JP2000036390A - Organic electroluminescent element - Google Patents
Organic electroluminescent elementInfo
- Publication number
- JP2000036390A JP2000036390A JP11128841A JP12884199A JP2000036390A JP 2000036390 A JP2000036390 A JP 2000036390A JP 11128841 A JP11128841 A JP 11128841A JP 12884199 A JP12884199 A JP 12884199A JP 2000036390 A JP2000036390 A JP 2000036390A
- Authority
- JP
- Japan
- Prior art keywords
- group
- electron
- injection layer
- light emitting
- hole injection
- 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
- 238000002347 injection Methods 0.000 claims abstract description 51
- 239000007924 injection Substances 0.000 claims abstract description 51
- 150000001875 compounds Chemical class 0.000 claims abstract description 46
- 150000004984 aromatic diamines Chemical class 0.000 claims abstract description 40
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 39
- 229920000570 polyether Polymers 0.000 claims abstract description 39
- 125000001424 substituent group Chemical group 0.000 claims abstract description 17
- 125000003118 aryl group Chemical group 0.000 claims abstract description 15
- 239000000758 substrate Substances 0.000 claims description 28
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 125000005843 halogen group Chemical group 0.000 claims description 8
- 125000005647 linker group Chemical group 0.000 claims description 4
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 239000000243 solution Substances 0.000 abstract description 7
- 125000006615 aromatic heterocyclic group Chemical group 0.000 abstract description 2
- 125000004122 cyclic group Chemical group 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 96
- 239000000463 material Substances 0.000 description 35
- 238000000034 method Methods 0.000 description 19
- -1 poly (p-phenylenevinylene) Polymers 0.000 description 19
- 239000010409 thin film Substances 0.000 description 18
- 230000005525 hole transport Effects 0.000 description 16
- 239000010408 film Substances 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 229910052782 aluminium Inorganic materials 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 239000011521 glass Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000000151 deposition Methods 0.000 description 8
- 230000008021 deposition Effects 0.000 description 8
- 230000009477 glass transition Effects 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
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- 238000001771 vacuum deposition Methods 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000004528 spin coating Methods 0.000 description 5
- 238000007740 vapor deposition Methods 0.000 description 5
- 239000005725 8-Hydroxyquinoline Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- 239000011733 molybdenum Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 229960003540 oxyquinoline Drugs 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000002861 polymer material Substances 0.000 description 4
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- 238000004506 ultrasonic cleaning Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 241000284156 Clerodendrum quadriloculare Species 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000004770 highest occupied molecular orbital Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 125000001624 naphthyl group Chemical group 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 3
- 229920000553 poly(phenylenevinylene) Polymers 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 229920003002 synthetic resin Polymers 0.000 description 3
- 239000000057 synthetic resin Substances 0.000 description 3
- 238000007738 vacuum evaporation Methods 0.000 description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 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 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000004453 alkoxycarbonyl group Chemical group 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
- 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 2
- 125000004104 aryloxy group Chemical group 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 125000000051 benzyloxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])O* 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 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
- 230000006866 deterioration Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 125000004663 dialkyl amino group Chemical group 0.000 description 2
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000003618 dip coating Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- HNOCXIWXNAZTRR-UHFFFAOYSA-N n-(4-anthracen-9-ylphenyl)-4-methyl-n-(4-methylphenyl)aniline Chemical compound C1=CC(C)=CC=C1N(C=1C=CC(=CC=1)C=1C2=CC=CC=C2C=C2C=CC=CC2=1)C1=CC=C(C)C=C1 HNOCXIWXNAZTRR-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000012044 organic layer Substances 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
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920000767 polyaniline Polymers 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000193 polymethacrylate Polymers 0.000 description 2
- 150000004033 porphyrin derivatives Chemical class 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- 150000003513 tertiary aromatic amines Chemical group 0.000 description 2
- 150000003518 tetracenes Chemical class 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- 238000000411 transmission spectrum Methods 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- PFNQVRZLDWYSCW-UHFFFAOYSA-N (fluoren-9-ylideneamino) n-naphthalen-1-ylcarbamate Chemical compound C12=CC=CC=C2C2=CC=CC=C2C1=NOC(=O)NC1=CC=CC2=CC=CC=C12 PFNQVRZLDWYSCW-UHFFFAOYSA-N 0.000 description 1
- 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
- MVVGSPCXHRFDDR-UHFFFAOYSA-N 2-(1,3-benzothiazol-2-yl)phenol Chemical compound OC1=CC=CC=C1C1=NC2=CC=CC=C2S1 MVVGSPCXHRFDDR-UHFFFAOYSA-N 0.000 description 1
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 description 1
- ZOKIJILZFXPFTO-UHFFFAOYSA-N 4-methyl-n-[4-[1-[4-(4-methyl-n-(4-methylphenyl)anilino)phenyl]cyclohexyl]phenyl]-n-(4-methylphenyl)aniline Chemical compound C1=CC(C)=CC=C1N(C=1C=CC(=CC=1)C1(CCCCC1)C=1C=CC(=CC=1)N(C=1C=CC(C)=CC=1)C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 ZOKIJILZFXPFTO-UHFFFAOYSA-N 0.000 description 1
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- 229910001148 Al-Li alloy Inorganic materials 0.000 description 1
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 240000004160 Capsicum annuum Species 0.000 description 1
- 235000008534 Capsicum annuum var annuum Nutrition 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
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
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- 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
- 239000007983 Tris buffer Substances 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 1
- JHYLKGDXMUDNEO-UHFFFAOYSA-N [Mg].[In] Chemical compound [Mg].[In] JHYLKGDXMUDNEO-UHFFFAOYSA-N 0.000 description 1
- ROZSPJBPUVWBHW-UHFFFAOYSA-N [Ru]=O Chemical class [Ru]=O ROZSPJBPUVWBHW-UHFFFAOYSA-N 0.000 description 1
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- 238000004220 aggregation Methods 0.000 description 1
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- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- SMWDFEZZVXVKRB-UHFFFAOYSA-N anhydrous quinoline Natural products N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 1
- 125000005577 anthracene group Chemical group 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
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- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 1
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- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
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- 239000003550 marker Substances 0.000 description 1
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- 150000005309 metal halides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000004866 oxadiazoles Chemical class 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical class [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 150000005041 phenanthrolines Chemical class 0.000 description 1
- 125000001644 phenoxazinyl group Chemical group C1(=CC=CC=2OC3=CC=CC=C3NC12)* 0.000 description 1
- 238000001420 photoelectron spectroscopy Methods 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical class N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
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- 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
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 125000005412 pyrazyl group Chemical group 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
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- YYMBJDOZVAITBP-UHFFFAOYSA-N rubrene Chemical compound C1=CC=CC=C1C(C1=C(C=2C=CC=CC=2)C2=CC=CC=C2C(C=2C=CC=CC=2)=C11)=C(C=CC=C2)C2=C1C1=CC=CC=C1 YYMBJDOZVAITBP-UHFFFAOYSA-N 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical class [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 150000003967 siloles Chemical class 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 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 1
- 150000001651 triphenylamine derivatives Chemical class 0.000 description 1
- 125000006617 triphenylamine group Chemical group 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Electroluminescent Light Sources (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyethers (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】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 electroluminescent device, and more particularly, to a thin film 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（一般に50〜1000Ｈｚ）、 ２）駆動電圧が高い（一般に200Ｖ程度）、 ３）フルカラー化が困難で特に青色に問題がある、 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 group II-VI compound semiconductor of an inorganic material, is used.
In general, S, CaS, SrS, and the like are doped with Mn or a rare earth element (Eu, Ce, Tb, Sm, or the like) which is a luminescence center. However, EL devices manufactured from the above inorganic materials include: 1) AC drive is required (generally 50 to 1000 Hz), 2) High drive voltage (generally about 200 V), 3) It is difficult to achieve full color, and there is a problem with blue in particular. 4) Cost of peripheral drive circuit is high. have.
【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、電極からのキャリア
ー注入の効率向上を目的として電極の種類の最適化を行
い、芳香族ジアミンから成る正孔輸送層と８−ヒドロキ
シキノリンのアルミニウム錯体から成る発光層とを設け
た有機電界発光素子の開発（Appl. Phys. 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ＥＬ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,
Development of EL devices using organic thin films has been started. In particular, in order to enhance the luminous efficiency, the type of the electrode was optimized for the purpose of improving the efficiency of carrier injection from the electrode, and a hole transport layer composed of an aromatic diamine and a luminescent layer composed of an aluminum complex of 8-hydroxyquinoline were used. Of an organic electroluminescent device equipped with an organic layer (Appl. Phys. Lett., Vol. 51,
913, 1987), the luminous efficiency has been greatly improved as compared with the conventional EL device using a single crystal such as anthracene or the like, and the practical characteristics have been approached.
【０００４】上記の様な低分子材料を用いた電界発光素
子の他にも、発光層の材料として、ポリ（ｐ−フェニレ
ンビニレン）、ポリ［2-メトキシ-5-(2-エチルヘキシル
オキシ)-1,4-フェニレンビニレン］、ポリ（3-アルキル
チオフェン）等の高分子材料を用いた電界発光素子の開
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の開発も行われて
いる。In addition to the electroluminescent device using a low molecular material as described above, poly (p-phenylenevinylene) and poly [2-methoxy-5- (2-ethylhexyloxy)- Development of electroluminescent devices using polymer materials such as 1,4-phenylenevinylene] and poly (3-alkylthiophene), and devices in which a low molecular light emitting material and an electron transfer material are mixed with a polymer such as polyvinyl carbazole Is also being developed.
【０００５】ところで、有機電界発光素子の最大の課題
は、駆動時の寿命であり、駆動時の不安定性の現像とし
ては、発光輝度の低下、定電流駆動時の電圧上昇、非発
光部分（ダークスポット）の発生等が挙げられる。これ
らの不安定性の原因はいくつか存在するが、有機層の薄
膜形状の劣化が支配的である。この薄膜形状の劣化は、
素子駆動時の発熱による有機非晶質膜の結晶化（または
凝集）等に起因すると考えられている。特に、駆動電圧
の上昇については陽極と正孔輸送層のコンタクトが重要
である。[0005] By the way, the biggest problem of the organic electroluminescent device is the life during driving, and the development of instability during driving includes a decrease in light emission luminance, a voltage increase during constant current driving, and a non-light emitting portion (dark). Spot). Although there are several causes of these instabilities, deterioration of the thin film shape of the organic layer is dominant. This deterioration of the thin film shape
This is considered to be caused by crystallization (or aggregation) of the organic amorphous film due to heat generated during element driving. In particular, the contact between the anode and the hole transport layer is important for increasing the drive voltage.
【０００６】そこで、陽極と正孔輸送層のコンタクトを
向上させるために、両層の間に正孔注入層を設け、駆動
電圧を低下させることが検討されている。この正孔注入
層に用いられる材料に要求される条件としては、陽極と
のコンタクトがよく、均一な薄膜が形成でき、熱的に安
定、即ち、融点及びガラス転移温度Tgが高いこと、好ま
しくは 300℃以上の融点と 100℃以上のTgを有すること
が要求される。さらに、イオン化ポテンシャルが低く陽
極からの正孔注入が容易なこと、正孔移動度が大きいこ
とが挙げられる。Therefore, in order to improve the contact between the anode and the hole transport layer, it has been studied to provide a hole injection layer between both layers to lower the driving voltage. The conditions required for the material used for the hole injection layer include good contact with the anode, formation of a uniform thin film, and thermal stability, that is, a high melting point and a high glass transition temperature Tg, preferably It is required to have a melting point of 300 ° C or higher and a Tg of 100 ° C or higher. In addition, the ionization potential is low, holes can be easily injected from the anode, and the hole mobility is high.
【０００７】従来、正孔注入層の材料としても種々のも
のが検討されており、例えばポルフィリン誘導体やフタ
ロシアニン化合物（特開昭63−295695号公報）、スター
バスト型芳香族トリアミン（特開平４−308688号公
報）、ヒドラゾン化合物（特開平４−320483号公報）、
アルコキシ置換の芳香族ジアミン誘導体（特開平４−22
0995号公報）、p-（9-アントリル）-N,N-ジ-p- トリル
アニリン、ポリチエニレンビニレンやポリ−ｐ−フェニ
レンビニレン、ポリアニリン等の有機化合物や、スパッ
タ・カーボン膜や、バナジウム酸化物、ルテニウム酸化
物、モリブデン酸化物等の金属酸化物などが報告されて
いる。Conventionally, various materials have been studied as a material for the hole injection layer. For example, porphyrin derivatives and phthalocyanine compounds (Japanese Patent Application Laid-Open No. 63-295695), starburst type aromatic triamines (Japanese Patent Application Laid-Open No. 308688), hydrazone compounds (JP-A-4-320483),
Alkoxy-substituted aromatic diamine derivatives (Japanese Unexamined Patent Publication No.
0995), p- (9-anthryl) -N, N-di-p-tolylaniline, organic compounds such as polythienylenevinylene, poly-p-phenylenevinylene, polyaniline, sputtered carbon films, and vanadium Metal oxides such as oxides, ruthenium oxides and molybdenum oxides have been reported.
【０００８】[0008]
【発明が解決しようとする課題】しかしながら、陽極と
正孔輸送層との間に正孔注入層を挿入する方法におい
て、ポルフィリン誘導体やフタロシアニン化合物を正孔
注入層として用いた場合、これらの膜自体による光吸収
のためにスペクトルが変化したり、外観上着色して透明
でなくなるという問題がある。However, when a porphyrin derivative or a phthalocyanine compound is used as the hole injection layer in the method of inserting the hole injection layer between the anode and the hole transport layer, these films themselves are not used. There is a problem that the spectrum is changed due to light absorption by the light source, or the external appearance is colored and becomes invisible.
【０００９】スターバスト型芳香族トリアミン、ヒドラ
ゾン化合物、アルコキシ置換の芳香族ジアミン誘導体、
p-(9-アントリル)-N,N-ジ-p-トリルアニリン等では、イ
オン化ポテンシャルが低く透明性がよいという利点はあ
るものの、ガラス転移点や融点が低いために耐熱性に劣
り、連続駆動時の局所加熱に対する安定性が悪く、輝度
低下や電圧上昇が問題になる。A star bust type aromatic triamine, a hydrazone compound, an alkoxy-substituted aromatic diamine derivative,
Although p- (9-anthryl) -N, N-di-p-tolylaniline has the advantage of low ionization potential and good transparency, it has poor heat resistance due to low glass transition point and melting point, and continuous The stability to local heating during driving is poor, and the problem of a decrease in luminance and an increase in voltage is a problem.
【００１０】一方、ポリチエニレンビニレン、ポリ−ｐ
−フェニレンビニレン、ポリアニリン等のポリマー系材
料では、駆動電圧の低電圧化と駆動寿命の改善に関する
報告はない。On the other hand, polythienylenevinylene, poly-p
-For polymer materials such as phenylene vinylene and polyaniline, there is no report on lowering the driving voltage and improving the driving life.
【００１１】有機電界発光素子の駆動時における電圧が
高いこと、そして、耐熱性を含めた安定性が低いこと
は、ファクシミリ、複写機、液晶ディスプレイのバック
ライト等の光源としては大きな問題であり、特にフルカ
ラーフラットパネル・ディスプレイ等の表示素子として
も望ましくない。The high voltage at the time of driving the organic electroluminescent device and the low stability including heat resistance are serious problems as a light source for a facsimile, a copying machine, a backlight of a liquid crystal display, and the like. In particular, it is not desirable as a display element such as a full-color flat panel display.
【００１２】従って、本発明は、低電圧、高発光効率で
駆動させることができ、かつ良好な耐熱性を有し、長期
間に亙って安定な発光特性を維持することができる有機
電界発光素子を提供することを目的とする。Accordingly, the present invention provides an organic electroluminescent device which can be driven at low voltage and high luminous efficiency, has good heat resistance, and can maintain stable luminescent characteristics for a long period of time. It is intended to provide an element.
【００１３】[0013]
【課題を解決するための手段】本発明の有機電界発光素
子は、基板上に、陽極及び陰極により挟持された発光層
が形成されると共に、該発光層と陽極との間に正孔注入
層が形成された有機電界発光素子において、該正孔注入
層が、下記一般式（Ｉ）または（II）で表わされる繰り
返し単位を有し、かつ、重量平均分子量が1,000〜1,00
0,000である芳香族ジアミン含有ポリエーテルと、電子
受容性化合物とを含有することを特徴とする。According to the organic electroluminescent device of the present invention, a light emitting layer sandwiched between an anode and a cathode is formed on a substrate, and a hole injection layer is provided between the light emitting layer and the anode. Is formed, the hole injection layer has a repeating unit represented by the following general formula (I) or (II), and has a weight average molecular weight of 1,000 to 1,000.
It is characterized by containing an aromatic diamine-containing polyether of 0.000 and an electron-accepting compound.
【００１４】[0014]
【化６】 Embedded image
【００１５】[0015]
【化７】 Embedded image
【００１６】（式中、Ａr1，Ａr2，Ａr3，Ａr4，Ａr5，
Ａr6，Ａr7，Ａr8，Ａr9は、各々独立して置換基を有し
ていてもよい２価の芳香族環残基を示し、Ｒ1，Ｒ2，Ｒ
3，Ｒ4は置換基を有していてもよい芳香族環基または芳
香族複素環基を示し、Ｘ及びＹは直接結合、または下記
の連結基から選ばれる。）(Wherein, Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 ,
Ar 6 , Ar 7 , Ar 8 , and Ar 9 each independently represent a divalent aromatic ring residue which may have a substituent, and R 1 , R 2 , R
3 , R 4 represents an aromatic ring group or an aromatic heterocyclic group which may have a substituent, and X and Y are selected from a direct bond or the following linking group. )
【００１７】[0017]
【化８】 Embedded image
【００１８】（式中、Ｒ′は置換基を有していてもよい
アルキレン基を示し、Ｒ″はアルキル基または置換基を
有していてもよい芳香族環基を示す。） 即ち、本発明者らは、従来の問題点を解決し、高温にお
いて安定な発光特性を維持できる有機電界発光素子を提
供するべく鋭意検討した結果、基板上に、陽極及び陰極
により挟持された発光層を有する有機電界発光素子にお
いて、陽極と発光層との間に、電子受容性化合物を含有
し、かつ、高いTgを有する芳香族ジアミン含有ポリエー
テルからなる正孔注入層を設けることで、上記課題を解
決することができることを見出し、本発明を完成するに
至った。(In the formula, R ′ represents an alkylene group which may have a substituent, and R ″ represents an alkyl group or an aromatic ring group which may have a substituent.) The present inventors have solved the conventional problems, and as a result of diligent studies to provide an organic electroluminescent device that can maintain stable light emitting characteristics at high temperature, have a light emitting layer sandwiched between an anode and a cathode on a substrate. In the organic electroluminescent device, the above problem is solved by providing a hole injection layer made of an aromatic diamine-containing polyether containing an electron accepting compound and having a high Tg between an anode and a light emitting layer. And found that the present invention was completed.
【００１９】本発明においては、正孔注入層に、100℃
以上のTgを有する芳香族ジアミン含有ポリエーテルと電
子受容性化合物を混合して用いることで、素子の発光特
性と耐熱性を同時に改善することを可能とした。即ち、
電子供与性の芳香族ジアミン含有ポリエーテルに電子受
容性化合物を混合することにより、電荷移動が起こり、
結果としてフリーキャリアである正孔が生成し、正孔注
入層の電気電導度が高くなる。発光層と陽極との電気的
接合が、本発明による正孔注入層を設けることで改善さ
れ、駆動電圧が低下すると同時に連続駆動時の安定性も
向上する。また、 100℃以上のガラス転移温度を有する
芳香族ジアミン含有ポリエーテルを正孔注入層の母体と
することにより、素子の耐熱性も大きく改善される。本
発明で用いる芳香族ジアミン含有ポリエーテルのガラス
転移温度は特に120℃以上、とりわけ150℃以上であるこ
とが好ましい。In the present invention, 100 ° C.
By mixing and using the aromatic diamine-containing polyether having the above Tg and the electron-accepting compound, it was possible to simultaneously improve the light emitting characteristics and the heat resistance of the device. That is,
By mixing an electron-accepting compound with an electron-donating aromatic diamine-containing polyether, charge transfer occurs,
As a result, holes as free carriers are generated, and the electric conductivity of the hole injection layer is increased. The electrical connection between the light emitting layer and the anode is improved by providing the hole injection layer according to the present invention, and the driving voltage is reduced and the stability during continuous driving is also improved. Further, by using an aromatic diamine-containing polyether having a glass transition temperature of 100 ° C. or higher as the base of the hole injection layer, the heat resistance of the device is greatly improved. The glass transition temperature of the aromatic diamine-containing polyether used in the present invention is preferably at least 120 ° C, particularly preferably at least 150 ° C.
【００２０】本発明において、正孔注入層の芳香族ジア
ミン含有ポリエーテルのイオン化ポテンシャルから電子
受容性化合物の電子親和力を引いた値は0.7ｅＶ以下で
あることが好ましく、また、正孔注入層中の電子受容性
化合物の含有量は、芳香族ジアミン含有ポリエーテルに
対して0.1〜50重量％の範囲であることが好ましい。In the present invention, the value obtained by subtracting the electron affinity of the electron accepting compound from the ionization potential of the aromatic diamine-containing polyether in the hole injection layer is preferably 0.7 eV or less. Is preferably in the range of 0.1 to 50% by weight based on the aromatic diamine-containing polyether.
【００２１】本発明において、電子受容性化合物は、下
記一般式（III）で表される化合物或いは、下記化合物
群から選ばれる化合物の少なくとも１種であることが好
ましい。In the present invention, the electron accepting compound is preferably a compound represented by the following general formula (III) or at least one compound selected from the following compound group.
【００２２】[0022]
【化９】 Embedded image
【００２３】（式中、Ｚはハロゲン原子を示し、Ｒ5は
水素原子、ハロゲン原子、置換基を有していてもよいア
ルキル基、シアノ基またはニトロ基を示す。）(Wherein, Z represents a halogen atom, and R 5 represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, a cyano group or a nitro group.)
【００２４】[0024]
【化１０】 Embedded image
【００２５】[0025]
【発明の実施の形態】以下に図面を参照して本発明の有
機電界発光素子の実施の形態を詳細に説明する。DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the organic electroluminescent device of the present invention will be described in detail with reference to the drawings.
【００２６】図１〜３は本発明の有機電界発光素子の実
施の形態を示す模式的な断面図であり、１は基板、２は
陽極、３は正孔注入層、４は正孔輸送層、５は発光層、
６は電子輸送層、７は陰極を各々表わす。1 to 3 are schematic sectional views showing an embodiment of the organic electroluminescent device of the present invention, wherein 1 is a substrate, 2 is an anode, 3 is a hole injection layer, and 4 is a hole transport layer. 5 is a light emitting layer,
6 represents an electron transport layer, and 7 represents a cathode.
【００２７】基板１は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。特にガラ
ス板や、ポリエステル、ポリメタクリレート、ポリカー
ボネート、ポリスルホンなどの透明な合成樹脂の板が好
ましい。合成樹脂基板を使用する場合にはガスバリア性
に留意する必要がある。基板のガスバリヤ性が低すぎる
と、基板を通過する外気により有機電界発光素子が劣化
することがあるので好ましくない。このため、合成樹脂
基板のどちらか片側もしくは両側に緻密なシリコン酸化
膜等を設けてガスバリア性を確保する方法も好ましい方
法の一つである。The substrate 1 serves as a support for the organic electroluminescent device, and is made of a quartz or glass plate, a metal plate or a metal foil, a plastic film or a sheet, or the like. Particularly, a glass plate or a plate of a transparent synthetic resin such as polyester, polymethacrylate, polycarbonate, and polysulfone is preferable. When using a synthetic resin substrate, it is necessary to pay attention to gas barrier properties. If the gas barrier property of the substrate is too low, the organic air-emitting device may be deteriorated by outside air passing through the substrate, which is not preferable. Therefore, a method of providing a dense silicon oxide film or the like on one or both sides of the synthetic resin substrate to ensure gas barrier properties is also a preferable method.
【００２８】基板１上には陽極２が設けられる。陽極２
は正孔注入層３への正孔注入の役割を果たすものであ
る。この陽極２は、通常、アルミニウム、金、銀、ニッ
ケル、パラジウム、白金等の金属、インジウム及び／ま
たはスズの酸化物などの金属酸化物、ヨウ化銅などのハ
ロゲン化金属、カーボンブラック等により構成される。
陽極２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。また、銀などの金属微粒
子、ヨウ化銅などの微粒子、カーボンブラック、導電性
の金属酸化物微粒子等を適当なバインダー樹脂溶液に分
散し、基板１上に塗布することにより陽極２を形成する
こともできる。陽極２は異なる物質で積層して形成する
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。透明性が必要とされる場合は、可視光の
透過率を、通常60％以上、好ましくは80％以上とするこ
とが望ましく、この場合、厚みは、通常10〜1000nm、好
ましくは20〜500nm 程度である。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、上記の陽極２の上
に異なる導電材料を積層することも可能である。An anode 2 is provided on a substrate 1. Anode 2
Plays a role of injecting holes into the hole injection layer 3. The anode 2 is usually made of a metal such as aluminum, gold, silver, nickel, palladium, and platinum; a metal oxide such as an oxide of indium and / or tin; a metal halide such as copper iodide; and carbon black. Is done.
Usually, the formation of the anode 2 is often performed by a sputtering method, a vacuum evaporation method, or the like. Further, the anode 2 is formed by dispersing metal fine particles such as silver, fine particles such as copper iodide, carbon black, conductive metal oxide fine particles, and the like in an appropriate binder resin solution and applying the dispersion on the substrate 1. Can also. The anode 2 can be formed by laminating different materials. The thickness of the anode 2 depends on the required transparency. When transparency is required, the transmittance of visible light is usually at least 60%, preferably at least 80%. In this case, the thickness is usually about 10 to 1000 nm, preferably about 20 to 500 nm. It is. If opaque, the anode 2 may be the same as the substrate 1. It is also possible to stack different conductive materials on the anode 2.
【００２９】本発明では、図１〜３の素子構造において
は、陽極２の上に正孔注入層３が設けられる。この正孔
注入層３に用いられる材料に要求される条件としては、
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挙
げられる。そのためには、イオン化ポテンシャルが小さ
く、可視光の光に対して透明性が高く、しかも正孔移動
度が大きく、さらに安定性に優れ、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。
上記の一般的な要求条件以外に、車載表示用の応用を考
えた場合、さらに 100℃以上の耐熱性が要求される。In the present invention, a hole injection layer 3 is provided on the anode 2 in the element structure shown in FIGS. Conditions required for the material used for the hole injection layer 3 include:
It is a material having a high hole injection efficiency from the anode 2 and capable of efficiently transporting the injected holes. For that purpose, the ionization potential is small, the transparency to visible light is high, the hole mobility is large, the stability is high, and impurities serving as traps are unlikely to be generated during production or use. Required.
In addition to the above general requirements, when considering applications for vehicle display, heat resistance of 100 ° C or more is required.
【００３０】本発明の有機電界発光素子は、正孔注入層
が、前記一般式（Ｉ）または（II）で表わされる繰り返
し単位を有する、重量平均分子量1,000〜1,000,000の芳
香族ジアミン含有ポリエーテルと、電子受容性化合物を
含有することを特徴とする。The organic electroluminescent device of the present invention is characterized in that the hole injection layer has an aromatic diamine-containing polyether having a weight average molecular weight of 1,000 to 1,000,000 and having a repeating unit represented by the general formula (I) or (II). And an electron accepting compound.
【００３１】本発明においては、この100℃以上のTgを
有する芳香族ジアミン含有ポリエーテルと電子受容性化
合物を混合して用いることで、素子の発光特性と耐熱性
を同時に改善することを可能とした。即ち、電子供与性
の芳香族ジアミン含有ポリエーテルに電子受容性化合物
を混合することにより、電荷移動が起こり、結果として
フリーキャリアである正孔が生成し、正孔注入層の電気
電導度が高くなる。このため、このような正孔注入層を
設けることで、発光層と陽極との電気的接合が改善さ
れ、駆動電圧が低下すると同時に連続駆動時の安定性も
向上する。また、100℃以上のガラス転移温度を有する
芳香族ジアミン含有ポリエーテルを正孔注入層の母体と
することにより、素子の耐熱性も大きく改善される。本
発明で用いる芳香族ジアミン含有ポリエーテルのガラス
転移温度は特に120℃以上、とりわけ150℃以上であるこ
とが好ましい。In the present invention, by using a mixture of the aromatic diamine-containing polyether having a Tg of 100 ° C. or more and an electron-accepting compound, it is possible to simultaneously improve the luminous characteristics and heat resistance of the device. did. That is, by mixing the electron-accepting compound with the electron-donating aromatic diamine-containing polyether, charge transfer occurs, as a result, holes serving as free carriers are generated, and the electric conductivity of the hole injection layer is high. Become. For this reason, by providing such a hole injection layer, the electrical junction between the light emitting layer and the anode is improved, and the driving voltage is reduced, and at the same time, the stability during continuous driving is also improved. Further, by using an aromatic diamine-containing polyether having a glass transition temperature of 100 ° C. or higher as a base of the hole injection layer, the heat resistance of the element is greatly improved. The glass transition temperature of the aromatic diamine-containing polyether used in the present invention is preferably at least 120 ° C, particularly preferably at least 150 ° C.
【００３２】前記一般式（Ｉ）および（II）において、
Ａr1〜Ａr9は、好ましくは、各々独立して置換基を有し
ていてもよい２価のベンゼン環、ナフタレン環、アント
ラセン環、ビフェニルであり、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；ジエチルアミノ基、ジイソ
プロピルアミノ基等のジアルキルアミノ基が挙げられ
る。前記置換基としては、好ましくは炭素数１〜３のア
ルキル基が、特に好ましくはメチル基が挙げられる。In the above general formulas (I) and (II),
Ar 1 to Ar 9 are preferably a divalent benzene ring, a naphthalene ring, an anthracene ring, or a biphenyl, each of which may independently have a substituent, wherein the substituent is a halogen atom; a methyl group; An alkyl group having 1 to 6 carbon atoms such as an ethyl group; an alkenyl group such as a vinyl group; an alkoxycarbonyl group having 1 to 6 carbon atoms such as a methoxycarbonyl group and an ethoxycarbonyl group; 6, an alkoxy group; an aryloxy group such as a phenoxy group and a benzyloxy group; and a dialkylamino group such as a diethylamino group and a diisopropylamino group. As the substituent, an alkyl group having 1 to 3 carbon atoms is preferable, and a methyl group is particularly preferable.
【００３３】Ｒ1〜Ｒ4は、好ましくは、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、ピリジル基、トリアジル基、ピラジル基、キ
ノキサリル基、チエニル基、ビフェニル基であり、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；ジエ
チルアミノ基、ジイソプロピルアミノ基等のジアルキル
アミノ基が挙げられる。R 1 to R 4 are preferably a phenyl group, a naphthyl group, an anthryl group, a pyridyl group, a triazyl group, a pyrazyl group, a quinoxalyl group, a thienyl group, each of which may independently have a substituent. A biphenyl group, wherein the substituent is a halogen atom; an alkyl group having 1 to 6 carbon atoms such as a methyl group and an ethyl group; an alkenyl group such as a vinyl group; and a 1 to 6 carbon atom such as a methoxycarbonyl group and an ethoxycarbonyl group. An alkoxycarbonyl group; a methoxy group,
An alkoxy group having 1 to 6 carbon atoms such as an ethoxy group; an aryloxy group such as a phenoxy group and a benzyloxy group; and a dialkylamino group such as a diethylamino group and a diisopropylamino group.
【００３４】Ｘ及びＹは直接結合または以下に示す連結
基から選ばれる。X and Y are selected from a direct bond or a linking group shown below.
【００３５】[0035]
【化１１】 Embedded image
【００３６】上記連結基において、Ｒ′は、好ましくは
メチレン基、ジメチルメチレン基、エチレン基、プロピ
レン基であり、Ｒ″は、好ましくはメチル基、エチル基
等の炭素数１〜６のアルキル基；フェニル基、ナフチル
基、アントリル基、トリル基等の芳香族環基である。In the above linking group, R 'is preferably a methylene group, a dimethylmethylene group, an ethylene group or a propylene group, and R "is preferably an alkyl group having 1 to 6 carbon atoms such as a methyl group or an ethyl group. An aromatic ring group such as a phenyl group, a naphthyl group, an anthryl group and a tolyl group;
【００３７】前記一般式（Ｉ）及び（II）で表される化
合物は、例えば、城戸らの方法（Polymers for Advance
d Technologies， 7巻，31頁，1996年；特開平９−1887
56号公報）に開示されている経路で合成される。The compounds represented by the general formulas (I) and (II) can be prepared, for example, by the method of Kido et al. (Polymers for Advance).
d Technologies, 7, 31 pages, 1996; JP-A-9-1887
No. 56).
【００３８】前記一般式（Ｉ）で表される、本発明の芳
香族ジアミン含有ポリエーテルが有する繰り返し単位の
好ましい具体例を表１〜表３に示すが、これらに限定す
るものではない。Preferred specific examples of the repeating unit represented by the general formula (I) and contained in the aromatic diamine-containing polyether of the present invention are shown in Tables 1 to 3, but are not limited thereto.
【００３９】[0039]
【表１】 [Table 1]
【００４０】[0040]
【表２】 [Table 2]
【００４１】[0041]
【表３】 [Table 3]
【００４２】また、前記一般式（II）で表される、本発
明の芳香族ジアミン含有ポリエーテルが有する繰り返し
単位の好ましい具体例を表４，表５に示すが、これらに
限定するものではない。Preferred specific examples of the repeating unit of the aromatic diamine-containing polyether of the present invention represented by the general formula (II) are shown in Tables 4 and 5, but are not limited thereto. .
【００４３】[0043]
【表４】 [Table 4]
【００４４】[0044]
【表５】 [Table 5]
【００４５】上述の芳香族ジアミン含有ポリエーテルと
組み合わせて用いる電子受容性化合物としては、該芳香
族ジアミン含有ポリエーテルとの間で電荷移動を起こす
ものであればよいが、本発明者が鋭意検討した結果、芳
香族ジアミン含有ポリエーテルのイオン化ポテンシャ
ル：ＩＰ（ポリエーテル）と、電子受容性化合物（アク
セプタ）の電子親和力：ＥＡ（アクセプタ）の２つの物
性値が、 ＩＰ（ポリエーテル）−ＥＡ（アクセプタ）≦ 0.7ｅＶ の関係式で表される場合に本発明の目的に有効であるこ
とを見出した。The electron-accepting compound used in combination with the above-mentioned aromatic diamine-containing polyether may be any as long as it causes charge transfer with the aromatic diamine-containing polyether. As a result, two physical property values of the ionization potential of the aromatic diamine-containing polyether: IP (polyether) and the electron affinity of the electron-accepting compound (acceptor): EA (acceptor) are expressed by IP (polyether) -EA ( It has been found that, when represented by the relational expression of (acceptor) ≦ 0.7 eV, it is effective for the purpose of the present invention.
【００４６】このことを図４のエネルギー準位図を用い
て説明する。一般に、イオン化ポテンシャル及び電子親
和力は真空準位を基準として決定される。イオン化ポテ
ンシャルは物質のＨＯＭＯ（最高被占分子軌道）レベル
にある電子を真空準位に放出するのに必要なエネルギー
で定義され、電子親和力は真空準位にある電子が物質の
ＬＵＭＯ（最低空分子軌道）レベルに落ちて安定化する
エネルギーで定義される。本発明において、図４に示す
芳香族ジアミン含有ポリエーテルのＨＯＭＯレベルのイ
オン化ポテンシャルと、電子受容性化合物のＬＵＭＯレ
ベルの電子親和力の差が 0.7eV以下であることが好まし
い。イオン化ポテンシャルは光電子分光法で直接測定さ
れるか、電気化学的に測定した酸化電位を基準電極に対
して補正しても求められる。後者の方法の場合は、例え
ば、飽和甘コウ電極（ＳＣＥ）を基準電極として用いた
とき、 イオン化ポテンシャル＝酸化電位（vs.SCE）＋4.3 ｅＶ で表される（"Molecular Semiconductors", Springer-V
erlag, 1985年、98頁）。電子親和力は、上述のイオン
化ポテンシャルから光学的バンドギャップを差し引いて
求められるか、電気化学的な還元電位から上記の式で同
様に求められる。This will be described with reference to the energy level diagram of FIG. Generally, the ionization potential and the electron affinity are determined based on the vacuum level. The ionization potential is defined as the energy required to release electrons at the HOMO (highest occupied molecular orbital) level of a substance to a vacuum level, and the electron affinity is determined by the LUMO (lowest empty molecule) of the substance at a vacuum level. Orbit) is defined as the energy that falls to a level and stabilizes. In the present invention, the difference between the ionization potential at the HOMO level of the aromatic diamine-containing polyether shown in FIG. 4 and the electron affinity at the LUMO level of the electron-accepting compound is preferably 0.7 eV or less. The ionization potential is directly measured by photoelectron spectroscopy, or can be obtained by correcting an electrochemically measured oxidation potential with respect to a reference electrode. In the case of the latter method, for example, when a saturated sweet pepper electrode (SCE) is used as a reference electrode, ionization potential = oxidation potential (vs. SCE) +4.3 eV (“Molecular Semiconductors”, Springer- V
erlag, 1985, p. 98). The electron affinity can be obtained by subtracting the optical band gap from the above-mentioned ionization potential, or similarly from the above-mentioned formula from the electrochemical reduction potential.
【００４７】前記イオン化ポテンシャルと電子親和力の
関係式は、酸化電位と還元電位を用いて、 ポリエーテルの酸化電位−アクセプタの還元電位≦ 0.7
ｅＶ と表現することもできる。The relational expression between the ionization potential and the electron affinity is obtained by using the oxidation potential and the reduction potential as follows: oxidation potential of polyether−reduction potential of acceptor ≦ 0.7.
It can also be expressed as eV.
【００４８】正孔注入層中の電子受容性化合物の芳香族
ジアミン含有ポリエーテルに対する含有量は、通常0.1
〜50重量％、特に１〜30重量％の範囲にあることが好ま
しい。The content of the electron accepting compound in the hole injection layer with respect to the aromatic diamine-containing polyether is usually 0.1%.
Preferably it is in the range of from 50 to 50% by weight, especially from 1 to 30% by weight.
【００４９】電子受容性化合物としては、上記の関係を
満たすものであれば特に限定はされないが、好ましく
は、以下に示す一般式（III）で表される化合物から選
ばれる。The electron accepting compound is not particularly limited as long as it satisfies the above relationship, but is preferably selected from compounds represented by the following general formula (III).
【００５０】[0050]
【化１２】 Embedded image
【００５１】上記一般式（III）において、Ｚは好まし
くは塩素、フッ素、臭素等のハロゲン原子であり、Ｒ5
は好ましくは、水素原子；塩素、フッ素、臭素等のハロ
ゲン原子；メチル基、エチル基等の炭素数１〜６のアル
キル基；トリフロロメチル基等のハロアルキル基；シア
ノ基；ニトロ基である。置換位置は中心窒素原子に対し
てオルト位、メタ位、パラ位のいずれでもよい。[0051] In the general formula (III), Z is preferably chlorine, fluorine, halogen atom such as bromine, R 5
Is preferably a hydrogen atom; a halogen atom such as chlorine, fluorine and bromine; an alkyl group having 1 to 6 carbon atoms such as a methyl group and an ethyl group; a haloalkyl group such as a trifluoromethyl group; a cyano group; The substitution position may be any of the ortho, meta and para positions with respect to the central nitrogen atom.
【００５２】前記一般式（III）で表される電子受容性
化合物の具体例としては、以下に示す化合物が挙げられ
る。Specific examples of the electron accepting compound represented by the general formula (III) include the following compounds.
【００５３】[0053]
【化１３】 Embedded image
【００５４】電子受容性化合物の他の好ましい例を、以
下に省略名とともに示す。Other preferred examples of the electron accepting compound are shown below with their abbreviations.
【００５５】[0055]
【化１４】 Embedded image
【００５６】本発明において、芳香族ジアミン含有ポリ
エーテルと電子受容性化合物とを含有する正孔注入層３
は通常塗布法により前記陽極２上に形成される。例え
ば、前記一般式（Ｉ）または（II）で表されるポリエー
テルと電子受容性化合物の所定量に、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塗布性改良剤など
の添加剤等を添加し、溶解して塗布溶液を調製し、スピ
ンコート法やディップコート法などの方法により陽極２
上に塗布し、乾燥して正孔注入層３を形成する。In the present invention, the hole injection layer 3 containing the aromatic diamine-containing polyether and the electron-accepting compound is used.
Is usually formed on the anode 2 by a coating method. For example, if necessary, an additive such as a binder resin which does not trap holes or an additive such as a coating improver is added to a predetermined amount of the polyether represented by the above general formula (I) or (II) and the electron accepting compound. And dissolve to prepare a coating solution. The anode 2 is formed by a method such as spin coating or dip coating.
It is applied on top and dried to form the hole injection layer 3.
【００５７】このようにして形成される正孔注入層３の
膜厚は、通常5〜1000 nm、好ましくは10〜500 nmであ
る。The thickness of the hole injection layer 3 thus formed is usually 5 to 1000 nm, preferably 10 to 500 nm.
【００５８】正孔注入層３の上には発光層５が設けられ
る。発光層５は、電界を与えられた電極間において陰極
７から注入された電子と正孔注入層３から輸送された正
孔を効率よく再結合し、かつ、再結合により効率よく発
光する材料から形成される。The light emitting layer 5 is provided on the hole injection layer 3. The light emitting layer 5 is made of a material that efficiently recombines electrons injected from the cathode 7 and holes transported from the hole injection layer 3 between the electrodes to which an electric field is applied, and emits light efficiently by the recombination. It is formed.
【００５９】このような条件を満たす材料としては、８
−ヒドロキシキノリンのアルミニウム錯体などの金属錯
体（特開昭59−194393号公報）、10-ヒドロキシベンゾ
[h]キノリンの金属錯体（特開平６−322362号公報）、
ビススチリルベンゼン誘導体（特開平１−245087号公
報、同２−222484号公報）、ビススチリルアリーレン誘
導体（特開平２−247278号公報）、(2-ヒドロキシフェ
ニル)ベンゾチアゾールの金属錯体（特開平８−315983
号公報）、シロール誘導体等が挙げられる。これらの発
光層材料は、通常は真空蒸着法により正孔注入層３上に
積層形成される。As a material satisfying such conditions, 8
Metal complexes such as aluminum complexes of -hydroxyquinoline (JP-A-59-194393);
[h] quinoline metal complex (JP-A-6-322362),
Bisstyrylbenzene derivatives (Japanese Patent Application Laid-Open Nos. 1-245087 and 2-222484), bisstyrylarylene derivatives (Japanese Patent Application Laid-Open No. 2-247278), and metal complexes of (2-hydroxyphenyl) benzothiazole (Japanese Patent Application Laid-open No. −315983
Publication), silole derivatives and the like. These light emitting layer materials are usually formed on the hole injection layer 3 by vacuum evaporation.
【００６０】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. Phys., 65
巻, 3610頁, 1989年）等が行われている。この方法の利
点は、 １）高効率の蛍光色素により発光効率が向上、 ２）蛍光色素の選択により発光波長が可変、 ３）濃度消光を起こす蛍光色素も使用可能、 ４）薄膜性のわるい蛍光色素も使用可能、 等が挙げられる。For the purpose of improving the luminous efficiency of the device and changing the luminescent color, for example, doping a fluorescent dye for laser such as coumarin using an aluminum complex of 8-hydroxyquinoline as a host material (J. Appl. Phys. , 65
Vol. 3610, 1989). The advantages of this method are: 1) improved luminous efficiency by high-efficiency fluorescent dye, 2) variable emission wavelength by selecting fluorescent dye, 3) fluorescent dye which causes concentration quenching can be used, 4) fluorescent light with poor thin film property Dyes can also be used.
【００６１】素子の駆動寿命を改善する目的において
も、前記発光層材料をホスト材料として、蛍光色素をド
ープすることは有効である。例えば、８−ヒドロキシキ
ノリンのアルミニウム錯体などの金属錯体をホスト材料
として、ルブレンに代表されるナフタセン誘導体（特開
平４−335087号公報）、キナクリドン誘導体（特開平５
− 70773号公報）、ペリレン等の縮合多環芳香族環（特
開平５−198377号公報）を、ホスト材料に対して 0.1〜
10重量％ドープすることにより、素子の発光特性、特に
駆動安定性を大きく向上させることができる。発光層の
ホスト材料に上記ナフタセン誘導体、キナクリドン誘導
体、ペリレン等の蛍光色素をドープする方法としては、
共蒸着による方法と蒸着源を予め所定の濃度で混合して
おく方法がある。For the purpose of improving the driving life of the device, it is effective to dope a fluorescent dye by using the light emitting layer material as a host material. For example, using a metal complex such as an aluminum complex of 8-hydroxyquinoline as a host material, a naphthacene derivative represented by rubrene (Japanese Patent Laid-Open No. 4-335087) and a quinacridone derivative (Japanese Patent Laid-Open No.
No. 70773), condensed polycyclic aromatic rings such as perylene (JP-A-5-198377) are added to the host material in an amount of 0.1 to 0.1%.
By doping at 10% by weight, the light emitting characteristics of the device, particularly the driving stability, can be greatly improved. As a method of doping a fluorescent dye such as the naphthacene derivative, quinacridone derivative, or perylene into the host material of the light-emitting layer,
There are a method of co-evaporation and a method of mixing evaporation sources at a predetermined concentration in advance.
【００６２】高分子系の発光層材料としては、先に挙げ
たポリ（p-フェニレンビニレン）、ポリ［2-メトキシ-5
-（2-エチルヘキシルオキシ）-1,4-フェニレンビニレ
ン］、ポリ（3-アルキルチオフェン）等の高分子材料
や、ポリビニルカルバゾール等の高分子に発光材料と電
子移動材料を混合した系等が挙げられる。これらの材料
は正孔注入層と同様にスピンコートやディップコート等
の方法により正孔注入層３上に塗布して薄膜形成される このようにして形成される発光層５の膜厚は、通常10〜
200 nm、好ましくは30〜100 nmである。Examples of the polymer-based light emitting layer materials include poly (p-phenylenevinylene) and poly [2-methoxy-5] described above.
-(2-ethylhexyloxy) -1,4-phenylenevinylene], a polymer material such as poly (3-alkylthiophene), a system in which a luminescent material and an electron transfer material are mixed with a polymer such as polyvinylcarbazole, and the like. Can be These materials are coated on the hole injection layer 3 by a method such as spin coating or dip coating in the same manner as the hole injection layer to form a thin film. Ten~
It is 200 nm, preferably 30-100 nm.
【００６３】素子の発光特性を向上させるために、図２
に示すように、正孔輸送層４を正孔注入層３と発光層５
との間に設けたり、さらには、図３に示す様に電子輸送
層６を発光層５と陰極７との間に設けるなど機能分離型
にすることが行われる。In order to improve the light emitting characteristics of the device, FIG.
As shown in the figure, the hole transport layer 4 is
And a function-separated type such as providing the electron transport layer 6 between the light emitting layer 5 and the cathode 7 as shown in FIG.
【００６４】図２及び図３の機能分離型素子において、
正孔輸送層４の材料としては、正孔注入層３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、さらに安定性に優れ、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。In the function-separated element shown in FIGS. 2 and 3,
The material of the hole transport layer 4 needs to be a material having high hole injection efficiency from the hole injection layer 3 and 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 further excellent, and impurities serving as traps are hardly generated during production or use.
【００６５】このような正孔輸送材料としては、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）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）、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４−290851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５−320634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（特開平７−138562号公報）、ジアミノフェニルフ
ェナントリジン誘導体（特開平７−252474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）等が挙げられる。こ
れらの化合物は、単独で用いてもよいし、必要に応じ
て、２種以上を混合して用いてもよい。As such a hole transporting material, for example, an aromatic diamine compound linked to a tertiary aromatic amine unit such as 1,1-bis (4-di-p-tolylaminophenyl) cyclohexane (Japanese Unexamined Patent Application Publication No. JP-A-59-194393), 4,4'-
Aromatic amines containing two or more tertiary amines represented by bis [N- (1-naphthyl) -N-phenylamino] biphenyl and having two or more condensed aromatic rings substituted by nitrogen atoms (Japanese Unexamined Patent Application Publication No. -234681), an aromatic triamine having a starburst structure as a derivative of triphenylbenzene (U.S. Pat. No. 4,923,774), N, N'-diphenyl-N, N'-bis (3-
Aromatic diamines such as methylphenyl) biphenyl-4,4′-diamine (US Pat. No. 4,764,625) and triphenylamine derivatives which are sterically asymmetric as a whole molecule
JP-A-129271), 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 by an ethylene group (JP-A-4-264189) Japanese Patent Application Laid-Open No. 4-290851, an aromatic diamine having a styryl structure (JP-A-4-290851), an aromatic tertiary amine unit linked by a thiophene group (JP-A-4-304466), a starburst type aromatic triamine (JP-A-4-308688), a benzylphenyl compound (JP-A-4-364153), a tertiary amine linked by a fluorene group (JP-A-5-25473), and a triamine compound (JP-A-5-253473). 239455),
Bisdipyridylaminobiphenyl (JP-A-5-320634), N, N, N-triphenylamine derivative (JP-A-6-320634)
1972), an aromatic diamine having a phenoxazine structure (JP-A-7-138562), a diaminophenylphenanthridine derivative (JP-A-7-252474), a silazane compound (US Pat. No. 4,950,950), Examples thereof include silanamine derivatives (JP-A-6-49079) and phosphamine derivatives (JP-A-6-25659). These compounds may be used alone or, if necessary, in combination of two or more.
【００６６】上記の化合物以外に、正孔輸送層４の材料
としては、ポリビニルカルバゾールやポリシラン、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５−310949号公報）、ポリビニルトリフェニ
ルアミン（特開平７−53953号公報）、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）、
芳香族アミンを含有するポリメタクリレート等の高分子
材料が挙げられる。In addition to the above compounds, materials for the hole transport layer 4 include polyvinyl carbazole, polysilane, polyphosphazene (JP-A-5-310949), polyamide (JP-A-5-310949), and polyvinyltriazole. Phenylamine (JP-A-7-53953), a polymer having a triphenylamine skeleton (JP-A-4-133065),
A polymer material such as polymethacrylate containing an aromatic amine may be used.
【００６７】正孔輸送層４は上記の正孔輸送材料を塗布
法あるいは真空蒸着法により前記正孔注入層３上に積層
することにより形成される。The hole transport layer 4 is formed by laminating the above hole transport material on the hole injection layer 3 by a coating method or a vacuum evaporation method.
【００６８】塗布法の場合は、正孔輸送材料の１種また
は２種以上に、必要により正孔のトラップにならないバ
インダー樹脂や塗布性改良剤などの添加剤とを添加し、
溶解して塗布溶液を調製し、スピンコート法などの方法
により正孔注入層３上に塗布し、乾燥して正孔輸送層４
を形成する。ここで、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、通常５０重量％以
下が好ましい。In the case of the coating method, if necessary, an additive such as a binder resin or a coating property improving agent which does not trap holes is added to one or more of the hole transporting materials.
The solution is dissolved to prepare a coating solution, applied to the hole injection layer 3 by a method such as spin coating, dried, and dried to form the hole transport layer 4.
To form Here, examples of the binder resin include polycarbonate, polyarylate, and polyester. If the amount of the binder resin added is large, the hole mobility is lowered. Therefore, a small amount is desirable, and usually 50% by weight or less is preferable.
【００６９】真空蒸着法の場合には、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10-4Pa程度にまで排気した後、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、陽極２および正孔注入層３が形成された基
板１上に正孔輸送層４を形成する。In the case of the vacuum vapor deposition method, the hole transporting material is put into a crucible placed in a vacuum vessel, and the inside of the vacuum vessel is evacuated to about 10 -4 Pa by a suitable vacuum pump, and then the crucible is heated. Then, the hole transporting material is evaporated, and the hole transporting layer 4 is formed on the substrate 1 on which the anode 2 and the hole injection layer 3 are formed facing the crucible.
【００７０】このようにして形成される正孔輸送層４の
膜厚は、通常10〜300nm、好ましくは30〜100nmである。
このように薄い膜を一様に形成するためには、一般に真
空蒸着法がよく用いられる。The thickness of the hole transport layer 4 thus formed is usually 10 to 300 nm, preferably 30 to 100 nm.
In order to uniformly form such a thin film, generally, a vacuum deposition method is often used.
【００７１】また、この電子輸送層６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。このような電子輸送
材料としては、既に発光層材料として挙げた８−ヒドロ
キシキノリンのアルミ錯体、オキサジアゾール誘導体
（Appl. Phys. Lett., 55巻, 1489頁, 1989年） やそれ
らをポリメタクリル酸メチル（ＰＭＭＡ）等の樹脂に分
散した系、フェナントロリン誘導体（特開平５−331459
号公報）、2-t-ブチル-9,10-N,N'-ジシアノアントラキ
ノンジイミン、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
６の膜厚は、通常5〜200nm、好ましくは10〜100 nmであ
る。The compound used for the electron transport layer 6 is required to be capable of easily injecting electrons from the cathode and having a higher electron transport ability. Examples of such an electron transporting material include an aluminum complex of 8-hydroxyquinoline, an oxadiazole derivative (Appl. Phys. Lett., 55, 1489, 1989), which has already been mentioned as a light emitting layer material, and polymethacrylic acid. Phenanthroline derivatives dispersed in a resin such as methyl methacrylate (PMMA) (JP-A-5-331459)
Publication), 2-t-butyl-9,10-N, N'-dicyanoanthraquinone diimine, n-type hydrogenated amorphous silicon carbide, n-type zinc sulfide, n-type zinc selenide, and the like. The thickness of the electron transport layer 6 is usually 5 to 200 nm, preferably 10 to 100 nm.
【００７２】陰極７は、発光層５に電子を注入する役割
を果たす。陰極７として用いられる材料は、前記陽極２
に使用される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、カルシウム、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。具体例としては、マグネシウム−銀合金、マ
グネシウム−インジウム合金、アルミニウム−リチウム
合金等の低仕事関数合金電極が挙げられる。The cathode 7 plays a role of injecting electrons into the light emitting layer 5. The material used for the cathode 7 is the anode 2
It is possible to use a material used for the above, but for efficient electron injection, a metal having a low work function is preferable, and an appropriate metal such as tin, magnesium, indium, calcium, aluminum, silver or the like, An alloy is used. Specific examples include a low work function alloy electrode such as a magnesium-silver alloy, a magnesium-indium alloy, and an aluminum-lithium alloy.
【００７３】陰極７の膜厚は通常、陽極２と同様であ
る。低仕事関数金属から成る陰極を保護する目的で、こ
の上にさらに、仕事関数が高く大気に対して安定な金属
層を積層することは素子の安定性を増す上で有効であ
る。この目的のために、アルミニウム、銀、銅、ニッケ
ル、クロム、金、白金等の金属が使われる。The thickness of the cathode 7 is usually the same as that of the anode 2. In order to protect the cathode made of a low work function metal, it is effective to further stack a metal layer having a high work function and being stable to the atmosphere to increase the stability of the device. For this purpose, metals such as aluminum, silver, copper, nickel, chromium, gold, platinum and the like are used.
【００７４】さらに、陰極７と発光層５または電子輸送
層６の界面にＬｉＦ、ＭｇＦ2、Ｌｉ2Ｏ等の極薄絶縁膜
（0.1〜5nm）を挿入することも、素子の効率を向上させ
る有効な方法である（Appl. Phys. Lett., 70巻，152
頁，1997年；特開平10− 74586号公報；IEEE Trans. El
ectron. Devices，44巻，1245頁，1997年）。Further, inserting an ultra-thin insulating film (0.1 to 5 nm) of LiF, MgF 2 , Li 2 O or the like at the interface between the cathode 7 and the light emitting layer 5 or the electron transporting layer 6 also improves the efficiency of the device. It is an effective method (Appl. Phys. Lett., 70, 152
Page, 1997; JP-A-10-74586; IEEE Trans. El.
ectron. Devices, 44, 1245, 1997).
【００７５】図１〜３は、本発明で採用される素子構造
の一例であって、本発明は何ら図示のものに限定される
ものではない。例えば、図１とは逆の構造、即ち、基板
１上に陰極７、発光層５、正孔注入層３、陽極２の順に
積層することも可能であり、既述したように少なくとも
一方が透明性の高い２枚の基板の間に本発明の有機電界
発光素子を設けることも可能である。同様に、図２及び
図３に示したものについても、前記各構成層を逆の構造
に積層することも可能である。FIGS. 1 to 3 show an example of an element structure employed in the present invention, and the present invention is not limited to those shown in the drawings. For example, it is also possible to stack the cathode 7, the light emitting layer 5, the hole injection layer 3, and the anode 2 in this order on the substrate 1, that is, at least one of them is transparent as described above. It is also possible to provide the organic electroluminescent device of the present invention between two highly-substrate substrates. Similarly, the components shown in FIGS. 2 and 3 can be stacked in the opposite structure.
【００７６】[0076]
【実施例】次に、本発明を実験例、比較実験例、実施例
及び比較例によって更に具体的に説明するが、本発明は
その要旨を超えない限り、以下の実施例の記載に限定さ
れるものではない。Next, the present invention will be described in more detail with reference to Experimental Examples, Comparative Experimental Examples, Examples and Comparative Examples, but the present invention is limited to the following Examples unless it exceeds the gist thereof. Not something.
【００７７】実験例１ ガラス基板を、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、既述の方法により合成し
た芳香族ジアミン含有ポリエーテル（表１の番号（Ｉ−
１）に示す繰り返し単位１００％からなる；重量平均分
子量9300；ガラス転移温度 190℃）を下記の条件で、上
記ガラス基板上にスピンコートした。Experimental Example 1 A glass substrate was subjected to ultrasonic cleaning with acetone, water cleaning with pure water, ultrasonic cleaning with isopropyl alcohol, and drying with dry nitrogen.
After performing UV / ozone cleaning, the aromatic diamine-containing polyether synthesized by the method described above (the number (I-
(1) consisting of 100% of repeating units; weight average molecular weight of 9300; glass transition temperature of 190 ° C.) was spin-coated on the above glass substrate under the following conditions.
【００７８】 溶媒 1,2-ジクロロエタン 塗布液濃度 30［mg／ml］ スピナ回転数 2500［rpm］ スピナ回転時間 25［秒］ 乾燥条件 90分間−自然乾燥 上記のスピンコートにより30nmの膜厚の均一な薄膜が形
成された。この薄膜試料のイオン化ポテンシャルを理研
計器（株）製の紫外線電子分析装置（ＡＣ−１）を用い
て測定したところ、5.23eVの値を示した。Solvent 1,2-dichloroethane Coating solution concentration 30 [mg / ml] Spinner rotation speed 2500 [rpm] Spinner rotation time 25 [second] Drying condition 90 minutes-natural drying Uniform film thickness of 30 nm by the above spin coating A thin film was formed. When the ionization potential of this thin film sample was measured using an ultraviolet electron analyzer (AC-1) manufactured by Riken Keiki Co., Ltd., a value of 5.23 eV was shown.
【００７９】還元電位が報告されているいくつかの電子
受容性化合物について、電子親和力を表６に示す。ま
た、上記芳香族ジアミン含有ポリエーテルのイオン化ポ
テンシャルとの差を表６に併記する。Table 6 shows the electron affinities of some electron accepting compounds for which reduction potentials are reported. Table 6 also shows the difference between the aromatic diamine-containing polyether and the ionization potential.
【００８０】[0080]
【表６】 [Table 6]
【００８１】実験例２ 芳香族ジアミン含有ポリエーテル（表１の番号（Ｉ−
１）に示す繰り返し単位１００％からなる）に電子受容
性化合物のＤＤＱを混合し、下記条件で、実験例１と同
様にしてガラス基板上にスピンコートした。EXPERIMENTAL EXAMPLE 2 Aromatic diamine-containing polyether (No. (I-
DDQ as an electron-accepting compound was mixed with a repeating unit (100%) shown in 1) and spin-coated on a glass substrate in the same manner as in Experimental Example 1 under the following conditions.
【００８２】 溶媒 1,2-ジクロロエタン Ｉ−１ 30mg ＤＤＱ 2mg 塗布液濃度 30［mg／ml］ スピナ回転数 2500［rpm］ スピナ回転時間 25［秒］ 乾燥条件 90分間−自然乾燥 上記のスピンコートにより30nmの膜厚の均一な、ＤＤＱ
を６重量％含む薄膜が形成された。この薄膜試料の可視
部分の吸収スペクトルを測定した結果を図５に示す。図
５に示す如く、可視光領域において透明な膜が得られ
た。Solvent 1,2-dichloroethane I-1 30 mg DDQ 2 mg Coating solution concentration 30 [mg / ml] Spinner rotation speed 2500 [rpm] Spinner rotation time 25 [sec] Drying condition 90 minutes-natural drying DDQ with uniform thickness of 30nm
Was formed in a thin film containing 6% by weight. FIG. 5 shows the result of measuring the absorption spectrum of the visible portion of the thin film sample. As shown in FIG. 5, a transparent film was obtained in the visible light region.
【００８３】実験例３ 芳香族ジアミン含有ポリエーテルとして、既述の方法に
より合成した芳香族ジアミン含有ポリエーテル（表３の
番号（Ｉ−23）に示す繰り返し単位１００％からなる；
重量平均分子量25100；ガラス転移温度183℃）を用いた
こと以外は実験例１と同様にしてガラス基板上にスピン
コートを行い、40nmの膜厚の均一な薄膜を形成した。こ
の薄膜試料のイオン化ポテンシャルを測定したところ、
5.12eVの値を示した。EXPERIMENTAL EXAMPLE 3 As an aromatic diamine-containing polyether, an aromatic diamine-containing polyether synthesized by the above-described method (consisting of 100% of repeating units shown in Table 3 as number (I-23);
Spin coating was performed on a glass substrate in the same manner as in Experimental Example 1 except that a weight average molecular weight of 25100; a glass transition temperature of 183 ° C.) was used to form a uniform thin film having a thickness of 40 nm. When the ionization potential of this thin film sample was measured,
It showed a value of 5.12 eV.
【００８４】従って、この（Ｉ−23）からなる芳香族ジ
アミン含有ポリエーテルのイオン化ポテンシャルと電子
受容性化合物であるTBPAHの電子親和力との差は−0.24e
Vであることが確認された。Accordingly, the difference between the ionization potential of the aromatic diamine-containing polyether comprising (I-23) and the electron affinity of TBPAH, which is an electron-accepting compound, is -0.24 e
V was confirmed.
【００８５】比較実験例１ 実験例１と同様にして洗浄したガラス基板を真空蒸着装
置内に設置した。上記装置の粗排気を油回転ポンプによ
り行った後、装置内の真空度が2×10-6Torr（約2.7×10
-4Pa）以下になるまで液体窒素トラップを備えた油拡散
ポンプを用いて排気した。上記装置内に配置されたモリ
ブデンボートに入れた、下記構造式で示される銅フタロ
シアニンを加熱して蒸着を行った。蒸着時の真空度は2
×10-6Torr（約2.7×10-4Pa）で、蒸着速度 0.2nm／秒
で膜厚30nmの膜を成膜した。Comparative Experimental Example 1 A glass substrate washed in the same manner as in Experimental Example 1 was set in a vacuum evaporation apparatus. After the rough evacuation of the above apparatus is performed by an oil rotary pump, the degree of vacuum in the apparatus is 2 × 10 −6 Torr (about 2.7 × 10
(−4 Pa) or less, using an oil diffusion pump equipped with a liquid nitrogen trap. The copper phthalocyanine represented by the following structural formula, which was placed in a molybdenum boat placed in the above apparatus, was heated to perform vapor deposition. The degree of vacuum during evaporation is 2
A film having a thickness of 30 nm was formed at × 10 −6 Torr (approximately 2.7 × 10 −4 Pa) at a deposition rate of 0.2 nm / sec.
【００８６】[0086]
【化１５】 Embedded image
【００８７】この薄膜試料の可視部分の透過スペクトル
を図５に示す。図５に示す如く、550〜700nmにおいて吸
収があり、この膜はフルカラー表示への適用には問題が
ある。FIG. 5 shows the transmission spectrum of the visible portion of the thin film sample. As shown in FIG. 5, there is absorption at 550 to 700 nm, and this film has a problem in application to full color display.
【００８８】実施例１ 図２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。Example 1 An organic electroluminescent device having the structure shown in FIG. 2 was manufactured by the following method.
【００８９】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（ジオマテ
ック社製；電子ビーム成膜品；シート抵抗15Ω）を通常
のフォトリソグラフィ技術と塩酸エッチングを用いて 2
mm幅のストライプにパターニングして陽極２を形成し
た。パターン形成したＩＴＯ基板を、アセトンによる超
音波洗浄、純水による水洗、イソプロピルアルコールに
よる超音波洗浄の順で洗浄後、窒素ブローで乾燥させ、
最後に紫外線オゾン洗浄を行った。A transparent conductive film of indium tin oxide (ITO) having a thickness of 120 nm was deposited on a glass substrate (manufactured by Geomatic Corporation; an electron beam film-formed product; sheet resistance of 15Ω) using a normal photolithography technique and hydrochloric acid etching. Two
The anode 2 was formed by patterning into a stripe having a width of mm. The patterned ITO substrate is cleaned by ultrasonic cleaning with acetone, water cleaning with pure water, and ultrasonic cleaning with isopropyl alcohol, and then dried by nitrogen blowing.
Finally, ultraviolet ozone cleaning was performed.
【００９０】このＩＴＯガラス基板上に、芳香族ジアミ
ン含有ポリエーテル（表１の番号（Ｉ−１）に示す繰り
返し単位１００％からなる）とＤＤＱとの混合物を実験
例２と同一条件でスピンコートし、27nmの膜厚の均一な
薄膜形状を有する正孔注入層３を形成した。On this ITO glass substrate, a mixture of an aromatic diamine-containing polyether (consisting of 100% of the repeating unit shown in the number (I-1) in Table 1) and DDQ was spin-coated under the same conditions as in Experimental Example 2. Then, a hole injection layer 3 having a uniform thin film shape with a thickness of 27 nm was formed.
【００９１】次に、上記正孔注入層３を塗布成膜した基
板１を真空蒸着装置内に設置した。上記装置の粗排気を
油回転ポンプにより行った後、装置内の真空度が2×10
-6Torr（約2.7×10-4Pa）以下になるまで液体窒素トラ
ップを備えた油拡散ポンプを用いて排気した。上記装置
内に配置されたセラミックるつぼに入れた下記構造式で
示される芳香族アミン化合物：4,4'-ビス［N-（1-ナフ
チル）-N-フェニルアミノ］ビフェニルを加熱して蒸着
を行った。蒸着時の真空度は1.3×10-6Torr（約1.7×10
-4Pa）、蒸着速度は0.3nm/秒で、膜厚60nmの膜をポリエ
ーテルからなる正孔注入層３の上に積層して正孔輸送層
４を完成させた。Next, the substrate 1 on which the hole injection layer 3 was applied and formed was set in a vacuum evaporation apparatus. After rough exhaust of the above device was performed by an oil rotary pump, the degree of vacuum in the device was 2 × 10
Evacuation was performed using an oil diffusion pump equipped with a liquid nitrogen trap until the pressure became -6 Torr (about 2.7 × 10 -4 Pa) or less. An aromatic amine compound represented by the following structural formula: 4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl, which is placed in a ceramic crucible placed in the above apparatus, is heated for vapor deposition. went. The degree of vacuum during vapor deposition is 1.3 × 10 −6 Torr (about 1.7 × 10
-4 Pa), a deposition rate of 0.3 nm / sec, and a film having a thickness of 60 nm was laminated on the hole injection layer 3 made of polyether to complete the hole transport layer 4.
【００９２】[0092]
【化１６】 Embedded image
【００９３】引続き、発光層５の材料として、下記構造
式で示されるアルミニウムの８−ヒドロキシキノリン錯
体：Ａｌ（Ｃ9Ｈ6ＮＯ）3を正孔輸送層４と同様にして
蒸着を行った。この時のアルミニウムの８−ヒドロキシ
キノリン錯体のるつぼ温度は275〜285℃の範囲で制御
し、蒸着時の真空度は1.1×10-6Torr（約1.5×10-4P
a）、蒸着速度は0.4nm/秒で、蒸着された発光層の膜厚
は75nmであった。Subsequently, as a material for the light emitting layer 5, aluminum 8-hydroxyquinoline complex represented by the following structural formula: Al (C 9 H 6 NO) 3 was deposited in the same manner as the hole transport layer 4. At this time, the crucible temperature of the aluminum 8-hydroxyquinoline complex was controlled in the range of 275 to 285 ° C., and the degree of vacuum at the time of vapor deposition was 1.1 × 10 −6 Torr (about 1.5 × 10 −4 P).
a), the deposition rate was 0.4 nm / sec, and the thickness of the deposited light emitting layer was 75 nm.
【００９４】[0094]
【化１７】 Embedded image
【００９５】なお、上記の正孔輸送層４及び発光層５を
真空蒸着する時の基板温度は室温に保持した。The substrate temperature during the vacuum deposition of the hole transport layer 4 and the light emitting layer 5 was kept at room temperature.
【００９６】ここで、発光層５までの蒸着を行った素子
を一度前記真空蒸着装置内より大気中に取り出して、陰
極蒸着用のマスクとして 2mm幅のストライプ状シャドー
マスクを、陽極２のＩＴＯストライプとは直交するよう
に素子に密着させて、別の真空蒸着装置内に設置して有
機層と同様にして装置内の真空度が2×10-6Torr（約2.7
×10-4Pa）以下になるまで排気した。その後、陰極７と
して、まず、フッ化マグネシウム（ＭｇＦ2）をモリブ
デンボートを用いて、蒸着速度0.1nm／秒、真空度7.0×
10-6Torr（約9.3×10-4Pa）で、 0.5nmの膜厚で発光層
５の上に成膜した。次に、アルミニウムを同様にモリブ
デンボートにより加熱して、蒸着速度0.5nm/秒、真空度
1×10-5Torr（約1.3×10-3Pa）で膜厚40nmのアルミニウ
ム層を形成した。さらに、その上に、陰極の導電性を高
めるために銅を、同様にモリブデンボートにより加熱し
て、蒸着速度0.5nm/秒、真空度1×10-5Torr（約1.3×10
-3Pa）で膜厚40nmの銅層を形成して陰極７を完成させ
た。以上の３層型陰極７の蒸着時の基板温度は室温に保
持した。Here, the element on which the light-emitting layer 5 was deposited was once taken out of the vacuum deposition apparatus into the atmosphere, and a 2 mm-wide stripe-shaped shadow mask was used as a cathode deposition mask, and the ITO stripe of the anode 2 was used. In close contact with the element so as to be orthogonal to the device, it is placed in another vacuum deposition apparatus and the degree of vacuum in the apparatus is set to 2 × 10 −6 Torr (about 2.7
(× 10 −4 Pa) or less. Then, as a cathode 7, first, magnesium fluoride (MgF 2 ) was deposited using a molybdenum boat at a deposition rate of 0.1 nm / sec and a degree of vacuum of 7.0 ×.
A film was formed on the light emitting layer 5 at 10 −6 Torr (about 9.3 × 10 −4 Pa) with a thickness of 0.5 nm. Next, the aluminum was similarly heated by a molybdenum boat, and the deposition rate was 0.5 nm / sec.
An aluminum layer having a thickness of 40 nm was formed at 1 × 10 −5 Torr (about 1.3 × 10 −3 Pa). Further, copper is further heated thereon by a molybdenum boat in order to increase the conductivity of the cathode, and the deposition rate is 0.5 nm / sec, the degree of vacuum is 1 × 10 −5 Torr (about 1.3 × 10 5 Torr).
A negative electrode 7 was completed by forming a copper layer having a thickness of 40 nm at -3 Pa). The substrate temperature during the deposition of the three-layer cathode 7 was kept at room temperature.
【００９７】以上のようにして、2mmx×2mmのサイズの
発光面積部分を有する有機電界発光素子が得られた。こ
の素子の発光特性を表７に示す。表７において、発光輝
度は250mA／cm2の電流密度での値、発光効率は 100cd／
m2での値、輝度／電流は輝度−電流密度特性の傾きを、
電圧は 100cd／m2での値を各々示す。As described above, an organic electroluminescent device having a light emitting area of 2 mm × 2 mm was obtained. Table 7 shows the emission characteristics of this device. In Table 7, the emission luminance is a value at a current density of 250 mA / cm 2 , and the emission efficiency is 100 cd / cm 2.
The slope of the current density characteristic, - the value of m 2, and the luminance / current intensity
The voltage shows a value at 100 cd / m 2 .
【００９８】表７より、低電圧で高輝度かつ高発光効率
で発光する素子が得られたことが明らかである。From Table 7, it is clear that an element which emits light with high luminance and high luminous efficiency at a low voltage was obtained.
【００９９】実施例２ ＤＤＱの代わりにＴＢＰＡＨ（tris(4-bromophenyl)ami
nium hexachloroantimonate）を用いた他は、実施例１
と同様にして図２に示す構造を有する有機電界発光素子
を作製した。正孔注入層３に含まれるＴＢＰＡＨの量は
14重量％とした。この素子の発光特性を表７に示す。Example 2 TBPAH (tris (4-bromophenyl) amido was used instead of DDQ)
Example 1 except that nium hexachloroantimonate) was used.
An organic electroluminescent device having the structure shown in FIG. The amount of TBPAH contained in the hole injection layer 3 is
It was 14% by weight. Table 7 shows the emission characteristics of this device.
【０１００】表７より、駆動電圧の低下が達成され、高
輝度、高効率の素子が得られたことが明らかである。It is apparent from Table 7 that the drive voltage was reduced and a device with high luminance and high efficiency was obtained.
【０１０１】実施例３ 正孔注入層を芳香族ジアミン含有ポリエーテル（表３の
番号（Ｉ−23）に示す繰り返し単位１００％からなる）
に電子受容性化合物としてTBPAHを9重量％ドープして膜
厚40nmで形成したこと以外は実施例２と同様にして有機
電界発光素子を作製した。この素子の発光特性を表７に
示す。Example 3 The hole injecting layer was made of an aromatic diamine-containing polyether (consisting of 100% of the repeating unit shown in Table 3 by number (I-23)).
An organic electroluminescent device was produced in the same manner as in Example 2 except that the film was formed to a thickness of 40 nm by doping 9% by weight of TBPAH as an electron accepting compound. Table 7 shows the emission characteristics of this device.
【０１０２】表７より、駆動電圧の低下が達成され、高
輝度、高効率の素子が得られたことが明らかである。It is apparent from Table 7 that the drive voltage was reduced and a device with high luminance and high efficiency was obtained.
【０１０３】比較例１ 電子受容性化合物を用いないで正孔注入層３を形成した
他は、実施例１と同様にして素子を作製した。この素子
の発光特性を表７に示す。Comparative Example 1 A device was produced in the same manner as in Example 1, except that the hole injection layer 3 was formed without using an electron accepting compound. Table 7 shows the emission characteristics of this device.
【０１０４】比較例２ 正孔注入層を設けない他は、実施例１と同様にして素子
を作製した。この素子の発光特性を表７に示す。Comparative Example 2 An element was fabricated in the same manner as in Example 1 except that no hole injection layer was provided. Table 7 shows the emission characteristics of this device.
【０１０５】[0105]
【表７】 [Table 7]
【０１０６】[0106]
【発明の効果】以上詳述した通り、特定の芳香族ジアミ
ン含有ポリエーテルと電子受容性化合物とを含有する正
孔注入層を形成した本発明の有機電界発光素子によれ
ば、低電圧での高発光効率駆動が可能で、しかも耐熱性
が良好な素子が提供される。As described in detail above, according to the organic electroluminescent device of the present invention in which a hole injection layer containing a specific aromatic diamine-containing polyether and an electron-accepting compound is formed, low-voltage operation is possible. An element which can be driven with high luminous efficiency and has good heat resistance is provided.
【０１０７】従って、本発明による有機電界発光素子
は、フラットパネル・ディスプレイ（例えばＯＡコンピ
ュータ用や壁掛けテレビ）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、特に、高耐熱性が要求される車載用表示
素子として、その技術的価値は大きいものである。Accordingly, the organic electroluminescent device according to the present invention can be used as a light source (for example, a light source of a copier, a liquid crystal display, or an instrument) utilizing the characteristics of a flat panel display (for example, for an OA computer or a wall-mounted television) or a surface light emitter. It can be applied to various types of backlight light sources, display boards, and marker lights, and has a great technical value particularly as a display element for vehicles that requires high heat resistance.
【図１】本発明の有機電界発光素子の実施の形態の一例
を示す模式的な断面図である。FIG. 1 is a schematic cross-sectional view showing an example of an embodiment of an organic electroluminescent device of the present invention.
【図２】本発明の有機電界発光素子の実施の形態の他の
例を示す模式的な断面図である。FIG. 2 is a schematic sectional view showing another example of the embodiment of the organic electroluminescent device of the present invention.
【図３】本発明の有機電界発光素子の実施の形態の別の
例を示す模式的な断面図である。FIG. 3 is a schematic sectional view showing another example of the embodiment of the organic electroluminescent device of the present invention.
【図４】イオン化ポテンシャルと電子親和力の関係を示
したエネルギー準位図である。FIG. 4 is an energy level diagram showing the relationship between ionization potential and electron affinity.
【図５】実験例２及び比較実験例１で形成した薄膜の可
視部分における透過スペクトルを示すグラフである。FIG. 5 is a graph showing transmission spectra in the visible part of the thin films formed in Experimental Example 2 and Comparative Experimental Example 1.
１ 基板 ２ 陽極 ３ 正孔注入層 ４ 正孔輸送層 ５ 発光層 ６ 電子輸送層 ７ 陰極 Reference Signs List 1 substrate 2 anode 3 hole injection layer 4 hole transport layer 5 light emitting layer 6 electron transport layer 7 cathode
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ０８Ｋ 5/55 Ｃ０８Ｋ 5/55 Ｃ０８Ｌ 71/00 Ｃ０８Ｌ 71/00 Ｈ０５Ｂ 33/14 Ｈ０５Ｂ 33/14 Ａ // Ｃ０９Ｋ 11/06 ６８０ Ｃ０９Ｋ 11/06 ６８０ (72)発明者 緒方 朋行 神奈川県横浜市青葉区鴨志田町1000番地 三菱化学株式会社横浜総合研究所内──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) C08K 5/55 C08K 5/55 C08L 71/00 C08L 71/00 H05B 33/14 H05B 33/14 A // C09K 11/06 680 C09K 11/06 680 (72) Inventor: Tomoyuki Ogata 1000 Kamoshida-cho, Aoba-ku, Aoba-ku, Yokohama-shi, Kanagawa Pref.
Claims (4)
た発光層が形成されると共に、該発光層と陽極との間に
正孔注入層が形成された有機電界発光素子において、該
正孔注入層が、下記一般式（Ｉ）または（II）で表わさ
れる繰り返し単位を有し、かつ、重量平均分子量が1,00
0〜1,000,000である芳香族ジアミン含有ポリエーテル
と、電子受容性化合物とを含有することを特徴とする有
機電界発光素子。 【化１】 【化２】 （式中、Ａr1，Ａr2，Ａr3，Ａr4，Ａr5，Ａr6，Ａr7，
Ａr8，Ａr9は、各々独立して置換基を有していてもよい
２価の芳香族環残基を示し、Ｒ1，Ｒ2，Ｒ3，Ｒ4は置換
基を有していてもよい芳香族環基または芳香族複素環基
を示し、Ｘ及びＹは直接結合、または下記の連結基から
選ばれる。） 【化３】 （式中、Ｒ′は置換基を有していてもよいアルキレン基
を示し、Ｒ″はアルキル基または置換基を有していても
よい芳香族環基を示す。）1. An organic electroluminescent device having a light emitting layer sandwiched between an anode and a cathode formed on a substrate and a hole injection layer formed between the light emitting layer and the anode. The injection layer has a repeating unit represented by the following general formula (I) or (II), and has a weight average molecular weight of 1,00
An organic electroluminescent device comprising an aromatic diamine-containing polyether of 0 to 1,000,000 and an electron-accepting compound. Embedded image Embedded image (Where Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 , Ar 6 , Ar 7 ,
Ar 8 and Ar 9 each independently represent a divalent aromatic ring residue which may have a substituent, and R 1 , R 2 , R 3 and R 4 each have a substituent. And X and Y are selected from the group consisting of a direct bond and the following linking groups. ) (In the formula, R ′ represents an alkylene group which may have a substituent, and R ″ represents an alkyl group or an aromatic ring group which may have a substituent.)
イオン化ポテンシャルから前記電子受容性化合物の電子
親和力を引いた値が0.7ｅＶ以下であり、前記正孔注入
層中の該電子受容性化合物の含有量が、該芳香族ジアミ
ン含有ポリエーテルに対して0.1〜50重量％の範囲であ
ることを特徴とする請求項１に記載の有機電界発光素
子。2. The value obtained by subtracting the electron affinity of the electron-accepting compound from the ionization potential of the aromatic diamine-containing polyether is 0.7 eV or less, and the content of the electron-accepting compound in the hole injection layer. The organic electroluminescent device according to claim 1, wherein the content is in the range of 0.1 to 50% by weight based on the aromatic diamine-containing polyether.
（III）で表される化合物の少なくとも１種であること
を特徴とする請求項１または２に記載の有機電界発光素
子。 【化４】 （式中、Ｚはハロゲン原子を示し、Ｒ5は水素原子、ハ
ロゲン原子、置換基を有していてもよいアルキル基、シ
アノ基またはニトロ基を示す。）3. The organic electroluminescent device according to claim 1, wherein the electron accepting compound is at least one compound represented by the following general formula (III). Embedded image (In the formula, Z represents a halogen atom, and R 5 represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, a cyano group or a nitro group.)
から選ばれる少なくとも１種であることを特徴とする請
求項１または２に記載の有機電界発光素子。 【化５】 4. The organic electroluminescent device according to claim 1, wherein the electron accepting compound is at least one selected from the following compound group. Embedded image
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12884199A JP4058842B2 (en) | 1998-05-13 | 1999-05-10 | Organic electroluminescence device |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13033998 | 1998-05-13 | ||
| JP10-130339 | 1998-05-13 | ||
| JP12884199A JP4058842B2 (en) | 1998-05-13 | 1999-05-10 | Organic electroluminescence device |
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| Publication Number | Publication Date |
|---|---|
| JP2000036390A true JP2000036390A (en) | 2000-02-02 |
| JP4058842B2 JP4058842B2 (en) | 2008-03-12 |
Family
ID=26464416
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