JP2003257677A - Organic electroluminescence element and its manufacturing method - Google Patents
Organic electroluminescence element and its manufacturing methodInfo
- Publication number
- JP2003257677A JP2003257677A JP2002057521A JP2002057521A JP2003257677A JP 2003257677 A JP2003257677 A JP 2003257677A JP 2002057521 A JP2002057521 A JP 2002057521A JP 2002057521 A JP2002057521 A JP 2002057521A JP 2003257677 A JP2003257677 A JP 2003257677A
- Authority
- JP
- Japan
- Prior art keywords
- layer
- organic electroluminescence
- chemical formula
- chemical
- anode layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000005401 electroluminescence Methods 0.000 title claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 21
- 239000001301 oxygen Substances 0.000 claims abstract description 21
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 14
- 239000011737 fluorine Substances 0.000 claims abstract description 14
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 13
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 13
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000011521 glass Substances 0.000 claims abstract description 8
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000010410 layer Substances 0.000 claims description 145
- 239000000758 substrate Substances 0.000 claims description 16
- 238000004381 surface treatment Methods 0.000 claims description 9
- 150000002894 organic compounds Chemical class 0.000 claims description 4
- 239000000470 constituent Substances 0.000 claims description 3
- 239000012044 organic layer Substances 0.000 claims description 3
- 230000005525 hole transport Effects 0.000 abstract description 20
- 238000000034 method Methods 0.000 abstract description 17
- -1 polyethylene tetrafluoride Polymers 0.000 abstract description 16
- 238000002347 injection Methods 0.000 abstract description 15
- 239000007924 injection Substances 0.000 abstract description 15
- 239000000243 solution Substances 0.000 abstract description 11
- 230000004888 barrier function Effects 0.000 abstract description 10
- 239000003795 chemical substances by application Substances 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 5
- 229920005989 resin Polymers 0.000 abstract description 3
- 239000011347 resin Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 description 126
- 239000010408 film Substances 0.000 description 36
- 238000007740 vapor deposition Methods 0.000 description 15
- 229920000642 polymer Polymers 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 230000000903 blocking effect Effects 0.000 description 9
- 238000009832 plasma treatment Methods 0.000 description 8
- 229910052709 silver Inorganic materials 0.000 description 8
- 239000004332 silver Substances 0.000 description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 229910052749 magnesium Inorganic materials 0.000 description 7
- 239000011777 magnesium Substances 0.000 description 7
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 7
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 6
- 238000011282 treatment Methods 0.000 description 6
- 229920002554 vinyl polymer Polymers 0.000 description 6
- 238000000576 coating method Methods 0.000 description 5
- 229920001940 conductive polymer Polymers 0.000 description 5
- 239000002019 doping agent Substances 0.000 description 5
- 229920002098 polyfluorene Polymers 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 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 4
- 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 3
- 239000004793 Polystyrene Substances 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 229920002857 polybutadiene Polymers 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 2
- CRGSMSNUTNRNQM-UHFFFAOYSA-N 2-(4-tert-butylphenyl)-1,3,4-oxadiazole Chemical compound C1=CC(C(C)(C)C)=CC=C1C1=NN=CO1 CRGSMSNUTNRNQM-UHFFFAOYSA-N 0.000 description 2
- FQJQNLKWTRGIEB-UHFFFAOYSA-N 2-(4-tert-butylphenyl)-5-[3-[5-(4-tert-butylphenyl)-1,3,4-oxadiazol-2-yl]phenyl]-1,3,4-oxadiazole Chemical compound C1=CC(C(C)(C)C)=CC=C1C1=NN=C(C=2C=C(C=CC=2)C=2OC(=NN=2)C=2C=CC(=CC=2)C(C)(C)C)O1 FQJQNLKWTRGIEB-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 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
- 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 2
- UEEXRMUCXBPYOV-UHFFFAOYSA-N iridium;2-phenylpyridine Chemical compound [Ir].C1=CC=CC=C1C1=CC=CC=N1.C1=CC=CC=C1C1=CC=CC=N1.C1=CC=CC=C1C1=CC=CC=N1 UEEXRMUCXBPYOV-UHFFFAOYSA-N 0.000 description 2
- 239000012280 lithium aluminium hydride Substances 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
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920000553 poly(phenylenevinylene) Polymers 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- ZSYMVHGRKPBJCQ-UHFFFAOYSA-N 1,1'-biphenyl;9h-carbazole Chemical group C1=CC=CC=C1C1=CC=CC=C1.C1=CC=C2C3=CC=CC=C3NC2=C1 ZSYMVHGRKPBJCQ-UHFFFAOYSA-N 0.000 description 1
- FKASFBLJDCHBNZ-UHFFFAOYSA-N 1,3,4-oxadiazole Chemical compound C1=NN=CO1 FKASFBLJDCHBNZ-UHFFFAOYSA-N 0.000 description 1
- UHXOHPVVEHBKKT-UHFFFAOYSA-N 1-(2,2-diphenylethenyl)-4-[4-(2,2-diphenylethenyl)phenyl]benzene Chemical compound C=1C=C(C=2C=CC(C=C(C=3C=CC=CC=3)C=3C=CC=CC=3)=CC=2)C=CC=1C=C(C=1C=CC=CC=1)C1=CC=CC=C1 UHXOHPVVEHBKKT-UHFFFAOYSA-N 0.000 description 1
- VEUMBMHMMCOFAG-UHFFFAOYSA-N 2,3-dihydrooxadiazole Chemical compound N1NC=CO1 VEUMBMHMMCOFAG-UHFFFAOYSA-N 0.000 description 1
- YMMGRPLNZPTZBS-UHFFFAOYSA-N 2,3-dihydrothieno[2,3-b][1,4]dioxine Chemical compound O1CCOC2=C1C=CS2 YMMGRPLNZPTZBS-UHFFFAOYSA-N 0.000 description 1
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 1
- MUNFOTHAFHGRIM-UHFFFAOYSA-N 2,5-dinaphthalen-1-yl-1,3,4-oxadiazole Chemical compound C1=CC=C2C(C3=NN=C(O3)C=3C4=CC=CC=C4C=CC=3)=CC=CC2=C1 MUNFOTHAFHGRIM-UHFFFAOYSA-N 0.000 description 1
- STTGYIUESPWXOW-UHFFFAOYSA-N 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline Chemical compound C=12C=CC3=C(C=4C=CC=CC=4)C=C(C)N=C3C2=NC(C)=CC=1C1=CC=CC=C1 STTGYIUESPWXOW-UHFFFAOYSA-N 0.000 description 1
- ONKCIMOQGCARHN-UHFFFAOYSA-N 3-methyl-n-[4-[4-(3-methylanilino)phenyl]phenyl]aniline Chemical compound CC1=CC=CC(NC=2C=CC(=CC=2)C=2C=CC(NC=3C=C(C)C=CC=3)=CC=2)=C1 ONKCIMOQGCARHN-UHFFFAOYSA-N 0.000 description 1
- ZNJRONVKWRHYBF-VOTSOKGWSA-N 4-(dicyanomethylene)-2-methyl-6-julolidyl-9-enyl-4h-pyran Chemical compound O1C(C)=CC(=C(C#N)C#N)C=C1\C=C\C1=CC(CCCN2CCC3)=C2C3=C1 ZNJRONVKWRHYBF-VOTSOKGWSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- QCYVGMAKZXSURH-UHFFFAOYSA-N C1=CC=CC=2SC3=CC=CC=C3N(C1=2)C1=C(C=CC=C1)C1=CC=CC=C1 Chemical group C1=CC=CC=2SC3=CC=CC=C3N(C1=2)C1=C(C=CC=C1)C1=CC=CC=C1 QCYVGMAKZXSURH-UHFFFAOYSA-N 0.000 description 1
- LPKVSKJMSDTMSX-UHFFFAOYSA-N CC1=CC=C(C=C1)C(=CC1=C(C=CC=C1)C1=CC=CC=C1)C1=CC=C(C=C1)C Chemical group CC1=CC=C(C=C1)C(=CC1=C(C=CC=C1)C1=CC=CC=C1)C1=CC=C(C=C1)C LPKVSKJMSDTMSX-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- UJOBWOGCFQCDNV-UHFFFAOYSA-N Carbazole Natural products C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229920001157 Poly(2-vinylnaphthalene) Polymers 0.000 description 1
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 1
- 229920001054 Poly(ethylene‐co‐vinyl acetate) Polymers 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- GANNOFFDYMSBSZ-UHFFFAOYSA-N [AlH3].[Mg] Chemical compound [AlH3].[Mg] GANNOFFDYMSBSZ-UHFFFAOYSA-N 0.000 description 1
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229920000109 alkoxy-substituted poly(p-phenylene vinylene) Polymers 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Polymers C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 1
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 1
- VBVAVBCYMYWNOU-UHFFFAOYSA-N coumarin 6 Chemical compound C1=CC=C2SC(C3=CC4=CC=C(C=C4OC3=O)N(CC)CC)=NC2=C1 VBVAVBCYMYWNOU-UHFFFAOYSA-N 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 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
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- CUONGYYJJVDODC-UHFFFAOYSA-N malononitrile Chemical compound N#CCC#N CUONGYYJJVDODC-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910001512 metal fluoride Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- SZDXPEWZZGNIBB-UHFFFAOYSA-N n-[4-[4-(naphthalen-1-ylamino)phenyl]phenyl]naphthalen-1-amine Chemical compound C1=CC=C2C(NC=3C=CC(=CC=3)C=3C=CC(NC=4C5=CC=CC=C5C=CC=4)=CC=3)=CC=CC2=C1 SZDXPEWZZGNIBB-UHFFFAOYSA-N 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical compound C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 description 1
- HDBWAWNLGGMZRQ-UHFFFAOYSA-N p-Vinylbiphenyl Chemical group C1=CC(C=C)=CC=C1C1=CC=CC=C1 HDBWAWNLGGMZRQ-UHFFFAOYSA-N 0.000 description 1
- JZRYQZJSTWVBBD-UHFFFAOYSA-N pentaporphyrin i Chemical compound N1C(C=C2NC(=CC3=NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 JZRYQZJSTWVBBD-UHFFFAOYSA-N 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 125000001484 phenothiazinyl group Chemical group C1(=CC=CC=2SC3=CC=CC=C3NC12)* 0.000 description 1
- 229920000301 poly(3-hexylthiophene-2,5-diyl) polymer Polymers 0.000 description 1
- 229920005593 poly(benzyl methacrylate) Polymers 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920001088 polycarbazole Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film 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
- 238000001771 vacuum deposition Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Classifications
-
- 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
- H10K50/80—Constructional details
- H10K50/805—Electrodes
- H10K50/81—Anodes
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、高輝度での発光が
可能な有機エレクトロルミネッセンス素子に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic electroluminescence device capable of emitting light with high brightness.
【０００２】[0002]
【従来の技術】有機エレクトロルミネッセンス素子に用
いる透明陽極層の材料としてインジウム錫酸化物膜（Ｉ
ＴＯ膜）が代表的である。このものは、透明性と導電性
とに優れ、良好な特性の透明導電膜を歩留まり良く形成
することができる。2. Description of the Related Art Indium tin oxide film (I) is used as a material for a transparent anode layer used in an organic electroluminescence device.
A TO film) is typical. This is excellent in transparency and conductivity, and can form a transparent conductive film having good characteristics with good yield.
【０００３】ところで、ＩＴＯ膜のイオン化ポテンシャ
ルは、一般に４．５ｅＶ以下と比較的小さいため、これ
を有機エレクトロルミネッセンス素子の陽極層に用いた
場合、陽極層に隣接して形成される正孔注入層や正孔輸
送層を構成する正孔注入性物質や正孔輸送性物質のイオ
ン化ポテンシャルとの格差が生じ、これに起因して正孔
注入障壁が高くなる。そして、この結果、高い駆動電圧
が必要となり有機エレクトロルミネッセンス素子の発光
効率が悪化する。By the way, since the ionization potential of the ITO film is generally as small as 4.5 eV or less, when it is used for the anode layer of the organic electroluminescence device, the hole injection layer formed adjacent to the anode layer. And the ionization potential of the hole-injecting substance or the hole-transporting substance forming the hole-transporting layer is different, which causes the hole-injection barrier to increase. As a result, a high driving voltage is required, and the luminous efficiency of the organic electroluminescent element deteriorates.
【０００４】このため、従来、ＩＴＯ膜に対してＵＶオ
ゾン処理や酸素プラズマ処理を行って、ＩＴＯ膜を清浄
すると共にこのもののイオン化ポテンシャルを向上させ
ることが知られている。このようにして、ＩＴＯ膜のイ
オン化ポテンシャルは、ＵＶオゾン処理による場合に最
大５．１ｅＶ、酸素プラズマ処理による場合に最大５．
５ｅＶに増大させることができる。このようにイオン化
ポテンシャルを向上させたＩＴＯ膜は、例えば、正孔注
入性低分子及び正孔輸送性低分子として代表的な、Therefore, it is conventionally known that the ITO film is subjected to UV ozone treatment or oxygen plasma treatment to clean the ITO film and improve the ionization potential of the ITO film. In this way, the ionization potential of the ITO film is 5.1 eV at the maximum when the UV ozone treatment is performed, and is 5. 5 at the maximum when the oxygen plasma treatment is performed.
It can be increased to 5 eV. The ITO film having improved ionization potential as described above is, for example, typical as a hole injecting low molecule and a hole transporting low molecule,
【０００５】[0005]
【化１】 [Chemical 1]
【０００６】［化１］に示すカッパーフタロシアニン
（以下ＣｕＰｃとも言う。）のイオン化ポテンシャル
（５．４ｅＶ）や、正孔注入性高分子として代表的な、The ionization potential (5.4 eV) of copper phthalocyanine (hereinafter also referred to as CuPc) shown in [Chemical formula 1], and a typical hole-injecting polymer,
【０００７】[0007]
【化２】 [Chemical 2]
【０００８】［化２］に示すポリ（３，４）エチレンジ
オキシチオフェン（以下ＰＥＤＴともいう。）のイオン
化ポテンシャル（５．１ｅＶ）と同水準であり、上記の
正孔注入障壁は軽減される。It is at the same level as the ionization potential (5.1 eV) of poly (3,4) ethylenedioxythiophene (hereinafter also referred to as PEDT) shown in [Chemical formula 2], and the above hole injection barrier is reduced. .
【０００９】[0009]
【発明が解決しようとする課題】ところで、さらなる駆
動電圧の低下により素子の発光効率を向上させるため、
発光層や正孔輸送層に導電性高分子を用いることが検討
されている。このような導電性高分子として、By the way, in order to improve the luminous efficiency of the device by further lowering the driving voltage,
The use of a conductive polymer for the light emitting layer and the hole transport layer has been studied. As such a conductive polymer,
【００１０】[0010]
【化３】 [Chemical 3]
【００１１】（一般式［化３］中、Ｒは水素、脂肪族炭
化水素基、芳香族炭化水素基、エーテル基または複素環
基のいずれかを示す。）
一般式[化３]で表される繰り返し単位を有するポリフル
オレン化合物、例えば、(In the general formula [Chemical Formula 3], R represents hydrogen, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, an ether group or a heterocyclic group.) A polyfluorene compound having a repeating unit of, for example,
【００１２】[0012]
【化４】 [Chemical 4]
【００１３】［化４］で示されるジノルマルオクチルポ
リフルオレンを挙げることができる。An example is dinormal octyl polyfluorene represented by the formula [4].
【００１４】ところが、この［化４］で示されるジノル
マルオクチルポリフルオレンのイオン化ポテンシャルは
５．８ｅＶとさらに高い。However, the ionization potential of the dinormal octyl polyfluorene represented by [Chemical Formula 4] is as high as 5.8 eV.
【００１５】一方、上記従来の有機エレクトロルミネッ
センス素子の発光方法として、励起三重項状態からの発
光、即ち、燐光を用いると、発光の量子効率を向上させ
ることができる。励起一重項状態による発光、即ち、蛍
光のみを利用して発光させる場合の内部量子効率の理論
的限界が２５％であるのに対し、燐光による発光は、三
重項状態の励起エネルギーが発光に寄与するため内部量
子効率の理論的限界を１００％と考えてよい。したがっ
て、駆動電圧に対する発光輝度で定義される発光効率の
向上が期待でき、このような燐光発光による有機エレク
トロルミネッセンス素子が検討されている。On the other hand, when light emission from an excited triplet state, that is, phosphorescence is used as a light emission method of the above-mentioned conventional organic electroluminescence device, the quantum efficiency of light emission can be improved. The theoretical limit of internal quantum efficiency is 25% in the case of light emission by excited singlet state, that is, in the case of emitting light only by fluorescence, whereas in light emission by phosphorescence, excitation energy of triplet state contributes to light emission. Therefore, the theoretical limit of the internal quantum efficiency may be considered to be 100%. Therefore, it is expected that the light emission efficiency defined by the light emission luminance with respect to the driving voltage is improved, and such an organic electroluminescence device by phosphorescence emission has been studied.
【００１６】このとき、燐光発光のための発光層ホスト
剤として一般的な、At this time, a general host material for the light emitting layer for phosphorescence emission,
【００１７】[0017]
【化５】 [Chemical 5]
【００１８】［化５］に示すカルバゾールビフェニル
（以下、ＣＢＰとも言う。）のイオン化ポテンシャルも
６．１ｅＶとさらに高く、このとき、正孔輸送層に用い
る正孔輸送性物質にも大きなイオン化ポテンシャルを有
するものを用いた方が、発光層と正孔輸送層との間の正
孔注入障壁が小さくなる。このような正孔輸送性物質と
しては、イオン化ポテンシャルが６．０ｅＶの、The ionization potential of carbazole biphenyl (hereinafter also referred to as CBP) shown in [Chemical formula 5] is as high as 6.1 eV, and at this time, a large ionization potential is also present in the hole transporting material used in the hole transport layer. The hole injection barrier between the light emitting layer and the hole transport layer becomes smaller when the one having the above is used. Such a hole-transporting substance has an ionization potential of 6.0 eV,
【００１９】[0019]
【化６】 [Chemical 6]
【００２０】[化６]で表されるポリ（Ｎ−ビニルカルバ
ゾール）（以下ＰＶＫとも言う。）が挙げられるが、こ
れを用いると、今度は陽極層と正孔輸送層との間の障壁
が大きくなってしまう。Poly (N-vinylcarbazole) represented by [Chemical Formula 6] (hereinafter, also referred to as PVK) can be mentioned. When this is used, a barrier between the anode layer and the hole transport layer is formed. It gets bigger.
【００２１】そこで、陽極層に用いるＩＴＯ膜のイオン
化ポテンシャルをさらに向上させるため、陽極層の形成
時に成膜条件を変更して、ＩＴＯ膜の隣接層側にイオン
化ポテンシャルが比較的大きい界面層を形成することが
考えられる。例えば、特開２０００−６８０７３号公報
においては、ＩＴＯ膜の成膜用のスパッタガス中の酸素
濃度を高くして上記界面層のイオン化ポテンシャルを向
上させ、このようにして形成された陽極層からの正孔注
入を容易にしている。Therefore, in order to further improve the ionization potential of the ITO film used for the anode layer, the film formation conditions are changed at the time of forming the anode layer to form an interface layer having a relatively large ionization potential on the adjacent layer side of the ITO film. It is possible to do it. For example, in Japanese Unexamined Patent Publication No. 2000-68073, the oxygen concentration in the sputtering gas for forming the ITO film is increased to improve the ionization potential of the interface layer. It facilitates hole injection.
【００２２】しかしながら、このように陽極層上に中間
層を介在させると工程が増加し、成膜条件の管理が必要
になるという不具合が避けられない。However, if the intermediate layer is interposed on the anode layer in this way, the number of processes is increased, and it is inevitable that the film formation conditions must be controlled.
【００２３】本発明は、上記問題点に鑑み、隣接層に対
して簡便に正孔注入障壁を軽減し、確実に正孔注入を行
うことが可能な陽極層を有する有機エレクトロルミネッ
センス素子及びこれを製造する方法を提供することを課
題としている。In view of the above problems, the present invention provides an organic electroluminescence device having an anode layer capable of easily reducing a hole injection barrier to an adjacent layer and surely injecting holes, and an organic electroluminescence device including the anode layer. It is an object to provide a manufacturing method.
【００２４】[0024]
【課題を解決するための手段】上記課題を解決するた
め、本発明は、陽極層及び陰極層の両電極層とこの両電
極層間に形成される発光層を有する有機エレクトロルミ
ネッセンス素子において、陽極層として、フッ素含有量
を１重量％以下とする酸素を用いたプラズマ表面処理を
施した透明性金属酸化物を用いる。In order to solve the above problems, the present invention provides an organic electroluminescence device having both electrode layers of an anode layer and a cathode layer and a light emitting layer formed between the electrode layers. As the transparent metal oxide, a transparent metal oxide subjected to plasma surface treatment with oxygen having a fluorine content of 1% by weight or less is used.
【００２５】このものでは、フッ素を含有した酸素によ
るプラズマ処理により、表面のみで金属フッ化物が形成
され、これにより陽極層のバンドギャップが拡大されて
イオン化ポテンシャルが増大するものと考えられる。In this case, it is considered that the metal fluoride is formed only on the surface by the plasma treatment with the oxygen containing fluorine, whereby the band gap of the anode layer is expanded and the ionization potential is increased.
【００２６】そして、このような陽極層は、５．５ｅＶ
以上の比較的高いイオン化ポテンシャルを有することが
できるため、隣接する発光層や正孔輸送層に導電性高分
子を用いる場合、または発光層における発光を燐光によ
るものとする場合に、高いイオン化ポテンシャルを有す
る発光層や正孔輸送層と同水準のイオン化ポテンシャル
に簡易に揃えることができる。即ち、陽極層とこれに隣
接する発光層や正孔輸送層との間の正孔注入障壁を軽減
でき、互いに隣接する両層間で確実な正孔注入を行うこ
とができる。なお、上記の陽極層のイオン化ポテンシャ
ルの上限は６．５ｅＶ程度である。And, such an anode layer has 5.5 eV.
Since it can have a relatively high ionization potential as described above, when a conductive polymer is used for the adjacent light emitting layer or hole transporting layer, or when light emission in the light emitting layer is caused by phosphorescence, a high ionization potential is required. The ionization potential can be easily adjusted to the same level as that of the light emitting layer and the hole transporting layer. That is, the hole injection barrier between the anode layer and the light emitting layer or hole transport layer adjacent thereto can be reduced, and reliable hole injection can be performed between both layers adjacent to each other. The upper limit of the ionization potential of the anode layer is about 6.5 eV.
【００２７】そして、上記した酸素中のフッ素は、実際
には、四フッ化炭素の構成原子やポリ４フッ化エチレン
などのフッ素樹脂として酸素中に含有して供給するのが
好適である。The above-mentioned fluorine in oxygen is actually preferably contained in oxygen as a constituent atom of carbon tetrafluoride or a fluorine resin such as polytetrafluoroethylene and supplied.
【００２８】また、陽極層に隣接して積層される発光層
や正孔輸送層や正孔注入層などの有機層を構成する有機
化合物として、イオン化ポテンシャルが５．５ｅＶ以上
のものを使用する時、上記した正孔注入障壁の軽減効果
が大きくなる。When an organic compound having an ionization potential of 5.5 eV or more is used as an organic compound forming an organic layer such as a light emitting layer, a hole transporting layer or a hole injecting layer which is laminated adjacent to the anode layer. The effect of reducing the above-mentioned hole injection barrier is increased.
【００２９】さらに、陽極層に用いるものとして上記し
た透明性金属酸化物をインジウム錫酸化物（ＩＴＯ）で
構成することが最適である。Further, it is optimal that the above-mentioned transparent metal oxide used as the anode layer is composed of indium tin oxide (ITO).
【００３０】また、ガラス基板上に透明性金属酸化物を
積層した後に、この透明性金属酸化物に対して、フッ素
含有量を１重量％以下とする酸素を用いたプラズマ表面
処理を行って陽極層を形成する際に、同じ真空プロセス
内で透明性金属酸化物の積層成膜とプラズマ表面処理と
を行うようにすれば、簡便な方法で有機エレクトロルミ
ネッセンス素子を製造することが可能となる。Further, after laminating a transparent metal oxide on a glass substrate, the transparent metal oxide is subjected to plasma surface treatment using oxygen having a fluorine content of 1% by weight or less, and an anode is formed. When forming a layer, if the laminated film formation of the transparent metal oxide and the plasma surface treatment are performed in the same vacuum process, the organic electroluminescence device can be manufactured by a simple method.
【００３１】[0031]
【発明の実施の形態】図１は、発光効率の向上を目的と
して多層に積層された素子構造を有する有機エレクトロ
ルミネッセンス素子の基本構造を示す。有機エレクトロ
ルミネッセンス素子の素子構造は、図外の基板上に形成
された陽極層１０に、正孔輸送層２０、電子ブロック層
３０、発光層４０、正孔ブロック層５０及び電子輸送層
６０の各薄膜層が、陽極層１０と陰極層７０との両電極
層間で順次積層されて成る多層積層構造であり、発光層
４０は、発光層ドープ剤４１と発光層ホスト剤４２とを
有して構成されている。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS FIG. 1 shows a basic structure of an organic electroluminescence device having a device structure laminated in multiple layers for the purpose of improving luminous efficiency. The element structure of the organic electroluminescence element is such that each of the hole transport layer 20, the electron block layer 30, the light emitting layer 40, the hole block layer 50, and the electron transport layer 60 is formed on the anode layer 10 formed on a substrate (not shown). The thin film layer has a multi-layered structure in which the anode layer 10 and the cathode layer 70 are sequentially laminated between both electrode layers, and the light emitting layer 40 includes a light emitting layer doping agent 41 and a light emitting layer host agent 42. Has been done.
【００３２】図１で示される素子構造において、陽極層
１０は、例えばガラス基板のような透明絶縁性支持体に
形成された透明な導電性物質が用いられ、その材料とし
ては、酸化錫、酸化インジウム、酸化錫インジウム（Ｉ
ＴＯ）などの導電性酸化物、あるいは、金、銀、クロム
などの金属、よう化銅、硫化銅などの無機導電性物質、
ポリチオフェン、ポリピロール、ポリアニリン等の導電
性ポリマーなどを用いることができる。In the element structure shown in FIG. 1, for the anode layer 10, a transparent conductive substance formed on a transparent insulating support such as a glass substrate is used, and the material thereof is tin oxide or oxide. Indium, indium tin oxide (I
Conductive oxides such as TO) or metals such as gold, silver and chromium, inorganic conductive substances such as copper iodide and copper sulfide,
Conductive polymers such as polythiophene, polypyrrole, and polyaniline can be used.
【００３３】また、図１で示される素子構造において、
陰極層７０には、ニオブ、リチウム、ナトリウム、カリ
ウム、ルビジウム、セシウム、マグネシウム、カルシウ
ム、ストロンチウム、バリウム、硼素、アルミニウム、
銅、銀、金などの単体または合金が使用できる。さら
に、これらを積層して使用することもできる。また、テ
トラヒドロアルミン酸塩により湿式で形成することもで
きる。この場合、陰極層７０に用いられるテトラヒドロ
アルミン酸塩としては、特に、水素化アルミニウムリチ
ウム、水素化アルミニウムカリウム、水素化アルミニウ
ムマグネシウム、水素化アルミニウムカルシウムを挙げ
ることができる。この中で、水素化アルミニウムリチウ
ムが、特に電子輸送層への電子注入性に優れている。Further, in the device structure shown in FIG.
The cathode layer 70 includes niobium, lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, boron, aluminum,
A simple substance such as copper, silver or gold or an alloy can be used. Further, these may be laminated and used. It can also be formed by a wet process using tetrahydroaluminate. In this case, examples of the tetrahydroaluminate used for the cathode layer 70 include lithium aluminum hydride, potassium aluminum hydride, magnesium aluminum hydride, and aluminum calcium hydride. Among these, lithium aluminum hydride is particularly excellent in the electron injection property into the electron transport layer.
【００３４】また、正孔輸送層２０は、陽極層１０から
注入される正孔を輸送するための層であり、正孔輸送性
有機物を含む有機層である。正孔輸送層性有機物の例と
して、一般式[化３]で表される繰り返し単位を有するポ
リフルオレン化合物、例えば、［化４］で示されるジノ
ルマルオクチルポリフルオレン、［化６］に示すＰＶ
Ｋ、The hole transport layer 20 is a layer for transporting holes injected from the anode layer 10, and is an organic layer containing a hole transporting organic substance. As an example of the hole transport layer organic compound, a polyfluorene compound having a repeating unit represented by the general formula [Chemical Formula 3], for example, dinormal octyl polyfluorene represented by the [Chemical Formula 4], and a PV represented by the [Chemical Formula 6]
K,
【００３５】[0035]
【化７】 [Chemical 7]
【００３６】［化７］に示すポリ（パラ−フェニレンビ
ニレン）などの高分子からなることが好ましい。It is preferably composed of a polymer such as poly (para-phenylene vinylene) shown in [Chemical Formula 7].
【００３７】あるいは、［化１］に示すカッパーフタロ
シアニン、［化５］に示すＣＢＰ、Alternatively, copper phthalocyanine represented by [Chemical formula 1], CBP represented by [Chemical formula 5],
【００３８】[0038]
【化８】 [Chemical 8]
【００３９】［化８］に示すＮ，Ｎ’−ジフェニル−
Ｎ，Ｎ’−ビス（１−ナフチル）―１，１’−ビフェニ
ル−４，４’−ジアミン（以下ＮＰＤとも言う。）、N, N'-diphenyl-shown in [Chemical Formula 8]
N, N′-bis (1-naphthyl) -1,1′-biphenyl-4,4′-diamine (hereinafter also referred to as NPD),
【００４０】[0040]
【化９】 [Chemical 9]
【００４１】［化９］に示すＮ，Ｎ’−ジフェニル−
Ｎ，Ｎ’−ビス（３−メチルフェニル）−１，１’−ビ
フェニル−４，４’−ジアミン（以下ＴＰＤともい
う。）、N, N'-diphenyl-shown in [Chemical Formula 9]
N, N'-bis (3-methylphenyl) -1,1'-biphenyl-4,4'-diamine (hereinafter also referred to as TPD),
【００４２】[0042]
【化１０】 [Chemical 10]
【００４３】［化１０］に示す４，４’−ビス（１０−
フェノチアジニル）ビフェニルなどの低分子を用いるこ
ともできる。4,4'-bis (10-
Smaller molecules such as phenothiazinyl) biphenyl can also be used.
【００４４】また、電子ブロック層３０は、陰極層７０
から発光層４０へ注入された電子がそのまま陽極層１０
へ通過してしまうことを防ぐため電子をブロックするた
めの層であり、電子ブロック性物質で構成される。電子
ブロック性物質としては、例えば、［化５］に示すＣＢ
Ｐ、［化６］に示すＰＶＫ、［化７］に示すポリ（パラ
−フェニレンビニレン）、［化８］に示すＮＰＤ、[化
９]に示すＴＰＤ、［化１０］に示す４，４’−ビス
（１０−フェノチアジニル）ビフェニルや、The electron block layer 30 is the cathode layer 70.
Electrons injected into the light emitting layer 40 from the anode layer 10 as they are.
It is a layer for blocking electrons in order to prevent it from passing through, and is composed of an electron blocking substance. Examples of the electron blocking substance include CB shown in [Chemical Formula 5].
P, PVK shown in [Chemical Formula 6], poly (para-phenylene vinylene) shown in [Chemical Formula 7], NPD shown in [Chemical Formula 8], TPD shown in [Chemical Formula 9], 4,4 ′ shown in [Chemical Formula 10] -Bis (10-phenothiazinyl) biphenyl,
【００４５】[0045]
【化１１】 [Chemical 11]
【００４６】[化１１]に示す２，４，６−トリフェニル
−１，３，５−トリアゾール、2,4,6-triphenyl-1,3,5-triazole represented by [Chemical Formula 11],
【００４７】[0047]
【化１２】 [Chemical 12]
【００４８】[化１２]に示すフローレンなどを挙げるこ
とができる。Examples include fluorene shown in [Chemical Formula 12] and the like.
【００４９】また、発光層４０はドープ剤４１とホスト
剤４２とを有し、これらドープ剤４１とホスト剤４２と
を均一に分散させるため、バインダ高分子を添加するこ
とも可能である。ホスト剤４２は、陽極層１０及び陰極
層７０からそれぞれ注入された正孔と電子とが発光層４
０において再結合する際に賦活されて励起子として作用
する物質であり、［化３］に示す繰り返し単位を有する
ポリフルオレン化合物（例えば［化４］で示されるジノ
ルマルオクチルポリフルオレン）、［化５］に示すＣＢ
Ｐ、［化６］に示すＰＶＫや、Further, the light emitting layer 40 has a doping agent 41 and a host agent 42, and in order to disperse the doping agent 41 and the host agent 42 uniformly, it is possible to add a binder polymer. In the host agent 42, holes and electrons injected from the anode layer 10 and the cathode layer 70, respectively, are emitted from the light emitting layer 4.
Is a substance that is activated when recombining at 0 and acts as an exciton, and has a repeating unit represented by [Chemical Formula 3] (for example, dinormaloctylpolyfluorene represented by [Chemical Formula 4]), CB shown in [5]
P, PVK shown in [Chemical 6],
【００５０】[0050]
【化１３】 [Chemical 13]
【００５１】[化１３]に示すポリ（２-メトキシ-５-
（２-エチルヘキシオキシ）-１，４-フェニレンビニレ
ン）（以下ＭＥＨ-ＰＰＶとも言う。）Poly (2-methoxy-5-) shown in [Chemical Formula 13]
(2-Ethylhexoxy) -1,4-phenylene vinylene) (hereinafter also referred to as MEH-PPV)
【００５２】[0052]
【化１４】 [Chemical 14]
【００５３】[化１４]に示すポリ（３-ヘキシルチオフ
ェン）、Poly (3-hexylthiophene) shown in [Chemical Formula 14],
【００５４】[0054]
【化１５】 [Chemical 15]
【００５５】［化１５］に示す１，３，５−トリ（５−
（４−ｔｅｒｔ−ブチルフェニル）−１，３，４−オキ
サジアゾール）フェニル（以下ＯＸＤ−１ともい
う。）、1,3,5-tri (5-
(4-tert-butylphenyl) -1,3,4-oxadiazole) phenyl (hereinafter also referred to as OXD-1),
【００５６】[0056]
【化１６】 [Chemical 16]
【００５７】［化１６］に示される１，３―ジ（５−
（４−ｔｅｒｔ−ブチルフェニル）−１，３，４−オキ
サジアゾール）フェニル（以下ＯＸＤ−７ともい
う。）、1,3-di (5-
(4-tert-butylphenyl) -1,3,4-oxadiazole) phenyl (hereinafter also referred to as OXD-7),
【００５８】[0058]
【化１７】 [Chemical 17]
【００５９】[化１７] に示す２−（４−ビフェニリ
ル）−５−（４−ｔｅｒｔ−ブチルフェニル）−１，
３，４−オキサジアゾール、（以下ＰＢＤともい
う。）、2- (4-biphenylyl) -5- (4-tert-butylphenyl) -1, shown in [Chemical Formula 17],
3,4-oxadiazole, (hereinafter also referred to as PBD),
【００６０】[0060]
【化１８】 [Chemical 18]
【００６１】［化１８］で示されるＮ-フェニルポリカ
ルバゾール、N-phenyl polycarbazole represented by the formula:
【００６２】[0062]
【化１９】 [Chemical 19]
【００６３】[化１９]に示すバソキュプロイン（以下Ｂ
ＣＰともいう。）、Bathocuproine (hereinafter referred to as B)
Also called CP. ),
【００６４】[0064]
【化２０】 [Chemical 20]
【００６５】［化２０］に示すトリス（８−ヒドロキシ
キノリナート）アルミニウム（以下Ａｌｑ３ともい
う。）などが挙げられる。Examples include tris (8-hydroxyquinolinato) aluminum (hereinafter also referred to as Alq3) shown in [Chemical Formula 20].
【００６６】一方、発光層４０のドープ剤４１は、励起
子たるホスト剤４２の励起エネルギーにより燐光を放射
する物質であり、On the other hand, the doping agent 41 of the light emitting layer 40 is a substance which emits phosphorescence by the excitation energy of the host agent 42 which is an exciton,
【００６７】[0067]
【化２１】 [Chemical 21]
【００６８】［化２１］に示すトリ（２フェニルピリジ
ン）イリジウム錯体（以下Ｉｒ（ｐｐｙ）3とも言
う。）、A tri (2phenylpyridine) iridium complex represented by [Chemical Formula 21] (hereinafter, also referred to as Ir (ppy) 3 ),
【００６９】[0069]
【化２２】 [Chemical formula 22]
【００７０】[0070]
【化２３】 [Chemical formula 23]
【００７１】[0071]
【化２４】 [Chemical formula 24]
【００７２】[0072]
【化２５】 [Chemical 25]
【００７３】[0073]
【化２６】 [Chemical formula 26]
【００７４】[0074]
【化２７】 [Chemical 27]
【００７５】（化学式[化２７]中、ａｃａｃは、(In the chemical formula [Chemical Formula 27], acac is
【００７６】[0076]
【化２８】 [Chemical 28]
【００７７】[化２８]で示される官能基を示す。下記
[化２９]乃至[化３３]に示す化学式において同じ。）The functional group represented by [Chemical Formula 28] is shown below. following
The same applies to the chemical formulas shown in [Chemical Formula 29] to [Chemical Formula 33]. )
【００７８】[0078]
【化２９】 [Chemical 29]
【００７９】[0079]
【化３０】 [Chemical 30]
【００８０】[0080]
【化３１】 [Chemical 31]
【００８１】[0081]
【化３２】 [Chemical 32]
【００８２】[0082]
【化３３】 [Chemical 33]
【００８３】[化２２]乃至[化２７]、[化２９]乃至[化
３３]で示されるイリジウム錯体化合物、Iridium complex compounds represented by [Chemical formula 22] to [Chemical formula 27] and [Chemical formula 29] to [Chemical formula 33],
【００８４】[0084]
【化３４】 [Chemical 34]
【００８５】［化３４］に示す２，３，７，８，１２，
１３，１７，１８−オクタエチル−２１Ｈ，２３Ｈ−白
金（II）ポルフィン（以下ＰｔＯＥＰとも言う。）、2, 3, 7, 8, 12, shown in [Chemical 34]
13,17,18-octaethyl-21H, 23H-platinum (II) porphine (hereinafter also referred to as PtOEP),
【００８６】[0086]
【化３５】 [Chemical 35]
【００８７】［化３５］に示す３-（２’-ベンゾチアゾ
リル）-７-ジエチルアミノクマリン（以下、クマリン６
とも言う。）3- (2'-benzothiazolyl) -7-diethylaminocoumarin (hereinafter referred to as coumarin 6) shown in [Chemical Formula 35]
Also say. )
【００８８】[0088]
【化３６】 [Chemical 36]
【００８９】［化３６］に示す（２-メチル-６-（２-
（２，３，６，７-テトラハイドロ-１Ｈ、５Ｈ-ベンゾ
（ｉｊ）クイノリジン-９-イル）エテニル）-４Ｈ-ピラ
ン-４-イリデン）プロパン-ジニトリル（以下ＤＣＭ２
とも言う。）などを挙げることができる。[2-methyl-6- (2-
(2,3,6,7-Tetrahydro-1H, 5H-benzo (ij) quinolidin-9-yl) ethenyl) -4H-pyran-4-ylidene) propane-dinitrile (hereinafter DCM2
Also say. ) And the like.
【００９０】また、発光層４０に添加可能なバインダ高
分子の例として、ポリスチレン、ポリビニルビフェニ
ル、ポリビニルフェナントレン、ポリビニルアントラセ
ン、ポリビニルペリレン、ポリ（エチレン−ｃｏ−ビニ
ルアセテート）、ポリブタジエンのｃｉｓとｔｒａｎ
ｓ、ポリ（２−ビニルナフタレン）、ポリビニルピロリ
ドン、ポリスチレン、ポリ（メチルメタクリレート）、
ポリ（ビニルアセテート）、ポリ（２−ビニルピリジン
−ｃｏ−スチレン）、ポリアセナフチレン、ポリ（アク
リロニトリル−ｃｏ−ブタジエン）、ポリ（ベンジルメ
タクリレート）、ポリ（ビニルトルエン）、ポリ（スチ
レン−ｃｏ−アクリロニトリル）、ポリ（４−ビニルビ
フェニル）、ポリエチレングリコールなどが挙げられ
る。Examples of the binder polymer that can be added to the light emitting layer 40 include polystyrene, polyvinyl biphenyl, polyvinyl phenanthrene, polyvinyl anthracene, polyvinyl perylene, poly (ethylene-co-vinyl acetate), polybutadiene cis and tran.
s, poly (2-vinylnaphthalene), polyvinylpyrrolidone, polystyrene, poly (methylmethacrylate),
Poly (vinyl acetate), poly (2-vinyl pyridine-co-styrene), polyacenaphthylene, poly (acrylonitrile-co-butadiene), poly (benzyl methacrylate), poly (vinyltoluene), poly (styrene-co-) Acrylonitrile), poly (4-vinylbiphenyl), polyethylene glycol and the like.
【００９１】また、正孔ブロック層５０は、陽極層１０
から発光層４０へ注入された正孔がそのまま陰極層７０
へ通過してしまうことを防ぐため正孔をブロックするた
めの層であり、正孔ブロック性物質で構成される。正孔
ブロック性物質としては、例えば、[化１５]に示すＯＸ
Ｄ−１、[化１７] に示すＰＢＤ、 [化１９]に示すＢＣ
Ｐ、［化２０］に示すＡｌｑ３、Further, the hole blocking layer 50 is the anode layer 10
The holes injected into the light emitting layer 40 from the cathode layer 70 as they are.
It is a layer for blocking holes in order to prevent the holes from passing through and is composed of a hole blocking substance. Examples of the hole blocking substance include OX shown in [Chemical Formula 15].
D-1, PBD shown in [Chemical Formula 17], BC shown in [Chemical Formula 19]
P, Alq3 shown in [Chemical Formula 20],
【化３７】 [Chemical 37]
【００９２】［化３７］に示す３−（４−ビフェニリ
ル）−５−（４−ｔｅｒｔ−ブチルフェニル）−４−フ
ェニル−１，２，４−トリアゾール（以下、ＴＡＺとも
いう。）、3- (4-biphenylyl) -5- (4-tert-butylphenyl) -4-phenyl-1,2,4-triazole (hereinafter also referred to as TAZ) shown in [Chemical Formula 37],
【００９３】[0093]
【化３８】 [Chemical 38]
【００９４】［化３８］に示す４，４’−ビス（１，１
−ジフェニルエテニル）ビフェニル（以下にＤＰＶＢｉ
ともいう。）、4,4'-bis (1,1) shown in [Chemical Formula 38]
-Diphenylethenyl) biphenyl (hereinafter DPVBi
Also called. ),
【００９５】[0095]
【化３９】 [Chemical Formula 39]
【００９６】［化３９］に示す２，５−ビス（１−ナフ
チル）−１．３．４−オキサジアゾール（以下にＢＮＤ
ともいう。）2,5-bis (1-naphthyl) -1.3.4-oxadiazole (hereinafter referred to as BND
Also called. )
【００９７】[0097]
【化４０】 [Chemical 40]
【００９８】［化４０］に示される４，４’−ビス
（１，１−ビス（４−メチルフェニル）エテニル）ビフ
ェニル（以下ＤＴＶＢｉとも言う。）、4,4'-bis (1,1-bis (4-methylphenyl) ethenyl) biphenyl (hereinafter also referred to as DTVBi) represented by [Chemical Formula 40],
【００９９】[0099]
【化４１】 [Chemical 41]
【０１００】［化４１］に示される２，５−ビス（４−
ビフェニリル）−１，３，４−オキサジアゾール（以下
ＢＢＤともいう。）、2,5-bis (4-) shown in [Chemical Formula 41]
Biphenylyl) -1,3,4-oxadiazole (hereinafter also referred to as BBD),
【０１０１】[0101]
【化４２】 [Chemical 42]
【０１０２】［化４２］に示すようなポリビニルオキサ
ジアゾール系高分子化合物（以下ＰＶ-ＯＸＤとも言
う。）などを挙げることができる。Examples thereof include polyvinyl oxadiazole type polymer compounds (hereinafter also referred to as PV-OXD) as shown in [Chemical Formula 42].
【０１０３】また、電子輸送層６０は、陰極層７０から
注入される電子を輸送するための層であり、電子輸送剤
を含む。電子輸送剤は、電子輸送性高分子で構成され、
さらに電子輸送性低分子を含む構成が可能である。The electron transport layer 60 is a layer for transporting electrons injected from the cathode layer 70, and contains an electron transport agent. The electron transport agent is composed of an electron transporting polymer,
Further, a structure containing a low molecule having an electron transport property is possible.
【０１０４】ここで、電子輸送性低分子の例として、
［化１６］に示されるＯＸＤ−７、［化１７］に示すＰ
ＢＤ、[化１９]に示すＢＣＰ、［化２０］に示すＡｌｑ
３、［化３７］に示すＴＡＺ、［化３８］に示すＤＰＶ
Ｂｉ、［化３９］に示すＢＮＤ、［化４０］に示すＤＴ
ＶＢｉ、［化４１］に示すＢＢＤ、Here, as an example of the electron transporting low molecule,
OXD-7 shown in [Chemical Formula 16] and P shown in [Chemical Formula 17]
BD, BCP shown in [Chemical formula 19], Alq shown in [Chemical formula 20]
3, TAZ shown in [Chemical 37], DPV shown in [Chemical 38]
Bi, BND shown in [Chemical 39], DT shown in [Chemical 40]
VBi, the BBD shown in [Chemical 41],
【０１０５】[0105]
【化４３】 [Chemical 43]
【０１０６】［化４３］で示される２，５-ジフェニル-
１，３，４-オキサジアゾール（以下ＰＰＤとも言
う。）などがある。2,5-diphenyl-represented by [Chemical Formula 43]
1,3,4-oxadiazole (hereinafter also referred to as PPD) and the like.
【０１０７】また、電子輸送性高分子の例として、［化
４２］に示すＰＶ-ＯＸＤなどが挙げられる。Further, as an example of the electron transporting polymer, PV-OXD shown in [Chemical Formula 42] and the like can be mentioned.
【０１０８】構造の簡素化のため、図１に示す有機エレ
クトロルミネッセンス素子の基本構造に変更を加えたも
のとして、図２に示す素子構造が可能である。For simplification of the structure, the element structure shown in FIG. 2 is possible by modifying the basic structure of the organic electroluminescence element shown in FIG.
【０１０９】図２で示される有機エレクトロルミネッセ
ンス素子の素子構造は、本発明による有機エレクトロル
ミネッセンス素子の実施形態を示す。図１で示す素子構
造において、電子ブロック層３０と正孔ブロック層５０
と電子輸送層６０とを省略したものである。The element structure of the organic electroluminescent element shown in FIG. 2 shows an embodiment of the organic electroluminescent element according to the present invention. In the device structure shown in FIG. 1, the electron blocking layer 30 and the hole blocking layer 50
And the electron transport layer 60 are omitted.
【０１１０】次に、本発明の実施形態たる図２に示す素
子構造を用いて、有機エレクトロルミネッセンス素子の
製造方法を説明する。Next, a method of manufacturing an organic electroluminescence device will be described using the device structure shown in FIG. 2, which is an embodiment of the present invention.
【０１１１】まず、基板（図示せず）となる透明絶縁性
支持体、例えばガラス基板上に陽極層１０を蒸着法また
はスパッタ法にて形成する。そして、陽極層１０の表面
に対して、四フッ化炭素やポリ四フッ化エチレン樹脂を
混入させてフッ素含有量を１重量％以下とした酸素を用
いたプラズマ表面処理を行う。このとき、同じ真空プロ
セス内において、基板上の陽極層の積層成膜とこれに対
するプラズマ表面処理とを行うようにすれば工程が簡便
になる。First, the anode layer 10 is formed on a transparent insulating support, which is a substrate (not shown), such as a glass substrate, by a vapor deposition method or a sputtering method. Then, the surface of the anode layer 10 is subjected to plasma surface treatment using oxygen in which carbon tetrafluoride or polytetrafluoroethylene resin is mixed to make the fluorine content 1% by weight or less. At this time, if the laminated film formation of the anode layer on the substrate and the plasma surface treatment for the same are performed in the same vacuum process, the process becomes simple.
【０１１２】次に、正孔輸送性高分子または正孔輸送性
低分子を溶媒に溶解または分散した第１の溶液を作成す
る。ここで、第１の溶液に、さらにバインダ高分子を溶
解または分散することも可能である。そして、第１の溶
液を用いた湿式法によって、陽極層１０上に、正孔輸送
層２０を形成する。Next, a first solution is prepared by dissolving or dispersing the hole transporting polymer or the hole transporting low molecule in a solvent. Here, it is also possible to further dissolve or disperse the binder polymer in the first solution. Then, the hole transport layer 20 is formed on the anode layer 10 by a wet method using the first solution.
【０１１３】さらに、発光層４０のドープ剤４１とホス
ト剤４２とを溶媒に溶解または分散した第２の溶液を作
成する。ここで、第２の溶液に、さらにバインダ高分子
を溶解または分散することも可能である。そして、その
第２の溶液を用いた湿式法によって、上記正孔輸送層２
０上に発光層４０を形成する。Further, a second solution is prepared by dissolving or dispersing the doping agent 41 and the host agent 42 of the light emitting layer 40 in a solvent. Here, it is also possible to further dissolve or disperse the binder polymer in the second solution. Then, the hole transport layer 2 is formed by the wet method using the second solution.
The light emitting layer 40 is formed on the transparent layer 0.
【０１１４】また、第２の溶液に用いた溶媒の溶解度パ
ラメータは、発光層４０の成膜温度において、正孔輸送
層２０に含まれる物質（正孔輸送性高分子または正孔輸
送性低分子など）に対して可溶範囲外を示す値を有し、
このような溶媒を用いた湿式法による発光層４０の形成
において、下層の正孔輸送層２０に含まれる有機物を溶
解することがない。The solubility parameter of the solvent used in the second solution is determined by the substance contained in the hole transport layer 20 (hole transporting polymer or hole transporting low molecule) at the film formation temperature of the light emitting layer 40. Etc.) has a value outside the soluble range,
When the light emitting layer 40 is formed by a wet method using such a solvent, the organic substance contained in the lower hole transport layer 20 is not dissolved.
【０１１５】このとき上記の第１または第２の溶液に用
いる溶媒は自然乾燥によって蒸発することにより、正孔
輸送層２０と発光層４０とが形成される。この場合、加
熱、紫外線の照射による重合、硬化等の処理を行う必要
がなく、従って製造工程が簡単であり生産効率を向上さ
せることができる。At this time, the solvent used for the above-mentioned first or second solution is evaporated by natural drying to form the hole transport layer 20 and the light emitting layer 40. In this case, there is no need to perform treatments such as heating, polymerization by irradiation of ultraviolet rays, and curing, and therefore the manufacturing process is simple and the production efficiency can be improved.
【０１１６】本発明で使用される湿式法には、たとえば
キャスティング法、ブレードコート法、浸漬塗工法、ス
ピンコート法、スプレイコート法、ロール塗工法、イン
クジェット塗工法などの通常の塗工法が含まれる。The wet method used in the present invention includes ordinary coating methods such as casting method, blade coating method, dip coating method, spin coating method, spray coating method, roll coating method and ink jet coating method. .
【０１１７】最後に、発光層４０上に、蒸着法などを用
いて陰極層７０を形成し、本発明による有機エレクトロ
ルミネッセンス素子が得られる。Finally, the cathode layer 70 is formed on the light emitting layer 40 by using the vapor deposition method or the like to obtain the organic electroluminescence device according to the present invention.
【０１１８】なお、溶解度パラメータＳＰは、モル蒸発
熱ΔＨ、モル体積Ｖの液体の絶対温度Ｔにおいて、
ＳＰ＝｛（ΔＨ−ＲＴ）／Ｖ｝1/2
で定義される。ただし、上記式中、ＳＰは溶解度パラメ
ータ（単位：（ｃａｌ／ｃｍ3）1/2）であり、ΔＨはモ
ル蒸発熱（単位：ｃａｌ／ｍｏｌ）であり、Ｒは気体定
数（単位：ｃａｌ／（ｍｏｌ・Ｋ））であり、Ｔは絶対
温度（単位：Ｋ）であり、Ｖはモル体積（単位：ｃｍ3
／ｍｏｌ）である。The solubility parameter SP is defined by SP = {(ΔH-RT) / V} 1/2 at the absolute temperature T of the liquid having a molar evaporation heat ΔH and a molar volume V. However, in the above formula, SP is a solubility parameter (unit: (cal / cm 3 ) 1/2 ), ΔH is a heat of molar evaporation (unit: cal / mol), and R is a gas constant (unit: cal / mol). (Mol · K)), T is the absolute temperature (unit: K), and V is the molar volume (unit: cm 3).
/ Mol).
【０１１９】[0119]
【実施例】［実施例１］ダウンフロー式のプラズマ装置
にて、０．５ｋＷ、酸素流量１５０ｃｃ／ｍｉｎ、四フ
ッ化炭素流量１ｃｃ／ｍｉｎ、処理時間１分の条件でプ
ラズマ処理を行ったＩＴＯガラス基板（市販ＩＴＯ、旭
硝子社製：２０Ω／□以下、イオン化ポテンシャル５．
９ｅＶ）上に、ゲルパーエイションクロマトグラフィー
により測定したポリスチレン換算重量平均量（以下分子
量と言う。）として５４，０００の［化６］で示される
ＰＶＫとして７ｍｇを１ｍｌのジクロロエタンに溶解さ
せて作成した溶液１を用いて、１０００ｒｐｍで１秒間
スピンコートを行い、５０ｎｍの膜厚の正孔輸送層を形
成した。[Example 1] ITO subjected to plasma treatment in a down-flow type plasma apparatus under the conditions of 0.5 kW, oxygen flow rate 150 cc / min, carbon tetrafluoride flow rate 1 cc / min, and treatment time 1 minute. Glass substrate (commercial ITO, manufactured by Asahi Glass Co., Ltd .: 20 Ω / □ or less, ionization potential 5.
9 eV) was prepared by dissolving 7 mg of PVK represented by [Chemical Formula 6] of 54,000 as a polystyrene-reduced weight average amount (hereinafter referred to as molecular weight) measured by gel permeation chromatography in 1 ml of dichloroethane. The solution 1 prepared above was spin-coated at 1000 rpm for 1 second to form a hole transport layer having a film thickness of 50 nm.
【０１２０】さらに、真空蒸着装置を用い、圧力条件
１．０×１０-3Ｐａ、蒸着速度１ｎｍ／ｓｅｃで、［化
２０］に示すＡｌｑ３を蒸着して、正孔輸送層上に５０
ｎｍの膜厚の電子輸送性発光層を形成した。Further, using a vacuum vapor deposition apparatus, Alq3 shown in [Chemical Formula 20] is vapor-deposited under a pressure condition of 1.0 × 10 −3 Pa and a vapor deposition rate of 1 nm / sec.
An electron-transporting light-emitting layer having a thickness of nm was formed.
【０１２１】さらに、電子輸送性発光層上に、抵抗加熱
方式の蒸着装置を用いて０．２ｎｍ／ｓｅｃの蒸着速度
で、マグネシウムが９０ｗｔ％となるように重量比を調
整した銀とマグネシウムとの共蒸着を行い、２．０ｎｍ
の膜厚の金属膜を形成して、さらにその上にカバーとし
て銀のみを用いて０．５ｎｍ／ｓｅｃの蒸着速度で蒸着
を行い、２００ｎｍの膜厚の金属膜を形成して陰極と
し、図２に示す素子を作成した。Further, on the electron-transporting light-emitting layer, the weight ratio of silver and magnesium was adjusted by a resistance heating type vapor deposition apparatus at a vapor deposition rate of 0.2 nm / sec so that magnesium was 90 wt%. Co-deposited to 2.0 nm
A metal film having a film thickness of 5 nm, and then using only silver as a cover on the metal film at a deposition rate of 0.5 nm / sec to form a metal film having a film thickness of 200 nm as a cathode. The element shown in 2 was prepared.
【０１２２】この時、駆動電圧６．０Ｖ、電流密度２０
ｍＡ／ｃｍ2で１０００ｃｄ／ｍ2の輝度の発光が得られ
た。At this time, the driving voltage was 6.0 V and the current density was 20.
emission luminance of 1000 cd / m 2 was obtained in mA / cm 2.
【０１２３】なお、ＩＴＯ基板のイオン化ポテンシャル
の測定は、大気中紫外線光電子分光装置（理研計器製Ａ
Ｃ−１）で行った。The measurement of the ionization potential of the ITO substrate was carried out in the atmosphere using an ultraviolet photoelectron spectrometer (A, manufactured by Riken Keiki Co., Ltd.).
C-1).
【０１２４】［比較例１］ＩＴＯ基板のプラズマ処理時
に、四フッ化炭素を用いず、酸素のみ流量１５０ｃｃ／
ｍｉｎ、処理時間１分の条件とした以外は［実施例１］
と同様にして図２に示す素子を作成した。このときのＩ
ＴＯ基板のイオン化ポテンシャルは５．５ｅＶである。[Comparative Example 1] At the time of plasma treatment of an ITO substrate, carbon tetrafluoride was not used and only oxygen was supplied at a flow rate of 150 cc /
Example 1 except that the conditions were min and processing time was 1 minute.
A device shown in FIG. 2 was prepared in the same manner as in. I at this time
The ionization potential of the TO substrate is 5.5 eV.
【０１２５】この時、駆動電圧９．０Ｖ、電流密度２０
ｍＡ／ｃｍ2で１０００ｃｄ／ｍ2の輝度の発光が得られ
た。At this time, the driving voltage was 9.0 V and the current density was 20.
emission luminance of 1000 cd / m 2 was obtained in mA / cm 2.
【０１２６】［実施例１］と［比較例１］とにより、四
フッ化炭素を含有させてプラズマ処理をした方がＩＴＯ
基板のイオン化ポテンシャルが増大して、素子を低電圧
で駆動できる事が分る。According to [Example 1] and [Comparative Example 1], it was better to perform the plasma treatment with the inclusion of carbon tetrafluoride.
It can be seen that the ionization potential of the substrate increases and the device can be driven at a low voltage.
【０１２７】［実施例２〜４］四フッ化炭素の流量を下
記［表１］に示すようにした以外は［実施例１］と同様
にして図２に示す素子を作成したところ、［実施例１］
と同じ１０００ｃｄ／ｍ2の輝度の発光を得るための発
光効率は［表１］に示すようになった。[Examples 2 to 4] The elements shown in FIG. 2 were prepared in the same manner as in [Example 1] except that the flow rate of carbon tetrafluoride was changed as shown in [Table 1] below. Example 1]
Luminous efficiency for obtaining light emission with the same luminance of 1000 cd / m 2 as shown in [Table 1].
【０１２８】[0128]
【表１】 [Table 1]
【０１２９】［表１］により、四フッ化炭素の流量を増
やすとＩＴＯ基板のイオン化ポテンシャルは増大する
が、［比較例２］及び［比較例３］のようにその流量が
１．５ｃｃ／ｍｉｎより大きくなるとＰＶＫとの濡れ性
が悪くなり、成膜が困難になり発光性能が低下すること
が分る。[Table 1] shows that when the flow rate of carbon tetrafluoride is increased, the ionization potential of the ITO substrate is increased, but the flow rate is 1.5 cc / min as in [Comparative Example 2] and [Comparative Example 3]. It can be seen that the larger the value, the poorer the wettability with PVK, the more difficult the film formation becomes, and the lower the light emitting performance.
【０１３０】［実施例５］ダウンフロー式のプラズマ装
置にて、０．５ｋＷ、酸素流量１５０ｃｃ／ｍｉｎ、四
フッ化炭素流量１ｃｃ／ｍｉｎ、処理時間１分の条件で
プラズマ処理を行ったＩＴＯガラス基板（市販ＩＴＯ、
旭硝子社製：２０Ω／□以下、イオン化ポテンシャル
５．９ｅＶ）上に、真空蒸着装置を用い、圧力条件１．
０×１０-3Ｐａ、蒸着速度１ｎｍ／ｓｅｃで、［化５］
で示されるＣＢＰを蒸着して５０ｎｍの膜厚の正孔輸送
層を形成した。[Embodiment 5] ITO glass plasma-treated in a down-flow type plasma apparatus under the conditions of 0.5 kW, oxygen flow rate 150 cc / min, carbon tetrafluoride flow rate 1 cc / min, and treatment time 1 minute. Substrate (commercial ITO,
Asahi Glass Co., Ltd .: 20 Ω / □ or less, ionization potential of 5.9 eV), a vacuum deposition apparatus was used, and pressure conditions were 1.
[Chemical formula 5] at 0 × 10 −3 Pa and vapor deposition rate of 1 nm / sec.
CBP was vapor-deposited to form a hole transport layer having a thickness of 50 nm.
【０１３１】さらに、真空蒸着装置を用い、圧力条件
１．０×１０-3Ｐａ、蒸着速度１ｎｍ／ｓｅｃで、［化
１５］に示すＯＸＤ−１を蒸着して、正孔輸送層上に５
０ｎｍの膜厚の電子輸送性発光層を形成した。Further, OXD-1 shown in [Chemical Formula 15] was vapor-deposited using a vacuum vapor deposition apparatus at a pressure condition of 1.0 × 10 −3 Pa and a vapor deposition rate of 1 nm / sec, and 5 was deposited on the hole transport layer.
An electron-transporting light-emitting layer having a thickness of 0 nm was formed.
【０１３２】さらに、電子輸送性発光層上に、抵抗加熱
方式の蒸着装置を用いて０．２ｎｍ／ｓｅｃの蒸着速度
で、マグネシウムが９０ｗｔ％となるように重量比を調
整した銀とマグネシウムとの共蒸着を行い、２．０ｎｍ
の膜厚の金属膜を形成して、さらにその上にカバーとし
て銀のみを用いて０．５ｎｍ／ｓｅｃの蒸着速度で蒸着
を行い、２００ｎｍの膜厚の金属膜を形成して陰極と
し、図２に示す素子を作成した。Further, on the electron transporting light emitting layer, a weight ratio of silver and magnesium was adjusted by a resistance heating type vapor deposition apparatus at a vapor deposition rate of 0.2 nm / sec so that magnesium was 90 wt%. Co-deposited to 2.0 nm
A metal film having a film thickness of 5 nm, and then using only silver as a cover on the metal film at a deposition rate of 0.5 nm / sec to form a metal film having a film thickness of 200 nm as a cathode. The element shown in 2 was prepared.
【０１３３】この時、駆動電圧６．０Ｖ、電流密度２５
ｍＡ／ｃｍ2で１０００ｃｄ／ｍ2の輝度の発光が得られ
た。At this time, the driving voltage was 6.0 V and the current density was 25.
emission luminance of 1000 cd / m 2 was obtained in mA / cm 2.
【０１３４】［比較例４］ＩＴＯ基板のプラズマ処理時
に、四フッ化炭素を用いず、酸素のみ流量１５０ｃｃ／
ｍｉｎ、処理時間１分の条件とした以外は［実施例５］
と同様にして図２に示す素子を作成した。このとき、駆
動電圧１０Ｖ、電流密度２５ｍＡ／ｃｍ2で１０００ｃ
ｄ／ｍ2の輝度の発光が得られた。[Comparative Example 4] At the time of plasma treatment of an ITO substrate, carbon tetrafluoride was not used and only oxygen was supplied at a flow rate of 150 cc /
Example 5 except that the conditions were min and processing time was 1 minute.
A device shown in FIG. 2 was prepared in the same manner as in. At this time, 1000c at a driving voltage of 10V and a current density of 25mA / cm 2 .
Light emission with a brightness of d / m 2 was obtained.
【０１３５】［実施例６〜８］四フッ化炭素の流量を下
記［表２］に示すようにした以外は［実施例５］と同様
にして図２に示す素子を作成したところ、［実施例５］
と同じ１０００ｃｄ／ｍ2の輝度の発光を得るための発
光効率は［表２］に示すようになった。[Examples 6 to 8] The devices shown in Fig. 2 were prepared in the same manner as in [Example 5] except that the flow rate of carbon tetrafluoride was changed as shown in [Table 2] below. Example 5]
The light emission efficiency for obtaining light emission with the same luminance of 1000 cd / m 2 as shown in [Table 2].
【０１３６】[0136]
【表２】 [Table 2]
【０１３７】［表２］により、［比較例５］及び［比較
例６］のように四フッ化炭素の流量が１．５ｃｃ／ｍｉ
ｎより大きくなると成膜が困難になり発光性能が低下す
ることが分る。According to [Table 2], the flow rate of carbon tetrafluoride was 1.5 cc / mi as in [Comparative Example 5] and [Comparative Example 6].
It can be seen that if it is larger than n, film formation becomes difficult and the light emission performance is deteriorated.
【０１３８】［実施例９］ダウンフロー式のプラズマ装
置にて、プラズマを発生させる石英管中にポリ四フッ化
エチレンを入れフッ素源とし、０．５ｋＷ、酸素流量１
５０ｃｃ／ｍｉｎ、処理時間１分の条件でプラズマ処理
を行ったＩＴＯガラス基板（市販ＩＴＯ、旭硝子社製：
２０Ω／□以下、イオン化ポテンシャル５．９ｅＶ）上
に、分子量５４，０００の［化６］で示されるＰＶＫと
して７ｍｇを１ｍｌのジクロロエタンに溶解させて作成
した溶液１を用いて、１０００ｒｐｍで１秒間スピンコ
ートを行い、５０ｎｍの膜厚の正孔輸送層を形成した。[Embodiment 9] In a down-flow type plasma apparatus, polytetrafluoroethylene was put in a quartz tube for generating plasma to be a fluorine source, 0.5 kW, and an oxygen flow rate was 1
An ITO glass substrate (commercial ITO, manufactured by Asahi Glass Co., Ltd.) subjected to plasma treatment under the conditions of 50 cc / min and a treatment time of 1 minute:
A solution 1 prepared by dissolving 7 mg of PVK represented by [Chemical Formula 6] having a molecular weight of 54,000 in 1 ml of dichloroethane on 20 Ω / □ or less and an ionization potential of 5.9 eV was spun at 1000 rpm for 1 second. Coating was performed to form a hole transport layer having a film thickness of 50 nm.
【０１３９】さらに、真空蒸着装置を用い、圧力条件
１．０×１０-3Ｐａ、蒸着速度１ｎｍ／ｓｅｃで、［化
２０］に示すＡｌｑ３を蒸着して、正孔輸送層上に５０
ｎｍの膜厚の電子輸送性発光層を形成した。Further, Alq3 shown in [Chemical Formula 20] is vapor-deposited using a vacuum vapor deposition apparatus under a pressure condition of 1.0 × 10 −3 Pa and a vapor deposition rate of 1 nm / sec, and 50 is deposited on the hole transport layer.
An electron-transporting light-emitting layer having a thickness of nm was formed.
【０１４０】さらに、電子輸送性発光層上に、抵抗加熱
方式の蒸着装置を用いて０．２ｎｍ／ｓｅｃの蒸着速度
で、マグネシウムが９０ｗｔ％となるように重量比を調
整した銀とマグネシウムとの共蒸着を行い、２．０ｎｍ
の膜厚の金属膜を形成して、さらにその上にカバーとし
て銀のみを用いて０．５ｎｍ／ｓｅｃの蒸着速度で蒸着
を行い、２００ｎｍの膜厚の金属膜を形成して陰極と
し、図２に示す素子を作成した。Further, on the electron-transporting light-emitting layer, the weight ratio of silver and magnesium was adjusted by a resistance heating type vapor deposition apparatus at a vapor deposition rate of 0.2 nm / sec so that magnesium was 90 wt%. Co-deposited to 2.0 nm
A metal film having a film thickness of 5 nm, and then using only silver as a cover on the metal film at a deposition rate of 0.5 nm / sec to form a metal film having a film thickness of 200 nm as a cathode. The element shown in 2 was prepared.
【０１４１】この時、駆動電圧５．５Ｖ、電流密度１８
ｍＡ／ｃｍ2で１０００ｃｄ／ｍ2の輝度の発光が得られ
た。At this time, the driving voltage was 5.5 V and the current density was 18
emission luminance of 1000 cd / m 2 was obtained in mA / cm 2.
【０１４２】[0142]
【発明の効果】以上の説明から明らかなように、本発明
による有機エレクトロルミネッセンス素子は、これを構
成するＩＴＯなどの金属酸化物から成る陽極層がフッ素
を含有した酸素のプラズマ表面処理を経て、５．５ｅＶ
以上の比較的高いイオン化ポテンシャルを有して形成さ
れるので、陽極層に隣接して形成される発光層や正孔輸
送層に導電性高分子を用いる場合や燐光発光のための発
光層ホスト剤を用いる場合でも正孔注入障壁を軽減でき
る。このため、正孔注入層や陽極層中の界面層を介設し
なくても陽極層から発光層へ正孔が確実に注入できて電
気的接合が向上し、駆動電圧を低下することができる。
このような陽極層は簡便なプラズマ表面処理により形成
されるので、これを用いた有機エレクトロルミネッセン
ス素子は簡易に形成でき、また、良好な発光効率を備え
ている。As is clear from the above description, the organic electroluminescence device according to the present invention is obtained by subjecting the anode layer made of a metal oxide such as ITO constituting the anode layer to plasma surface treatment of oxygen containing fluorine, 5.5 eV
Since it is formed with a relatively high ionization potential as described above, when a conductive polymer is used in the light emitting layer or hole transporting layer formed adjacent to the anode layer, or a light emitting layer host agent for phosphorescence emission Even when using, the hole injection barrier can be reduced. For this reason, holes can be surely injected from the anode layer to the light emitting layer without interposing an interface layer in the hole injection layer or the anode layer, electrical connection is improved, and the driving voltage can be lowered. .
Since such an anode layer is formed by a simple plasma surface treatment, an organic electroluminescence device using the same can be easily formed and has good luminous efficiency.
【図１】有機エレクトロルミネッセンス素子の素子構造FIG. 1 is a device structure of an organic electroluminescence device.
【図２】本発明により形成した素子構造の実施形態FIG. 2 is an embodiment of a device structure formed according to the present invention.
１０ 陽極層 ４０ 発光層 ７０ 陰極層 10 Anode layer 40 light emitting layer 70 cathode layer
Claims (6)
間に形成される発光層を有する有機エレクトロルミネッ
センス素子において、前記陽極層が、フッ素含有量を１
重量％以下とする酸素を用いたプラズマ表面処理を施し
た透明性金属酸化物から成ることを特徴とする有機エレ
クトロルミネッセンス素子。1. In an organic electroluminescence device having both electrode layers of an anode layer and a cathode layer and a light emitting layer formed between the both electrode layers, the anode layer has a fluorine content of 1 or less.
An organic electroluminescence device comprising a transparent metal oxide which has been subjected to plasma surface treatment using oxygen in an amount of not more than 10% by weight.
して前記酸素中に含有されることを特徴とする請求項１
に記載の有機エレクトロルミネッセンス素子。2. The fluorine is contained in the oxygen as a constituent atom of carbon tetrafluoride.
The organic electroluminescence device described in 1.
て前記酸素中に含有されることを特徴とする請求項１に
記載の有機エレクトロルミネッセンス素子。3. The organic electroluminescence device according to claim 1, wherein the fluorine is contained in the oxygen as a constituent atom of the fluororesin.
機化合物のイオン化ポテンシャルが５．５ｅＶ以上であ
ることを特徴とする請求項１乃至３のいずれか１項に記
載の有機エレクトロルミネッセンス素子。4. The organic electroluminescence device according to claim 1, wherein the organic compound forming the organic layer laminated on the anode layer has an ionization potential of 5.5 eV or more. .
化物から成ることを特徴とする請求項１乃至４のいずれ
か１項に記載の有機エレクトロルミネッセンス素子。5. The organic electroluminescence device according to claim 1, wherein the transparent metal oxide is indium tin oxide.
間に形成される発光層を有する有機エレクトロルミネッ
センス素子を製造する方法において、ガラス基板上に透
明性金属酸化物を積層した後に、該透明性金属酸化物に
対して、フッ素含有量を１重量％以下とする酸素を用い
たプラズマ表面処理を行って前記陽極層を形成すること
を特徴とする有機エレクトロルミネッセンス素子の製造
方法。6. A method for producing an organic electroluminescent device having both electrode layers of an anode layer and a cathode layer and a light emitting layer formed between the electrode layers, wherein a transparent metal oxide is laminated on a glass substrate. A method for producing an organic electroluminescence device, comprising: performing a plasma surface treatment on the transparent metal oxide with oxygen having a fluorine content of 1% by weight or less to form the anode layer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100625032B1 (en) | 2004-12-07 | 2006-09-20 | 엘지전자 주식회사 | Organic Electro-Luminescence Display Device And Fabricating Method Thereof |
| JP2007115800A (en) * | 2005-10-19 | 2007-05-10 | Hitachi Displays Ltd | Organic el display and its manufacturing method |
| JP2007134210A (en) * | 2005-11-11 | 2007-05-31 | Nippon Seiki Co Ltd | Organic electroluminescent element |
| JP2007266160A (en) * | 2006-03-28 | 2007-10-11 | Canon Inc | Organic light emitting element array |
| JP2009267393A (en) * | 2008-04-02 | 2009-11-12 | Hitachi Chem Co Ltd | Organic electronics material |
| JP2010225997A (en) * | 2009-03-25 | 2010-10-07 | Tdk Corp | Organic el element |
| JP2011501369A (en) * | 2007-10-24 | 2011-01-06 | メルク パテント ゲーエムベーハー | Optoelectronic device |
| WO2019188750A1 (en) * | 2018-03-30 | 2019-10-03 | 国立大学法人信州大学 | Inspection method |
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2002
- 2002-03-04 JP JP2002057521A patent/JP2003257677A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR100625032B1 (en) | 2004-12-07 | 2006-09-20 | 엘지전자 주식회사 | Organic Electro-Luminescence Display Device And Fabricating Method Thereof |
| JP2007115800A (en) * | 2005-10-19 | 2007-05-10 | Hitachi Displays Ltd | Organic el display and its manufacturing method |
| JP2007134210A (en) * | 2005-11-11 | 2007-05-31 | Nippon Seiki Co Ltd | Organic electroluminescent element |
| JP2007266160A (en) * | 2006-03-28 | 2007-10-11 | Canon Inc | Organic light emitting element array |
| JP2011501369A (en) * | 2007-10-24 | 2011-01-06 | メルク パテント ゲーエムベーハー | Optoelectronic device |
| KR101508800B1 (en) * | 2007-10-24 | 2015-04-06 | 메르크 파텐트 게엠베하 | Optoelectronic device |
| JP2009267393A (en) * | 2008-04-02 | 2009-11-12 | Hitachi Chem Co Ltd | Organic electronics material |
| JP2010225997A (en) * | 2009-03-25 | 2010-10-07 | Tdk Corp | Organic el element |
| WO2019188750A1 (en) * | 2018-03-30 | 2019-10-03 | 国立大学法人信州大学 | Inspection method |
| KR20200117036A (en) * | 2018-03-30 | 2020-10-13 | 신슈 다이가쿠 | method of inspection |
| CN111902977A (en) * | 2018-03-30 | 2020-11-06 | 国立大学法人信州大学 | Detection method |
| JPWO2019188750A1 (en) * | 2018-03-30 | 2021-02-12 | 国立大学法人信州大学 | Inspection methods |
| KR102278258B1 (en) | 2018-03-30 | 2021-07-15 | 신슈 다이가쿠 | method of inspection |
| CN111902977B (en) * | 2018-03-30 | 2021-09-24 | 国立大学法人信州大学 | Detection method |
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