はいず
れも高融点化合物であり、例えば、化合物(1)は39
0℃以上、化合物(2)は373℃、化合物(3)は3
85℃、化合物(8)は375℃、化合物(9)は42
0℃以上、化合物(12)は306℃である。有機発光層
4の膜厚は、通常、10〜200nm、好ましくは30
〜100nmである。All of the exemplified compounds shown in Tables 1 to 3 above are high melting point compounds. For example, compound (1) is 39
0 ° C or higher, Compound (2) is 373 ° C, Compound (3) is 3
85 ° C, compound (8) 375 ° C, compound (9) 42
The compound (12) has a temperature of 306 ° C at 0 ° C or higher. The thickness of the organic light emitting layer 4 is usually 10 to 200 nm, preferably 30.
-100 nm.
【0030】有機発光層も有機正孔輸送層と同様の方法
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。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、例えば、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.Phy
s.,65巻,3610頁,1989年)も行われてい
る。本発明においても上記の4,4’−ビス−トリアジ
ニルスチルベン誘導体をホスト材料として、レーザー用
の蛍光色素等を10 -3〜10モル%ドープすることによ
り、素子の発光特性をさらに向上させることができる。The same method as for the organic hole transport layer is used for the organic light emitting layer.
Can be formed by, but usually vacuum deposition method is not used.
Be done. Improves the luminous efficiency of the device and changes the luminescent color.
For the purpose of obtaining, for example, aluminum 8-hydroxyquinoline
For lasers such as coumarin, using the aluminum complex as a host material
Doping with a fluorescent dye (J. Appl. Phy
s. , 65, 3610, 1989).
You. Also in the present invention, the above 4,4'-bis-triazine
Nylstilbene derivative as host material for laser
10 fluorescent dyes -3By doping 10 mol%
Therefore, the light emission characteristics of the device can be further improved.
【0031】本発明の有機電界発光素子の構造として
は、以下に示すような層構成のものが挙げられる:The structure of the organic electroluminescent device of the present invention includes the following layered structures:
【0032】[0032]
【表4】陽極/有機正孔輸送層/有機発光層/陰極、 陽極/有機正孔輸送層/有機発光層/電子輸送層/陰
極、 陽極/有機正孔輸送層/有機発光層/界面層/陰極、 陽極/有機正孔輸送層/有機発光層/電子輸送層/界面
層/陰極。[Table 4] Anode / organic hole transport layer / organic light emitting layer / cathode, anode / organic hole transport layer / organic light emitting layer / electron transport layer / cathode, anode / organic hole transport layer / organic light emitting layer / interface layer / Cathode, anode / organic hole transport layer / organic light emitting layer / electron transport layer / interface layer / cathode.
【0033】上記の層構成で、電子輸送層は素子の効率
をさらに向上するためのものであり、有機発光層の上に
積層される。この電子輸送層に用いられる化合物には、
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。この様な電子輸送材料として
は、In the above layer structure, the electron transport layer is for further improving the efficiency of the device, and is laminated on the organic light emitting layer. The compounds used in this electron transport layer include
It is required that the electron injection from the cathode be easy and that the electron transporting capacity should be even greater. As such an electron transport material,
【0034】[0034]
【化3】 Embedded image
【0035】[0035]
【化4】 [Chemical 4]
【0036】などのオキサジアゾール誘導体(App
l.Phys.Lett.,55巻,1489頁,19
89年;Jpn.J.Appl.Phys.,31巻,
1812頁,1992年)やそれらをPMMA等の樹脂
に分散した系(Appl.Phys.Lett.,61
巻,2793頁,1992年)、または、n型水素化非
晶質炭化シリコン、n型硫化亜鉛、n型セレン化亜鉛等
が挙げられる。電子輸送層の膜厚は、通常、5〜200
nm、好ましくは10〜100nmである。Oxadiazole derivatives such as (App
l. Phys. Lett. , 55, 1489, 19
1989; Jpn. J. Appl. Phys. , 31 volumes,
1812, 1992) or a system in which they are dispersed in a resin such as PMMA (Appl. Phys. Lett., 61).
Vol., P. 2793, 1992), or n-type hydrogenated amorphous silicon carbide, n-type zinc sulfide, n-type zinc selenide and the like. The thickness of the electron transport layer is usually 5 to 200.
nm, preferably 10 to 100 nm.
【0037】また、同じく、上述の層構成で、界面層は
陰極と有機層とのコンタクトを向上させるためのもの
で、芳香族ジアミン化合物(特願平5−48075
号)、キナクリドン化合物(特願平5−116204
号)、ナフタセン誘導体(特願平5−116205
号)、有機シリコン化合物(特願平5−116206
号)、有機リン化合物(特願平5−116207号)等
が挙げられる。界面層の膜厚は、通常、2〜100n
m、好ましくは5〜30nmである。界面層を設ける代
わりに、有機発光層及び電子輸送層の陰極界面近傍に上
記界面層材料を50重量%以上含む領域を設けてもよ
い。Similarly, in the above layer structure, the interface layer is for improving the contact between the cathode and the organic layer, and is an aromatic diamine compound (Japanese Patent Application No. 5-48075).
No.), quinacridone compound (Japanese Patent Application No. 5-116204)
No.), naphthacene derivatives (Japanese Patent Application No. 5-116205)
No.), organosilicon compounds (Japanese Patent Application No. 5-116206)
No.), organic phosphorus compounds (Japanese Patent Application No. 5-116207). The thickness of the interface layer is usually 2 to 100 n
m, preferably 5 to 30 nm. Instead of providing the interface layer, a region containing 50% by weight or more of the interface layer material may be provided near the cathode interface of the organic light emitting layer and the electron transport layer.
【0038】尚、図1とは逆の構造、すなわち、基板上
に陰極5、有機発光層4、正孔輸送層3、陽極2の順に
積層することも可能であり、既述した様に少なくとも一
方が透明性の高い2枚の基板の間に本発明の有機電界発
光素子を設けることも可能である。同様に、前記各層構
成とは逆の構造に積層することも可能である。Incidentally, it is also possible to have a structure opposite to that of FIG. 1, that is, the cathode 5, the organic light emitting layer 4, the hole transport layer 3 and the anode 2 may be laminated in this order on the substrate, and at least as described above. It is also possible to provide the organic electroluminescent element of the present invention between two substrates, one of which is highly transparent. Similarly, it is also possible to stack in a structure opposite to the above-mentioned layer structure.
【0039】[0039]
【実施例】次に、本発明を合成例および実施例によって
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に示す構造を有する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 synthetic examples and 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.
【0040】ガラス基板上にインジウム・スズ酸化物
(ITO)透明導電膜を120nm堆積したものをアセ
トンで超音波洗浄、純水で水洗、イソプロピルアルコー
ルで超音波洗浄、乾燥窒素で乾燥、UV/オゾン洗浄を
行った後、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。An indium tin oxide (ITO) transparent conductive film having a thickness of 120 nm deposited on a glass substrate is ultrasonically cleaned with acetone, washed with pure water, ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen, and UV / ozone. After the cleaning, it was installed in a vacuum vapor deposition apparatus and evacuated using an oil diffusion pump until the degree of vacuum in the apparatus became 2 × 10 −6 Torr or less.
【0041】有機正孔輸送層材料として、以下に示す
4,4’−ビス[(N−1−ナフチル)−N−フェニル
アミノ]ビフェニル(H1)As the organic hole transport layer material, 4,4'-bis [(N-1-naphthyl) -N-phenylamino] biphenyl (H1) shown below is used.
【0042】[0042]
【化5】 Embedded image
【0043】を予め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蒸着を行った。こ
の時のるつぼの温度は、150〜180℃の範囲で制御
した。蒸着時の真空度は1.1〜0.9×10-6Tor
rで、蒸着時間2分30秒で膜厚60nmの有機正孔輸
送層3を得た。次に、有機発光層4の材料として、表1
に示した4,4’−ビス−トリアジニルスチルベン誘導
体(1)を、上記有機正孔輸送層3の上に同様にして蒸
着を行なった。この時のるつぼの温度は300〜350
℃の範囲で制御した。蒸着時の真空度は3.7〜1.1
×10-6Torr、蒸着時間は4分10秒、膜厚は60
nmであった。[0045] was placed in a ceramic crucible in advance, and vapor deposition was performed by heating with a tantalum wire heater around the crucible. The temperature of the crucible at this time was controlled in the range of 150 to 180 ° C. The degree of vacuum during vapor deposition is 1.1 to 0.9 × 10 -6 Tor.
The organic hole transport layer 3 having a film thickness of 60 nm was obtained at a deposition time of 2 minutes and 30 seconds at r. Next, as a material of the organic light emitting layer 4, Table 1
The 4,4′-bis-triazinyl stilbene derivative (1) shown in (4) was vapor-deposited on the organic hole transport layer 3 in the same manner. The temperature of the crucible at this time is 300-350.
The temperature was controlled in the range of ° C. The degree of vacuum during vapor deposition is 3.7 to 1.1.
× 10 -6 Torr, evaporation time 4 minutes 10 seconds, film thickness 60
was nm.
【0044】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150nmで蒸着
した。蒸着はモリブデンボートを用いて、真空度は4×
10 -6Torr、蒸着時間は2分40秒で光沢のある膜
が得られた。マグネシウムと銀の原子比は10:1.5
であった。この様にして作製した有機電界発光素子のI
TO電極(陽極)にプラス、マグネシウム・銀合金電極
(陰極)にマイナスの直流電圧を印加してすると、この
素子は一様な黄緑色の発光を示し、発光のピーク波長は
560nmであった。Finally, as a cathode, a mixture of magnesium and silver
Gold electrode is vapor-deposited with a film thickness of 150 nm by the two-source simultaneous vapor deposition method.
did. Vapor deposition uses a molybdenum boat and the degree of vacuum is 4 ×
10 -6Torr, vapor deposition time is 2 minutes and 40 seconds, and it is a glossy film.
was gotten. The atomic ratio of magnesium to silver is 10: 1.5.
Met. I of the organic electroluminescent device produced in this way
Plus to TO electrode (anode), magnesium / silver alloy electrode
When a negative DC voltage is applied to the (cathode),
The element emits a uniform yellow-green color, and the peak wavelength of the emission is
It was 560 nm.
【0045】上記の素子の作製直後及び乾燥窒素中で5
2日間保存した後の発光特性の結果を下記の表に示す。
駆動電圧の顕著な上昇はみられず、発光効率の低下もな
く、安定した素子の保存安定性が得られた。Immediately after preparation of the above-mentioned device and in dry nitrogen 5
The results of the emission characteristics after storage for 2 days are shown in the table below.
No remarkable increase in driving voltage was observed, no decrease in luminous efficiency was observed, and stable storage stability of the device was obtained.
【0046】[0046]
【表5】 [Table 5]
【0047】[0047]
【発明の効果】本発明の有機電界発光素子によれば、陽
極、正孔輸送層、有機発光層、陰極が基板上に順次設け
られ、しかも、有機発光層に特定の化合物を使用してい
るため、両導電層を電極として電圧を印加した場合、長
期に亙り、安定した発光特性を得ることができる。According to the organic electroluminescent device of the present invention, an anode, a hole transport layer, an organic light emitting layer and a cathode are sequentially provided on a substrate, and a specific compound is used in the organic light emitting layer. Therefore, when a voltage is applied using both conductive layers as electrodes, stable light emission characteristics can be obtained over a long period of time.
【0048】従って、本発明のEL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、その技術的価値は大きいものである。Therefore, the EL element of the present invention is used in the field of flat panel displays (for example, for OA computers and wall-mounted televisions) and light sources (for example, light sources for copiers, liquid crystal displays, and instruments) making the most of the characteristics as a surface light emitter. It can be applied to backlights, 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例を示した模式
断面図。FIG. 1 is a schematic cross-sectional view showing an example of an organic electroluminescence device of the present invention.
1 基板 2 陽極 3 正孔輸送層 4 有機発光層 5 陰極 1 Substrate 2 Anode 3 Hole Transport Layer 4 Organic Light Emitting Layer 5 Cathode
Claims (1)
た正孔輸送層および有機発光層を少なくとも含む有機電
界発光素子であって、有機発光層が下記一般式(I) 【化1】 (式中、Ar1 からAr4 は、各々独立して置換基を有し
ていてもよいアリール基、ビフェニル基または芳香族複
素環基を示す)で表わされる4,4’−ビス−トリアジ
ニルスチルベン誘導体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 at least a hole transport layer and an organic light emitting layer sandwiched by an anode and a cathode on a substrate, wherein the organic light emitting layer is represented by the following general formula (I): (In the formula, Ar 1 to Ar 4 each independently represent an aryl group, a biphenyl group or an aromatic heterocyclic group which may have a substituent), and 4,4′-bis-triazine An organic electroluminescent device comprising a nirstilbene derivative.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP14773094A JP3284766B2 (en) | 1994-06-29 | 1994-06-29 | Organic electroluminescent device |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP14773094A JP3284766B2 (en) | 1994-06-29 | 1994-06-29 | Organic electroluminescent device |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH0812967A true JPH0812967A (en) | 1996-01-16 |
JP3284766B2 JP3284766B2 (en) | 2002-05-20 |
Family
ID=15436861
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP14773094A Expired - Lifetime JP3284766B2 (en) | 1994-06-29 | 1994-06-29 | Organic electroluminescent device |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP3284766B2 (en) |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19628719A1 (en) * | 1996-07-17 | 1998-01-29 | Bosch Gmbh Robert | Electron-conducting layer in organic, electroluminescent arrangements |
JP2004063465A (en) * | 2002-07-26 | 2004-02-26 | Xerox Corp | Display device including anthracene derivative and triazine derivative |
US6824891B2 (en) * | 2000-08-24 | 2004-11-30 | Fuji Photo Film Co., Ltd. | Light-emitting device and material therefor |
US6942916B2 (en) | 2001-01-11 | 2005-09-13 | Hewlett-Packard Development Company, L.P. | Inkjet printable electroluminescent media |
JP2006225322A (en) * | 2005-02-17 | 2006-08-31 | Tosoh Corp | 1,3,5-triazine derivative and method for producing the same and thin film composed of the same |
JP2006225320A (en) * | 2005-02-17 | 2006-08-31 | Tosoh Corp | 1,3,5-triazine derivative |
JP2006225321A (en) * | 2005-02-17 | 2006-08-31 | Tosoh Corp | Thin film composed of 1,3,5-triazine derivative and method for producing the same thin film |
US7537842B2 (en) | 2001-02-20 | 2009-05-26 | Isis Innovation Limited | Asymmetric dendrimers |
US7592074B2 (en) | 2001-02-20 | 2009-09-22 | Isis Innovation Limited | Metal-containing dendrimers |
US7632576B2 (en) | 2001-02-20 | 2009-12-15 | Isis Innovation Limited | Aryl-aryl dendrimers |
-
1994
- 1994-06-29 JP JP14773094A patent/JP3284766B2/en not_active Expired - Lifetime
Cited By (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19628719B4 (en) * | 1996-07-17 | 2006-10-05 | Hans-Werner Prof. Dr. Schmidt | Electron-conducting layer in organic, electroluminescent arrangements |
DE19628719A1 (en) * | 1996-07-17 | 1998-01-29 | Bosch Gmbh Robert | Electron-conducting layer in organic, electroluminescent arrangements |
US6824891B2 (en) * | 2000-08-24 | 2004-11-30 | Fuji Photo Film Co., Ltd. | Light-emitting device and material therefor |
US6942916B2 (en) | 2001-01-11 | 2005-09-13 | Hewlett-Packard Development Company, L.P. | Inkjet printable electroluminescent media |
US7960725B2 (en) | 2001-02-20 | 2011-06-14 | Isis Innovation Limited | Aryl-aryl dendrimers |
US7537842B2 (en) | 2001-02-20 | 2009-05-26 | Isis Innovation Limited | Asymmetric dendrimers |
US7592074B2 (en) | 2001-02-20 | 2009-09-22 | Isis Innovation Limited | Metal-containing dendrimers |
US7632576B2 (en) | 2001-02-20 | 2009-12-15 | Isis Innovation Limited | Aryl-aryl dendrimers |
US7906902B2 (en) | 2001-02-20 | 2011-03-15 | Isis Innovation Limited | Metal-containing dendrimers |
US7960557B2 (en) | 2001-02-20 | 2011-06-14 | Isis Innovation Limited | Asymmetric dendrimers |
US8314549B2 (en) | 2001-02-20 | 2012-11-20 | Isis Innovation Limited | Metal-containing dendrimers |
US8319213B2 (en) | 2001-02-20 | 2012-11-27 | Isis Innovation Limited | Aryl-aryl dendrimers |
JP2004063465A (en) * | 2002-07-26 | 2004-02-26 | Xerox Corp | Display device including anthracene derivative and triazine derivative |
JP2006225320A (en) * | 2005-02-17 | 2006-08-31 | Tosoh Corp | 1,3,5-triazine derivative |
JP2006225321A (en) * | 2005-02-17 | 2006-08-31 | Tosoh Corp | Thin film composed of 1,3,5-triazine derivative and method for producing the same thin film |
JP2006225322A (en) * | 2005-02-17 | 2006-08-31 | Tosoh Corp | 1,3,5-triazine derivative and method for producing the same and thin film composed of the same |
Also Published As
Publication number | Publication date |
---|---|
JP3284766B2 (en) | 2002-05-20 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP4058842B2 (en) | Organic electroluminescence device | |
JPH0753953A (en) | Organic electroluminescent element | |
JPH06325871A (en) | Organic electroluminescent element | |
JPH06267658A (en) | Organic el element | |
JP3845941B2 (en) | Imidazole metal complex and organic electroluminescence device using the same | |
JPH07312289A (en) | Organic electroluminescent element | |
JPH09289081A (en) | Organic electroluminous element | |
JP2000150169A (en) | Organic electroluminescence element | |
JP3552317B2 (en) | Manufacturing method of organic electroluminescent device | |
JPH08199161A (en) | Organic electroluminescence element | |
JP3284766B2 (en) | Organic electroluminescent device | |
JP3463364B2 (en) | Organic electroluminescent device | |
JP4030608B2 (en) | Organic electroluminescent device and manufacturing method thereof | |
JPH0888083A (en) | Organic electric field light-emitting device | |
JPH11135262A (en) | Organic electroluminescent element | |
JP3284737B2 (en) | Organic electroluminescent device | |
JP3279014B2 (en) | Organic electroluminescent device | |
JP3807018B2 (en) | Organic electroluminescent device and fluorescent material | |
JPH06330032A (en) | Organic electroluminescent element | |
JPH0790255A (en) | Organic electroluminescent device | |
JPH06336586A (en) | Organic electroluminescent device | |
JPH08269445A (en) | Organic electroluminescent element | |
JPH0762526A (en) | Production of organic electroluminescence element | |
JP3189376B2 (en) | Organic electroluminescent device | |
JP3208833B2 (en) | Organic electroluminescent device |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090308 Year of fee payment: 7 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090308 Year of fee payment: 7 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100308 Year of fee payment: 8 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110308 Year of fee payment: 9 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120308 Year of fee payment: 10 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130308 Year of fee payment: 11 |