JP4013282B2 - Electroluminescent device - Google Patents
Electroluminescent device Download PDFInfo
- Publication number
- JP4013282B2 JP4013282B2 JP11916997A JP11916997A JP4013282B2 JP 4013282 B2 JP4013282 B2 JP 4013282B2 JP 11916997 A JP11916997 A JP 11916997A JP 11916997 A JP11916997 A JP 11916997A JP 4013282 B2 JP4013282 B2 JP 4013282B2
- Authority
- JP
- Japan
- Prior art keywords
- light emitting
- layer
- compound
- emitting layer
- organic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 150000001875 compounds Chemical class 0.000 claims description 11
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 9
- 125000001424 substituent group Chemical group 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 125000000732 arylene group Chemical group 0.000 claims description 3
- 150000002894 organic compounds Chemical class 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
- 229910052736 halogen Inorganic materials 0.000 claims 1
- 150000002367 halogens Chemical class 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- 239000010410 layer Substances 0.000 description 94
- -1 amino compound Chemical class 0.000 description 62
- 239000000463 material Substances 0.000 description 35
- 229910052757 nitrogen Inorganic materials 0.000 description 30
- 229920000642 polymer Polymers 0.000 description 23
- 239000000243 solution Substances 0.000 description 21
- 239000010409 thin film Substances 0.000 description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- 238000002347 injection Methods 0.000 description 14
- 239000007924 injection Substances 0.000 description 14
- 238000007740 vapor deposition Methods 0.000 description 12
- 239000000758 substrate Substances 0.000 description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 239000011521 glass Substances 0.000 description 10
- 230000005525 hole transport Effects 0.000 description 10
- 238000004528 spin coating Methods 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 229910052749 magnesium Inorganic materials 0.000 description 8
- 239000011777 magnesium Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 239000000975 dye Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 6
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 229910052709 silver Inorganic materials 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
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000010408 film Substances 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- 239000007983 Tris buffer Substances 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005401 electroluminescence Methods 0.000 description 4
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- PBWKHJKVLUGQON-UHFFFAOYSA-N 2-(4-tert-butylphenyl)-5-phenyl-1,3,4-oxadiazole Chemical compound C1=CC(C(C)(C)C)=CC=C1C1=NN=C(C=2C=CC=CC=2)O1 PBWKHJKVLUGQON-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- 238000003618 dip coating Methods 0.000 description 3
- 150000002366 halogen compounds Chemical class 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 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 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- BPIUIOXAFBGMNB-UHFFFAOYSA-N 1-hexoxyhexane Chemical compound CCCCCCOCCCCCC BPIUIOXAFBGMNB-UHFFFAOYSA-N 0.000 description 2
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 239000005749 Copper compound Substances 0.000 description 2
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 2
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 2
- 229910021590 Copper(II) bromide Inorganic materials 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- DZBUGLKDJFMEHC-UHFFFAOYSA-N acridine Chemical compound C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 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
- 150000007514 bases Chemical class 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- WDECIBYCCFPHNR-UHFFFAOYSA-N chrysene Chemical compound C1=CC=CC2=CC=C3C4=CC=CC=C4C=CC3=C21 WDECIBYCCFPHNR-UHFFFAOYSA-N 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 150000001880 copper compounds Chemical class 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 2
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 2
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 2
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical compound C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 2
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 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
- 238000006862 quantum yield reaction Methods 0.000 description 2
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 2
- 235000021286 stilbenes Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003623 transition metal compounds Chemical class 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 125000005259 triarylamine group Chemical group 0.000 description 2
- 238000001771 vacuum deposition Methods 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- LXVOEIQSRUCJFV-UHFFFAOYSA-N 1,3-benzothiazole;1,4-diethynylbenzene Chemical compound C1=CC=C2SC=NC2=C1.C1=CC=C2SC=NC2=C1.C#CC1=CC=C(C#C)C=C1 LXVOEIQSRUCJFV-UHFFFAOYSA-N 0.000 description 1
- 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 1
- LFMWZTSOMGDDJU-UHFFFAOYSA-N 1,4-diiodobenzene Chemical compound IC1=CC=C(I)C=C1 LFMWZTSOMGDDJU-UHFFFAOYSA-N 0.000 description 1
- GPYDMVZCPRONLW-UHFFFAOYSA-N 1-iodo-4-(4-iodophenyl)benzene Chemical group C1=CC(I)=CC=C1C1=CC=C(I)C=C1 GPYDMVZCPRONLW-UHFFFAOYSA-N 0.000 description 1
- CNVJJHKQIXYHCJ-UHFFFAOYSA-N 2-(4-tert-butylphenyl)-3,5-diphenyl-2H-1,3,4-oxadiazole Chemical compound C1=CC(C(C)(C)C)=CC=C1C1N(C=2C=CC=CC=2)N=C(C=2C=CC=CC=2)O1 CNVJJHKQIXYHCJ-UHFFFAOYSA-N 0.000 description 1
- PXMXBAVBERHHTA-UHFFFAOYSA-N 2-(4-tert-butylphenyl)-5-(2-phenylphenyl)-1,3,4-oxadiazole Chemical group C1=CC(C(C)(C)C)=CC=C1C1=NN=C(C=2C(=CC=CC=2)C=2C=CC=CC=2)O1 PXMXBAVBERHHTA-UHFFFAOYSA-N 0.000 description 1
- KKUWGQOOWSKPLT-UHFFFAOYSA-N 2-(4-tert-butylphenyl)-5-naphthalen-1-yl-1,3,4-oxadiazole Chemical compound C1=CC(C(C)(C)C)=CC=C1C1=NN=C(C=2C3=CC=CC=C3C=CC=2)O1 KKUWGQOOWSKPLT-UHFFFAOYSA-N 0.000 description 1
- SBMYBOVJMOVVQW-UHFFFAOYSA-N 2-[3-[[4-(2,2-difluoroethyl)piperazin-1-yl]methyl]-4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]pyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound FC(CN1CCN(CC1)CC1=NN(C=C1C=1C=NC(=NC=1)NC1CC2=CC=CC=C2C1)CC(=O)N1CC2=C(CC1)NN=N2)F SBMYBOVJMOVVQW-UHFFFAOYSA-N 0.000 description 1
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 1
- MGADZUXDNSDTHW-UHFFFAOYSA-N 2H-pyran Chemical compound C1OC=CC=C1 MGADZUXDNSDTHW-UHFFFAOYSA-N 0.000 description 1
- CAAMSDWKXXPUJR-UHFFFAOYSA-N 3,5-dihydro-4H-imidazol-4-one Chemical compound O=C1CNC=N1 CAAMSDWKXXPUJR-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
- XJYWOYRBUISMBM-UHFFFAOYSA-N 3-(4-tert-butylphenyl)-4,5-diphenyl-1,2,4-triazole Chemical compound C1=CC(C(C)(C)C)=CC=C1C(N1C=2C=CC=CC=2)=NN=C1C1=CC=CC=C1 XJYWOYRBUISMBM-UHFFFAOYSA-N 0.000 description 1
- ZVFQEOPUXVPSLB-UHFFFAOYSA-N 3-(4-tert-butylphenyl)-4-phenyl-5-(4-phenylphenyl)-1,2,4-triazole Chemical compound C1=CC(C(C)(C)C)=CC=C1C(N1C=2C=CC=CC=2)=NN=C1C1=CC=C(C=2C=CC=CC=2)C=C1 ZVFQEOPUXVPSLB-UHFFFAOYSA-N 0.000 description 1
- CCGYIVMDUOVUEG-UHFFFAOYSA-N 3-(4-tert-butylphenyl)-5-naphthalen-1-yl-4-phenyl-1,2,4-triazole Chemical compound C1=CC(C(C)(C)C)=CC=C1C(N1C=2C=CC=CC=2)=NN=C1C1=CC=CC2=CC=CC=C12 CCGYIVMDUOVUEG-UHFFFAOYSA-N 0.000 description 1
- OAIASDHEWOTKFL-UHFFFAOYSA-N 3-methyl-n-[4-[4-(n-(4-methylphenyl)anilino)phenyl]phenyl]-n-phenylaniline Chemical compound C1=CC(C)=CC=C1N(C=1C=CC(=CC=1)C=1C=CC(=CC=1)N(C=1C=CC=CC=1)C=1C=C(C)C=CC=1)C1=CC=CC=C1 OAIASDHEWOTKFL-UHFFFAOYSA-N 0.000 description 1
- CMSGUKVDXXTJDQ-UHFFFAOYSA-N 4-(2-naphthalen-1-ylethylamino)-4-oxobutanoic acid Chemical compound C1=CC=C2C(CCNC(=O)CCC(=O)O)=CC=CC2=C1 CMSGUKVDXXTJDQ-UHFFFAOYSA-N 0.000 description 1
- FDRNXKXKFNHNCA-UHFFFAOYSA-N 4-(4-anilinophenyl)-n-phenylaniline Chemical compound C=1C=C(C=2C=CC(NC=3C=CC=CC=3)=CC=2)C=CC=1NC1=CC=CC=C1 FDRNXKXKFNHNCA-UHFFFAOYSA-N 0.000 description 1
- KVCQTKNUUQOELD-UHFFFAOYSA-N 4-amino-n-[1-(3-chloro-2-fluoroanilino)-6-methylisoquinolin-5-yl]thieno[3,2-d]pyrimidine-7-carboxamide Chemical compound N=1C=CC2=C(NC(=O)C=3C4=NC=NC(N)=C4SC=3)C(C)=CC=C2C=1NC1=CC=CC(Cl)=C1F KVCQTKNUUQOELD-UHFFFAOYSA-N 0.000 description 1
- UYEBVQUTQHTYOU-UHFFFAOYSA-N 5-methyl-2-[4-[2-(5-methyl-1,3-benzoxazol-2-yl)ethenyl]phenyl]-1,3-benzoxazole Chemical compound CC1=CC=C2OC(C3=CC=C(C=C3)C=CC=3OC4=CC=C(C=C4N=3)C)=NC2=C1 UYEBVQUTQHTYOU-UHFFFAOYSA-N 0.000 description 1
- XPLXHDHGYSONMX-UHFFFAOYSA-N 5-methyl-2-[5-(5-methyl-1,3-benzoxazol-2-yl)thiophen-2-yl]-1,3-benzoxazole Chemical compound CC1=CC=C2OC(C3=CC=C(S3)C=3OC4=CC=C(C=C4N=3)C)=NC2=C1 XPLXHDHGYSONMX-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- CQTPRVJDDLSZBU-UHFFFAOYSA-N C1(=CC=CC=C1)N1N=C(OC1C1=CC=C(C=C1)C(C)(C)C)C1=C(C=CC=C1)C1=CC=CC=C1 Chemical group C1(=CC=CC=C1)N1N=C(OC1C1=CC=C(C=C1)C(C)(C)C)C1=C(C=CC=C1)C1=CC=CC=C1 CQTPRVJDDLSZBU-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- WRYCSMQKUKOKBP-UHFFFAOYSA-N Imidazolidine Chemical compound C1CNCN1 WRYCSMQKUKOKBP-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- UTGQNNCQYDRXCH-UHFFFAOYSA-N N,N'-diphenyl-1,4-phenylenediamine Chemical compound C=1C=C(NC=2C=CC=CC=2)C=CC=1NC1=CC=CC=C1 UTGQNNCQYDRXCH-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000006887 Ullmann reaction Methods 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- NTRBURYSRIHYAZ-UHFFFAOYSA-N [O-2].[Al+3].CC1=NC2=C(C=CC=C2C=C1)O.CC1=NC2=C(C=CC=C2C=C1)O.[O-2].[O-2].[Al+3] Chemical compound [O-2].[Al+3].CC1=NC2=C(C=CC=C2C=C1)O.CC1=NC2=C(C=CC=C2C=C1)O.[O-2].[O-2].[Al+3] NTRBURYSRIHYAZ-UHFFFAOYSA-N 0.000 description 1
- UMRSVAKGZBVPKD-UHFFFAOYSA-N acetic acid;copper Chemical compound [Cu].CC(O)=O UMRSVAKGZBVPKD-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000011162 ammonium carbonates Nutrition 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 150000004982 aromatic amines Chemical class 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
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 125000000319 biphenyl-4-yl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 1
- XZCJVWCMJYNSQO-UHFFFAOYSA-N butyl pbd Chemical compound C1=CC(C(C)(C)C)=CC=C1C1=NN=C(C=2C=CC(=CC=2)C=2C=CC=CC=2)O1 XZCJVWCMJYNSQO-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229940116318 copper carbonate Drugs 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 description 1
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 description 1
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 1
- WIVXEZIMDUGYRW-UHFFFAOYSA-L copper(i) sulfate Chemical compound [Cu+].[Cu+].[O-]S([O-])(=O)=O WIVXEZIMDUGYRW-UHFFFAOYSA-L 0.000 description 1
- GQDHEYWVLBJKBA-UHFFFAOYSA-H copper(ii) phosphate Chemical compound [Cu+2].[Cu+2].[Cu+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GQDHEYWVLBJKBA-UHFFFAOYSA-H 0.000 description 1
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 1
- 229960000956 coumarin Drugs 0.000 description 1
- 235000001671 coumarin Nutrition 0.000 description 1
- 229940076286 cupric acetate Drugs 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- 229940112669 cuprous oxide Drugs 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- SMBQBQBNOXIFSF-UHFFFAOYSA-N dilithium Chemical compound [Li][Li] SMBQBQBNOXIFSF-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000007857 hydrazones Chemical class 0.000 description 1
- NBGMRMDAEWWFIR-UHFFFAOYSA-N imidazole-2-thione Chemical compound S=C1N=CC=N1 NBGMRMDAEWWFIR-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- YAXXPIKOJGJMBA-UHFFFAOYSA-N lithium yttrium Chemical compound [Li].[Y] YAXXPIKOJGJMBA-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- BSEKBMYVMVYRCW-UHFFFAOYSA-N n-[4-[3,5-bis[4-(n-(3-methylphenyl)anilino)phenyl]phenyl]phenyl]-3-methyl-n-phenylaniline Chemical compound CC1=CC=CC(N(C=2C=CC=CC=2)C=2C=CC(=CC=2)C=2C=C(C=C(C=2)C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=C(C)C=CC=2)C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=C(C)C=CC=2)=C1 BSEKBMYVMVYRCW-UHFFFAOYSA-N 0.000 description 1
- 229910001120 nichrome Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229960003540 oxyquinoline Drugs 0.000 description 1
- 150000002941 palladium compounds Chemical class 0.000 description 1
- DGBWPZSGHAXYGK-UHFFFAOYSA-N perinone Chemical compound 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
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 1
- 229920000548 poly(silane) polymer Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical compound O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 description 1
- DNXIASIHZYFFRO-UHFFFAOYSA-N pyrazoline Chemical compound C1CN=NC1 DNXIASIHZYFFRO-UHFFFAOYSA-N 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 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
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- IBBLKSWSCDAPIF-UHFFFAOYSA-N thiopyran Chemical compound S1C=CC=C=C1 IBBLKSWSCDAPIF-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- JFLKFZNIIQFQBS-FNCQTZNRSA-N trans,trans-1,4-Diphenyl-1,3-butadiene Chemical compound C=1C=CC=CC=1\C=C\C=C\C1=CC=CC=C1 JFLKFZNIIQFQBS-FNCQTZNRSA-N 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Images
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Electroluminescent Light Sources (AREA)
- Luminescent Compositions (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、正孔注入電極と電子注入電極との間に少なくとも有機発光層を含む有機薄膜層を有する電界発光素子に関する。
【０００２】
【従来の技術】
近年、情報機器の多様化に伴って、ブラウン管（ＣＲＴ）より低消費電力で薄型の平面表示素子のニーズが高まっている。このような平面表示素子としては液晶、プラズマディスプレイ（ＰＤＰ）等があるが、特に、最近は自己発光型で、表示が鮮明で視野角の広い電界発光素子が注目されている。ここで、上記電界発光素子は構成する材料により無機電界発光素子と有機電界発光素子とに大別することができ、無機電界発光素子は既に実用化され商品として市販されている。
【０００３】
しかしながら、上記無機電界発光素子の駆動電圧は高電界の印加によって、加速された電子が発光中心に衝突して発光させるという、いわゆる衝突型励起発光であるため、１００Ｖ以上の高電圧で駆動させる必要がある。このため、周辺機器の高コスト化を招来するという課題を有していた。また、青色発光の良好な発光体がないためフルカラーの表示ができないという課題もあった。
【０００４】
これに対して、有機電界発光素子は、電極から注入された電荷（正孔および電子）が発光体中で再結合して励起子を生成し、それが発光材料の分子を励起して発光するという、いわゆる注入型発光であるため低電圧で駆動することができる。しかも、有機化合物であるため発光材料の分子構造を容易に変更することができ、任意の発光色を得ることができる。従って、有機電界発光素子はこれからの表示素子として非常に有望である。
【０００５】
ここで、有機電界発光素子は正孔輸送層と電子輸送性発光層の２層を備えた素子が、TangとVanSlykeによって提案された（C.W.Tang and S.A.VanSlyke;Appl.Phys.Lett.,51(1987)913）。その素子の構成は、ガラス基板上に形成した陰極、正孔輸送層、電子輸送性発光層、陰極であった。
【０００６】
上記素子では、正孔輸送層が陽極から電子輸送性発光層へ正孔を注入する働きをするとともに、陰極から注入された電子が正孔と再結合することなく陽極へ逃げるのを防ぎ、電子輸送性発光層内へ電子を封じ込める役割をも果たしている。このため、この正孔輸送層による電子の封じ込め効果により、従来の単層構造の素子に比べてより効率良く電子と正孔の再結合が起こり、駆動電圧の大幅な低下が可能になった。
【０００７】
また、斎藤らは、２層構造の素子において、電子輸送層だけでなく正孔輸送層も発光層と成り得ることを示した（C.Adachi,T.Tsutsui and S.Saito;Appl.Phys.Lett.,55(1989)1489）。
【０００８】
２層構成の改良として正孔輸送層と電子輸送層の間に有機発光層が挟まれた３層構造の有機電界発光素子を斎藤らが提案した（C.Adachi,S.Tokito,T.Tsutsui and S.Saito;Jpn.J.Appl.Phys.,27(1988)L269）。これは、硝子基板上に形成した陽極、正孔輸送層、発光層、電子輸送層、陰極からなり、正孔輸送層が電子を発光層に封じ込める働きをするとともに、電子輸送層が正孔を発光層に封じ込める働きをするため発光効率がさらに向上した。
【０００９】
【発明が解決しようとする課題】
このように有機電界発光素子の発光効率を向上させるために層構成からの改良が行われてきたが、まだまだ発光の高輝度化や高効率化が必要なのが現状である。
また、有機電界発光素子を長時間発光させるためにはより低電圧で低電流密度で発光させることが必要となってくる。
【００１０】
本発明は上記の点に鑑みなされたものであり、高輝度で高効率な発光を呈する耐久性に優れた電界発光素子を提供することを目的とする。
【００１１】
【課題を解決するための手段】
すなわち本発明は、一対の電極間に発光層または発光層を含む複数層の有機化合物薄層を備えた電界発光素子において少なくとも一層が下記一般式（Ｉ）で示される繰り返し単位からなる高分子アミノ化合物を含有することを特徴とする電界発光素子；
【化２】
【００１２】
一般式（Ｉ）で表わされる繰り返し単位からなる特定の高分子アミノ化合物は良好な正孔注入輸送材または有機発光材料となる。
これは、一般式(Ｉ)で表される繰り返し単位からなる高分子アミノ化合物が高い正孔輸送性を持ち、固体での蛍光の量子収率が高いためであると考えられる。
【００１３】
上記一般式（Ｉ）中、Ａr１およびＡr３は、それぞれ独立して、アリーレン基、例えばフェニレン、ジフェニレン等を表わす。それらの基は低級アルキル基、あるいは低級アルコキシ基等の置換基を有していてもよい。
【００１４】
好ましいＡｒ1およびＡｒ3は
【化５】
【００１５】
Ａr2およびＡr4は、それぞれ独立して、置換基を有してもよいアリール基、例えばフェニル、ジフェニル等または複素環基、例えばチエニル、フリル等を表わす。それらの基は低級アルキル基、あるいは低級アルコキシ基等の置換基を有していてもよい。
【００１６】
好ましいＡｒ2およびＡｒ4はフェニル基および低級アルキル基または低級アルコキシ基を置換基として有するフェニル基である。
【００１７】
ｌは０〜２、好ましくは０〜１の整数を表す。ｍは０〜２、好ましくは０〜１の整数を表す。ただし、ｌ、ｍは同時に０ではない。ｎは自然数であり、その値は特に限定されないが、例えば５〜１０００、好ましくは１０〜１０００とすることができる。
【００１８】
本発明において使用する一般式（Ｉ）で表される繰り返し単位からなる高分子アミノ化合物としては、具体的には以下のものが挙げられるが、これらの例示は本発明の範囲を限定するものとして例示するものではない。
【００１９】
【化６】
【化７】
【化８】
【化９】
【化１０】
【化１１】
【化１２】
【化１３】
一般式（Ｉ）で表わされる繰り返し単位からなる高分子アミノ化合物は、Makromol.Chem.193,909頁(1992)等記載の公知の方法で製造することが可能で、例えば、下記アミノ化合物とハロゲン化合物；
【化１６】
【化１７】
【００３０】
合成に用いられる塩基性化合物としては、アルカリ金属の水酸化物、炭酸塩、炭酸水素塩、アルコラートなどが一般的に用いられるが、第４級アンモニウム化合物や脂肪族アミンや芳香族アミンの様な有機塩基を用いることも可能である。このなかでアルカリ金属や第４級アンモニウムの炭酸塩や炭酸水素塩が好ましいものとして用いられる。更に、反応速度および熱安定性という観点からアルカリ金属の炭酸塩や炭酸水素塩が最も好ましい。
【００３１】
合成に用いられる遷移金属または遷移金属化合物としては、例えばＣu、Ｆe；Ｃo、Ｎi、Ｃr、Ｖ、Ｐd、Ｐt、Ａg等の金属およびそれらの化合物が用いられるが、収率の点から銅およびパラジウムとそれらの化合物が好ましい。銅化合物としては特に限定はなく、ほとんどの銅化合物が用いられるが、ヨウ化第一銅、塩化第一銅、酸化第一銅、臭化第一銅、シアン化第一銅、硫酸第一銅、硫酸第二銅、塩化第二銅、水酸化第二銅、酸化第二銅、臭化第二銅、リン酸第二銅、硝酸第一銅、硝酸第二銅、炭酸銅、酢酸第一銅、酢酸第二銅などが好ましい。その中でも特にＣuＣl、ＣuＣl2、ＣuＢr、ＣuＢr2、ＣuI、ＣuＯ、Ｃu2Ｏ、ＣuＳＯ4、Ｃu(ＯＣＯＣＨ3)2は容易に入手可能である点で好適である。パラジウム化合物としても、ハロゲン化物、硫酸塩、硝酸塩、有機酸塩などを用いることができる。遷移金属およびその化合物の使用量は、反応させるハロゲン化合物の０．５〜５００モル％である。
【００３２】
合成に用いられる溶媒は、一般的に用いられる溶媒であれば良いが、ニトロベンゼン、ジメチルホルムアミド、ジメチルスルホキシド、Ｎ−メチルピロリドン等の非プロトン性極性溶媒が好ましく用いられる。
【００３３】
合成反応は、一般的には常圧下１００〜２５０℃での温度で行なわれるが、加圧下に行なってももちろんかまわない。反応終了後、反応液中に析出した固形物を除去した後、溶媒を除去し生成物を得ることができる。
【００３４】
図１〜図４に本発明の電界発光素子の取り得る構成を模式的に示した。図１中、（１）は陽極であり、その上に、正孔注入輸送層（２）と有機発光層（３）および陰極（４）が順次積層された構成をとっており、該正孔注入輸送層に上記一般式（Ｉ）で表わされる繰り返し単位からなる高分子アミノ化合物を含有する。
【００３５】
図２において、（１）は陽極であり、その上に、正孔注入輸送層（２）と有機発光層（３）、電子注入輸送層（５）および陰極（４）が順次積層された構成をとっており、該正孔注入輸送層に上記一般式（Ｉ）で表わされる繰り返し単位からなる高分子アミノ化合物を含有する。
【００３６】
図３において、（１）は陽極であり、その上に、有機発光層（３）と電子注入輸送層（５）および陰極（４）が順次積層された構成をとっており、該有機発光層に上記一般式（Ｉ）で表わされる繰り返し単位からなる高分子アミノ化合物を含有する。
【００３７】
図４において、（１）は陽極であり、その上に、有機発光層（３）および陰極（４）が順次積層された構成をとっており、該有機発光層に有機発光材料（６）と電荷輸送材料（７）が含まれており、該有機発光材料または電荷輸送材料に上記一般式（Ｉ）で表わされる繰り返し単位からなる高分子アミノ化合物を使用する。
【００３８】
上記構成の電界発光素子は陽極（１）と陰極（４）がリード線（８）により接続され、陽極（１）と陰極（４）に電圧を印加することにより有機発光層（３）が発光する。
【００３９】
一般式（Ｉ）で表わされる繰り返し単位からなる特定の高分子アミノ化合物は良好な正孔注入輸送材または有機発光材料となる。
これは、特定の高分子アミノ化合物が高い正孔輸送性を持ち、固体での蛍光の量子収率が高いためであると考えられる。
【００４０】
電界発光素子の陽極（１）として使用される導電性物質としては４ｅＶよりも大きい仕事関数をもつものがよく、炭素、アルミニウム、バナジウム、鉄、コバルト、ニッケル、銅、亜鉛、タングステン、銀、錫、金などおよびそれらの合金、酸化錫、酸化インジウム、酸化アンチモン、酸化亜鉛、酸化ジルコニウムなどの導電性金属化合物が用いられる。
【００４１】
陰極（４）を形成する金属としては４ｅＶよりも小さい仕事関数を持つものがよく、マグネシウム、カルシウム、チタニウム、イットリウムリチウム、ガドリニウム、イッテルビウム、ルテニウム、マンガンおよびそれらの合金が用いられる。
【００４２】
電界発光素子においては、発光が見られるように、少なくとも陽極（１）あるいは陰極（４）は透明電極にする必要がある。この際、陰極に透明電極を使用すると、透明性が損なわれやすいので、陽極を透明電極にすることが好ましい。
【００４３】
透明電極を形成する場合、透明基板上に、上記したような導電性物質を用い、蒸着、スパッタリング等の手段やゾル・ゲル法あるいは樹脂等に分散させて塗布する等の手段を用いて所望の透光性と導電性が確保されるように形成すればよい。
【００４４】
透明基板としては、適度の強度を有し、電界発光素子作製時、蒸着等による熱に悪影響を受けず、透明なものであれば特に限定されないが、係るものを例示すると、ガラス基板、透明な樹脂、例えばポリエチレン、ポリプロピレン、ポリエーテルサルホン、ポリエーテルエーテルケトン等を使用することも可能である。ガラス基板上に透明電極が形成されたものとしてはＩＴＯ、ＮＥＳＡ等の市販品が知られているがこれらを使用してもよい。
【００４５】
上記電極を用いて図２の構成の電界発光素子の作製を例示的に説明する。
【００４６】
まず、上記した陽極（１）上に正孔注入輸送層（２）を形成する。正孔注入輸送層（２）は、一般式（Ｉ）で表される繰り返し単位からなる高分子アミノ化合物を溶解した溶液や適当な樹脂とともに溶解した液をディップコートやスピンコートして形成することができる。その厚さは、通常、５〜１０００ｎｍ、好ましくは１０〜５００ｎｍ程度にすればよい。
【００４７】
形成する膜厚が厚いほど発光させるための印加電圧を高くする必要があり発光効率が悪くなり、電界発光素子の劣化を招きやすい。また膜厚が薄くなると発光効率はよくなるがブレイクダウンしやすくなり電界発光素子の寿命が短くなる。
【００４８】
一般式（Ｉ）で表される繰り返し単位からなる高分子アミノ化合物は他の電荷輸送材料と併用してもよく、かかる電荷輸送材料としては、発光層または発光物質に対して優れたホール注入効果を有し、高移動度で、発光層で生成した励起子の電子注入層または電子輸送材料への移動を防止し、かつ薄膜形成能の優れた化合物が挙げられる。
【００４９】
具体的には、フタロシアニン化合物、ナフタロシアニン化合物、ポルフィリン化合物、オキサジアゾール、トリアゾール、イミダゾール、イミダゾロン、イミダゾールチオン、ピラゾリン、ピラゾロン、テトラヒドロイミダゾール、オキサゾール、オキサジアゾール、ヒドラゾン、アシルヒドラゾン、ポリアリールアルカン、スチルベン、ブタジエン、ベンジジン型トリアリールアミン、ジアミン型トリアリールアミン等と、それらの誘導体、およびポリビニルカルバゾール、ポリシラン、導電性高分子等の高分子材料等があるが、これらに限定されるものではない。
【００５０】
後述するように、一般式（Ｉ）で表される繰り返し単位からなる高分子アミノ化合物を有機発光層（３）の発光材料として使用する場合、正孔注入輸送層に用いられる正孔輸送材料としては、公知のもの、例えばＮ，Ｎ’−ジフェニル−Ｎ，Ｎ’−ビス（３−メチルフェニル）−１，１’−ジフェニル−４，４’−ジアミン、Ｎ，Ｎ’−ジフェニル−Ｎ，Ｎ’−ビス（４−メチルフェニル）−１，１’−ジフェニル−４，４’−ジアミン、Ｎ，Ｎ’−ジフェニル−Ｎ，Ｎ’−ビス（１−ナフチル）−１，１’−ジフェニル−４，４’−ジアミン、Ｎ，Ｎ’−ジフェニル−Ｎ，Ｎ’−ビス（２−ナフチル）−１，１’−ジフェニル−４，４’−ジアミン、Ｎ，Ｎ’−テトラ（４−メチルフェニル）−１，１’−ジフェニル−４，４’−ジアミン、Ｎ，Ｎ’−テトラ（４−メチルフェニル）−１，１’−ビス（３−メチルフェニル）−４，４’−ジアミン、Ｎ，Ｎ’−ジフェニル−Ｎ，Ｎ’−ビス（３−メチルフェニル）−１，１’−ビス（３−メチルフェニル）−４，４’−ジアミン、Ｎ，Ｎ’−ビス（Ｎ−カルバゾリル）−１，１’−ジフェニル−４，４’−ジアミン、４，４’，４”−トリス（Ｎ−カルバゾリル）トリフェニルアミン、Ｎ，Ｎ’，Ｎ”−トリフェニル−Ｎ，Ｎ’，Ｎ”−トリス（３−メチルフェニル）−１，３，５−トリ（４−アミノフェニル）ベンゼン、４，４’，４”−トリス［Ｎ，Ｎ’，Ｎ”−トリフェニル−Ｎ，Ｎ’，Ｎ”−トリス（３−メチルフェニル）］トリフェニルアミン等を挙げることができる。こららのものは２種以上を混合して使用してもよい。
【００５１】
次に、正孔注入輸送層（２）の上に有機発光層（３）を形成する。有機発光層に用いられる有機発光体、発光補助材料としては、公知のものを使用可能で、例えばエピドリジン、２，５−ビス［５，７−ジ−ｔ−ペンチル−２−ベンゾオキサゾリル］チオフェン、２，２’−（１，４−フェニレンジビニレン）ビスベンゾチアゾール、２，２’−（４，４’−ビフェニレン）ビスベンゾチアゾール、５−メチル−２−｛２−［４−（５−メチル−２−ベンゾオキサゾリル）フェニル］ビニル｝ベンゾオキサゾール、２，５−ビス（５−メチル−２−ベンゾオキサゾリル）チオフェン、アントラセン、ナフタレン、フェナントレン、ピレン、クリセン、ペリレン、ペリノン、１，４−ジフェニルブタジエン、テトラフェニルブタジエン、クマリン、アクリジン、スチルベン、２−（４−ビフェニル）−６−フェニルベンゾオキサゾール、アルミニウムトリスオキシン、マグネシウムビスオキシン、ビス（ベンゾ−８−キノリノール）亜鉛、ビス（２−メチル−８−キノリノール）アルミニウムオキサイド、インジウムトリスオキシン、アルミニウムトリス（５−メチルオキシン）、リチウムオキシン、ガリウムトリスオキシン、カルシウムビス（５−クロロオキシン）、ポリ亜鉛−ビス（８−ヒドロキシ−５−キノリノリル）メタン、ジリチウムエピンドリジオン、亜鉛ビスオキシン、１，２−フタロペリノン、１，２−ナフタロペリノンなどを挙げることができる。
【００５２】
また、一般的な螢光染料、例えば螢光クマリン染料、螢光ペリレン染料、螢光ピラン染料、螢光チオピラン染料、螢光ポリメチン染料、螢光メシアニン染料、螢光イミダゾール染料等も使用できる。このうち、特に、好ましいものとしては、キレート化オキシノイド化合物が挙げられる。
【００５３】
有機発光層は上記した発光物質の単層構成でもよいし、発光の色、発光の強度等の特性を調整するために、多層構成としてもよい。また、２種以上の発光物質を混合したり発光層にドープしてもよい。
【００５４】
有機発光層（３）は、上記のような発光物質を蒸着して形成してもよいし、該発光物質を溶解した溶液や適当な樹脂とともに溶解した液をディップコートやスピンコートして形成してもよい。
【００５５】
有機発光層には、一般式（Ｉ）で表わされる繰り返し単位からなる高分子アミノ化合物を発光物質として用いることもできる。有機発光層は高分子アミノ化合物の単層構成でもよいし、発光の色、発光の強度等の特性を調整するために、多層構成としてもよい。また、２種以上の発光物質を混合したり発光層にドープしてもよい。
【００５６】
一般式（Ｉ）で表される繰り返し単位からなる高分子アミノ化合物を用いて発光層を形成する場合、高分子アミノ化合物を溶解した溶液や適当な樹脂とともに溶解した液をディップコートやスピンコートして形成することができる。その厚さは、通常、５〜１０００ｎｍ程度、好ましくは１０〜５００ｎｍ程度にすればよい。
【００５７】
形成する膜厚が厚いほど発光させるための印加電圧を高くする必要があり発光効率が悪く有機電界発光素子の劣化を招きやすい。また膜厚が薄くなると発光効率はよくなるがブレイクダウンしやすくなり発光素子の寿命が短くなる。
【００５８】
有機発光層（３）の上には電子注入輸送層（５）を形成する。電子注入輸送層に使用される電子注入輸送材料としては、電子を輸送する能力を持ち、発光層または発光物質に対して優れた電子注入効果を有し、電子移動性が大きく正孔注入輸送材料から正孔の移動を防止し、かつ薄膜形成能の優れた化合物が挙げられる。
【００５９】
例えば、２−（４−ビフェニルイル）−５−（４−tert−ブチルフェニル）−１，３，４−オキサジアゾール、２−（１−ナフチル）−５−（４−tert−ブチルフェニル）−１，３，４−オキサジアゾール、１，４−ビス｛２−［５−（４−tert−ブチルフェニル）−１，３，４−オキサジアゾリル］｝ベンゼン、１，３−ビス｛２−［５−（４−tert−ブチルフェニル）−１，３，４−オキサジアゾリル］｝ベンゼン、４，４’−ビス｛２−［５−（４−tert−ブチルフェニル）−１，３，４−オキサジアゾリル］｝ビフェニル、２−（４−ビフェニルイル）−５−（４−tert−ブチルフェニル）−１，３，４−チオジアゾール、２−（１−ナフチル）−５−（４−tert−ブチルフェニル）−１，３，４−チオジアゾール、１，４−ビス｛２−［５−（４−tert−ブチルフェニル）−１，３，４−チオジアゾリル］｝ベンゼン、１，３−ビス｛２−［５−（４−tert−ブチルフェニル）−１，３，４−チオジアゾリル］｝ベンゼン、４，４’−ビス｛２−［５−（４−tert−ブチルフェニル）−１，３，４−チオジアゾリル］｝ビフェニル、３−（４−ビフェニルイル）−４−フェニル−５−（４−tert−ブチルフェニル）−１，２，４−トリアゾール、３−（１−ナフチル）−４−フェニル−５−（４−tert−ブチルフェニル）−１，２，４−トリアゾール、１，４−ビス｛３−［４−フェニル−５−（４−tert−ブチルフェニル）−１，２，４−トリアゾリル］｝ベンゼン、１，３−ビス｛３−［４−フェニル−５−（４−tert−ブチルフェニル）−１，３，４−オキサジアゾリル］｝ベンゼン、４，４’−ビス｛２−［４−フェニル−５−（４−tert−ブチルフェニル）−１，３，４−オキサジアゾリル］｝ビフェニル、１，３，５−トリス｛２−［５−（４−tert−ブチルフェニル）−１，３，４−オキサジアゾリル］｝ベンゼンなどを挙げることができる。これらのものは、２種以上を混合して使用してもよい。次に、電子注入輸送層の上に、前記した陰極を形成する。
【００６０】
以上、陽極（１）上に正孔注入輸送層（２）、発光層（３）および電子注入輸送層（５）、陰極（４）を順次積層して電界発光素子を形成する場合について説明したが、陽極（１）上に発光層（３）、電子注入輸送層（５）および陰極を順次積層したり（図３）、陰極（４）上に、電子注入輸送層（５）、有機感光層（３）および、陽極（１）を順次積層したり、陽極（１）上に正孔注入輸送層（２）、発光層（３）および、陰極（４）を順次積層したり（図１）、陰極（４）上に電子注入輸送層（５）、発光層（３）および、正孔注入輸送層（２）、陽極（１）を順次積層したりしてももちろん構わない。
【００６１】
陰極と陽極の１組の透明電極は、各電極にニクロム線、金線、銅線、白金線等の適当なリード線（８）を接続し、電界発光素子は両電極に適当な電圧（Ｖｓ）を印加することにより発光する。
【００６２】
本発明の電界発光素子は、各種の表示装置、あるいはディスプレイ装置等に適用可能である。
【００６３】
以下に実施例を記載し本発明を説明する。なお、本発明の有機電界発光素子は発光効率、発光輝度の向上と長寿命化を達成するものであり、併せて使用される発光物質、発光補助材料、電荷輸送材料、増感剤、樹脂、電極材料等および素子作製方法に限定されるものではない。
【００６４】
合成例１（化合物（１）の合成）
Ｎ，Ｎ’−ジフェニル−１，４−フェニレンジアミン１３．０ｇ（５０ｍｍｏｌ）をジヘキシルエーテル２５０ｍｌに溶解させ、その溶液に１００ｍｍｏｌのブチルリチウムのヘキサン溶液をゆっくりと滴下した。その後、１１０℃で２時間撹拌させた後、１６．５ｇ（５０ｍｍｏｌ）の１，４−ジヨードベンゼンと０．４８ｇ（２５ｍｍｏｌ）のヨウ化銅を加え、２００℃で１６時間反応させた。
【００６５】
冷却後、得られた反応液をろ過し、沸騰テトラヒドロフランで３回抽出した。テトラヒドロフラン溶液を濃縮し、メタノール溶液にパージさせて目的のポリマーを得た。この操作を３回繰り返した。
【００６６】
合成例２（化合物（８）の合成）
Ｎ，Ｎ’−ジフェニルベンジジン１６．８ｇ（５０ｍｍｏｌ）をジヘキシルエーテル２５０ｍｌに溶解させ、その溶液に１００ｍｍｏｌのブチルリチウムのヘキサン溶液をゆっくりと滴下した。その後、１１０℃で２時間撹拌させた後、１９．３ｇ（５０ｍｍｏｌ）の４，４’−ジヨードビフェニルと０．４８ｇ（２５ｍｍｏｌ）のヨウ化銅を加え、２００℃で２４時間反応させた。
【００６７】
冷却後、得られた反応液をろ過し、沸騰テトラヒドロフランで３回抽出した。ろ液とテトラヒドロフラン溶液を濃縮し、メタノール溶液にパージさせて目的のポリマーを得た。この操作を３回繰り返した。
【００６８】
実施例１
インジウムスズ酸化物被覆ガラスの基板上に有機ホール注入輸送層として高分子アミノ化合物（１）のジクロルメタン溶液をスピンコート法により厚さ５０ｎｍの薄膜を形成した。
【００６９】
次に、有機発光層としてアルミニウムトリスオキシンを真空蒸着により５０ｎｍの厚さになるように薄膜を形成した。
【００７０】
最後に、陰極としてマグネシウムを真空蒸着により２００ｎｍの厚さになるように薄膜を形成した。このようにして、有機電界発光素子装置を作製した。
【００７１】
実施例２〜４
実施例１において、高分子アミノ化合物（１）を使用する代わりに、高分子アミノ化合物（２）、（３）、（４）に代えること以外は実施例１と全く同様にして有機電界発光素子を作製した。
【００７２】
実施例５
インジウムスズ酸化物被覆ガラスの基板上に有機正孔注入輸送層として高分子アミノ化合物（７）のジクロルメタン溶液をスピンコート法により厚さ７０ｎｍの薄膜を形成した。
【００７３】
次に、有機発光層としてアルミニウムトリスオキシンを蒸着により１００ｎｍの厚さになるように薄膜を形成した。
【００７４】
さらに有機電子注入輸送層として下記のオキサジアゾール化合物（Ａ）を蒸着により５０ｎｍの厚さになるように薄膜を形成した。
【化１８】
【００７５】
実施例６〜８
実施例５において、高分子アミノ化合物（７）を使用する代わりに、高分子アミノ化合物（８）、（９）、（１０）に代えること以外は実施例５と全く同様にして有機電界発光素子を作製した。
【００７６】
実施例９
インジウムスズ酸化物被覆ガラスの基板上に発光層として高分子アミノ化合物（１１）のジクロルメタン溶液をスピンコート法により厚さ５０ｎｍの薄膜を形成した。
次に、有機電子注入輸送層としてオキサジアゾール化合物（Ａ）を蒸着により２０ｎｍの厚さになるように薄膜を形成した。
最後に、陰極として１０：１の原子比のＭｇおよびＡｇを蒸着により２００ｎｍの厚さになるように薄膜を形成した。このようにして、有機電界発光素子を作製した。
【００７７】
実施例１０
インジウムスズ酸化物被覆ガラスの基板上に有機正孔注入輸送層として高分子アミノ化合物（１３）のジクロルメタン溶液をスピンコート法により厚さ２０ｎｍの薄膜を形成した。
さらに、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’−ジアミンを真空蒸着して、膜厚４０ｎｍの正孔輸送層を得た。
次に、トリス（８−ヒドロキシキノリン）アルミニウム錯体を蒸着により５０ｎｍの厚さになるように薄膜を形成した。
最後に、陰極として１０：１の原子比のＭｇおよびＡｇを蒸着により２００ｎｍの厚さになるように薄膜を形成した。このようにして、有機電界発光素子を作製した。
【００７８】
実施例１１
インジウムスズ酸化物被覆ガラスの基板上に高分子アミノ化合物（１４）をジクロルメタンに溶解させ、スピンコーティングにより膜厚５０ｎｍの正孔注入層を得た。
次に、トリス（８−ヒドロキシキノリン）アルミニウム錯体を蒸着により２０ｎｍの厚さになるように発光層を形成した。
さらに真空蒸着法によりオキサジアゾール化合物（Ａ）の膜厚２０ｎｍの電子注入層を得た。
最後に、陰極として１０：１の原子比のＭｇおよびＡｇを蒸着により２００ｎｍの厚さになるように薄膜を形成した。このようにして、有機電界発光素子を作製した。
【００７９】
実施例１２〜１３および参考例１
実施例１１において、高分子アミノ化合物（１４）を使用する代わりに、高分子アミノ化合物（１８）、（１９）、（２１）に代えること以外は実施例１１と全く同様にして有機電界発光素子を作製した。
【００８０】
参考例２
インジウムスズ酸化物被覆ガラスの基板上に高分子アミノ化合物（２４）、トリス（８−ヒドロキシキノリン）アルミニウム錯体を３：２の比率でテトラヒドロフランに溶解させ、スピンコーティング法により膜厚１００ｎｍの発光層を得た。
次に、陰極として１０：１の原子比のＭｇおよびＡｇを蒸着により２００ｎｍの厚さになるように薄膜を形成した。このようにして、有機電界発光素子を作製した。
【００８１】
実施例１４〜１６
参考例２において、高分子アミノ化合物（２４）を使用する代わりに、高分子アミノ化合物（２９ ）、（３１）、（３６）に代えること以外は参考例２と全く同様にして有機電界発光素子を作製した。
【００８２】
評価
実施例１〜１６および参考例１および２で得られた電界発光素子を、そのガラス電極を陽極として、直流電圧を除々に電圧を印加した時に発光を開始する電圧および、最高発光輝度とその時の電圧を測定した。結果を表１にまとめて示す。
【００８３】
【表１】
表１からわかるように、本実施例の有機電界発光素子は低電位で発光を開始し、良好な発光輝度を示した。
また、実施例１で得られた素子を、窒素ガス不活性雰囲気下で初期６Ｖで連続発光させて、その発光輝度の半減期（輝度が半分になるまでの時間）を測定したところ２００時間であった。
【００８５】
本実施例の有機電界発光素子は出力低下が少なく、寿命の長い安定な発光を観測することができた。
【００８６】
【発明の効果】
本発明により、有機発光層に上記一般式（Ｉ）で表わされる繰り返し単位からなる高分子アミノ化合物を含有することにより、光強度が大きく発光開始電圧が低い耐久性に優れた電界発光素子を得ることができる。
【図面の簡単な説明】
【図１】 電界発光素子の一構成例の概略構成図。
【図２】 電界発光素子の一構成例の概略構成図。
【図３】 電界発光素子の一構成例の概略構成図。
【図４】 電界発光素子の一構成例の概略構成図。
【符号の説明】
１：陽極
２：正孔注入輸送層
３：有機発光層
４：陰極
５：電子注入輸送層
６：有機発光材料
７：電荷輸送材料
８：リード線[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an electroluminescent device having an organic thin film layer including at least an organic light emitting layer between a hole injection electrode and an electron injection electrode.
[0002]
[Prior art]
In recent years, with the diversification of information equipment, there is an increasing need for flat display elements that are lower in power consumption than cathode ray tubes (CRT). As such flat display elements, there are liquid crystal, plasma display (PDP) and the like. Recently, however, an electroluminescent element of a self-luminous type, a clear display and a wide viewing angle has attracted attention. Here, the electroluminescent element can be roughly classified into an inorganic electroluminescent element and an organic electroluminescent element depending on the constituent materials, and the inorganic electroluminescent element has already been put into practical use and is commercially available as a commercial product.
[0003]
However, the driving voltage of the inorganic electroluminescent element is so-called collision-type excitation light emission in which accelerated electrons collide with the light emission center to emit light when a high electric field is applied. Therefore, it is necessary to drive with a high voltage of 100 V or more. There is. For this reason, there has been a problem of incurring higher costs for peripheral devices. There is also a problem that full color display cannot be performed because there is no illuminant that emits blue light.
[0004]
On the other hand, in the organic electroluminescence device, charges (holes and electrons) injected from the electrodes recombine in the luminescent material to generate excitons, which excite molecules of the luminescent material to emit light. Since it is so-called injection type light emission, it can be driven at a low voltage. And since it is an organic compound, the molecular structure of a luminescent material can be changed easily and arbitrary luminescent colors can be obtained. Therefore, the organic electroluminescent element is very promising as a display element in the future.
[0005]
Here, an organic electroluminescent device having two layers of a hole transport layer and an electron transport light emitting layer was proposed by Tang and VanSlyke (CWTang and SAVanSlyke; Appl. Phys. Lett., 51 ( 1987) 913). The device was composed of a cathode, a hole transport layer, an electron transporting light emitting layer, and a cathode formed on a glass substrate.
[0006]
In the above element, the hole transport layer functions to inject holes from the anode to the electron transporting light emitting layer, and prevents electrons injected from the cathode from escaping to the anode without recombining with the holes. It also plays a role of containing electrons in the transporting light emitting layer. For this reason, due to the electron confinement effect by the hole transport layer, recombination of electrons and holes occurs more efficiently than the conventional single layer structure device, and the driving voltage can be greatly reduced.
[0007]
Saito et al. Also showed that not only an electron transport layer but also a hole transport layer can be a light-emitting layer in a two-layer device (C. Adachi, T. Tsutsui and S. Saito; Appl. Phys. Lett., 55 (1989) 1489).
[0008]
Saito et al. Proposed an organic electroluminescent device with a three-layer structure in which an organic light emitting layer is sandwiched between a hole transport layer and an electron transport layer (C. Adachi, S. Tokito, T. Tsutsui). and S. Saito; Jpn. J. Appl. Phys., 27 (1988) L269). This consists of an anode, a hole transport layer, a light emitting layer, an electron transport layer, and a cathode formed on a glass substrate. The hole transport layer functions to contain electrons in the light emitting layer, and the electron transport layer contains holes. Luminous efficiency is further improved because it functions to be contained in the light emitting layer.
[0009]
[Problems to be solved by the invention]
As described above, in order to improve the light emission efficiency of the organic electroluminescence device, the layer structure has been improved. However, the present situation is that it is necessary to increase the luminance and the efficiency of the light emission.
In addition, in order for the organic electroluminescence device to emit light for a long time, it is necessary to emit light at a lower voltage and a lower current density.
[0010]
The present invention has been made in view of the above points, and an object of the present invention is to provide an electroluminescent element excellent in durability that emits light with high luminance and high efficiency.
[0011]
[Means for Solving the Problems]
That is, according to the present invention, at least one layer is represented by the following general formula (I) in an electroluminescent element comprising a light emitting layer or a plurality of organic compound thin layers including a light emitting layer between a pair of electrodes.Consists of repeating unitsAn electroluminescent device comprising a polymeric amino compound;
[Chemical 2]
[0012]
Represented by general formula (I)Consists of repeating unitsCertain polymeric amino compounds are good hole injecting and transporting materials or organic light emitting materials.
This is represented by the general formula (I)Consists of repeating unitsThis is probably because the polymer amino compound has a high hole transport property and a high quantum yield of fluorescence in the solid state.
[0013]
In the general formula (I), Ar1And Ar3Each independently represents an arylene group such as phenylene, diphenylene and the like. These groups may have a substituent such as a lower alkyl group or a lower alkoxy group..
[0014]
Preferred Ar1And ArThreeIs
[Chemical formula 5]
[0015]
Ar2And ArFourEach independently represents an optionally substituted aryl group such as phenyl, diphenyl and the like or a heterocyclic group such as thienyl and furyl. These groups may have a substituent such as a lower alkyl group or a lower alkoxy group.
[0016]
Preferred Ar2And ArFourIs a phenyl group having a phenyl group and a lower alkyl group or lower alkoxy group as a substituent.
[0017]
l represents an integer of 0 to 2, preferably 0 to 1. m represents an integer of 0 to 2, preferably 0 to 1. However, l and m are not 0 at the same time. n is a natural number, and the value is not particularly limited, but may be, for example, 5 to 1000, preferably 10 to 1000.
[0018]
It is represented by the general formula (I) used in the present invention.Consists of repeating unitsSpecific examples of the polymer amino compound include the following, but these examples are not intended to limit the scope of the present invention.
[0019]
[Chemical 6]
[Chemical 7]
[Chemical 8]
[Chemical 9]
[Chemical Formula 10]
Embedded image
Embedded image
Embedded image
Represented by general formula (I)Consists of repeating unitsThe polymeric amino compound can be produced by a known method described in Makromol. Chem. 193, page 909 (1992), for example, the following amino compound and halogen compound;
Embedded image
Embedded image
[0030]
As basic compounds used for synthesis, alkali metal hydroxides, carbonates, hydrogen carbonates, alcoholates, etc. are generally used, but quaternary ammonium compounds, aliphatic amines, aromatic amines and the like are used. It is also possible to use organic bases. Of these, alkali metals and quaternary ammonium carbonates and hydrogen carbonates are preferably used. Further, alkali metal carbonates and hydrogen carbonates are most preferred from the viewpoints of reaction rate and thermal stability.
[0031]
As the transition metal or transition metal compound used in the synthesis, for example, metals such as Cu, Fe; Co, Ni, Cr, V, Pd, Pt, and Ag and their compounds are used. From the viewpoint of yield, copper and Palladium and their compounds are preferred. The copper compound is not particularly limited, and most copper compounds are used, but cuprous iodide, cuprous chloride, cuprous oxide, cuprous bromide, cuprous cyanide, cuprous sulfate , Cupric sulfate, cupric chloride, cupric hydroxide, cupric oxide, cupric bromide, cupric phosphate, cuprous nitrate, cupric nitrate, copper carbonate, first acetic acid Copper, cupric acetate and the like are preferable. Among them, especially CuCl, CuCl2, CuBr, CuBr2, CuI, CuO, Cu2O, CuSOFour, Cu (OCOCHThree)2Is preferable in that it is easily available. As the palladium compound, halides, sulfates, nitrates, organic acid salts and the like can be used. The amount of the transition metal and its compound used is 0.5 to 500 mol% of the halogen compound to be reacted.
[0032]
The solvent used in the synthesis may be any commonly used solvent, but an aprotic polar solvent such as nitrobenzene, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone is preferably used.
[0033]
The synthesis reaction is generally performed at a temperature of 100 to 250 ° C. under normal pressure, but may be performed under pressure. After completion of the reaction, the solid matter precipitated in the reaction solution is removed, and then the solvent is removed to obtain the product.
[0034]
1 to 4 schematically show possible configurations of the electroluminescent device of the present invention. In FIG. 1, (1) is an anode, on which a hole injection transport layer (2), an organic light emitting layer (3), and a cathode (4) are sequentially laminated. The injection transport layer is represented by the above general formula (I)Consists of repeating unitsContains high molecular amino compounds.
[0035]
In FIG. 2, (1) is an anode, on which a hole injecting and transporting layer (2), an organic light emitting layer (3), an electron injecting and transporting layer (5) and a cathode (4) are sequentially laminated. And is represented by the above general formula (I) in the hole injecting and transporting layer.Consists of repeating unitsContains high molecular amino compounds.
[0036]
In FIG. 3, (1) is an anode, on which an organic light emitting layer (3), an electron injecting and transporting layer (5), and a cathode (4) are sequentially laminated. Is represented by the above general formula (I)Consists of repeating unitsContains high molecular amino compounds.
[0037]
In FIG. 4, (1) is an anode, and an organic light emitting layer (3) and a cathode (4) are sequentially laminated thereon, and the organic light emitting material (6) and A charge transport material (7), and the organic light-emitting material or charge transport material includes the above general formula(I)Represented byConsists of repeating unitsHigh molecular amino compounds are used.
[0038]
In the electroluminescent element having the above structure, the anode (1) and the cathode (4) are connected by the lead wire (8), and the organic light emitting layer (3) emits light by applying a voltage to the anode (1) and the cathode (4). To do.
[0039]
Represented by general formula (I)Consists of repeating unitsCertain polymeric amino compounds are good hole injecting and transporting materials or organic light emitting materials.
This is considered to be because a specific polymer amino compound has high hole transportability and a high quantum yield of fluorescence in a solid.
[0040]
As the conductive material used as the anode (1) of the electroluminescent element, one having a work function larger than 4 eV is preferable, and carbon, aluminum, vanadium, iron, cobalt, nickel, copper, zinc, tungsten, silver, tin , Gold and their alloys, and conductive metal compounds such as tin oxide, indium oxide, antimony oxide, zinc oxide and zirconium oxide are used.
[0041]
The metal forming the cathode (4) is preferably one having a work function smaller than 4 eV, and magnesium, calcium, titanium, yttrium lithium, gadolinium, ytterbium, ruthenium, manganese, and alloys thereof are used.
[0042]
In the electroluminescent element, at least the anode (1) or the cathode (4) needs to be a transparent electrode so that light emission can be seen. At this time, if a transparent electrode is used for the cathode, the transparency is likely to be impaired. Therefore, the anode is preferably a transparent electrode.
[0043]
When forming a transparent electrode, a conductive material such as that described above is used on a transparent substrate, and a desired method using a means such as vapor deposition, sputtering, or a sol-gel method or a method of dispersing and applying to a resin or the like. What is necessary is just to form so that translucency and electroconductivity may be ensured.
[0044]
The transparent substrate is not particularly limited as long as it has an appropriate strength, is not adversely affected by heat due to vapor deposition or the like, and is transparent if an electroluminescent element is produced. It is also possible to use resins such as polyethylene, polypropylene, polyethersulfone, polyetheretherketone and the like. Commercial products such as ITO and NESA are known as transparent electrodes formed on a glass substrate, but these may be used.
[0045]
An example of manufacturing an electroluminescent element having the configuration shown in FIG. 2 using the above electrode will be described.
[0046]
First, a hole injection transport layer (2) is formed on the anode (1) described above. The hole injecting and transporting layer (2) is represented by the general formula (I)Consists of repeating unitsIt can be formed by dip-coating or spin-coating a solution in which a high molecular amino compound is dissolved or a solution in which an appropriate resin is dissolved. The thickness is usually 5 to 1000 nm, preferably about 10 to 500 nm.
[0047]
The thicker the film is formed, the higher the applied voltage for emitting light, and the lower the light emission efficiency, which tends to cause deterioration of the electroluminescent element. Further, when the film thickness is reduced, the light emission efficiency is improved, but breakdown is easily caused and the life of the electroluminescent element is shortened.
[0048]
Formula (I)Consisting of repeating units represented byThe polymeric amino compound may be used in combination with other charge transport materials, and as such a charge transport material, it has an excellent hole injection effect on the light emitting layer or the light emitting material, has high mobility, and is generated in the light emitting layer. The compound which prevented the movement of the exciton to the electron injection layer or electron transport material, and was excellent in the thin film formation ability is mentioned.
[0049]
Specifically, phthalocyanine compound, naphthalocyanine compound, porphyrin compound, oxadiazole, triazole, imidazole, imidazolone, imidazolethione, pyrazoline, pyrazolone, tetrahydroimidazole, oxazole, oxadiazole, hydrazone, acyl hydrazone, polyarylalkane, Examples include, but are not limited to, stilbene, butadiene, benzidine type triarylamine, diamine type triarylamine, and derivatives thereof, and polymer materials such as polyvinylcarbazole, polysilane, and conductive polymer. .
[0050]
As described later, it is represented by the general formula (I)Consists of repeating unitsWhen a polymeric amino compound is used as the light emitting material for the organic light emitting layer (3), the hole transporting material used for the hole injecting and transporting layer is a known material such as N, N′-diphenyl-N, N ′. -Bis (3-methylphenyl) -1,1'-diphenyl-4,4'-diamine, N, N'-diphenyl-N, N'-bis (4-methylphenyl) -1,1'-diphenyl- 4,4′-diamine, N, N′-diphenyl-N, N′-bis (1-naphthyl) -1,1′-diphenyl-4,4′-diamine, N, N′-diphenyl-N, N '-Bis (2-naphthyl) -1,1'-diphenyl-4,4'-diamine, N, N'-tetra (4-methylphenyl) -1,1'-diphenyl-4,4'-diamine, N, N′-tetra (4-methylphenyl) -1,1′-bis ( -Methylphenyl) -4,4'-diamine, N, N'-diphenyl-N, N'-bis (3-methylphenyl) -1,1'-bis (3-methylphenyl) -4,4'- Diamine, N, N′-bis (N-carbazolyl) -1,1′-diphenyl-4,4′-diamine, 4,4 ′, 4 ″ -tris (N-carbazolyl) triphenylamine, N, N ′ , N ″ -triphenyl-N, N ′, N ″ -tris (3-methylphenyl) -1,3,5-tri (4-aminophenyl) benzene, 4,4 ′, 4 ″ -tris [N, N ′, N ″ -triphenyl-N, N ′, N ″ -tris (3-methylphenyl)] triphenylamine and the like. These may be used as a mixture of two or more.
[0051]
Next, an organic light emitting layer (3) is formed on the hole injection transport layer (2). As an organic light emitting material and a light emitting auxiliary material used for the organic light emitting layer, known materials can be used, for example, epidolidine, 2,5-bis [5,7-di-t-pentyl-2-benzoxazolyl]. Thiophene, 2,2 ′-(1,4-phenylenedivinylene) bisbenzothiazole, 2,2 ′-(4,4′-biphenylene) bisbenzothiazole, 5-methyl-2- {2- [4- ( 5-methyl-2-benzoxazolyl) phenyl] vinyl} benzoxazole, 2,5-bis (5-methyl-2-benzoxazolyl) thiophene, anthracene, naphthalene, phenanthrene, pyrene, chrysene, perylene,
[0052]
In addition, general fluorescent dyes such as fluorescent coumarin dyes, fluorescent perylene dyes, fluorescent pyran dyes, fluorescent thiopyran dyes, fluorescent polymethine dyes, fluorescent mesocyanine dyes, fluorescent imidazole dyes and the like can also be used. Of these, particularly preferred are chelated oxinoid compounds.
[0053]
The organic light emitting layer may have a single layer structure of the light emitting material described above, or may have a multilayer structure in order to adjust characteristics such as light emission color and light emission intensity. Two or more kinds of luminescent materials may be mixed or doped in the luminescent layer.
[0054]
The organic light emitting layer (3) may be formed by vapor-depositing a light emitting material as described above, or formed by dip coating or spin coating a solution in which the light emitting material is dissolved or a solution dissolved with an appropriate resin. May be.
[0055]
The organic light emitting layer is represented by the general formula (I)Consists of repeating unitsHigh molecular amino compounds can also be used as the luminescent material. The organic light emitting layer may have a single layer structure of a polymer amino compound, or may have a multilayer structure in order to adjust characteristics such as light emission color and light emission intensity. Two or more kinds of luminescent materials may be mixed or doped in the luminescent layer.
[0056]
Represented by general formula (I)Consists of repeating unitsWhen the light emitting layer is formed using a polymer amino compound, it can be formed by dip coating or spin coating a solution in which the polymer amino compound is dissolved or a solution in which it is dissolved together with an appropriate resin. The thickness is usually about 5 to 1000 nm, preferably about 10 to 500 nm.
[0057]
The thicker the film is formed, the higher the applied voltage for causing light emission, and the lower the light emission efficiency, the more likely the deterioration of the organic electroluminescent device. Further, when the film thickness is reduced, the light emission efficiency is improved, but breakdown is easily caused and the life of the light emitting element is shortened.
[0058]
An electron injecting and transporting layer (5) is formed on the organic light emitting layer (3). The electron injecting and transporting material used for the electron injecting and transporting layer has the ability to transport electrons, has an excellent electron injecting effect on the light emitting layer or light emitting material, and has a high electron mobility and hole injecting and transporting material From the above, compounds that prevent the movement of holes and have excellent thin film forming ability can be mentioned.
[0059]
For example, 2- (4-biphenylyl) -5- (4-tert-butylphenyl) -1,3,4-oxadiazole, 2- (1-naphthyl) -5- (4-tert-butylphenyl) -1,3,4-oxadiazole, 1,4-bis {2- [5- (4-tert-butylphenyl) -1,3,4-oxadiazolyl]} benzene, 1,3-bis {2- [5- (4-tert-butylphenyl) -1,3,4-oxadiazolyl]} benzene, 4,4′-bis {2- [5- (4-tert-butylphenyl) -1,3,4- Oxadiazolyl]} biphenyl, 2- (4-biphenylyl) -5- (4-tert-butylphenyl) -1,3,4-thiodiazole, 2- (1-naphthyl) -5- (4-tert-butylphenyl) ) -1,3,4-thiodiazole, 1,4-bis {2- [5- (4-tert-butylphenyl) -1,3,4-thiodiazolyl]} benzene, 1,3-bis {2- [5- (4-tert-butylphenyl) -1,3,4-thiodiazolyl]} benzene 4,4′-bis {2- [5- (4-tert-butylphenyl) -1,3,4-thiodiazolyl]} biphenyl, 3- (4-biphenylyl) -4-phenyl-5- (4 -Tert-butylphenyl) -1,2,4-triazole, 3- (1-naphthyl) -4-phenyl-5- (4-tert-butylphenyl) -1,2,4-triazole, 1,4- Bis {3- [4-phenyl-5- (4-tert-butylphenyl) -1,2,4-triazolyl]} benzene, 1,3-bis {3- [4-phenyl-5- (4-tert -Butylphenyl) -1,3,4-oxadiazolyl]} benzene, 4,4′-bis {2- [4-phenyl-5- (4-tert-butylphenyl) -1,3,4-oxadiazolyl]} biphenyl, 1,3,5-tris {2- [5- ( 4-tert-butylphenyl) -1,3,4-oxadiazolyl]} benzene and the like. These may be used in combination of two or more. Next, the above-described cathode is formed on the electron injecting and transporting layer.
[0060]
The case where the electroluminescent element is formed by sequentially laminating the hole injecting and transporting layer (2), the light emitting layer (3), the electron injecting and transporting layer (5), and the cathode (4) on the anode (1) has been described. However, the light emitting layer (3), the electron injecting and transporting layer (5) and the cathode are sequentially laminated on the anode (1) (FIG. 3), the electron injecting and transporting layer (5) and the organic photosensitive layer on the cathode (4). The layer (3) and the anode (1) are sequentially stacked, or the hole injection / transport layer (2), the light emitting layer (3), and the cathode (4) are sequentially stacked on the anode (1) (FIG. 1). Of course, the electron injecting and transporting layer (5), the light emitting layer (3), the hole injecting and transporting layer (2), and the anode (1) may be sequentially laminated on the cathode (4).
[0061]
A pair of transparent electrodes of a cathode and an anode is connected to each electrode by an appropriate lead wire (8) such as a nichrome wire, a gold wire, a copper wire, a platinum wire, and the electroluminescent element has an appropriate voltage (Vs) applied to both electrodes. ) To emit light.
[0062]
The electroluminescent element of the present invention can be applied to various display devices or display devices.
[0063]
Hereinafter, the present invention will be described with reference to examples. The organic electroluminescent device of the present invention achieves improvement in luminous efficiency, luminous luminance, and long life, and a luminescent substance, a luminescent auxiliary material, a charge transport material, a sensitizer, a resin, It is not limited to the electrode material or the like and the element manufacturing method.
[0064]
Synthesis Example 1 (Synthesis of Compound (1))
13.0 g (50 mmol) of N, N′-diphenyl-1,4-phenylenediamine was dissolved in 250 ml of dihexyl ether, and 100 mmol of a hexane solution of butyllithium was slowly added dropwise to the solution. Then, after stirring at 110 ° C. for 2 hours, 16.5 g (50 mmol) of 1,4-diiodobenzene and 0.48 g (25 mmol) of copper iodide were added and reacted at 200 ° C. for 16 hours.
[0065]
After cooling, the resulting reaction solution was filtered and extracted three times with boiling tetrahydrofuran. The tetrahydrofuran solution was concentrated and purged with a methanol solution to obtain the desired polymer. This operation was repeated three times.
[0066]
Synthesis Example 2 (Synthesis of Compound (8))
16.8 g (50 mmol) of N, N′-diphenylbenzidine was dissolved in 250 ml of dihexyl ether, and 100 mmol of hexane solution of butyllithium was slowly added dropwise to the solution. Then, after stirring at 110 ° C. for 2 hours, 19.3 g (50 mmol) of 4,4′-diiodobiphenyl and 0.48 g (25 mmol) of copper iodide were added and reacted at 200 ° C. for 24 hours.
[0067]
After cooling, the resulting reaction solution was filtered and extracted three times with boiling tetrahydrofuran. The filtrate and tetrahydrofuran solution were concentrated and purged with methanol solution to obtain the desired polymer. This operation was repeated three times.
[0068]
Example 1
A thin film having a thickness of 50 nm was formed on a substrate of indium tin oxide-coated glass by a spin coating method using a dichloromethane solution of the polymer amino compound (1) as an organic hole injecting and transporting layer.
[0069]
Next, a thin film was formed as an organic light-emitting layer by vacuum evaporation of aluminum trisoxine to a thickness of 50 nm.
[0070]
Finally, a thin film was formed to a thickness of 200 nm by vacuum deposition of magnesium as a cathode. In this way, an organic electroluminescent element device was produced.
[0071]
Examples 2-4
In Example 1, an organic electroluminescent device was produced in the same manner as in Example 1 except that the polymer amino compound (2), (3) and (4) were used instead of using the polymer amino compound (1). Was made.
[0072]
Example 5
A thin film having a thickness of 70 nm was formed on a substrate of indium tin oxide-coated glass by a spin coating method using a dichloromethane solution of a polymer amino compound (7) as an organic hole injecting and transporting layer.
[0073]
Next, a thin film was formed as an organic light emitting layer by vapor deposition of aluminum trisoxine to a thickness of 100 nm.
[0074]
Further, a thin film was formed as an organic electron injecting and transporting layer by vapor deposition of the following oxadiazole compound (A) to a thickness of 50 nm.
Embedded image
[0075]
Examples 6-8
In Example 5, an organic electroluminescent device was produced in the same manner as in Example 5 except that instead of using the polymer amino compound (7), the polymer amino compound (8), (9), (10) was used. Was made.
[0076]
Example 9
A thin film having a thickness of 50 nm was formed on a substrate of indium tin oxide-coated glass by a spin coating method using a dichloromethane solution of a polymer amino compound (11) as a light emitting layer.
Next, a thin film was formed as an organic electron injecting and transporting layer by vapor deposition of the oxadiazole compound (A) to a thickness of 20 nm.
Finally, a thin film having a thickness of 200 nm was formed as a cathode by vapor deposition of Mg and Ag with an atomic ratio of 10: 1. In this way, an organic electroluminescent element was produced.
[0077]
Example 10
A thin film having a thickness of 20 nm was formed on a substrate of indium tin oxide-coated glass by a spin coating method using a dichloromethane solution of a polymer amino compound (13) as an organic hole injecting and transporting layer.
Further, N, N′-diphenyl-N, N ′-(3-methylphenyl) -1,1′-biphenyl-4,4′-diamine is vacuum-deposited to obtain a 40 nm-thick hole transport layer. It was.
Next, a thin film was formed by vapor deposition of a tris (8-hydroxyquinoline) aluminum complex to a thickness of 50 nm.
Finally, a thin film having a thickness of 200 nm was formed as a cathode by vapor deposition of Mg and Ag with an atomic ratio of 10: 1. In this way, an organic electroluminescent element was produced.
[0078]
Example 11
A polymer amino compound (14) was dissolved in dichloromethane on an indium tin oxide-coated glass substrate, and a hole injection layer having a thickness of 50 nm was obtained by spin coating.
Next, a light emitting layer was formed by vapor deposition of a tris (8-hydroxyquinoline) aluminum complex to a thickness of 20 nm.
Further, an electron injection layer of oxadiazole compound (A) having a film thickness of 20 nm was obtained by a vacuum deposition method.
Finally, a thin film having a thickness of 200 nm was formed as a cathode by vapor deposition of Mg and Ag with an atomic ratio of 10: 1. In this way, an organic electroluminescent element was produced.
[0079]
Example 12-13 and Reference Example 1
In Example 11, instead of using the polymer amino compound (14), the polymer amino compound (18), (19), and (21) were used instead of the polymer amino compound (14).11An organic electroluminescent element was produced in exactly the same manner as described above.
[0080]
Reference example 2
A polymeric amino compound (24) and tris (8-hydroxyquinoline) aluminum complex are dissolved in tetrahydrofuran at a ratio of 3: 2 on an indium tin oxide-coated glass substrate, and a light-emitting layer having a thickness of 100 nm is formed by spin coating. Obtained.
Next, a thin film was formed by vapor deposition of Mg and Ag with an atomic ratio of 10: 1 as a cathode to a thickness of 200 nm. In this way, an organic electroluminescent element was produced.
[0081]
Example14-16
Reference example 2Except that the polymer amino compound (29), (31), (36) is used instead of the polymer amino compound (24).Reference example 2An organic electroluminescent element was produced in exactly the same manner as described above.
[0082]
Evaluation
Example 116 and Reference Examples 1 and 2The electroluminescence device obtained in (1) was measured with the glass electrode as an anode, the voltage at which light emission was started when a voltage was gradually applied, and the maximum light emission luminance and the voltage at that time. The results are summarized in Table 1.
[0083]
[Table 1]
As can be seen from Table 1, the organic electroluminescent device of this example started to emit light at a low potential and showed good emission luminance.
Further, the device obtained in Example 1 was allowed to continuously emit light at an initial voltage of 6 V under an inert atmosphere of nitrogen gas, and the half-life of the emission luminance (time until the luminance was reduced to half) was measured. there were.
[0085]
The organic electroluminescent element of this example had a small output drop and could observe stable light emission with a long lifetime.
[0086]
【The invention's effect】
According to the present invention, the organic light emitting layer is represented by the general formula (I).Consists of repeating unitsBy containing the polymer amino compound, an electroluminescent device having excellent durability with high light intensity and low emission start voltage can be obtained.
[Brief description of the drawings]
FIG. 1 is a schematic configuration diagram of a configuration example of an electroluminescent element.
FIG. 2 is a schematic configuration diagram of a configuration example of an electroluminescent element.
FIG. 3 is a schematic configuration diagram of a configuration example of an electroluminescent element.
FIG. 4 is a schematic configuration diagram of a configuration example of an electroluminescent element.
[Explanation of symbols]
1: Anode
2: Hole injection transport layer
3: Organic light emitting layer
4: Cathode
5: Electron injection transport layer
6: Organic light emitting material
7: Charge transport material
8: Lead wire
Claims (2)
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| JP11916997A JP4013282B2 (en) | 1997-05-09 | 1997-05-09 | Electroluminescent device |
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| JP11916997A JP4013282B2 (en) | 1997-05-09 | 1997-05-09 | Electroluminescent device |
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| JP2006167225A Division JP4569526B2 (en) | 2006-06-16 | 2006-06-16 | Materials for electroluminescent elements |
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| JPH10308280A JPH10308280A (en) | 1998-11-17 |
| JP4013282B2 true JP4013282B2 (en) | 2007-11-28 |
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| JP11916997A Expired - Lifetime JP4013282B2 (en) | 1997-05-09 | 1997-05-09 | Electroluminescent device |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2004014985A1 (en) | 2002-08-09 | 2004-02-19 | Tosoh Corporation | Novel triarylamine polymer, process for producing the same, and use thereof |
| JP3913147B2 (en) * | 2002-08-30 | 2007-05-09 | キヤノン株式会社 | Electrophotographic photosensitive member, process cartridge, and electrophotographic apparatus |
| JP3913148B2 (en) * | 2002-08-30 | 2007-05-09 | キヤノン株式会社 | Electrophotographic photosensitive member, process cartridge, and electrophotographic apparatus |
| JP5299017B2 (en) * | 2002-10-24 | 2013-09-25 | 住友化学株式会社 | Polymer compound and polymer light emitting device using the same |
| GB0229659D0 (en) * | 2002-12-20 | 2003-01-22 | Avecia Ltd | Electronic devices |
| CN100558791C (en) | 2003-12-13 | 2009-11-11 | 默克专利有限公司 | Oligopolymer and polymkeric substance |
| JP4956898B2 (en) * | 2004-03-03 | 2012-06-20 | 東ソー株式会社 | Triarylamine polymer and method for producing the same |
| KR100565665B1 (en) | 2004-03-22 | 2006-03-30 | 엘지전자 주식회사 | organic electroluminescence device |
| KR101166087B1 (en) | 2004-03-25 | 2012-07-23 | 닛산 가가쿠 고교 가부시키 가이샤 | Charge-transporting varnish and organic electro-luminescent devices made by using the same |
| JP4557794B2 (en) * | 2005-05-16 | 2010-10-06 | 山本化成株式会社 | Polymer compound containing thiophene in main chain, and organic electroluminescence device containing the compound |
| CN101223254B (en) * | 2005-06-03 | 2010-12-15 | 日产化学工业株式会社 | Charge-transporting varnishes containing charge-transporting polymers and organic electroluminescent devices made by using the same |
| JP5018043B2 (en) * | 2005-12-01 | 2012-09-05 | 住友化学株式会社 | Polymer compound and polymer light emitting device using the same |
| JP4569526B2 (en) * | 2006-06-16 | 2010-10-27 | コニカミノルタホールディングス株式会社 | Materials for electroluminescent elements |
| JP5151812B2 (en) * | 2007-08-28 | 2013-02-27 | 三菱化学株式会社 | Organic compound, polymer compound, cross-linked polymer compound, composition for organic electroluminescence device, and organic electroluminescence device |
| US8980443B2 (en) | 2009-04-14 | 2015-03-17 | Konica Minolta Holdings, Inc. | Organic electroluminescent element |
| JP5685838B2 (en) * | 2010-06-22 | 2015-03-18 | 東ソー株式会社 | Novel triarylamine polymer, production method thereof and use thereof |
| CN103314463B (en) * | 2011-01-14 | 2017-04-05 | 三菱化学株式会社 | Organic electroluminescent device, compositionss and Organnic electroluminescent device |
| JP5699684B2 (en) * | 2011-02-25 | 2015-04-15 | 三菱化学株式会社 | Polymer, organic electroluminescent element material, composition for organic electroluminescent element, organic electroluminescent element, organic EL display device, and organic EL lighting |
| EP3597689A4 (en) * | 2017-03-15 | 2021-01-13 | Hodogaya Chemical Co., Ltd. | High-molecular-weight compound having substituted triarylamine skeleton |
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