JPH04132189A - Organic thin film el element - Google Patents
Organic thin film el elementInfo
- Publication number
- JPH04132189A JPH04132189A JP2252448A JP25244890A JPH04132189A JP H04132189 A JPH04132189 A JP H04132189A JP 2252448 A JP2252448 A JP 2252448A JP 25244890 A JP25244890 A JP 25244890A JP H04132189 A JPH04132189 A JP H04132189A
- Authority
- JP
- Japan
- Prior art keywords
- layer
- organic
- cathode
- electron
- light emitting
- 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
- 239000010409 thin film Substances 0.000 title claims description 24
- 238000002347 injection Methods 0.000 claims abstract description 40
- 239000007924 injection Substances 0.000 claims abstract description 40
- 229910052751 metal Inorganic materials 0.000 claims abstract description 33
- 239000002184 metal Substances 0.000 claims abstract description 30
- 239000000463 material Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 abstract description 11
- 239000000203 mixture Substances 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 2
- 230000008020 evaporation Effects 0.000 abstract 1
- 238000001704 evaporation Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 109
- 239000010408 film Substances 0.000 description 19
- 239000011777 magnesium Substances 0.000 description 17
- 239000000758 substrate Substances 0.000 description 13
- 239000011521 glass Substances 0.000 description 11
- -1 or AI Inorganic materials 0.000 description 10
- 229910052782 aluminium Inorganic materials 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 9
- 239000007983 Tris buffer Substances 0.000 description 7
- 229910045601 alloy Inorganic materials 0.000 description 7
- 239000000956 alloy Substances 0.000 description 7
- 229910052749 magnesium Inorganic materials 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 238000000151 deposition Methods 0.000 description 5
- 238000004544 sputter deposition Methods 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- VPUGDVKSAQVFFS-UHFFFAOYSA-N coronene Chemical compound C1=C(C2=C34)C=CC3=CC=C(C=C3)C4=C4C3=CC=C(C=C3)C4=C2C3=C1 VPUGDVKSAQVFFS-UHFFFAOYSA-N 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000002356 single layer Substances 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 229910052738 indium Inorganic materials 0.000 description 3
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 238000007740 vapor deposition Methods 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- KLCLIOISYBHYDZ-UHFFFAOYSA-N 1,4,4-triphenylbuta-1,3-dienylbenzene Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)=CC=C(C=1C=CC=CC=1)C1=CC=CC=C1 KLCLIOISYBHYDZ-UHFFFAOYSA-N 0.000 description 2
- QENGPZGAWFQWCZ-UHFFFAOYSA-N 3-Methylthiophene Chemical compound CC=1C=CSC=1 QENGPZGAWFQWCZ-UHFFFAOYSA-N 0.000 description 2
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminium flouride Chemical compound F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 2
- 229910019015 Mg-Ag Inorganic materials 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005566 electron beam evaporation Methods 0.000 description 2
- 239000011888 foil 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
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 2
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 2
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 238000001771 vacuum deposition Methods 0.000 description 2
- 229910052984 zinc sulfide Inorganic materials 0.000 description 2
- JCXLYAWYOTYWKM-UHFFFAOYSA-N (2,3,4-triphenylcyclopenta-1,3-dien-1-yl)benzene Chemical compound C1C(C=2C=CC=CC=2)=C(C=2C=CC=CC=2)C(C=2C=CC=CC=2)=C1C1=CC=CC=C1 JCXLYAWYOTYWKM-UHFFFAOYSA-N 0.000 description 1
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- AQVSFOFQUDBEEZ-UHFFFAOYSA-N 1,1,3,4-tetraphenylpenta-1,3-dien-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)=C(C=1C=CC=CC=1)C(C=1C=CC=CC=1)=C(C=1C=CC=CC=1)C1=CC=CC=C1 AQVSFOFQUDBEEZ-UHFFFAOYSA-N 0.000 description 1
- DYZYNUQMTZWZAO-UHFFFAOYSA-N 1-(2-phenylethynyl)anthracene Chemical compound C1=CC=CC=C1C#CC1=CC=CC2=CC3=CC=CC=C3C=C12 DYZYNUQMTZWZAO-UHFFFAOYSA-N 0.000 description 1
- XFYQEBBUVNLYBR-UHFFFAOYSA-N 12-phthaloperinone Chemical class C1=CC(N2C(=O)C=3C(=CC=CC=3)C2=N2)=C3C2=CC=CC3=C1 XFYQEBBUVNLYBR-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- ZCRUJAKCJLCJCP-UHFFFAOYSA-N 3-[methoxy(dimethyl)silyl]propyl prop-2-enoate Chemical compound CO[Si](C)(C)CCCOC(=O)C=C ZCRUJAKCJLCJCP-UHFFFAOYSA-N 0.000 description 1
- OXYZDRAJMHGSMW-UHFFFAOYSA-N 3-chloropropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCl OXYZDRAJMHGSMW-UHFFFAOYSA-N 0.000 description 1
- KNTKCYKJRSMRMZ-UHFFFAOYSA-N 3-chloropropyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)CCCCl KNTKCYKJRSMRMZ-UHFFFAOYSA-N 0.000 description 1
- OGGKVJMNFFSDEV-UHFFFAOYSA-N 3-methyl-n-[4-[4-(n-(3-methylphenyl)anilino)phenyl]phenyl]-n-phenylaniline Chemical compound CC1=CC=CC(N(C=2C=CC=CC=2)C=2C=CC(=CC=2)C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=C(C)C=CC=2)=C1 OGGKVJMNFFSDEV-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- YQHDQYPKFWETPO-UHFFFAOYSA-N 4-[methoxy(dimethyl)silyl]butan-1-amine Chemical compound CO[Si](C)(C)CCCCN YQHDQYPKFWETPO-UHFFFAOYSA-N 0.000 description 1
- XMFCIYUZZWZEHI-UHFFFAOYSA-N 4-[methoxy(dimethyl)silyl]butanenitrile Chemical compound CO[Si](C)(C)CCCC#N XMFCIYUZZWZEHI-UHFFFAOYSA-N 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
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910005540 GaP Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- JYMITAMFTJDTAE-UHFFFAOYSA-N aluminum zinc oxygen(2-) Chemical compound [O-2].[Al+3].[Zn+2] JYMITAMFTJDTAE-UHFFFAOYSA-N 0.000 description 1
- 150000005010 aminoquinolines Chemical class 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 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
- 229910052795 boron group element Inorganic materials 0.000 description 1
- 150000001640 boron group elements Chemical class 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052800 carbon group element Inorganic materials 0.000 description 1
- 150000001724 carbon group elements Chemical class 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010549 co-Evaporation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 238000001194 electroluminescence spectrum Methods 0.000 description 1
- 229920006332 epoxy adhesive Polymers 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- JEWCZPTVOYXPGG-UHFFFAOYSA-N ethenyl-ethoxy-dimethylsilane Chemical compound CCO[Si](C)(C)C=C JEWCZPTVOYXPGG-UHFFFAOYSA-N 0.000 description 1
- GGJQEMXRDJPGAH-UHFFFAOYSA-N ethenyl-ethoxy-diphenylsilane Chemical compound C=1C=CC=CC=1[Si](C=C)(OCC)C1=CC=CC=C1 GGJQEMXRDJPGAH-UHFFFAOYSA-N 0.000 description 1
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 1
- DRUOQOFQRYFQGB-UHFFFAOYSA-N ethoxy(dimethyl)silicon Chemical compound CCO[Si](C)C DRUOQOFQRYFQGB-UHFFFAOYSA-N 0.000 description 1
- RSIHJDGMBDPTIM-UHFFFAOYSA-N ethoxy(trimethyl)silane Chemical compound CCO[Si](C)(C)C RSIHJDGMBDPTIM-UHFFFAOYSA-N 0.000 description 1
- ZVJXKUWNRVOUTI-UHFFFAOYSA-N ethoxy(triphenyl)silane Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(OCC)C1=CC=CC=C1 ZVJXKUWNRVOUTI-UHFFFAOYSA-N 0.000 description 1
- FIHCECZPYHVEJO-UHFFFAOYSA-N ethoxy-dimethyl-phenylsilane Chemical compound CCO[Si](C)(C)C1=CC=CC=C1 FIHCECZPYHVEJO-UHFFFAOYSA-N 0.000 description 1
- ADLWTVQIBZEAGJ-UHFFFAOYSA-N ethoxy-methyl-diphenylsilane Chemical compound C=1C=CC=CC=1[Si](C)(OCC)C1=CC=CC=C1 ADLWTVQIBZEAGJ-UHFFFAOYSA-N 0.000 description 1
- PESLMYOAEOTLFJ-UHFFFAOYSA-N ethoxymethylsilane Chemical compound CCOC[SiH3] PESLMYOAEOTLFJ-UHFFFAOYSA-N 0.000 description 1
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- HZXMRANICFIONG-UHFFFAOYSA-N gallium phosphide Chemical compound [Ga]#P HZXMRANICFIONG-UHFFFAOYSA-N 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004770 highest occupied molecular orbital Methods 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- POPACFLNWGUDSR-UHFFFAOYSA-N methoxy(trimethyl)silane Chemical compound CO[Si](C)(C)C POPACFLNWGUDSR-UHFFFAOYSA-N 0.000 description 1
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound 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
- 229920002647 polyamide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 150000003873 salicylate salts Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Surface Heating Bodies (AREA)
- Electroluminescent Light Sources (AREA)
- Luminescent Compositions (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は、電気的な発光、すなわちＥＬ（エレクトロル
ミネセンス）を用いたＥＬ素子に関し、更に詳しくは陽
極、正孔注入輸送層、有機電子輸送発光層、陰極、もし
くは陽極、正孔注入輸送層、有機発光層、電子注入輸送
層、陰極の順で構成される有機薄膜ＥＬ素子に関するも
のである。[Detailed Description of the Invention] <Industrial Application Field> The present invention relates to an EL device using electrical light emission, that is, EL (electroluminescence), and more specifically relates to an anode, a hole injection transport layer, an organic electron The present invention relates to an organic thin film EL device comprising a transport light emitting layer, a cathode, or an anode, a hole injection transport layer, an organic light emitting layer, an electron injection transport layer, and a cathode, in this order.
〈従来技術とその問題点〉
従来のＥＬ素子は、電極間に高、抵抗な絶縁層を設けた
交流駆動型のものが主流で、それらは分散型ＥＬ素子と
薄膜型ＥＬ素子に大きく分類される。<Prior art and its problems> Conventional EL devices are mainly AC-driven devices with a high-resistance insulating layer between electrodes, and they are broadly classified into dispersed EL devices and thin-film EL devices. Ru.
分散型ＥＬ素子の構造は、樹脂バインダー中に分散させ
た高誘電率のチタン酸バリウム等の粉末を、背面電極と
なるアルミ箔上に数１０μｍの厚さにコーティングして
絶縁層とし、その上に樹脂バインダー中に分散した硫化
亜鉛系の発光体層を設け、更にその上に透明電極を積層
したものである。この型の素子は、安価で大面積、厚さ
１ｍｍ以下の面発光体を得られ、液晶表示装置用バック
ライト等の用途があるが、輝度が低下しやすい、ｆｌ膜
ＥＬ素子は、ガラス板に酸化インジウム錫（以下単にＩ
ＴＯという）等を被覆した透明電極基板上に、絶縁層と
してスパッタリング法等により酸化イツトリウム等の誘
導体薄膜層を数千人形成し、その上にＺｎＳ系、Ｚｎ５
ｅ系、ＳｒＳ系、ＣａＳ系等の蛍光体薄膜を電子ビーム
蒸着、スパッタリング法等で数千人程度積層し、さらに
誘電体薄膜層、アルミ等の背面電極の順に積層された構
造になっている。電極間の膜厚は１〜２μｍ以下である
。薄膜型ＥＬ素子は長寿命で高精細な表示が可能でポー
タプル型コンピュータ用デイスプレィ等の用途に適して
いるが高価である。The structure of a dispersed EL element is to coat an aluminum foil, which will serve as a back electrode, to a thickness of several tens of micrometers with powder such as barium titanate, which has a high dielectric constant and is dispersed in a resin binder, to form an insulating layer. A zinc sulfide-based luminescent layer dispersed in a resin binder is provided on top of the phosphor, and a transparent electrode is further laminated thereon. This type of element can produce a surface light emitting body with a large area and a thickness of 1 mm or less at low cost, and has applications such as backlights for liquid crystal display devices. Indium tin oxide (hereinafter simply I)
Thousands of dielectric thin film layers such as yttrium oxide are formed as an insulating layer on a transparent electrode substrate coated with a material such as yttrium oxide (TO), etc., as an insulating layer, and on top of that, ZnS-based, Zn5
It has a structure in which several thousand e-, SrS, CaS, etc. phosphor thin films are laminated by electron beam evaporation, sputtering, etc., and then a dielectric thin film layer and a back electrode such as aluminum are laminated in that order. . The film thickness between the electrodes is 1 to 2 μm or less. Thin-film EL elements have a long life and are capable of high-definition display, and are suitable for applications such as portable computer displays, but are expensive.
どちらの型のＥＬ素子の場合も十分な輝度を得るために
は１００ｖ以上の交流高電圧を要する。In the case of either type of EL element, an AC high voltage of 100 V or more is required to obtain sufficient brightness.
例えば、電池でＥＬ素子を発光させる際には昇圧トラン
スを要するためＥＬ素子が１ｍｍ以下の薄型であっても
組み込まれた機器全体の厚さを薄くするのは困難であっ
た。For example, when an EL element is made to emit light using a battery, a step-up transformer is required, so even if the EL element is as thin as 1 mm or less, it is difficult to reduce the thickness of the entire device in which it is incorporated.
そこで近年、昇圧トランス等の不要な低電圧直流駆動の
ＥＬ素子を自損した研究が行われており、その一つとし
て有機薄膜ＥＬ素子の研究が行われている。Therefore, in recent years, research has been carried out to eliminate the need for low-voltage DC-driven EL elements such as step-up transformers, and one example of this is research on organic thin film EL elements.
特開昭５７−５１７８１号公報、特開昭５９−１９４３
９３号公報、特開昭６３−２６４６９２号公報、特開昭
６３−２９５６９５号公報、ジャパニーズ・ジャーナル
・オプ・アプライド・フィジックス第２５巻第９号７７
３頁（１９８６年）、アプライド・フィジックス・レタ
ー第５１巻第１２号９１３頁（１９８７年）、ジャーナ
ル・オプ・アプライド・フィジックス第６５巻第９号３
６１Ｏ頁（１９８９年）等によれば、従来、この種の有
機薄膜ＥＬ素子は、陽極、正孔注入輸送層、有機電子輸
送発光層、陰極の順で構成され、以下のように作られて
いる。まず、ガラス等の透明絶縁基板（１）上に蒸着又
はスパッタリング法等で形成した金やＩＴＯの透明導電
被膜の陽極（２）上に、まず正孔注入輸送層（３）とし
て銅フタロシアニン、ポリ３−メチルチオフェン、又は
式％式％
ニル）シクロヘキサン、式（Ｂ）示される、Ｎ、Ｎ’−
ジフェニル−Ｎ、Ｎ’−ビス（３−メチルフェニル）−
１，１’−ビフェニル−４，４′−ジアミン等のテトラ
フエニルジアミン誘導体の層を蒸着や電解重合法等で１
μｍ程度以下の厚さに単層又は積層して形成する。JP-A-57-51781, JP-A-59-1943
93, JP 63-264692, JP 63-295695, Japanese Journal Op Applied Physics Vol. 25 No. 9 77
3 (1986), Applied Physics Letters Vol. 51 No. 12, p. 913 (1987), Journal of Applied Physics Vol. 65 No. 9 3
According to p. 61O (1989), this type of organic thin film EL device has conventionally been constructed in the following order: an anode, a hole injection transport layer, an organic electron transport light emitting layer, and a cathode. There is. First, a hole injecting and transporting layer (3) of copper phthalocyanine, polyamide, or 3-Methylthiophene, or cyclohexane, represented by formula (B), N, N'-
diphenyl-N,N'-bis(3-methylphenyl)-
A layer of a tetraphenyldiamine derivative such as 1,1'-biphenyl-4,4'-diamine is formed by vapor deposition or electrolytic polymerization.
It is formed as a single layer or a laminated layer to a thickness of about μm or less.
次に正孔注入輸送層（３）上に、テトラフェニルブタジ
ェン、アントラセン、ペリレン、コロネン、１２−フタ
ロペリノン誘導体、トリス（８−キノリツール）アルミ
ニウム等の有機蛍光体を蒸着、又は樹脂バインダー中に
分散させてコーティングすることにより有機電子輸送発
光層（４）を１、０μｍ程度以下の厚さで形成する。最
後に、その上に陰極（６）としてＭｇ、Ｉｎ、ＡＩの単
体金属、またはＭｇとＡｇの合金（原子比１０：１）等
を蒸着する。Next, organic phosphors such as tetraphenylbutadiene, anthracene, perylene, coronene, 12-phthaloperinone derivatives, and tris(8-quinolitool)aluminum are deposited on the hole injection transport layer (3) or dispersed in a resin binder. By coating the organic electron transporting light emitting layer (4) with a thickness of about 1.0 μm or less. Finally, a single metal such as Mg, In, or AI, or an alloy of Mg and Ag (atomic ratio 10:1) or the like is deposited thereon as a cathode (6).
以上のように作られた素子は、電源（１ｏ）にリード線
（９）で接続し、透明電極側を陽極として２０〜３０Ｖ
以下の直流低電圧を印加することにより発光層に正孔と
電子が注入され、その再結合により発光する。The element made as described above is connected to the power source (1o) with the lead wire (9), and the transparent electrode side is used as the anode to apply a voltage of 20 to 30V.
By applying the following low DC voltage, holes and electrons are injected into the light emitting layer, and light is emitted by their recombination.
また、有機電子輸送発光層（４）を有機発光層（１２）
と電子注入輸送層（１３）とに分離した有機ｉ１ Ｍ
Ｅ Ｌ素子を安達らは作製した〔アプライド・フィジッ
クス・レター、第５７−を第６号５３１頁（１９９０年
〕〕。In addition, the organic electron transporting light emitting layer (4) is replaced with the organic light emitting layer (12).
and an electron injection transport layer (13).
Adachi et al. produced an EL device [Applied Physics Letters, No. 57-6, p. 531 (1990)].
この素子は、ＩＴＯの陽極上に正孔注入輸送層（３）と
して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、有機発光層（１２）として１− （４−Ｎ、Ｎ−
ビス（Ｐ−メトキシフェニル）アミノスチリル〕ナフタ
レン、電子注入輸送層（１３）として、２−（４−ビフ
ェニル）−５−（４−ｔ−ブチルフェニル）−１，３，
４オキサジアゾール（以下ＢＰＢＤと略す）、陰極とし
てＭｇとＡｇの合金を順に積層し作られ、同様に２０〜
３０Ｖ以下の直流低電圧で１０００ｃｄ／ｍ２以上の輝
度のＥＬ素子を得ている。This device has N,N'-diphenyl-N,N"bis(3-methylphenyl)-1,1'-biphenyl-4,4°-diamine as a hole injection transport layer (3) on an ITO anode. , 1- (4-N, N-
Bis(P-methoxyphenyl)aminostyryl]naphthalene, 2-(4-biphenyl)-5-(4-t-butylphenyl)-1,3,
4 oxadiazole (hereinafter abbreviated as BPBD), made by sequentially laminating an alloy of Mg and Ag as a cathode, and similarly
An EL element with a luminance of 1000 cd/m2 or more was obtained at a low DC voltage of 30 V or less.
しかし、この種の有機薄膜ＥＬ素子は、ＩＯＶ程度以下
の低電圧で１０００ｃｄ／ｍ”以上の高輝度発光を得る
ためには効率的に電子を電子輸送発光層（４）または電
子注入輸送層（１３）に注入スる必要がある。そのため
に陰極材料は、電子を放出しやすいよう仕事関数が小さ
く、かつ有機電子輸送発光層（４）もしくは電子注入輸
送層（１３）との密着性が良い必要がある。However, in order to obtain high-luminance light emission of 1000 cd/m'' or more at a low voltage of about IOV or less, this type of organic thin-film EL device must efficiently transfer electrons to the electron transport light-emitting layer (4) or the electron injection transport layer (4). 13).For this purpose, the cathode material must have a small work function so that it can easily emit electrons, and have good adhesion to the organic electron-transporting light-emitting layer (4) or the electron-injecting and transporting layer (13). There is a need.
そこで、Ｃ１Ｗ、Ｔａｎｇらは、低仕事関数（３，６６
ｅＶ）だが有機膜への密着性の悪いＭｇの密着性を改善
するためＡｇやＣｕ、Ｉｎ、Ｓｎを添加した陰極を開発
した（特開平２−１５５９５号公報）。Therefore, C1W, Tang et al.
However, in order to improve the adhesion of Mg, which has poor adhesion to organic films, a cathode to which Ag, Cu, In, and Sn were added was developed (Japanese Patent Laid-Open No. 15595/1995).
しかし、Ｍｇ−Ａｇ合金等は表面に安定な酸化膜を形成
しないためＭｇ単体よりも逆に腐食が金属内部まで進行
し易い問題があった。However, since Mg-Ag alloys do not form a stable oxide film on their surfaces, there is a problem in that corrosion is more likely to progress to the inside of the metal than with Mg alone.
〈発明が解決しようとする課題〉
本発明は、上記の問題を鑑みて、Ａｇ等を添加せずにＭ
ｇ陰極の密着性を改善した高輝度の有機薄膜ＥＬ素子を
提供するためになされたものである。<Problems to be Solved by the Invention> In view of the above problems, the present invention provides M
This was done to provide a high-brightness organic thin film EL device with improved adhesion of the g-cathode.
〈課題を解決するための手段〉
有機蒸着薄膜上にＭｇを蒸着した場合に、Ｍｇが付着し
にくいのは、Ｍｇの莫気圧が高いため、−度付着したＭ
ｇ原子が有機膜上から再蒸発し、安定な核が形成されに
くいからである。そこで、ＴａｎｇらはＭｇよりも蒸気
圧が高く有機膜上に付着して安定な成長核となり易いＡ
ｇ、Ｉｎ、Ｃｕ、Ｓｎ等と共にＭｇを蒸着することによ
り密着性が高く、陰極表面が平滑で鏡面状のＭｇ合金陰
極を得た。<Means for solving the problem> When Mg is deposited on an organic vapor-deposited thin film, it is difficult for Mg to adhere because the Mg has a high enormous pressure.
This is because g atoms re-evaporate from the organic film, making it difficult to form stable nuclei. Therefore, Tang et al. discovered that A, which has a higher vapor pressure than Mg, is more likely to adhere to organic films and become stable growth nuclei.
By vapor-depositing Mg together with G, In, Cu, Sn, etc., an Mg alloy cathode with high adhesion and a smooth and mirror-like cathode surface was obtained.
本発明は、有機電子輸送発光層または電子注入輸送層と
陰極との間に有機電子輸送発光材料または電子注入輸送
材料と金属元素との混合層を設け、有機膜中に埋め込ま
れた金属元素が、陰極金属層形成時に安定成長核となる
ようにし、Ｍｇのような低仕事関数で蒸着圧が高い金属
を単体で蒸着した場合においても、付着性の良い陰極を
形成でき、高輝度発光を得られることを特徴とする有機
薄膜ＥＬ素子である。The present invention provides a mixed layer of an organic electron-transporting luminescent material or an electron-injecting-transporting material and a metal element between the organic electron-transporting luminescent layer or the electron-injecting-transporting layer and the cathode, and the metallic element embedded in the organic film is When forming the cathode metal layer, it becomes a stable growth nucleus, and even when a metal with a low work function and high deposition pressure, such as Mg, is deposited alone, a cathode with good adhesion can be formed and high luminance luminescence can be obtained. This is an organic thin film EL device characterized by:
〈発明の詳述・作用〉
以下、本発明における有機薄膜ＥＬ素子を陽極、正孔注
入輸送層、有機電子輸送発光層、混合層、陰極の順に構
成する場合（第１図）について主に説明するが、同様の
構成を基板上に陰極から構成することもできる（第２図
参照）、また、有機電子輸送発光層の機能を有機発光層
と電子輸送発光層とに分離し、陽極、正孔注入輸送層、
有機発光層、電子輸送発光層、混合層、陰極の順に構成
することもできる。（第３図参照）。<Detailed Description and Effects of the Invention> Hereinafter, the case where the organic thin film EL device of the present invention is configured in the order of an anode, a hole injection transport layer, an organic electron transport light emitting layer, a mixed layer, and a cathode (FIG. 1) will be mainly explained. However, it is also possible to construct a similar structure from a cathode on a substrate (see Figure 2).Also, it is also possible to separate the functions of the organic electron-transporting light-emitting layer into an organic light-emitting layer and an electron-transporting light-emitting layer. pore injection transport layer,
It is also possible to construct the organic light-emitting layer, the electron-transporting light-emitting layer, the mixed layer, and the cathode in this order. (See Figure 3).
陽極（２）は、ガラス等の透明絶縁体基板（１）上にＩ
ＴＯや酸化亜鉛アルミニウムのような透明導電性物質を
真空蒸着やスパッタリング法等で被覆した表面抵抗１０
〜５０Ω／平方、可視光線透過率８０％以上の透明電極
、又は金やプラチナ、パラジウムの単体、または合金を
薄く蒸着した半透明電極が望ましい。The anode (2) is placed on a transparent insulating substrate (1) such as glass.
Surface resistance 10 coated with a transparent conductive material such as TO or zinc aluminum oxide by vacuum deposition or sputtering method
A transparent electrode with ~50Ω/square and a visible light transmittance of 80% or more, or a translucent electrode made of thinly vapor-deposited gold, platinum, or palladium alone or an alloy is desirable.
しかし、別の場合には、陽極（２）は不透明で、有機電
子輸送発光層（４）へ正孔注入し易い仕事関数の大きい
金、プラチナ、ニッケル等の金属板、シリコン、ガリウ
ムリン、アモルファス炭化シリコン等の仕事関数が４．
８ｅＶ以上の半導体基板、又はそれらの金属や半導体を
絶縁体基板（１）上に被覆した陽極（２）を用いる。However, in other cases, the anode (2) is opaque and made of a metal plate such as gold, platinum, nickel, etc., silicon, gallium phosphide, amorphous, etc., which has a high work function that facilitates hole injection into the organic electron-transporting light-emitting layer (4). The work function of silicon carbide etc. is 4.
A semiconductor substrate having a voltage of 8 eV or higher, or an anode (2) in which an insulating substrate (1) is coated with such a metal or semiconductor is used.
しかし、陰極も陽極も不透明であれば有機電子輸送発光
層（４）または有機発光層（１２）の少なくとも一端が
透明である必要がある。However, if both the cathode and the anode are opaque, at least one end of the organic electron transporting light emitting layer (4) or the organic light emitting layer (12) needs to be transparent.
次に十分に研磨、洗浄を行なったＩＴＯガラス基板など
の透明な陽極（２）上に正孔注入輸送層（３）を形成す
るが、正孔注入輸送材料の好ましい条件は、酸化に対し
て安定で正孔移動度が大、イオン化エネルギーが陽極材
料と発光材料の中間にあり、成膜性が良く、少なくとも
発光層材料の蛍光波長領域において実質的に透明である
必要があり、銅フタロシアニン、無金属フタロシアニン
等のフタロシアニン類またはテトラフェニルジアミン誘
導体等を単層で、または積層して使用する。Next, a hole injection transport layer (3) is formed on a transparent anode (2) such as an ITO glass substrate that has been sufficiently polished and cleaned. It must be stable, have high hole mobility, have an ionization energy between that of the anode material and the light-emitting material, have good film formability, and be substantially transparent at least in the fluorescence wavelength region of the light-emitting layer material, such as copper phthalocyanine, Phthalocyanines such as metal-free phthalocyanine or tetraphenyldiamine derivatives are used in a single layer or in a stacked manner.
テトラフヱニルジアミン誘導体の代表的な材料としては
、１．１−ビス（４−ジ−パラ−トリルアミノフェニル
）シクロヘキサン、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、Ｎ、Ｎ’−ジフェニル−Ｎ、
Ｎ’−ビス（パラトリル）−１，１”−ビフェニル−４
，４゛−ジアミン、Ｎ、Ｎ、Ｎ’ Ｎ’ −テトラ
（パラ−トリル）−４，４”−ジアミノビフェニル、等
があげられるが、上記例に特に限定されるものではない
。Typical materials for tetraphenyldiamine derivatives include 1,1-bis(4-di-para-tolylaminophenyl)cyclohexane, N,N'-diphenyl-N,N'
-bis(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine, N,N'-diphenyl-N,
N'-bis(paratolyl)-1,1''-biphenyl-4
, 4'-diamine, N,N,N'N'-tetra(para-tolyl)-4,4''-diaminobiphenyl, and the like, but are not particularly limited to the above examples.
これらの化合物を用いた正孔注入輸送層（３）の製膜は
、透明電極の陽極（２）上に主に蒸着により形成される
が、ポリエステル、ポリカーボネート、ポリメチルフェ
ニルシラン等の樹脂中に、分散させてスピンコード等の
方法でコーティングすることによって形成することも可
能である。The hole injection transport layer (3) using these compounds is mainly formed by vapor deposition on the anode (2) of the transparent electrode, but it is It is also possible to form it by dispersing it and coating it by a method such as a spin code.
正孔注入輸送層（３）の膜厚は、単層または積層により
形成する場合においても１μｍ以下であり、好ましくは
０．０３〜０．１μｍである。The film thickness of the hole injection transport layer (3) is 1 μm or less, preferably 0.03 to 0.1 μm, even when formed as a single layer or a laminated layer.
次に正孔注入輸送層（３）上に、有機電子輸送発光層（
４）を形成するが、有機電子輸送発光層（４）に用いる
蛍光体は、可視領域に蛍光を有し、適当な方法で製膜で
きる任意の蛍光体が可能である。例えば、アントラセン
、サリチル酸塩、ピレン、コロネン、ペリレン、テトラ
フェニルブタジェン、９．１０−ビス（フェニルエチニ
ル）アントラセン、トリス（８−キノリツール）アルミ
ニウム、ビス（８−キノリツール）亜鉛、トリス（５−
フルオロ−８−キノリツール）アルミニウム、トリス（
５，７−ジクロロ−８−キノリツール）アルミニウム、
トリス（５−クロロ−８−キノリツール）アルミニウム
、ビス〔８−（パラ−トシル）アミノキノリン〕亜鉛お
よびカドミウム１体、１，２，３．４−テトラフェニル
シクロペンタジェン、ペンタフェニルペンタジェン等が
あげられる。Next, on the hole injection transport layer (3), an organic electron transport light emitting layer (
4), the phosphor used for the organic electron transporting light emitting layer (4) can be any phosphor that has fluorescence in the visible region and can be formed into a film by an appropriate method. For example, anthracene, salicylates, pyrene, coronene, perylene, tetraphenylbutadiene, 9.10-bis(phenylethynyl)anthracene, tris(8-quinolitool)aluminum, bis(8-quinolitool)zinc, tris(5-
Fluoro-8-quinolitool) aluminum, tris(
5,7-dichloro-8-quinolitool) aluminum,
Tris(5-chloro-8-quinolitool)aluminum, bis[8-(para-tosyl)aminoquinoline]zinc and one cadmium, 1,2,3,4-tetraphenylcyclopentadiene, pentaphenylpentadiene, etc. can give.
有機電子輸送発光層（４）中の蛍光体は、発光波長変換
、発光効率向上のために２種類以上の蛍光体を混合する
か、他種類の蛍光体の発光層を２層以上積層してもよく
、そのうちの一方は赤外域または紫外域に蛍光を示すも
のであってもよい。The phosphor in the organic electron-transporting light-emitting layer (4) may be a mixture of two or more types of phosphors or a stack of two or more layers of other types of phosphors in order to convert the emission wavelength and improve luminous efficiency. One of them may exhibit fluorescence in the infrared or ultraviolet region.
有機電子輸送発光層（４）の成膜方法は、真空蒸着法、
累積膜法、又は適当な樹脂バインダー中に分散させてス
ピンコードなどの方法でコーティングすることにより行
なわれる。The method of forming the organic electron transporting light emitting layer (4) is a vacuum evaporation method,
This is carried out by a cumulative film method, or by dispersing it in a suitable resin binder and coating it by a method such as a spin cord.
有機電子輸送発光層（４）の膜厚は、単層または積層に
より形成する場合においても１μｍ以下であり、好まし
くは０．０３〜０．１μｍである。The film thickness of the organic electron-transporting light-emitting layer (4) is 1 μm or less, preferably 0.03 to 0.1 μm, even when formed as a single layer or a laminated layer.
有機電子輸送発光層を発光層と電子注入輸送層とに機能
分離して配する場合は、電子注入輸送材料は、最高被占
分子軌道（）（ＯＭＯ）と最低空分子軌道（ＬＵＭＯ）
のエネルギー差が発光層よりも大きく、発光層からの光
を吸収せず、しかも電子移動度の大きく成膜性の良い物
質を選択すれば良い。When the organic electron-transporting light-emitting layer is functionally separated into the light-emitting layer and the electron-injecting-transporting layer, the electron-injecting and transporting material has the highest occupied molecular orbital () (OMO) and the lowest unoccupied molecular orbital (LUMO).
It is sufficient to select a material that has a larger energy difference than the light-emitting layer, does not absorb light from the light-emitting layer, has high electron mobility, and has good film-forming properties.
また、正孔注入輸送層、有機電子輸送発光層、電子注入
輸送層の耐熱性を上げるため、各層の構成材料の例にあ
げた有機分子にビニル基、アリル基、メタクリロイルオ
キシメチル基、メタクリロイルオキシ基、メタクリロイ
ルオキシエチル基、アクリロイル基、アクリロイルオキ
シメチル基、アクリロイルオキシエチル基等の重合性置
換基を１つ以上導入し、成膜後に各層をポリマー化して
もよい。In addition, in order to increase the heat resistance of the hole injection transport layer, organic electron transport light emitting layer, and electron injection transport layer, we added vinyl groups, allyl groups, methacryloyloxymethyl groups, methacryloyloxy organic molecules to the organic molecules listed as examples of the constituent materials of each layer. Each layer may be polymerized after film formation by introducing one or more polymerizable substituents such as methacryloyloxyethyl group, acryloyloxyethyl group, acryloyloxymethyl group, or acryloyloxyethyl group.
また、ＩＴＯガラス基板と正孔注入輸送層との密着性を
上げるため、ＩＴＯ膜をカップリング剤で処理した後、
正孔注入輸送層を設けてもよい。In addition, in order to improve the adhesion between the ITO glass substrate and the hole injection transport layer, after treating the ITO film with a coupling agent,
A hole injection transport layer may also be provided.
カップリング剤の例としては、ビニルトリメトキシシラ
ン、ビニルトリエトキシシラン、ビニルトリス（２−メ
トキシエトキシ）シラン、Ｎ−（２−アミノエチル）３
−アミノプロピルメチルジメトキシシラン、Ｎ−（２−
アミノエチル）３−アミノプロピルトリメトキシシラン
、Ｎ−（２アミノエチル）３−アミノプロピルトリメト
キシシラン、３−アミノプロピルトリエトキシシラン、
３−グリシドキシプロビルトリメトキシシラン、３−グ
リシドキシプロピルメチルジメトキシシラン、２−（３
，４−エポキシシクロヘキシル）エチルトリメトキシシ
ラン、３−クロロプロピルメチルジメトキシシラン、３
−クロロプロピルトリメトキンシラン、３−メタクリロ
キシプロピルトリメトキシシラン、３−メルカプトプロ
ピルトリメトキシシラン、３−アクリロキシプロピルジ
メチルメトキシシラン、４−アミノブチルジメチルメト
キシシラン、ビス（Ｎ−メチルヘンシルアミド）エトキ
シメチルシラン、３−シアノプロピルジメチルメトキシ
シラン、ジメチルエトキシシラン、ジフェニルメチルエ
トキシシラン、ジフェニルビニルエトキシシラン、フエ
ニルジメチルエトキシシラン、トリメチルエトキシシラ
ン、トリメチルメトキシシラン、トリフェニルエトキシ
シラン、ビニルジメチルエトキシシラン、イソプロピル
トリ（Ｎ−アミノエチル−アミノエチル）チタネート、
イソプロピルトリオクタノイルチタネート、イソプロピ
ルトリクミルフェニルチタネートなどがあげられ、この
中から選択することができる。Examples of coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)3
-aminopropylmethyldimethoxysilane, N-(2-
aminoethyl) 3-aminopropyltrimethoxysilane, N-(2aminoethyl)3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane,
3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3
, 4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3
-Chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-acryloxypropyldimethylmethoxysilane, 4-aminobutyldimethylmethoxysilane, bis(N-methylhensylamide) Ethoxymethylsilane, 3-cyanopropyldimethylmethoxysilane, dimethylethoxysilane, diphenylmethylethoxysilane, diphenylvinylethoxysilane, phenyldimethylethoxysilane, trimethylethoxysilane, trimethylmethoxysilane, triphenylethoxysilane, vinyldimethylethoxysilane, Isopropyl tri(N-aminoethyl-aminoethyl) titanate,
Examples include isopropyl trioctanoyl titanate, isopropyl tricumylphenyl titanate, and can be selected from these.
次に本発明による有機電子輸送発光材料と金属元素との
混合層（５）を有機電子輸送発光層（４）上に形成する
。混合層の厚さは１０人〜５００人であり好ましくは１
００人〜３００人である。Next, a mixed layer (5) of an organic electron transporting luminescent material and a metal element according to the present invention is formed on the organic electron transporting luminescent layer (4). The thickness of the mixed layer is 10 to 500, preferably 1
00 to 300 people.
形成方法は、通常は抵抗加熱方法により１０−’Ｔｏｒ
ｒオーダー以下の真空度の下で有機電子輸送発光材料と
金属元素を別々の莫着源より飛ばし、基板の横に置いた
２つの水晶振動子膜圧針等でそれぞれの膜厚をモニター
しながら共蒸着されるが、金属元素は電子ビーム蒸着、
スパッタなど他の方法を用いて蒸着させることもできる
。The forming method is usually a resistance heating method at 10-'Tor.
The organic electron-transporting light-emitting material and the metal element are blown from separate sources under a vacuum of R order or less, and the film thickness is monitored using two crystal oscillator film pressure needles placed next to the substrate. Metal elements are deposited by electron beam evaporation,
It can also be deposited using other methods such as sputtering.
金属元素の種類はＬｉなとのアルカリ金属元素、Ｍｇな
どのアルカリ土類金属元素、Ｔｉ、Ｃｒ、Ｃｕ、Ｚｎ、
Ｎｉ、Ａｇ、などの遷移元素、ＡＩ。Types of metal elements include alkali metal elements such as Li, alkaline earth metal elements such as Mg, Ti, Cr, Cu, Zn,
Transition elements such as Ni, Ag, AI.
Ｉｎなどのホウ素族元素、５ｉＳＧｅ、Ｓｎなどの炭素
族元素があげられる。Examples include boron group elements such as In, and carbon group elements such as 5iSGe and Sn.
混合層中の有機電子輸送発光材料と金属元素の比は、モ
ニターされる各膜厚の比で１＝１０〜１０：１の間が適
している。The ratio of the organic electron-transporting luminescent material to the metal element in the mixed layer is suitably between 1=10 and 10:1 in terms of the ratio of each film thickness to be monitored.
有機電子輸送発光層（４）を有機発光層（１２）と電子
注入輸送層（１３）とに分離して配した場合には、電子
注入輸送層（１３）上に電子注入輸送材料と金属元素と
の混合層を同様の方法で設ければ良い。When the organic electron transporting and emitting layer (4) is arranged separately into the organic emitting layer (12) and the electron injecting and transporting layer (13), the electron injecting and transporting material and the metal element are placed on the electron injecting and transporting layer (13). A mixed layer may be provided using the same method.
次にこの混合層上に低仕事関数金属の陰極（６）を１０
−’Ｔ、ｏ ｒ ｒ以下の真空度下で蒸着を行なうか、
スパッタリング等の他の方法で形成する。Next, a cathode (6) of a low work function metal is placed on this mixed layer for 10 minutes.
-'T, o r Is the deposition carried out under a degree of vacuum below
It is formed by other methods such as sputtering.
陰極金属の例としては、Ｍｇ（仕事関数３．６６ｅＶ）
、ＡＩ（同４．２８ｅＶ）、Ｅｒ （同２゜９７ｅＶＩ
、Ａｇ （同４．２６ｅＶ）、Ｉｎ （同４．０９ｅＶ
）、Ｚｎ （同３． ６３ ｅ Ｖ）などの単体金属ま
たはこれらの金属とＬｉ（同２．９３ｅＶ）、Ｓｒ （
同２．６ｅＶ）などの仕事関数３ｅＶ以下の金属との合
金があげられる。Examples of cathode metals include Mg (work function 3.66 eV)
, AI (4.28eV), Er (2°97eV
, Ag (4.26eV), In (4.09eV
), Zn (3.63 eV) or these metals together with Li (2.93 eV), Sr (
Examples include alloys with metals having a work function of 3 eV or less, such as 2.6 eV).
低仕事関数金属の陰極（６）の厚さは通常１０００〜３
０００人形成されるが、仕事関数が３゜５ｅＶ以下の場
合は陰極（６）の酸化を防ぐために５００Å以下に形成
し、その上に仕事関数３゜５ｅＶ以上の空気中で安定な
金属（化学便覧 改訂３版 基Ｗ編ｌｌ−４９３頁の表
１３・１参照）を５００Å以上形成し、低仕事関数の陰
極（６）内部まで酸化が進行しないようにした方がよい
。The thickness of the low work function metal cathode (6) is usually 1000-3.
However, if the work function is 3°5 eV or less, it is formed to a thickness of 500 Å or less to prevent oxidation of the cathode (6), and a metal (chemical It is better to form a layer of 500 Å or more in thickness (see Table 13/1 on page 493 of Handbook, Revised 3rd Edition, Base W Edition) to prevent oxidation from progressing to the inside of the low work function cathode (6).
最後にＥＬ素子の有機層、電極の酸化を防ぐためには、
ＥＬ素子上に封止層（７）を形成する。Finally, in order to prevent oxidation of the organic layer and electrodes of the EL element,
A sealing layer (7) is formed on the EL element.
封止層（７）は、陰極（６）の形成後直ちに５ｉ０１
、Ｓ ｉｏ、Ｃｒｅｗ、Ｍｏ０ａ等の酸化物、Ｍｇｌ’
！ 、Ｌ ｉＦ、ＢａＦｚ 、ＡｌＦ３ 、ＦｅＦｓ等
の沸化物等の無機物を蒸着、スパッタリング法等により
形成し、さらに水分の浸入を防ぐ為に、低吸湿性の光硬
化接着剤、エポキシ系接着剤等でガラス板や金属板又は
箔を接着し密封する。The sealing layer (7) is made of 5i01 immediately after the formation of the cathode (6).
, S io, Crew, oxides such as Mo0a, Mgl'
! , LiF, BaFz, AlF3, FeFs, and other fluorides are formed by vapor deposition, sputtering, etc., and in order to prevent the infiltration of moisture, a low hygroscopic photocurable adhesive, epoxy adhesive, etc. Glue and seal a glass plate, metal plate, or foil.
有機物層の紫外線による劣化を防ぎ、ＥＬ素子の長寿命
化を計るため、夏ＴＯガラス基板のガラス面上に、Ｚｎ
Ｏ膜等からなる紫外線吸収層を設けたり、ＥＬ発先のス
ペクトルを変化させるために、カラーフィルター層や、
ＥＬ発光を吸収して蛍光を発する物質の層を設けること
もできる。In order to prevent the organic layer from deteriorating due to ultraviolet rays and extend the life of the EL element, Zn was added on the glass surface of the NatsuTO glass substrate.
In order to provide an ultraviolet absorbing layer made of an O film, etc., or change the spectrum of the EL source, a color filter layer,
A layer of material that absorbs EL emission and emits fluorescence can also be provided.
また、陽極のＩＴＯガラス基板上に金、白金、パラジウ
ム等の単体金属または合金のＥＬ発光波長に対する半透
明膜を積層した陽極と、不透明でＥＬ発光波長において
高い反射率を有する陰極を用い、陽極と陰極の間隔がＥ
Ｌ発光波長の２分の１の整数倍に有機薄膜の屈折率で補
正した値の厚さになるよう正孔注入輸送層、有機電子輸
送発光層等を積層し光弁振器化することにより、ＥＬ発
発光波長域域おいて半値巾の狭いＥＬスペクトルを得る
こともできる。In addition, we use an anode in which a semi-transparent film of a single metal or alloy such as gold, platinum, or palladium for the EL emission wavelength is laminated on the ITO glass substrate of the anode, and a cathode that is opaque and has a high reflectance at the EL emission wavelength. and the distance between the cathode and the cathode is E
By laminating a hole injection transport layer, an organic electron transport light emitting layer, etc. to a thickness equal to an integer multiple of 1/2 of the L emission wavelength corrected by the refractive index of the organic thin film to form a light valve. , it is also possible to obtain an EL spectrum with a narrow half-width in the EL emission wavelength range.
以上のように構成した有機薄膜ＥＬ素子は、正孔注入輸
送層側を正として直流電圧を印加することにより発光す
るが、交流電圧を印加した場合にも正孔注入輸送層（３
）側の電極が正に電圧印加されている間は発光する。The organic thin film EL device configured as described above emits light by applying a DC voltage with the hole injection transport layer side as positive. However, when an AC voltage is applied, the hole injection transport layer (3
) side electrode emits light while a positive voltage is applied.
〈実施例〉
以下、本発明のＥＬ素子の実施例を第１図に従って、説
明する。まず、透明絶縁基板（１）として、厚さ１．１
ｍｍのガラス板を用い、この上に１２００人のＩＴＯを
被覆して陽極（２）とした。<Example> Hereinafter, an example of the EL element of the present invention will be described with reference to FIG. First, a transparent insulating substrate (1) with a thickness of 1.1
A glass plate with a diameter of 1.2 mm was used, and 1,200 ITO was coated thereon to form an anode (2).
この透明導電性ガラス基板をアルコールで洗浄後、約４
００°Ｃで１０分間加熱し脱脂を行つた０次に正孔注入
輸送層（３）として、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゛−ジアミンを５００人痕着した。次に、有機
電子輸送発光層（４）としてトリス（８−キノリツール
）アルミニウムを５００人蒸着し、その上面に有機電子
輸送発光材料と金属元素の混合層（５）としてトリス（
８−キノリツール）アルミニウムとマグネシウムをそれ
ぞれ６人／秒の割合で飛ばし、２００人の混合層を形成
した。After cleaning this transparent conductive glass substrate with alcohol,
N,N'-diphenyl-N,N
500 traces of '-bis(3-methylphenyl)1,1'-biphenyl-4,4'-diamine were deposited. Next, 500 people vapor-deposited tris(8-quinolite) aluminum as an organic electron-transporting light-emitting layer (4), and on the top surface, a mixed layer (5) of an organic electron-transporting light-emitting material and a metal element was formed using tris(8-quinolitool).
8-Kinori Tool) Aluminum and magnesium were each flown at a rate of 6 people/second to form a mixed layer of 200 people.
次に低仕事関数陰極（６）としてＭｇを２０人／秒の蒸
着速度で２１００人蒸着した。Next, Mg was deposited as a low work function cathode (6) by 2100 people at a deposition rate of 20 people/second.
この素子は、３■以上で黄緑色に発光し、２０■におい
て輝度は５３９０ ｃ ｄ ７ｍ” 、＠＠密度は２５
１ｍＡ／ｃｍ”であった。This element emits yellow-green light at 3■ or more, and at 20■ the brightness is 5390 c d 7m'' and the density is 25
1 mA/cm".
〈比較例１〉
実施例１と同様に、透明導電性ガラス上に正孔注入輸送
層（３）、有機電子輸送発光層（４）を順に蒸着した上
に、陽極（６）としてＭｇを２０人／秒の蒸着速度で２
７００人蒸着した。<Comparative Example 1> In the same manner as in Example 1, a hole injection transport layer (3) and an organic electron transport light emitting layer (4) were sequentially deposited on a transparent conductive glass, and then 20% Mg was deposited as an anode (6). 2 at a deposition rate of 2 people/sec
700 people were evaporated.
この素子は５ｖ以上で黄緑色の発光をし、２０■におい
て輝度は１６５０ｃｄ／ｍ”でしかなく、電流密度は２
０４ｍＡ／ｃｍ”であった。This element emits yellow-green light at 5V or more, and at 20V, the luminance is only 1650cd/m'', and the current density is 2
04 mA/cm".
〈比較例２〉
実施例２と同様に、透明導電性ガラス上に正孔注入輸送
層（３）、有機電子輸送発光層（４）を順に蒸着した上
に、陰極としてＭｇ−Ａｇ合金（蒸着速度はＭｇが２０
人／秒、Ａｇが２．０人／秒）を共蒸着により２３００
人蒸着した。<Comparative Example 2> In the same manner as in Example 2, a hole injection transport layer (3) and an organic electron transport light emitting layer (4) were sequentially deposited on transparent conductive glass, and then an Mg-Ag alloy (deposited) was deposited as a cathode. The speed is Mg 20
2300 people/sec, Ag 2.0 people/sec) by co-evaporation
People were deposited.
この素子は３■以上で黄緑色に発光し、１７Ｖにおいて
輝度は３５１０ｃｄ／ｍ”でしかなく、電流密度は２１
２ｍＡ／ｃｍ”であった。This element emits yellow-green light at 3μ or more, the brightness is only 3510cd/m'' at 17V, and the current density is 21
2 mA/cm".
〈発明の効果〉
以上述べたように、陽極、正孔注入輸送層、有機電子輸
送発光層、陰極の順で構成される有機薄膜ＥＬ素子また
は陽極、正孔注入輸送層、有機発光層、電子注入輸送層
、陰極の順で構成される有機薄膜ＥＬ素子において、有
機電子輸送発光層または電子注入輸送層と陰極間に、そ
れぞれ有機電子輸送発光材料と金属元素または電子注入
輸送材料と金属元素からなる混合層を設けることにより
、蒸気圧が高いＭｇのような金属を単体で蒸着した場合
においても密着性の良い陰極が形成でき、有機薄膜ＥＬ
素子の高輝度化に効果がある。<Effects of the Invention> As described above, an organic thin film EL element or an anode, a hole injection transport layer, an organic light emitting layer, and an electron In an organic thin film EL device composed of an injection transport layer and a cathode, an organic electron transport luminescent material and a metal element or an electron injection transport material and a metal element are provided between the organic electron transport luminescent layer or the electron injection transport layer and the cathode, respectively. By providing a mixed layer of
It is effective in increasing the brightness of the element.
第１図は、本発明の有機薄膜ＥＬ素子の一実施例を示す
説明図である。
第２図は、本発明の有機薄膜ＥＬ素子の他の実施例を示
す説明図である。
第３図は、本発明の有機’ｉｌｌ膜ＥＬ素子の他の実施
例を示す説明図である。
（１）基板
（２）陽極
（３）正孔注入輸送層
（４）有機電子輸送発光層
（５）混合層
（６）陰極
（７）機密封止層
（８）陰極取り出し口
（９）リード線
（１０）電線
（１１）陽極取り出し口
（１２）有機発光層
電子注入輸送層
特
許
出
願
人
凸版印刷株式会社
代表者
鈴木和夫
第
図
第
図
第
図FIG. 1 is an explanatory diagram showing one embodiment of the organic thin film EL element of the present invention. FIG. 2 is an explanatory diagram showing another embodiment of the organic thin film EL device of the present invention. FIG. 3 is an explanatory diagram showing another embodiment of the organic 'ill film EL device of the present invention. (1) Substrate (2) Anode (3) Hole injection transport layer (4) Organic electron transport light emitting layer (5) Mixed layer (6) Cathode (7) Airtight sealing layer (8) Cathode outlet (9) Lead Wire (10) Electric wire (11) Anode outlet (12) Organic light-emitting layer Electron injection transport layer Patent applicant Toppan Printing Co., Ltd. Representative Kazuo Suzuki Figure Figure Figure
Claims (2)
極の順で構成される有機薄膜ＥＬ素子において、該有機
電子輸送発光層と該陰極との間に有機電子輸送発光材料
と金属元素との混合層を設けたことを特徴とする有機薄
膜ＥＬ素子。(1) In an organic thin film EL device composed of an anode, a hole injection transport layer, an organic electron transport light emitting layer, and a cathode, an organic electron transport light emitting material and a metal are disposed between the organic electron transport light emitting layer and the cathode. An organic thin film EL device characterized by providing a mixed layer with elements.
送層、陰極の順で構成される有機薄膜ＥＬ素子において
、該電子注入輸送層と該陰極との間に電子注入輸送材料
と、金属元素との混合層を設けたことを特徴とする有機
薄膜ＥＬ素子。(2) In an organic thin film EL device composed of an anode, a hole injection transport layer, an organic light emitting layer, an electron injection transport layer, and a cathode, an electron injection transport material is provided between the electron injection transport layer and the cathode. An organic thin film EL device characterized by having a mixed layer with a metal element.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2252448A JPH04132189A (en) | 1990-09-21 | 1990-09-21 | Organic thin film el element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2252448A JPH04132189A (en) | 1990-09-21 | 1990-09-21 | Organic thin film el element |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04132189A true JPH04132189A (en) | 1992-05-06 |
Family
ID=17237522
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2252448A Pending JPH04132189A (en) | 1990-09-21 | 1990-09-21 | Organic thin film el element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04132189A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997020355A1 (en) * | 1995-11-28 | 1997-06-05 | International Business Machines Corporation | Organic/inorganic alloys used to improve organic electroluminescent devices |
| US5710484A (en) * | 1994-07-13 | 1998-01-20 | Matsushita Electric Industrial Co., Ltd. | Organic thin film electroluminescent device having a carbon layer between the hole injection layer and the organic thin film layer |
| US6280860B1 (en) | 1997-09-29 | 2001-08-28 | Minolta Co., Ltd. | Organic electroluminescent element |
| JP2001319789A (en) * | 2000-02-29 | 2001-11-16 | Semiconductor Energy Lab Co Ltd | Light emission device and its preparation method |
| US6395409B2 (en) | 1997-09-29 | 2002-05-28 | Minolta Co., Ltd. | Organic electroluminescent element |
| JP2002367780A (en) * | 2001-06-08 | 2002-12-20 | Nec Corp | Organic el device and manufacturing method therefor |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03274695A (en) * | 1990-03-23 | 1991-12-05 | Nec Corp | Organic thin film electroluminescence (el) element |
-
1990
- 1990-09-21 JP JP2252448A patent/JPH04132189A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03274695A (en) * | 1990-03-23 | 1991-12-05 | Nec Corp | Organic thin film electroluminescence (el) element |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5710484A (en) * | 1994-07-13 | 1998-01-20 | Matsushita Electric Industrial Co., Ltd. | Organic thin film electroluminescent device having a carbon layer between the hole injection layer and the organic thin film layer |
| US5857886A (en) * | 1994-07-13 | 1999-01-12 | Matsushita Electric Industrial Co., Ltd. | Organic thin film electroluminescent device and its manufacturing method |
| WO1997020355A1 (en) * | 1995-11-28 | 1997-06-05 | International Business Machines Corporation | Organic/inorganic alloys used to improve organic electroluminescent devices |
| KR100332186B1 (en) * | 1995-11-28 | 2002-05-09 | 포만 제프리 엘 | Organic/inorganic alloys used to improve organic electroluminescent devices |
| EP1347518A3 (en) * | 1995-11-28 | 2005-11-09 | International Business Machines Corporation | Organic/inorganic alloys used to improve organic electroluminescent devices |
| US6280860B1 (en) | 1997-09-29 | 2001-08-28 | Minolta Co., Ltd. | Organic electroluminescent element |
| US6395409B2 (en) | 1997-09-29 | 2002-05-28 | Minolta Co., Ltd. | Organic electroluminescent element |
| JP2001319789A (en) * | 2000-02-29 | 2001-11-16 | Semiconductor Energy Lab Co Ltd | Light emission device and its preparation method |
| JP4601843B2 (en) * | 2000-02-29 | 2010-12-22 | 株式会社半導体エネルギー研究所 | Light emitting device |
| JP2002367780A (en) * | 2001-06-08 | 2002-12-20 | Nec Corp | Organic el device and manufacturing method therefor |
| JP4717265B2 (en) * | 2001-06-08 | 2011-07-06 | 三星モバイルディスプレイ株式會社 | Organic EL device and manufacturing method thereof |
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