WO2006072015A2 - Organometallic complexes - Google Patents
Organometallic complexes Download PDFInfo
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- WO2006072015A2 WO2006072015A2 PCT/US2005/047501 US2005047501W WO2006072015A2 WO 2006072015 A2 WO2006072015 A2 WO 2006072015A2 US 2005047501 W US2005047501 W US 2005047501W WO 2006072015 A2 WO2006072015 A2 WO 2006072015A2
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- WIPO (PCT)
- Prior art keywords
- complex
- deposited
- alkyl
- layer thickness
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- 125000002524 organometallic group Chemical group 0.000 title claims abstract description 15
- 239000000463 material Substances 0.000 claims description 155
- 239000003446 ligand Substances 0.000 claims description 31
- 239000000203 mixture Substances 0.000 claims description 26
- 229910052782 aluminium Inorganic materials 0.000 claims description 25
- 229910052751 metal Inorganic materials 0.000 claims description 22
- 239000002184 metal Substances 0.000 claims description 22
- 125000003118 aryl group Chemical group 0.000 claims description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 239000005725 8-Hydroxyquinoline Substances 0.000 claims description 10
- 229960003540 oxyquinoline Drugs 0.000 claims description 10
- -1 fluoroalkylphenyl Chemical group 0.000 claims description 9
- 229910052726 zirconium Inorganic materials 0.000 claims description 7
- UHBIKXOBLZWFKM-UHFFFAOYSA-N 8-hydroxy-2-quinolinecarboxylic acid Chemical group C1=CC=C(O)C2=NC(C(=O)O)=CC=C21 UHBIKXOBLZWFKM-UHFFFAOYSA-N 0.000 claims description 6
- 150000004325 8-hydroxyquinolines Chemical class 0.000 claims description 5
- 230000002708 enhancing effect Effects 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 3
- 125000003107 substituted aryl group Chemical group 0.000 claims description 3
- NBYLBWHHTUWMER-UHFFFAOYSA-N 2-Methylquinolin-8-ol Chemical group C1=CC=C(O)C2=NC(C)=CC=C21 NBYLBWHHTUWMER-UHFFFAOYSA-N 0.000 claims description 2
- 239000006057 Non-nutritive feed additive Substances 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000005036 alkoxyphenyl group Chemical group 0.000 claims description 2
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 2
- 125000005037 alkyl phenyl group Chemical group 0.000 claims description 2
- 125000004104 aryloxy group Chemical group 0.000 claims description 2
- 230000000903 blocking effect Effects 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 125000004428 fluoroalkoxy group Chemical group 0.000 claims description 2
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 2
- 125000004407 fluoroaryl group Chemical group 0.000 claims description 2
- 125000001207 fluorophenyl group Chemical group 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 20
- 238000000429 assembly Methods 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 210
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 99
- 239000000243 solution Substances 0.000 description 61
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 45
- 238000000151 deposition Methods 0.000 description 39
- 238000010438 heat treatment Methods 0.000 description 37
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 37
- 239000007788 liquid Substances 0.000 description 33
- 230000008021 deposition Effects 0.000 description 32
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 30
- 230000005525 hole transport Effects 0.000 description 23
- 239000000872 buffer Substances 0.000 description 22
- 239000000047 product Substances 0.000 description 22
- 238000003756 stirring Methods 0.000 description 21
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 20
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 18
- 238000002360 preparation method Methods 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 238000007792 addition Methods 0.000 description 16
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 15
- 239000000758 substrate Substances 0.000 description 15
- 238000007740 vapor deposition Methods 0.000 description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
- 239000012044 organic layer Substances 0.000 description 14
- 238000002207 thermal evaporation Methods 0.000 description 14
- 229910001868 water Inorganic materials 0.000 description 14
- 238000010992 reflux Methods 0.000 description 12
- 239000013078 crystal Substances 0.000 description 11
- 238000001704 evaporation Methods 0.000 description 10
- 230000008020 evaporation Effects 0.000 description 10
- 239000010408 film Substances 0.000 description 10
- 238000001914 filtration Methods 0.000 description 10
- 239000003960 organic solvent Substances 0.000 description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- MQAFLSYQGINCKM-UHFFFAOYSA-N C1=CC=CC2=NC(C)=CC=C21.C1=CC=C(O)C2=NC(C)=CC=C21 Chemical compound C1=CC=CC2=NC(C)=CC=C21.C1=CC=C(O)C2=NC(C)=CC=C21 MQAFLSYQGINCKM-UHFFFAOYSA-N 0.000 description 8
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 8
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 8
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 8
- 230000008901 benefit Effects 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 238000002347 injection Methods 0.000 description 7
- 239000007924 injection Substances 0.000 description 7
- 150000002739 metals Chemical class 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 7
- 239000002322 conducting polymer Substances 0.000 description 6
- 229920001940 conductive polymer Polymers 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 150000004696 coordination complex Chemical class 0.000 description 6
- 238000005187 foaming Methods 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 230000005855 radiation Effects 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- GZFGOTFRPZRKDS-UHFFFAOYSA-N 4-bromophenol Chemical compound OC1=CC=C(Br)C=C1 GZFGOTFRPZRKDS-UHFFFAOYSA-N 0.000 description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- 238000005401 electroluminescence Methods 0.000 description 5
- 229910052741 iridium Inorganic materials 0.000 description 5
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 description 4
- FSEXLNMNADBYJU-UHFFFAOYSA-N 2-phenylquinoline Chemical compound C1=CC=CC=C1C1=CC=C(C=CC=C2)C2=N1 FSEXLNMNADBYJU-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000006071 cream Substances 0.000 description 4
- 239000002178 crystalline material Substances 0.000 description 4
- 235000019439 ethyl acetate Nutrition 0.000 description 4
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 4
- 238000007641 inkjet printing Methods 0.000 description 4
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000004528 spin coating Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 239000007983 Tris buffer Substances 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 229920000547 conjugated polymer Polymers 0.000 description 3
- 230000001419 dependent effect Effects 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 230000006870 function Effects 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- CBHCDHNUZWWAPP-UHFFFAOYSA-N pecazine Chemical compound C1N(C)CCCC1CN1C2=CC=CC=C2SC2=CC=CC=C21 CBHCDHNUZWWAPP-UHFFFAOYSA-N 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 3
- 229920000767 polyaniline Polymers 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 239000003039 volatile agent Substances 0.000 description 3
- DJGHSJBYKIQHIK-UHFFFAOYSA-N (3,5-dimethylphenyl)boronic acid Chemical compound CC1=CC(C)=CC(B(O)O)=C1 DJGHSJBYKIQHIK-UHFFFAOYSA-N 0.000 description 2
- IYZMXHQDXZKNCY-UHFFFAOYSA-N 1-n,1-n-diphenyl-4-n,4-n-bis[4-(n-phenylanilino)phenyl]benzene-1,4-diamine Chemical compound C1=CC=CC=C1N(C=1C=CC(=CC=1)N(C=1C=CC(=CC=1)N(C=1C=CC=CC=1)C=1C=CC=CC=1)C=1C=CC(=CC=1)N(C=1C=CC=CC=1)C=1C=CC=CC=1)C1=CC=CC=C1 IYZMXHQDXZKNCY-UHFFFAOYSA-N 0.000 description 2
- OXPDQFOKSZYEMJ-UHFFFAOYSA-N 2-phenylpyrimidine Chemical compound C1=CC=CC=C1C1=NC=CC=N1 OXPDQFOKSZYEMJ-UHFFFAOYSA-N 0.000 description 2
- YLDFTMJPQJXGSS-UHFFFAOYSA-N 6-bromo-2-naphthol Chemical compound C1=C(Br)C=CC2=CC(O)=CC=C21 YLDFTMJPQJXGSS-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VKZIZIKRZSYNOK-UHFFFAOYSA-N C1=CC=C2C=CC(C)(C(O)=O)NC2=C1O Chemical group C1=CC=C2C=CC(C)(C(O)=O)NC2=C1O VKZIZIKRZSYNOK-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000003849 aromatic solvent Substances 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- YXVFYQXJAXKLAK-UHFFFAOYSA-N biphenyl-4-ol Chemical compound C1=CC(O)=CC=C1C1=CC=CC=C1 YXVFYQXJAXKLAK-UHFFFAOYSA-N 0.000 description 2
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- YMWUJEATGCHHMB-DICFDUPASA-N dichloromethane-d2 Chemical compound [2H]C([2H])(Cl)Cl YMWUJEATGCHHMB-DICFDUPASA-N 0.000 description 2
- 229960004132 diethyl ether Drugs 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000001194 electroluminescence spectrum Methods 0.000 description 2
- 238000005538 encapsulation Methods 0.000 description 2
- 239000007850 fluorescent dye Substances 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- JVZRCNQLWOELDU-UHFFFAOYSA-N gamma-Phenylpyridine Natural products C1=CC=CC=C1C1=CC=NC=C1 JVZRCNQLWOELDU-UHFFFAOYSA-N 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 229920002959 polymer blend Polymers 0.000 description 2
- 229920000123 polythiophene Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 239000012047 saturated solution Substances 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 125000005259 triarylamine group Chemical group 0.000 description 2
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- IERDDDBDINUYCD-UHFFFAOYSA-N 1-[4-[4-(9h-carbazol-1-yl)phenyl]phenyl]-9h-carbazole Chemical group C12=CC=CC=C2NC2=C1C=CC=C2C(C=C1)=CC=C1C(C=C1)=CC=C1C1=C2NC3=CC=CC=C3C2=CC=C1 IERDDDBDINUYCD-UHFFFAOYSA-N 0.000 description 1
- XOFCSEHNWYJNIO-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)phenol Chemical compound CC1=CC(C)=CC(C=2C=CC(O)=CC=2)=C1 XOFCSEHNWYJNIO-UHFFFAOYSA-N 0.000 description 1
- BLPSRWHAQDYHTQ-UHFFFAOYSA-N 4-(4-aminophenyl)-2,3,5,6-tetrakis(4-methylphenyl)aniline Chemical compound C1=CC(C)=CC=C1C(C(=C1C=2C=CC(N)=CC=2)C=2C=CC(C)=CC=2)=C(N)C(C=2C=CC(C)=CC=2)=C1C1=CC=C(C)C=C1 BLPSRWHAQDYHTQ-UHFFFAOYSA-N 0.000 description 1
- NXIXRLZJEZGKGY-UHFFFAOYSA-N 4-(4-tert-butylphenyl)phenol Chemical compound C1=CC(C(C)(C)C)=CC=C1C1=CC=C(O)C=C1 NXIXRLZJEZGKGY-UHFFFAOYSA-N 0.000 description 1
- YGBCLRRWZQSURU-UHFFFAOYSA-N 4-[(diphenylhydrazinylidene)methyl]-n,n-diethylaniline Chemical compound C1=CC(N(CC)CC)=CC=C1C=NN(C=1C=CC=CC=1)C1=CC=CC=C1 YGBCLRRWZQSURU-UHFFFAOYSA-N 0.000 description 1
- PGDARWFJWJKPLY-UHFFFAOYSA-N 4-[2-[3-[4-(diethylamino)phenyl]-2-phenyl-1,3-dihydropyrazol-5-yl]ethenyl]-n,n-diethylaniline Chemical compound C1=CC(N(CC)CC)=CC=C1C=CC1=CC(C=2C=CC(=CC=2)N(CC)CC)N(C=2C=CC=CC=2)N1 PGDARWFJWJKPLY-UHFFFAOYSA-N 0.000 description 1
- KBXXZTIBAVBLPP-UHFFFAOYSA-N 4-[[4-(diethylamino)-2-methylphenyl]-(4-methylphenyl)methyl]-n,n-diethyl-3-methylaniline Chemical compound CC1=CC(N(CC)CC)=CC=C1C(C=1C(=CC(=CC=1)N(CC)CC)C)C1=CC=C(C)C=C1 KBXXZTIBAVBLPP-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
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- NULSTLHFBMHPPS-UHFFFAOYSA-N 6-(3,5-dimethylphenyl)naphthalen-2-ol Chemical compound CC1=CC(C)=CC(C=2C=C3C=CC(O)=CC3=CC=2)=C1 NULSTLHFBMHPPS-UHFFFAOYSA-N 0.000 description 1
- FSUYQOYAPVYVHS-UHFFFAOYSA-N 6-bromonaphthalen-1-ol Chemical compound BrC1=CC=C2C(O)=CC=CC2=C1 FSUYQOYAPVYVHS-UHFFFAOYSA-N 0.000 description 1
- PZOXFBPKKGTQDZ-UHFFFAOYSA-N 6-phenylnaphthalen-2-ol Chemical compound C1=CC2=CC(O)=CC=C2C=C1C1=CC=CC=C1 PZOXFBPKKGTQDZ-UHFFFAOYSA-N 0.000 description 1
- 229920001621 AMOLED Polymers 0.000 description 1
- SXTHKEJHKFYKKJ-UHFFFAOYSA-N CC(C=C(C)O1)=[O]C1=C Chemical compound CC(C=C(C)O1)=[O]C1=C SXTHKEJHKFYKKJ-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- PMPVIKIVABFJJI-UHFFFAOYSA-N Cyclobutane Chemical compound C1CCC1 PMPVIKIVABFJJI-UHFFFAOYSA-N 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910052768 actinide Inorganic materials 0.000 description 1
- 150000001255 actinides Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000001246 colloidal dispersion Methods 0.000 description 1
- 239000006059 cover glass Substances 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229940093499 ethyl acetate Drugs 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
- 239000006260 foam Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 238000007646 gravure printing Methods 0.000 description 1
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000005055 memory storage Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- JGOAZQAXRONCCI-SDNWHVSQSA-N n-[(e)-benzylideneamino]aniline Chemical compound C=1C=CC=CC=1N\N=C\C1=CC=CC=C1 JGOAZQAXRONCCI-SDNWHVSQSA-N 0.000 description 1
- IBHBKWKFFTZAHE-UHFFFAOYSA-N n-[4-[4-(n-naphthalen-1-ylanilino)phenyl]phenyl]-n-phenylnaphthalen-1-amine Chemical compound C1=CC=CC=C1N(C=1C2=CC=CC=C2C=CC=1)C1=CC=C(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C3=CC=CC=C3C=CC=2)C=C1 IBHBKWKFFTZAHE-UHFFFAOYSA-N 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- UQPUONNXJVWHRM-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 UQPUONNXJVWHRM-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
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000548 poly(silane) polymer Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920002098 polyfluorene Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- YYMBJDOZVAITBP-UHFFFAOYSA-N rubrene Chemical compound C1=CC=CC=C1C(C1=C(C=2C=CC=CC=2)C2=CC=CC=C2C(C=2C=CC=CC=2)=C11)=C(C=CC=C2)C2=C1C1=CC=CC=C1 YYMBJDOZVAITBP-UHFFFAOYSA-N 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000007764 slot die coating Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000010129 solution processing Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000000427 thin-film deposition Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 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 1
- 230000000007 visual effect Effects 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
- C07C39/12—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
- C07C39/12—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings
- C07C39/14—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings with at least one hydroxy group on a condensed ring system containing two rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/06—Aluminium compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/06—Aluminium compounds
- C07F5/069—Aluminium compounds without C-aluminium linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/645—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having two nitrogen atoms as the only ring hetero atoms
- C07F9/6509—Six-membered rings
- C07F9/6512—Six-membered rings having the nitrogen atoms in positions 1 and 3
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/12—Light sources with substantially two-dimensional radiating surfaces
- H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/12—Light sources with substantially two-dimensional radiating surfaces
- H05B33/20—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the material in which the electroluminescent material is embedded
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/321—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3]
- H10K85/324—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3] comprising aluminium, e.g. Alq3
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/186—Metal complexes of the light metals other than alkali metals and alkaline earth metals, i.e. Be, Al or Mg
Definitions
- This disclosure relates generally to organometallic complexes, for example, those found in organic electronic devices, and materials and methods for fabrication of the same.
- Organic electronic devices convert electrical energy into radiation, detect signals through electronic processes, convert radiation into electrical energy, or include one or more organic semiconductor layers.
- An organic light-emitting diode is an organic electronic device comprising an organic layer capable of electroluminescence.
- these photoactive organic layers comprise simple organic molecules, conjugated polymers, or organometallic complexes.
- Organometallic complexes are provided, and methods for making, and devices and sub-assemblies including, the same.
- Fig. 1 is a schematic diagram of an organic electronic device.
- Organometallic complexes having at least one ligand having
- Ri is alkyl or aryl.
- the bond crossed by the wavy line indicates a bond to the metal.
- Ri is in the para-position.
- Ri is an alkyl group. In one embodiment, Ri is a C4-C5 alkyl. In one embodiment, R 1 is t-butyl.
- Ri is aryl. In one embodiment, R 1 is phenyl.
- R-i can be further substituted with any substituent that increases the solubility of the ligand in a non-polar solvent.
- an organometallic complex comprising a formula:
- n 1 , 2, or 3;
- M is a metal in a +2, +3, or +4 oxidation state
- Y is a ligand comprising 8-hydroxyquinoline or alkyl-substituted 8- hydroxyquinoline at each occurrence;
- Z is a ligand of Formula I or Il as described above.
- M is Al, Zn, Zr, or Ga. In one embodiment, M is Al.
- the alkyl-substituted 8-hydroxyquinoline is 2-alkyl-8- hydroxyquinoline. In one embodiment, the alkyl-substituted 8-hydroxyquinoline is 2- methyl-8-hydroxyquinoline.
- Jrganometallic complex is electroluminescent. [0019] In one embodiment, there is provided an organometallic complex having the formula:
- n 1 , 2, or 3;
- M is a metal in a +2, +3, or +4 oxidation state
- Y is selected from 8-hydroxyquinolate and substituted 8-hydroxyquinolate
- Z is a compound of Formula III or IV:
- R'i is one or more solvent-solubilizing or Tg enhancing groups
- R 2 , R 3 , and R 4 are independently one or more selected from the group consisting of H, alkyl, substituted alkyl, aryl, substituted aryl, F, CN, a solvent-solubilizing group, and a Tg enhancing group.
- M is Al, Zn, Zr, In or Ga. In one embodiment, M is Al.
- R 1 is an alkyl group.
- Ri is a C1-C6 alkyl. In one embodiment, Ri is cyano, alkyl, fluoroalkyl, aryl, fluoroaryl, alkylaryl, alkoxy, aryloxy, fluoroalkoxy, or fluoroaryloxy, or their hetero-analogs. In one embodiment, Ri is phenyl, fluorophenyl, alkylphenyl, fluoroalkylphenyl, alkoxy phenyl, or fluoroalkoxyphenyl.
- all R 2 , R 3 , and R 4 are H.
- Tg enhancing indicates that the glass transition temperature of the material has been raised over that of the standard
- substituted 8-hydroxyquinolate indicates 8-hydroxyquinolate having at least one alkyi, aryl, substituted alkyl, or substituted aryl substituent.
- hetero indicates that one or more carbon atoms have been replaced with a different atom.
- fluoro indicates that one or more hydrogen atoms have been replaced with a fluorine atom.
- Y and Z are intended to mean ligands on a metal complex.
- compositions comprising the above- described compounds and at least one solvent, processing aid, charge transporting material, or charge blocking material.
- These compositions can be in any form, including, but not limited to solvents, emulsions, and colloidal dispersions.
- the device 100 includes a substrate 105.
- the substrate 105 may be rigid or flexible, for example, glass, ceramic, metal, or plastic. When voltage is applied, emitted light is visible through the substrate 105.
- a first electrical contact layer 110 is deposited on the substrate 105.
- the layer 110 is an anode layer.
- Anode layers may be deposited as lines.
- the anode can be made of, for example, materials containing or comprising metal, mixed metals, alloy, metal oxides or mixed-metal oxide.
- the anode may comprise a conducting polymer, polymer blend or polymer mixtures. Suitable metals include the Group 11 metals, the metals in Groups 4, 5, and 6, and the Group 8, 10 transition metals. If the anode is to be light-transmitting, mixed-metal oxides of Groups 12, 13 and 14 metals, such as indium-tin-oxide, are generally used.
- the anode may also comprise an organic material, especially a conducting polymer such as polyaniline, including exemplary materials as described in Flexible Light-Emitting Diodes Made From Soluble Conducting Polymer, Nature 1992, 357, 477-479. At least one of the anode and cathode should be at least partially transparent to allow the generated light to be observed.
- a conducting polymer such as polyaniline
- An optional buffer layer 120 such as hole transport materials, may be deposited over the anode layer 110, the latter being sometimes referred to as the "hole- injecting contact layer.”
- hole transport materials suitable for use as the layer I2 ⁇ " Have Been” : s£jmfeaVfeA5; :: tDr example, in Kirk Othmer, Encyclopedia of Chemical Technology, Vol. 18, 837-860 (4 th ed. 1996). Both hole transporting "small” molecules as well as oligomers and polymers may be used.
- Hole transporting molecules include, but are not limited to: N 1 N 1 diphenyl-N,N'-bis(3-methylphenyl)-[1 ,1'- bipbenyl]-4,4'-diamine (TPD), 1 ,1 bis[(di-4-tolylamino) phenyljcyclohexane (TAPC), N 1 N 1 bis(4-methylphenyl)-N,N I -bis(4-ethylphenyl)-[1 ,1'-(3,3'-dimethyl)biphenyl]-4,4'-diamine (ETPD), tetrakis (3-methylphenyl)-N,N,N',N'-2,5-phenylenediamine (PDA), a-phenyl 4- N,N-diphenylaminostyrene (TPS), p (diethylamino)benzaldehyde diphenylhydrazone (DEH), triphenyl
- Useful hole transporting polymers include, but are not limited to, polyvinylcarbazole, (phenylmethyl)polysilane, and polyaniline. Conducting polymers are useful as a class. It is also possible to obtain hole transporting polymers by doping hole transporting moieties, such as those mentioned above, into polymers such as polystyrenes and polycarbonates.
- An organic layer 130 may be deposited over the buffer layer 120 when present, or over the first electrical contact layer 110.
- the organic layer 130 may be a number of discrete layers comprising a variety of components.
- the organic layer 130 can be a light- emitting layer that is activated by an applied voltage (such as in a light-emitting diode or light-emitting electrochemical cell), or a layer of material that responds to radiant energy and generates a signal with or without an applied bias voltage (such as in a photodetector).
- EL organic electroluminescent
- materials include, but are not limited to, fluorescent dyes, small molecule organic fluorescent compounds, fluorescent and phosphorescent metal complexes, conjugated polymers, and mixtures thereof.
- fluorescent dyes include, but are not limited to, pyrene, perylene, rubrene, derivatives thereof, and mixtures thereof.
- metal complexes include, but are not limited to, metal chelated oxinoid compounds, such as tris(8-hydroxyquinolato)aluminum (Alq3); cyclor ⁇ fe4latl! ⁇ l8i ⁇ a3dipi ⁇ tH ⁇ electroluminescent compounds, such as complexes of Iridium with phenylpyridine, phenylquinoline, or phenylpyrimidine ligands as disclosed in Petrov et al., Published PCT Application WO 02/02714, and organometallic complexes described in, for example, published applications US 2001/0019782, EP 1191612, WO 02/15645, and EP 1191614; and mixtures thereof.
- metal chelated oxinoid compounds such as tris(8-hydroxyquinolato)aluminum (Alq3)
- cyclor ⁇ fe4latl! ⁇ l8i ⁇ a3dipi ⁇ tH ⁇ electroluminescent compounds such as complexes of Iridium with phen
- Electroluminescent emissive layers comprising a charge carrying host material and a metal complex have been described by Thompson et al., in U.S. Patent 6,303,238, and by Burrows and Thompson in published PCT applications WO 00/70655 and WO 01/41512.
- conjugated polymers include, but are not limited to poly(phenylenevinylenes), polyfluorenes, poly(spirobifluorenes), polythiophenes, poly(p- phenylenes), copolymers thereof, and mixtures thereof.
- the photoactive material can be an organometallic complex.
- the photoactive material is a cyclometalated complex of iridium or platinum.
- Electroluminescent emissive layers comprising a charge carrying host material and a phosphorescent platinum complex have been described by Thompson et al., in U.S. Patent 6,303,238, Bradley et al., in Synth. Met. 2001 , 116 (1-3), 379-383, and Campbell et al., in Phys. Rev. B, Vol. 65 085210.
- a second electrical contact layer 160 is deposited on the organic layer 130.
- the layer 160 is a cathode layer.
- Cathode layers may be deposited as lines or as a film.
- the cathode can be any metal or nonmetal having a lower work function than the anode.
- Exemplary materials for the cathode can include alkali metals, especially lithium, the Group 2 (alkaline earth) metals, the Group 12 metals, including the rare earth elements and lanthanides, and the actinides. Materials such as aluminum, indium, calcium, barium, samarium and magnesium, as well as combinations, can be used. Lithium-containing and other compounds, such as LiF and Li 2 O, may also be deposited between an lower the operating voltage of the system.
- An electron transport layer 140 or electron injection layer 150 is optionally disposed adjacent to the cathode, the cathode being sometimes referred to as the "electron-injecting contact layer.”
- An encapsulation layer 170 is deposited over the contact layer 160 to prevent entry of undesirable components, such as water and oxygen, into the device 100. Such components can have a deleterious effect on the organic layer 130.
- the encapsulation layer 170 is a barrier layer or film.
- the device 100 may comprise additional layers. For example, there can be a layer (not shown) between the anode 110 and hole transport layer 120 to facilitate positive charge transport and/or band-gap matching of the layers, or to function as a protective layer. Other layers that are known in the art or otherwise may be used. In addition, any of the above-described layers may comprise two or more sub-layers or may form a laminar structure.
- anode layer 110 the hole transport layer 120, the electron transport layers 140 and 150, cathode layer 160, and other layers may be treated, especially surface treated, to increase charge carrier transport efficiency or other physical properties of the devices.
- the choice of materials for each of the component layers is preferably determined by balancing the goals of providing a device with high device efficiency with device operational lifetime considerations, fabrication time and complexity factors and other considerations appreciated by persons skilled in the art. It will be appreciated that determining optimal components, component configurations, and compositional identities would be routine to those of ordinary skill of in the art.
- the different layers have the following range of thicknesses: anode 110, 500-5000 A, in one embodiment 1000-2000A; hole transport layer 120, 50-2000 A, in one embodiment 200-1000 A; photoactive layer 130, 10-2000 A, in one embodiment 100-1000 A; layers 140 and 150, 50-2000 A, in one embodiment 100-1000 A; cathode 160, 200-10000 A, in one embodiment 300-5000 A.
- the location of the electron-hole recombination zone in the device, and thus the emission spectrum of the device can be affected by the relative thickness of each layer.
- the thickness of the electron-transport layer should be chosen so that the electron-hole recombination zone is in the light-emitting layer.
- the desired ratio of layer thicknesses will depend on the exact nature of the materials used.
- the device has the following structure, in order: anode, buffer layer, hole transport layer, photoactive layer, electron transport layer, electron injection ⁇ y ⁇ M ⁇ Obe.'frforiU' ⁇ rkbod ⁇ rnent, the anode is made of indium tin oxide or indium zinc oxide.
- the buffer layer comprises a conducting polymer selected from the group consisting of polythiophenes, polyanilines, polypyrroles, copolymers thereof, and mixtures thereof.
- the buffer layer comprises a complex of a conducting polymer and a colloid-forming polymeric acid.
- the buffer layer comprises a compound having triarylamine or triarylmethane groups.
- the buffer layer comprises a material selected from the group consisting of TPD, MPMP, NPB, CBP, and mixtures thereof, as defined above.
- the hole transport layer comprises polymeric hole transport material. In one embodiment, the hole transport layer is crosslinkable. In one embodiment, the hole transport layer comprises a compound having triarylamine or triarylmethane groups. In one embodiment, the buffer layer comprises a material selected from the group consisting of TPD, MPMP, NPB, CBP, and mixtures thereof, as defined above.
- the photoactive layer comprises an electroluminescent metal complex and a host material.
- the host can be a charge transport material.
- the host material is an organometallic complex having the formula MYnZ, as defined herein.
- the electroluminescent complex is present in an amount of at least 1 % by weight. In one embodiment, the electroluminescent complex is 2-20% by weight. In one embodiment, the electroluminescent complex is 20-50% by weight. In one embodiment, the electroluminescent complex is 50-80% by weight. In one embodiment, the electroluminescent complex is 80-99% by weight.
- the metal complex is a cyclometalated complex of iridium, platinum, rhenium, or osmium.
- the photoactive layer further comprises a second host material.
- the second host can be a charge transport material.
- the second host is a hole transport material.
- the second host is an electron transport material.
- the second host material is a metal complex of a hydroxyaryl-N-heterocycle.
- the hydroxyaryl-N-heterocycle is unsubstituted or substituted 8-hydroxyquinoline.
- the metal is aluminum.
- the second host is a material selected from the group consisting of tris(8-hydroxyquinolinato)aluminum, bis(8-hydroxyquinolinato)(4- phenylphenolato)aluminum, tetrakis(8-hydroxyquinolinato)zirconium, and mixtures thereof.
- the ratio of the first host to the second host can be 1 :100 to 100:1. In one emiollmenAfeytlB 1s ferrfM ⁇ o 10:1. In one embodiment, the ratio is from 1 :10 to 1 :5. In one embodiment, the ratio is from 1 :5 to 1 :1. In one embodiment, the ratio is from 1 :1 to 5:1. In one embodiment, the ratio is from 5:1 to 5:10.
- the electron transport layer comprises a metal complex of a hydroxyaryl-N-heterocycle.
- the hydroxyaryl-N-heterocycle is unsubstituted or substituted 8-hydroxyquinoline.
- the metal is aluminum.
- the electron transport layer comprises a material selected from the group consisting of tris(8-hydroxyquinolinato)aluminum, bis(8- hydroxyquinolinato)(4-phenylphenolato)aluminum, tetrakis(8- hydroxyquinolinato)zirconium, and mixtures thereof.
- the electron injection layer is LiF or LJ02.
- the cathode is Al or Ba/AI.
- the device is fabricated by liquid deposition of the buffer layer, the hole transport layer, and the photoactive layer, and by vapor deposition of the electron transport layer, the electron injection layer, and the cathode.
- the buffer layer can be deposited from any liquid medium in which it is dissolved or dispersed and from which it will form a film.
- the liquid medium consists essentially of one or more organic solvents.
- the liquid medium consists essentially of water or water and an organic solvent.
- the organic solvent is selected from the group consisting of alcohols, ketones, cyclic ethers, and polyols.
- the organic liquid is selected from dimethylacetamide ("DMAc”), N methylpyrrolidone (“NMP”), dimethylformamide (“DMF”), ethylene glycol (“EG”), aliphatic alcohols, and mixtures thereof.
- the buffer material can be present in the liquid medium in an amount from 0.5 to 10 percent by weight. Other weight percentages of buffer material may be used depending upon the liquid medium.
- the buffer layer can be applied by any continuous or discontinuous liquid deposition technique. In one embodiment, the buffer layer is applied by spin coating. In one embodiment, the buffer layer is applied by ink jet printing. After liquid deposition, the liquid medium can be removed in air, in an inert atmosphere, or by vacuum, at room temperature or with heating.
- the layer is heated to a temperature less than 275 0 C.
- the heating temperature is between 100 0 C and 275 0 C. In one embodiment, the heating temperature is between 100°C and 120 0 C. In one embodiment, the heating temperature is between 12O 0 C and 14O 0 C. In one embodiment, the heating temperature is between 140 0 C and 160 0 CIn one embodiment, the heating temperature is between 160 0 C and 180 0 C. In one embodiment, the heating temperature is between 18O 0 C and 200°C. In one embodiment, Iri ' e is between 200 0 C and 220 0 CIn one embodiment, the heating temperature is between 190 0 C and 220 0 C.
- the heating temperature is between 220 0 C and 24O 0 C. In one embodiment, the heating temperature is between 240°C and 260°C. In one embodiment, the heating temperature is between 260°C and 275 0 C.
- the heating time is dependent upon the temperature, and is generally between 5 and 60 minutes.
- the final layer thickness is between 5 and 200 nm. In one embodiment, the final layer thickness is between 5 and 40 nm. In one embodiment, the final layer thickness is between 40 and 80 nm. In one embodiment, the final layer thickness is between 80 and 120 nm. In one embodiment, the final layer thickness is between 120 and 160 nm. In one embodiment, the final layer thickness is between 160 and 200 nm.
- the hole transport layer can be deposited from any liquid medium in which it is dissolved or dispersed and from which it will form a film.
- the liquid medium consists essentially of one or more organic solvents.
- the liquid medium consists essentially of water or water and an organic solvent.
- the organic solvent is an aromatic solvent.
- the organic liquid is selected from chloroform, dichloromethane, toluene, anisole, and mixtures thereof.
- the hole transport material can be present in the liquid medium in a concentration of 0.2 to 2 percent by weight. Other weight percentages of hole transport material may be used depending upon the liquid medium.
- the hole transport layer can be applied by any continuous or discontinuous liquid deposition technique.
- the hole transport layer is applied by spin coating. In one embodiment, the hole transport layer is applied by ink jet printing. After liquid deposition, the liquid medium can be removed in air, in an inert atmosphere, or by vacuum, at room temperature or with heating. In one embodiment, the layer is heated to a temperature less than 275 0 C. In one embodiment, the heating temperature is between 17O 0 C and 275°C. In one embodiment, the heating temperature is between 17O 0 C and 200 0 C. In one embodiment, the heating temperature is between 19O 0 C and 220°C. In one embodiment, the heating temperature is between 21O 0 C and 24O 0 C. In one embodiment, the heating temperature is between 230 0 C and 27O 0 C.
- the heating time is dependent upon the temperature, and is generally between 5 and 60 minutes.
- the final layer thickness is between 5 and 50 nm. In one embodiment, the final layer thickness is between 5 and 15 nm. In one embodiment, the final layer thickness is between 15 and 25 nm. In one embodiment, the final layer thickness is between 25 and 35 nm. In one embodiment, the final layer thickness is between 35 and 50 nm.
- the photoactive layer can be deposited from any liquid medium in which it is dissolved or dispersed and from which it will form a film.
- the liquid medium consists essentially of one or more organic solvents.
- the liquid medium consists essentially of water or water and an organic solvent.
- the organic solvent is an aromatic solvent.
- the organic liquid is selected from chloroform, dichloromethane, toluene, anisole, and mixtures thereof.
- the photoactive material can be present in the liquid medium in a concentration of 0.2 to 2 percent by weight. Other weight percentages of photoactive material may be used depending upon the liquid medium.
- the photoactive layer can be applied by any continuous or discontinuous liquid deposition technique.
- the photoactive layer is applied by spin coating. In one embodiment, the photoactive layer is applied by ink jet printing. After liquid deposition, the liquid medium can be removed in air, in an inert atmosphere, or by vacuum, at room temperature or with heating. In one embodiment, the deposited layer is heated to a temperature that is less than the Tg of the material having the lowest Tg. In one embodiment, the heating temperature is at least 1O 0 C less than the lowest Tg. In one embodiment, the heating temperature is at least 2O 0 C less than the lowest Tg. In one embodiment, the heating temperature is at least 30 0 C less than the lowest Tg. In one embodiment, the heating temperature is between 50 0 C and 150 0 C.
- the heating temperature is between 50 0 C and 75°C. In one embodiment, the heating temperature is between 75°C and 100 0 C. In one embodiment, the heating temperature is between 100 0 C and 125°C. In one embodiment, the heating temperature is between 125°C and 150 0 C.
- the heating time is dependent upon the temperature, and is generally between 5 and 60 minutes.
- the final layer thickness is between 25 and 100 nm. In one embodiment, the final layer thickness is between 25 and 40 nm. In one embodiment, the final layer thickness is between 40 and 65 nm. In one embodiment, the final layer thickness is between 65 and 80 nm. In one embodiment, the final layer thickness is between 80 and 100 nm.
- the electron transport layer can be deposited by any vapor deposition method. In one embodiment, it is deposited by thermal evaporation under vacuum. In one embodiment, the final layer thickness is between 1 and 100 nm. In one embodiment, the final layer thickness is between 1 and 15 nm. In one embodiment, the final layer thickness is between 15 and 30 nm. In one embodiment, the final layer thickness is between 30 and 45 nm. In one embodiment, the final layer thickness is between 45 and 60 layer thickness is between 60 and 75 nm. In one embodiment, the final layer thickness is between 75 and 90 nm. In one embodiment, the final layer thickness is between 90 and 100 nm.
- the electron injection layer can be deposited by any vapor deposition method. In one embodiment, it is deposited by thermal evaporation under vacuum. In one embodiment, the vacuum is less than 10-6 torr. In one embodiment, the vacuum is less than 10-7 torr. In one embodiment, the vacuum is less than 10-8 torr. In one embodiment, the material is heated to a temperature in the range of 100oC to 400oC; 150oC to 350oC peferrably. In one embodiment, the material is deposited at a rate of 0.5 to 10 A/sec. In one embodiment, the material is deposited at a rate of 0.5 to 1 A/sec. In one embodiment, the material is deposited at a rate of 1 to 2 A/sec.
- the material is deposited at a rate of 2 to 3 A/sec. In one embodiment, the material is deposited at a rate of 3 to 4 A/sec. In one embodiment, the material is deposited at a rate of 4 to 5 A/sec. In one embodiment, the material is deposited at a rate of 5 to 6 A/sec. In one embodiment, the material is deposited at a rate of 6 to 7 A/sec. In one embodiment, the material is deposited at a rate of 7 to 8 A/sec. In one embodiment, the material is deposited at a rate of 8 to 9 A/sec. In one embodiment, the material is deposited at a rate of 9 to 10 A/sec. In one embodiment, the final layer thickness is between 0.1 and 3 nm.
- the final layer thickness is between 0.1 and 1 nm. In one embodiment, the final layer thickness is between 1 and 2 nm. In one embodiment, the final layer thickness is between 2 and 3 nm.
- the cathode can be deposited by any vapor deposition method. In one embodiment, it is deposited by thermal evaporation under vacuum. In one embodiment, the vacuum is less than 10-6 torr. In one embodiment, the vacuum is less than 10-7 torr. In one embodiment, the vacuum is less than 10-8 torr. In one embodiment, the material is heated to a temperature in the range of 100oC to 400oC; 150oC to 350oC peferrably.
- the material is deposited at a rate of 0.5 to 10 A/sec. In one embodiment, the material is deposited at a rate of 0.5 to 1 A/sec. In one embodiment, the material is deposited at a rate of 1 to 2 A/sec. In one embodimentm, the material is deposited at a rate of 2 to 3 A/sec. In one embodiment, the material is deposited at a rate of 3 to 4 A/sec. In one embodiment, the material is deposited at a rate of 4 to 5 A/sec. In one embodiment, the material is deposited at a rate of 5 to 6 A/sec. In one embodiment, the material is deposited at a rate of 6 to 7 A/sec. In one embodiment, the material is deposited at a rate of 7 to 8 A/sec.
- the material is deposited at a rate of 8 to 9 A/sec. In one embodiment, the material is In one embodiment, the final layer thickness is between 10 and 10000 nm. In one embodiment, the final layer thickness is between 10 and 1000 nm. In one embodiment, the final layer thickness is between 10 and 50 nm. In one embodiment, the final layer thickness is between 50 and 100 nm. In one embodiment, the final layer thickness is between 100 and 200 nm. In one embodiment, the final layer thickness is between 200 and 300 nm. In one embodiment, the final layer thickness is between 300 and 400 nm. In one embodiment, the final layer thickness is between 400 and 500 nm. In one embodiment, the final layer thickness is between 500 and 600 nm.
- the final layer thickness is between 600 and 700 nm. In one embodiment, the final layer thickness is between 700 and 800 nm. In one embodiment, the final layer thickness is between 800 and 900 nm. In one embodiment, the final layer thickness is between 900 and 1000 nm. In one embodiment, the final layer thickness is between 1000 and 2000 nm. In one embodiment, the final layer thickness is between 2000 and 3000 nm. In one embodiment, the final layer thickness is between 3000 and 4000 nm. In one embodiment, the final layer thickness is between 4000 and 5000 nm. In one embodiment, the final layer thickness is between 5000 and 6000 nm. In one embodiment, the final layer thickness is between 6000 and 7000 nm.
- the final layer thickness is between 7000 and 8000 nm. In one embodiment, the final layer thickness is between 8000 and 9000 nm. In one embodiment, the final layer thickness is between 9000 and 10000 nm. In one embodiment, the device is fabricated by vapor deposition of the buffer layer, the hole transport layer, and the photoactive layer, the electron transport layer, the electron injection layer, and the cathode.
- the buffer layer is applied by vapor deposition. In one embodiment, it is deposited by thermal evaporation under vacuum. In one embodiment, the vacuum is less than 10-6 torr. In one embodiment, the vacuum is less than 10-7 torr. In one embodiment, the vacuum is less than 10-8 torr. In one embodiment, the material is heated to a temperature in the range of 100oC to 400oC; 150oC to 350oC peferrably. In one embodiment, the material is deposited at a rate of 0.5 to 10 A/sec. In one embodiment, the material is deposited at a rate of 0.5 to 1 A/sec. In one embodiment, the material is deposited at a rate of 1 to 2 A/sec.
- the material is deposited at a rate of 2 to 3 A/sec. In one embodiment, the material is deposited at a rate of 3 to 4 A/sec. In one embodiment, the material is deposited at a rate of 4 to 5 A/sec. In one embodiment, the material is deposited at a rate of 5 to 6 A/sec. In one embodiment, the material is deposited at a rate of 6 to 7 A/sec. In one emS ⁇ SfmentHii mlb ⁇ af ⁇ l'dijjillted at a rate of 7 to 8 A/sec. In one embodiment, the material is deposited at a rate of 8 to 9 A/sec. In one embodiment, the material is deposited at a rate of 9 to 10 A/sec.
- the final layer thickness is between 5 and 200 nm. In one embodiment, the final layer thickness is between 5 and 30 nm. In one embodiment, the final layer thickness is between 30 and 60 nm. In one embodiment, the final layer thickness is between 60 and 90 nm. In one embodiment, the final layer thickness is between 90 and 120 nm. In one embodiment, the final layer thickness is between 120 and 150 nm. In one embodiment, the final layer thickness is between 150 and 280 nm. In one embodiment, the final layer thickness is between 180 and 200 nm.
- the hole transport layer is applied by vapor deposition. In one embodiment, it is deposited by thermal evaporation under vacuum. In one embodiment, the vacuum is less than 10-6 torr. In one embodiment, the vacuum is less than 10-7 torr. In one embodiment, the vacuum is less than 10-8 torr. In one embodiment, the material is heated to a temperature in the range of 100oC to 400oC; 150oC to 350oC peferrably. In one embodiment, the material is deposited at a rate of 0.5 to 10 A/sec. In one embodiment, the material is deposited at a rate of 0.5 to 1 A/sec. In one embodiment, the material is deposited at a rate of 1 to 2 A/sec.
- the material is deposited at a rate of 2 to 3 A/sec. In one embodiment, the material is deposited at a rate of 3 to 4 A/sec. In one embodiment, the material is deposited at a rate of 4 to 5 A/sec. In one embodiment, the material is deposited at a rate of 5 to 6 A/sec. In one embodiment, the material is deposited at a rate of 6 to 7 A/sec. In one embodiment, the material is deposited at a rate of 7 to 8 A/sec. In one embodiment, the material is deposited at a rate of 8 to 9 A/sec. In one embodiment, the material is deposited at a rate of 9 to 10 A/sec. In one embodiment, the final layer thickness is between 5 and 200 nm.
- the final layer thickness is between 5 and 30 nm. In one embodiment, the final layer thickness is between 30 and 60 nm. In one embodiment, the final layer thickness is between 60 and 90 nm. In one embodiment, the final layer thickness is between 90 and 120 nm. In one embodiment, the final layer thickness is between 120 and 150 nm. In one embodiment, the final layer thickness is between 150 and 280 nm. In one embodiment, the final layer thickness is between 180 and 200 nm.
- the photoactive layer is applied by vapor deposition. In one embodiment, it is deposited by thermal evaporation under vacuum. In one embodiment, the photoactive layer consists essentially of a single electroluminescent evaporation under vacuum. In one embodiment, the vacuum is less than 10-6 torr. In one embodiment, the vacuum is less than 10-7 torr. In one embodiment, the vacuum is less than 10-8 torr. In one embodiment, the material is heated to a temperature in the range of 100oC to 400oC; 150oC to 350oC peferrably. In one embodiment, the material is deposited at a rate of 0.5 to 10 A/sec. In one embodiment, the material is deposited at a rate of 0.5 to 1 A/sec.
- the material is deposited at a rate of 1 to 2 A/sec. In one embodimentm, the material is deposited at a rate of 2 to 3 A/sec. In one embodiment, the material is deposited at a rate of 3 to 4 A/sec. In one embodiment, the material is deposited at a rate of 4 to 5 A/sec. In one embodiment, the material is deposited at a rate of 5 to 6 A/sec. In one embodiment, the material is deposited at a rate of 6 to 7 A/sec. In one embodiment, the material is deposited at a rate of 7 to 8 A/sec. In one embodiment, the material is deposited at a rate of 8 to 9 A/sec. In one embodiment, the material is deposited at a rate of 9 to 10 A/sec.
- the final layer thickness is between 5 and 200 nm. In one embodiment, the final layer thickness is between 5 and 30 nm. In one embodiment, the final layer thickness is between 30 and 60 nm. In one embodiment, the final layer thickness is between 60 and 90 nm. In one embodiment, the final layer thickness is between 90 and 120 nm. In one embodiment, the final layer thickness is between 120 and 150 nm. In one embodiment, the final layer thickness is between 150 and 280 nm. In one embodiment, the final layer thickness is between 180 and 200 nm.
- the photoactive layer comprises two electroluminescent materials, each of which is applied by thermal evaporation under vacuum. Any of the above listed vacuum conditions and temperatures can be used. Any of the above listed deposition rates can be used.
- the relative deposition rates can be from 50:1 to 1 :50. In one embodiment, the relative deposition rates are from 1 :1 to 1 :3. In one embodiment, the relative deposition rates are from 1 :3 to 1 :5. In one embodiment, the relative deposition rates are from 1 :5 to 1 :8. In one embodiment, the relative deposition rates are from 1 :8 to 1 :10. In one embodiment, the relative deposition rates are from 1 :10 to 1 :20.
- the relative deposition rates are from 1 :20 to 1 :30. In one embodiment, the relative deposition rates are from 1 :30 to 1 :50.
- the total thickness of the layer can be the same as that described above for a single-component photoactive layer.
- the photoactive layer comprises one electroluminescent material and at least one host material, each of which is applied by thermal evaporation vacuum conditions and temperatures can be used. Any of the above listed deposition rates can be used.
- the relative deposition rate of electroluminescent material to host can be from 1 :1 to 1 :99. In one embodiment, the relative deposition rates are from 1 :1 to 1 :3. In one embodiment, the relative deposition rates are from 1 :3 to 1 :5. In one embodiment, the relative deposition rates are from 1 :5 to 1 :8. In one embodiment, the relative deposition rates are from 1 :8 to 1 :10. In one embodiment, the relative deposition rates are from 1 :10 to 1 :20.
- the relative deposition rates are from 1 :20 to 1 :30. In one embodiment, the relative deposition rates are from 1 :30 to 1 :40. In one embodiment, the relative deposition rates are from 1 :40 to 1 :50. In one embodiment, the relative deposition rates are from 1 :50 to 1 :60. In one embodiment, the relative deposition rates are from 1 :60 to 1 :70. In one embodiment, the relative deposition rates are from 1 :70 to 1 :80. In one embodiment, the relative deposition rates are from 1 :80 to 1 :90. In one embodiment, the relative deposition rates are from 1 :90 to 1 :99.
- the electron transport layer is applied by vapor deposition. In one embodiment, it is deposited by thermal evaporation under vacuum. In one embodiment, the vacuum is less than 10-6 torr. In one embodiment, the vacuum is less than 10-7 torr. In one embodiment, the vacuum is less than 10-8 torr. In one embodiment, the material is heated to a temperature in the range of 100oC to 400oC; 150oC to 350oC peferrably. In one embodiment, the material is deposited at a rate of 0.5 to 10 A/sec. In one embodiment, the material is deposited at a rate of 0.5 to 1 A/sec.
- the material is deposited at a rate of 1 to 2 A/sec. In one embodimentm, the material is deposited at a rate of 2 to 3 A/sec. In one embodiment, the material is deposited at a rate of 3 to 4 A/sec. In one embodiment, the material is deposited at a rate of 4 to 5 A/sec. In one embodiment, the material is deposited at a rate of 5 to 6 A/sec. In one embodiment, the material is deposited at a rate of 6 to 7 A/sec. In one embodiment, the material is deposited at a rate of 7 to 8 A/sec. In one embodiment, the material is deposited at a rate of 8 to 9 A/sec. In one embodiment, the material is deposited at a rate of 9 to 10 A/sec.
- the final layer thickness is between 5 and 200 nm. In one embodiment, the final layer thickness is between 5 and 30 nm. In one embodiment, the final layer thickness is between 30 and 60 nm. In one embodiment, the final layer thickness is between 60 and 90 nm. In one embodiment, the final layer thickness is between 90 and 120 nm. In one embodiment, the final layer thickness is between 120 and 150 nm. In one embodiment, the final layer thicl ⁇ n ⁇ sl is In one embodiment, the final layer thickness is between 180 and 200 nm.
- the electron injection layer is applied by vapor deposition, as described above.
- the cathode is applied by vapor deposition, as describe above.
- the device is fabricated by vapor deposition of some of the organic layers, and liquid deposition of some of the organic layers.
- the device is fabricated by liquid deposition of the buffer layer, and vapor deposition of all of the other layers.
- OLEDs called active matrix OLED displays
- individual deposits of photoactive organic films may be independently excited by the passage of current, leading to individual pixels of light emission.
- OLEDs called passive matrix OLED displays
- deposits of photoactive organic films may be excited by rows and columns of electrical contact layers.
- Devices can be prepared employing a variety of techniques. These include, by way of non-limiting exemplification, vapor deposition techniques and liquid deposition.
- Devices may also be sub-assembled into separate articles of manufacture that can then be combined to form the device.
- active materials include, but are not limited to, materials which conduct, inject, transport, or block a charge, where the charge can be either an electron or a hole.
- inactive materials include, but are not limited to, planarization materials, insulating materials, anf SKmSaI iaff ' iMi ⁇ lrtak
- the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having” or any other variation thereof, are intended to cover a non-exclusive inclusion.
- a process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
- "or” refers to an inclusive or and not to an exclusive or. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).
- the term "layer” is used interchangeably with the term “film” and refers to a coating covering a desired area.
- the area can be as large as an entire device or a specific functional area such as the actual visual display, or as small as a single sub- pixel.
- Films can be formed by any conventional deposition technique, including vapor deposition and liquid deposition.
- Liquid deposition techniques include, but are not limited to, continuous deposition techniques such as spin coating, gravure coating, curtain coating, dip coating, slot-die coating, spray-coating, and continuous nozzle coating; and discontinuous deposition techniques such as ink jet printing, gravure printing, and screen printing.
- Organic electronic device is intended to mean a device including one or more semiconductor layers or materials.
- Organic electronic devices include, but are not limited to: (1 ) devices that convert electrical energy into radiation (e.g., a light- emitting diode, light emitting diode display, diode laser, or lighting panel), (2) devices that detect signals through electronic processes (e.g., photodetectors photoconductive cells, photoresistors, photoswitches, phototransistors, phototubes, infrared (“IR”) detectors, or biosensors), (3) devices that convert radiation into electrical energy (e.g., a photovoltaic device or solar cell), and (4) devices that include one or more electronic components that include one or more organic semiconductor layers (e.g., a transistor or diode).
- the term device also includes coating materials for memory storage devices, antistatic films, biosensors, electrochromic devices, solid electrolyte capacitors, energy storage devices such as a rechargeable battery, and electromagnetic shielding applications.
- substrate is intended to mean a workpiece that can be either rigid or flexible and may include one or more layers of one or more materials, which can include, but are not limited to, glass, polymer, metal, or ceramic materials, or coAH ⁇ o' ⁇ l ⁇ ifia-
- a degassed solution of K 2 CO 3 (8.2 g, 5.9 mmol) in H2O (100 ml_) was added to a mixture of 6-bromo-2-naphthol (3.43 g, 1.54 mmol), 4-(t-butylphenyl)boronic acid (3.21 g, 1.80 mmol) and Pd(PPh 3 ) 4 (0.89 g, 0.77 mmol) in monoglyme (100 ml_) and then heated to 80 0 C for two days. Upon cooling, the mixture was diluted with diethylether and 1M HCI ( ⁇ 20mL) was added.
- the organic layer was preabsorbed onto silica gel and eluted down a silica column with hexanes 80%/ethylacetate 20%.
- the eluted organic material was concentrated and taken up in ethanol and stirred with activated carbon, filtered and concentrated_to precipitate the desired phenolic ligand in 75% yield.
- Example 9 Device fabrication and characterization data
- OLED devices were fabricated by a combination of solution processing and thermal evaporation techniques. Patterned indium tin oxide (ITO) coated glass substrates from Thin Film Devices, lnc were used. These ITO substrates are based on Corning 1737 glass coated with 1400 A of ITO having a sheet resistance of 30 ohms/square and 80% light transmission. The patterned ITO substrates were cleaned ultrasonically in aqueous detergent solution and rinsed with distilled water. The patterned ITO was subsequently cleaned ultrasonically in acetone, rinsed with isopropanol, and dried in a stream of nitro ⁇ en. Immediately before device fabrication the cfeaned"!
- ITO indium tin oxide
- Example 9.1 the host was a mixture of the material of Example 3 and Host
- the emitter was Red emitter 2.
- Example 9.2 the host was a mixture of the material of Example 5 and Host
- the emitter was Red emitter 1.
- the current efficiency of the device at a certain voltage is determined by dividing the electroluminescence radiance of the LED by the current density needed to run the device.
- the unit is a cd/A.
- the power efficiency is the current efficiency divided by the operating voltage.
- the unit is
- Buffer 1 was an aqueous dispersion of poly(3,4-dioxythiophene) and a polymeric fluorinated sulfonic acid. The material was prepared using a procedure similar to that described in Example 3 of published U.S. patent application no. 2004/0254297.
- Hole Transport 1 was a crosslinkable polymeric hole transport material.
- Red emitter 1
- OLED devices were fabricated by the thermal evaporation technique.
- the base vacuum for all of the thin film deposition was in the range of 10 ⁇ 8 torr.
- Patterned indium tin oxide coated glass substrates from Thin Film Devices, lnc were used. These ITO's are based on Coming 1737 glass coated with 1400A ITO coating, with sheet resistance of 30 ohms/square and 80% light transmission.
- the patterned ITO substrates were then cleaned ultrasonically in aqueous detergent solution.
- the substrates were then rinsed with distilled water, followed by isopropanol, and then degreased in toluene vapor.
- an aqueous dispersion of Buffer 1 was spin-coated over the ITO surface and heated to remove solvent.
- the substrate was then loaded into the vacuum chamber and multiple layers of thin films were then deposited sequentially onto the buffer layer by thermal evaporation. Patterned layers of LiF and Al were deposited through a mask.
- the completed OLED device was then taken out of the vacuum chamber, encapsulated with a cover glass using epoxy, and characterized. The device layers are given in Table 10.1 below.
- the OLED samples were characterized by measuring their (1 ) current-voltage (I-V) curves, (2) electroluminescence radiance versus voltage, and (3) electroluminescence spectra versus voltage. All three measurements were performed at the same time and controlled by a computer.
- the current efficiency of the device at a certain voltage is determined by dividing the electroluminescence radiance of the LED by the current density needed to run the device.
- the unit is a cd/A.
- the power efficiency is the current efficiency divided by the operating voltage.
- the unit is Im/W. [0096]
- the materials used in device fabrication are listed below: NPB: N,N'-Bis(naphthalen-1 -yl)-N,N'-bis-(phenyl)benzidine
- TDATA 4,4',4"-Tris-(N,N-diphenyl-amino)-triphenylamine
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Abstract
Organometallic complexes are provided, methods for making the same, and their use in devices and sub-assemblies.
Description
ORGANOMETALLIC COMPLEXES
CROSS REFERENCE
[0001] This application claims benefit to U.S. Provisional Application Serial Nos. 60/640,493, filed December 30, 2004 and 60/694,943, filed June 28, 2005, the disclosures of which are each incorporated herein by reference in their entireties.
FIELD
[0002] This disclosure relates generally to organometallic complexes, for example, those found in organic electronic devices, and materials and methods for fabrication of the same.
BACKGROUND
[0003] Organic electronic devices convert electrical energy into radiation, detect signals through electronic processes, convert radiation into electrical energy, or include one or more organic semiconductor layers. An organic light-emitting diode (OLED) is an organic electronic device comprising an organic layer capable of electroluminescence. In some OLEDs, these photoactive organic layers comprise simple organic molecules, conjugated polymers, or organometallic complexes. [0004] As can be appreciated, it is important to develop organometallic complexes.
SUMMARY
[0005] Organometallic complexes are provided, and methods for making, and devices and sub-assemblies including, the same.
[0006] The foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention, as defined in the appended claims.
BRIEF DESCRIPTION OF THE DRAWINGS
[0007] Embodiments are illustrated in the accompanying figures to improve understanding of concepts as presented herein.
[0008] Fig. 1 is a schematic diagram of an organic electronic device.
[0009] The figures are provided by way of example and are not intended to limit the invention. Skilled artisans appreciate that objects in the figures are illustrated for
drawn to scale. For example, the dimensions of some of the objects in the figures may be exaggerated relative to other objects to help to improve understanding of embodiments.
DETAILED DESCRIPTION
[0010] Organometallic complexes are provided having at least one ligand having
Formula I or II:
wherein Ri is alkyl or aryl. The bond crossed by the wavy line indicates a bond to the metal.
[0011] In one embodiment, Ri is in the para-position.
[0012] In one embodiment, Ri is an alkyl group. In one embodiment, Ri is a C4-C5 alkyl. In one embodiment, R1 is t-butyl.
[0013] In one embodiment, Ri is aryl. In one embodiment, R1 is phenyl.
[0014] It is understood that R-i can be further substituted with any substituent that increases the solubility of the ligand in a non-polar solvent.
[0015] In one embodiment, an organometallic complex is provided comprising a formula:
[Y]nMZ wherein: n is 1 , 2, or 3;
M is a metal in a +2, +3, or +4 oxidation state;
Y is a ligand comprising 8-hydroxyquinoline or alkyl-substituted 8- hydroxyquinoline at each occurrence; and
Z is a ligand of Formula I or Il as described above.
[0016] In one embodiment, M is Al, Zn, Zr, or Ga. In one embodiment, M is Al. [0017] In one embodiment, the alkyl-substituted 8-hydroxyquinoline is 2-alkyl-8- hydroxyquinoline. In one embodiment, the alkyl-substituted 8-hydroxyquinoline is 2- methyl-8-hydroxyquinoline.
Jrganometallic complex is electroluminescent. [0019] In one embodiment, there is provided an organometallic complex having the formula:
MYnZ wherein: n is 1 , 2, or 3;
M is a metal in a +2, +3, or +4 oxidation state;
Y is selected from 8-hydroxyquinolate and substituted 8-hydroxyquinolate; and
Z is a compound of Formula III or IV:
IV
wherein:
R'i is one or more solvent-solubilizing or Tg enhancing groups;
R2, R3, and R4 are independently one or more selected from the group consisting of H, alkyl, substituted alkyl, aryl, substituted aryl, F, CN, a solvent-solubilizing group, and a Tg enhancing group.
[0020] In one embodiment, M is Al, Zn, Zr, In or Ga. In one embodiment, M is Al. [0021] In one embodiment, R1 is an alkyl group. In one embodiment, Ri is a C1-C6 alkyl. In one embodiment, Ri is cyano, alkyl, fluoroalkyl, aryl, fluoroaryl, alkylaryl, alkoxy, aryloxy, fluoroalkoxy, or fluoroaryloxy, or their hetero-analogs. In one embodiment, Ri is phenyl, fluorophenyl, alkylphenyl, fluoroalkylphenyl, alkoxy phenyl, or fluoroalkoxyphenyl.
[0022] In one embodiment, all R2, R3, and R4 are H.
[0023] As used herein, the term "solvent-solubilizing" indicates that the solubility or dispersability of a material in at least one organic solvent has been increased over that of the standard parent molecules, BAIQ, (MY2Z where Y = 2-methyl-8- hydroxyquinolinate and Z = 4-phenylphenol) about 1.9wt% in toluene, or BAInapQ (MY2Z where Y = 2-methyl-8-hydroxyquinolinate and Z = 6-phenyl-naphth-2-ol) about 1.3wt% in toluene, all at room temperature. The term "Tg enhancing" indicates that the glass transition temperature of the material has been raised over that of the standard
[0024] The term "substituted 8-hydroxyquinolate" indicates 8-hydroxyquinolate having at least one alkyi, aryl, substituted alkyl, or substituted aryl substituent. [0025] The prefix "hetero" indicates that one or more carbon atoms have been replaced with a different atom. The prefix "fluoro" indicates that one or more hydrogen atoms have been replaced with a fluorine atom.
[0026] As used herein, "Y" and "Z" are intended to mean ligands on a metal complex. [0027] Any number of other configurations for the containment structure are contemplated.
[0028] In one embodiment, compositions are provided comprising the above- described compounds and at least one solvent, processing aid, charge transporting material, or charge blocking material. These compositions can be in any form, including, but not limited to solvents, emulsions, and colloidal dispersions.
Device
[0029] Referring to Fig. 1 , an exemplary organic electronic device 100 is shown. The device 100 includes a substrate 105. The substrate 105 may be rigid or flexible, for example, glass, ceramic, metal, or plastic. When voltage is applied, emitted light is visible through the substrate 105.
[0030] A first electrical contact layer 110 is deposited on the substrate 105. For illustrative purposes, the layer 110 is an anode layer. Anode layers may be deposited as lines. The anode can be made of, for example, materials containing or comprising metal, mixed metals, alloy, metal oxides or mixed-metal oxide. The anode may comprise a conducting polymer, polymer blend or polymer mixtures. Suitable metals include the Group 11 metals, the metals in Groups 4, 5, and 6, and the Group 8, 10 transition metals. If the anode is to be light-transmitting, mixed-metal oxides of Groups 12, 13 and 14 metals, such as indium-tin-oxide, are generally used. The anode may also comprise an organic material, especially a conducting polymer such as polyaniline, including exemplary materials as described in Flexible Light-Emitting Diodes Made From Soluble Conducting Polymer, Nature 1992, 357, 477-479. At least one of the anode and cathode should be at least partially transparent to allow the generated light to be observed.
[0031] An optional buffer layer 120, such as hole transport materials, may be deposited over the anode layer 110, the latter being sometimes referred to as the "hole- injecting contact layer." Examples of hole transport materials suitable for use as the
layer I2θ" Have Been":s£jmfeaVfeA5;::tDr example, in Kirk Othmer, Encyclopedia of Chemical Technology, Vol. 18, 837-860 (4th ed. 1996). Both hole transporting "small" molecules as well as oligomers and polymers may be used. Hole transporting molecules include, but are not limited to: N1N1 diphenyl-N,N'-bis(3-methylphenyl)-[1 ,1'- bipbenyl]-4,4'-diamine (TPD), 1 ,1 bis[(di-4-tolylamino) phenyljcyclohexane (TAPC), N1N1 bis(4-methylphenyl)-N,NI-bis(4-ethylphenyl)-[1 ,1'-(3,3'-dimethyl)biphenyl]-4,4'-diamine (ETPD), tetrakis (3-methylphenyl)-N,N,N',N'-2,5-phenylenediamine (PDA), a-phenyl 4- N,N-diphenylaminostyrene (TPS), p (diethylamino)benzaldehyde diphenylhydrazone (DEH), triphenylamine (TPA), bis[4 (N,N-diethylamino)-2-methylphenyl](4- methylphenyl)methane (MPMP), 1 phenyl-3-[p-(diethylamino)styryl]-5-[p- (diethylamino)phenyl] pyrazoline (PPR or DEASP), 1 ,2 trans-bis(9H-carbazol-9- yl)cyclobutane (DCZB), N, N, N', N1 tetrakis(4-methylphenyl)-(1 ,1'-biphenyl)-4,4'-diamine (TTB); 4,4', N1N', dicarbazolyl-biphenyl (CBP); and porphyrinic compounds, such as copper phthalocyanine. Useful hole transporting polymers include, but are not limited to, polyvinylcarbazole, (phenylmethyl)polysilane, and polyaniline. Conducting polymers are useful as a class. It is also possible to obtain hole transporting polymers by doping hole transporting moieties, such as those mentioned above, into polymers such as polystyrenes and polycarbonates.
[0032] An organic layer 130 may be deposited over the buffer layer 120 when present, or over the first electrical contact layer 110. In some embodiments, the organic layer 130 may be a number of discrete layers comprising a variety of components. Depending upon the application of the device, the organic layer 130 can be a light- emitting layer that is activated by an applied voltage (such as in a light-emitting diode or light-emitting electrochemical cell), or a layer of material that responds to radiant energy and generates a signal with or without an applied bias voltage (such as in a photodetector).
[0033] Other layers in the device can be made of any materials which are known to be useful in such layers upon consideration of the function to be served by such layers. [0034] Any organic electroluminescent ("EL") material can be used as a photoactive material (e.g., in layer 130). Such materials include, but are not limited to, fluorescent dyes, small molecule organic fluorescent compounds, fluorescent and phosphorescent metal complexes, conjugated polymers, and mixtures thereof. Examples of fluorescent dyes include, but are not limited to, pyrene, perylene, rubrene, derivatives thereof, and mixtures thereof. Examples of metal complexes include, but are not limited to, metal chelated oxinoid compounds, such as tris(8-hydroxyquinolato)aluminum (Alq3);
cyclorτfe4latl!ά^l8i^a3dipi§tHά^ electroluminescent compounds, such as complexes of Iridium with phenylpyridine, phenylquinoline, or phenylpyrimidine ligands as disclosed in Petrov et al., Published PCT Application WO 02/02714, and organometallic complexes described in, for example, published applications US 2001/0019782, EP 1191612, WO 02/15645, and EP 1191614; and mixtures thereof. Electroluminescent emissive layers comprising a charge carrying host material and a metal complex have been described by Thompson et al., in U.S. Patent 6,303,238, and by Burrows and Thompson in published PCT applications WO 00/70655 and WO 01/41512. Examples of conjugated polymers include, but are not limited to poly(phenylenevinylenes), polyfluorenes, poly(spirobifluorenes), polythiophenes, poly(p- phenylenes), copolymers thereof, and mixtures thereof. [0035] In one embodiment of the devices, the photoactive material can be an organometallic complex. In another embodiment, the photoactive material is a cyclometalated complex of iridium or platinum. Other useful photoactive materials may be employed as well. Complexes of iridium with phenylpyridine, phenylquinoline, or phenylpyrimidine ligands have been disclosed as electroluminescent compounds in Petrov et al., Published PCT Application WO 02/02714. Other organometallic complexes have been described in, for example, published applications US 2001/0019782, EP 1191612, WO 02/15645, and EP 1191614. Electroluminescent devices with an active layer of polyvinyl carbazole (PVK) doped with metallic complexes of iridium have been described by Burrows and Thompson in published PCT applications WO 00/70655 and WO 01/41512. Electroluminescent emissive layers comprising a charge carrying host material and a phosphorescent platinum complex have been described by Thompson et al., in U.S. Patent 6,303,238, Bradley et al., in Synth. Met. 2001 , 116 (1-3), 379-383, and Campbell et al., in Phys. Rev. B, Vol. 65 085210.
[0036] A second electrical contact layer 160 is deposited on the organic layer 130. For illustrative purposes, the layer 160 is a cathode layer.
[0037] Cathode layers may be deposited as lines or as a film. The cathode can be any metal or nonmetal having a lower work function than the anode. Exemplary materials for the cathode can include alkali metals, especially lithium, the Group 2 (alkaline earth) metals, the Group 12 metals, including the rare earth elements and lanthanides, and the actinides. Materials such as aluminum, indium, calcium, barium, samarium and magnesium, as well as combinations, can be used. Lithium-containing and other compounds, such as LiF and Li2O, may also be deposited between an
lower the operating voltage of the system. [0038] An electron transport layer 140 or electron injection layer 150 is optionally disposed adjacent to the cathode, the cathode being sometimes referred to as the "electron-injecting contact layer."
[0039] An encapsulation layer 170 is deposited over the contact layer 160 to prevent entry of undesirable components, such as water and oxygen, into the device 100. Such components can have a deleterious effect on the organic layer 130. In one embodiment, the encapsulation layer 170 is a barrier layer or film. [0040] Though not depicted, it is understood that the device 100 may comprise additional layers. For example, there can be a layer (not shown) between the anode 110 and hole transport layer 120 to facilitate positive charge transport and/or band-gap matching of the layers, or to function as a protective layer. Other layers that are known in the art or otherwise may be used. In addition, any of the above-described layers may comprise two or more sub-layers or may form a laminar structure. Alternatively, some or all of anode layer 110 the hole transport layer 120, the electron transport layers 140 and 150, cathode layer 160, and other layers may be treated, especially surface treated, to increase charge carrier transport efficiency or other physical properties of the devices. The choice of materials for each of the component layers is preferably determined by balancing the goals of providing a device with high device efficiency with device operational lifetime considerations, fabrication time and complexity factors and other considerations appreciated by persons skilled in the art. It will be appreciated that determining optimal components, component configurations, and compositional identities would be routine to those of ordinary skill of in the art. [0041] In one embodiment, the different layers have the following range of thicknesses: anode 110, 500-5000 A, in one embodiment 1000-2000A; hole transport layer 120, 50-2000 A, in one embodiment 200-1000 A; photoactive layer 130, 10-2000 A, in one embodiment 100-1000 A; layers 140 and 150, 50-2000 A, in one embodiment 100-1000 A; cathode 160, 200-10000 A, in one embodiment 300-5000 A. The location of the electron-hole recombination zone in the device, and thus the emission spectrum of the device, can be affected by the relative thickness of each layer. Thus the thickness of the electron-transport layer should be chosen so that the electron-hole recombination zone is in the light-emitting layer. The desired ratio of layer thicknesses will depend on the exact nature of the materials used.
[0042] In one embodiment, the device has the following structure, in order: anode, buffer layer, hole transport layer, photoactive layer, electron transport layer, electron
injection \^y^^M\Obe.'frforiU'^rkbod\rnent, the anode is made of indium tin oxide or indium zinc oxide. In one embodiment, the buffer layer comprises a conducting polymer selected from the group consisting of polythiophenes, polyanilines, polypyrroles, copolymers thereof, and mixtures thereof. In one embodiment, the buffer layer comprises a complex of a conducting polymer and a colloid-forming polymeric acid. In one embodiment, the buffer layer comprises a compound having triarylamine or triarylmethane groups. In one embodiment, the buffer layer comprises a material selected from the group consisting of TPD, MPMP, NPB, CBP, and mixtures thereof, as defined above.
In one embodiment, the hole transport layer comprises polymeric hole transport material. In one embodiment, the hole transport layer is crosslinkable. In one embodiment, the hole transport layer comprises a compound having triarylamine or triarylmethane groups. In one embodiment, the buffer layer comprises a material selected from the group consisting of TPD, MPMP, NPB, CBP, and mixtures thereof, as defined above.
[0043] In one embodiment, the photoactive layer comprises an electroluminescent metal complex and a host material. The host can be a charge transport material. In one embodiment, the host material is an organometallic complex having the formula MYnZ, as defined herein. In one embodiment, the electroluminescent complex is present in an amount of at least 1 % by weight. In one embodiment, the electroluminescent complex is 2-20% by weight. In one embodiment, the electroluminescent complex is 20-50% by weight. In one embodiment, the electroluminescent complex is 50-80% by weight. In one embodiment, the electroluminescent complex is 80-99% by weight. In one embodiment, the metal complex is a cyclometalated complex of iridium, platinum, rhenium, or osmium. In one embodiment, the photoactive layer further comprises a second host material. The second host can be a charge transport material. In one embodiment, the second host is a hole transport material. In one embodiment, the second host is an electron transport material. In one embodiment, the second host material is a metal complex of a hydroxyaryl-N-heterocycle. In one embodiment, the hydroxyaryl-N-heterocycle is unsubstituted or substituted 8-hydroxyquinoline. In one embodiment, the metal is aluminum. In one embodiment, the second host is a material selected from the group consisting of tris(8-hydroxyquinolinato)aluminum, bis(8-hydroxyquinolinato)(4- phenylphenolato)aluminum, tetrakis(8-hydroxyquinolinato)zirconium, and mixtures thereof. The ratio of the first host to the second host can be 1 :100 to 100:1. In one
emiollmenAfeytlB 1s ferrfMΛo 10:1. In one embodiment, the ratio is from 1 :10 to 1 :5. In one embodiment, the ratio is from 1 :5 to 1 :1. In one embodiment, the ratio is from 1 :1 to 5:1. In one embodiment, the ratio is from 5:1 to 5:10.
[0044] In one embodiment, the electron transport layer comprises a metal complex of a hydroxyaryl-N-heterocycle. In one embodiment, the hydroxyaryl-N-heterocycle is unsubstituted or substituted 8-hydroxyquinoline. In one embodiment, the metal is aluminum. In one embodiment, the electron transport layer comprises a material selected from the group consisting of tris(8-hydroxyquinolinato)aluminum, bis(8- hydroxyquinolinato)(4-phenylphenolato)aluminum, tetrakis(8- hydroxyquinolinato)zirconium, and mixtures thereof. In one embodiment, the electron injection layer is LiF or LJ02. In one embodiment, the cathode is Al or Ba/AI. [0045] In one embodiment, the device is fabricated by liquid deposition of the buffer layer, the hole transport layer, and the photoactive layer, and by vapor deposition of the electron transport layer, the electron injection layer, and the cathode. [0046] The buffer layer can be deposited from any liquid medium in which it is dissolved or dispersed and from which it will form a film. In one embodiment, the liquid medium consists essentially of one or more organic solvents. In one embodiment, the liquid medium consists essentially of water or water and an organic solvent. In one embodiment the organic solvent is selected from the group consisting of alcohols, ketones, cyclic ethers, and polyols. In one embodiment, the organic liquid is selected from dimethylacetamide ("DMAc"), N methylpyrrolidone ("NMP"), dimethylformamide ("DMF"), ethylene glycol ("EG"), aliphatic alcohols, and mixtures thereof. The buffer material can be present in the liquid medium in an amount from 0.5 to 10 percent by weight. Other weight percentages of buffer material may be used depending upon the liquid medium. The buffer layer can be applied by any continuous or discontinuous liquid deposition technique. In one embodiment, the buffer layer is applied by spin coating. In one embodiment, the buffer layer is applied by ink jet printing. After liquid deposition, the liquid medium can be removed in air, in an inert atmosphere, or by vacuum, at room temperature or with heating. In one embodiment, the layer is heated to a temperature less than 2750C. In one embodiment, the heating temperature is between 1000C and 2750C. In one embodiment, the heating temperature is between 100°C and 1200C. In one embodiment, the heating temperature is between 12O0C and 14O0C. In one embodiment, the heating temperature is between 1400C and 1600CIn one embodiment, the heating temperature is between 1600C and 1800C. In one embodiment, the heating temperature is between 18O0C and 200°C. In one
embodiment, Iri'e
is between 2000C and 2200CIn one embodiment, the heating temperature is between 1900C and 2200C. In one embodiment, the heating temperature is between 2200C and 24O0C. In one embodiment, the heating temperature is between 240°C and 260°C. In one embodiment, the heating temperature is between 260°C and 2750C. The heating time is dependent upon the temperature, and is generally between 5 and 60 minutes. In one embodiment, the final layer thickness is between 5 and 200 nm. In one embodiment, the final layer thickness is between 5 and 40 nm. In one embodiment, the final layer thickness is between 40 and 80 nm. In one embodiment, the final layer thickness is between 80 and 120 nm. In one embodiment, the final layer thickness is between 120 and 160 nm. In one embodiment, the final layer thickness is between 160 and 200 nm.
[0047] The hole transport layer can be deposited from any liquid medium in which it is dissolved or dispersed and from which it will form a film. In one embodiment, the liquid medium consists essentially of one or more organic solvents. In one embodiment, the liquid medium consists essentially of water or water and an organic solvent. In one embodiment the organic solvent is an aromatic solvent. In one embodiment, the organic liquid is selected from chloroform, dichloromethane, toluene, anisole, and mixtures thereof. The hole transport material can be present in the liquid medium in a concentration of 0.2 to 2 percent by weight. Other weight percentages of hole transport material may be used depending upon the liquid medium.The hole transport layer can be applied by any continuous or discontinuous liquid deposition technique. In one embodiment, the hole transport layer is applied by spin coating. In one embodiment, the hole transport layer is applied by ink jet printing. After liquid deposition, the liquid medium can be removed in air, in an inert atmosphere, or by vacuum, at room temperature or with heating. In one embodiment, the layer is heated to a temperature less than 2750C. In one embodiment, the heating temperature is between 17O0C and 275°C. In one embodiment, the heating temperature is between 17O0C and 2000C. In one embodiment, the heating temperature is between 19O0C and 220°C. In one embodiment, the heating temperature is between 21O0C and 24O0C. In one embodiment, the heating temperature is between 2300C and 27O0C. The heating time is dependent upon the temperature, and is generally between 5 and 60 minutes. In one embodiment, the final layer thickness is between 5 and 50 nm. In one embodiment, the final layer thickness is between 5 and 15 nm. In one embodiment, the final layer thickness is between 15 and 25 nm. In one embodiment, the final layer thickness is between 25 and 35 nm. In one embodiment, the final layer thickness is between 35 and
50 nm.
[0048] The photoactive layer can be deposited from any liquid medium in which it is dissolved or dispersed and from which it will form a film. In one embodiment, the liquid medium consists essentially of one or more organic solvents. In one embodiment, the liquid medium consists essentially of water or water and an organic solvent. In one embodiment the organic solvent is an aromatic solvent. In one embodiment, the organic liquid is selected from chloroform, dichloromethane, toluene, anisole, and mixtures thereof. The photoactive material can be present in the liquid medium in a concentration of 0.2 to 2 percent by weight. Other weight percentages of photoactive material may be used depending upon the liquid medium.The photoactive layer can be applied by any continuous or discontinuous liquid deposition technique. In one embodiment, the photoactive layer is applied by spin coating. In one embodiment, the photoactive layer is applied by ink jet printing. After liquid deposition, the liquid medium can be removed in air, in an inert atmosphere, or by vacuum, at room temperature or with heating. In one embodiment, the deposited layer is heated to a temperature that is less than the Tg of the material having the lowest Tg. In one embodiment, the heating temperature is at least 1O0C less than the lowest Tg. In one embodiment, the heating temperature is at least 2O0C less than the lowest Tg. In one embodiment, the heating temperature is at least 300C less than the lowest Tg. In one embodiment, the heating temperature is between 500C and 1500C. In one embodiment, the heating temperature is between 500C and 75°C. In one embodiment, the heating temperature is between 75°C and 1000C. In one embodiment, the heating temperature is between 1000C and 125°C. In one embodiment, the heating temperature is between 125°C and 1500C. The heating time is dependent upon the temperature, and is generally between 5 and 60 minutes. In one embodiment, the final layer thickness is between 25 and 100 nm. In one embodiment, the final layer thickness is between 25 and 40 nm. In one embodiment, the final layer thickness is between 40 and 65 nm. In one embodiment, the final layer thickness is between 65 and 80 nm. In one embodiment, the final layer thickness is between 80 and 100 nm.
[0049] The electron transport layer can be deposited by any vapor deposition method. In one embodiment, it is deposited by thermal evaporation under vacuum. In one embodiment, the final layer thickness is between 1 and 100 nm. In one embodiment, the final layer thickness is between 1 and 15 nm. In one embodiment, the final layer thickness is between 15 and 30 nm. In one embodiment, the final layer thickness is between 30 and 45 nm. In one embodiment, the final layer thickness is between 45 and
60
layer thickness is between 60 and 75 nm. In one embodiment, the final layer thickness is between 75 and 90 nm. In one embodiment, the final layer thickness is between 90 and 100 nm.
[0050] The electron injection layer can be deposited by any vapor deposition method. In one embodiment, it is deposited by thermal evaporation under vacuum. In one embodiment, the vacuum is less than 10-6 torr. In one embodiment, the vacuum is less than 10-7 torr. In one embodiment, the vacuum is less than 10-8 torr. In one embodiment, the material is heated to a temperature in the range of 100oC to 400oC; 150oC to 350oC peferrably. In one embodiment, the material is deposited at a rate of 0.5 to 10 A/sec. In one embodiment, the material is deposited at a rate of 0.5 to 1 A/sec. In one embodiment, the material is deposited at a rate of 1 to 2 A/sec. In one embodimentm, the material is deposited at a rate of 2 to 3 A/sec. In one embodiment, the material is deposited at a rate of 3 to 4 A/sec. In one embodiment, the material is deposited at a rate of 4 to 5 A/sec. In one embodiment, the material is deposited at a rate of 5 to 6 A/sec. In one embodiment, the material is deposited at a rate of 6 to 7 A/sec. In one embodiment, the material is deposited at a rate of 7 to 8 A/sec. In one embodiment, the material is deposited at a rate of 8 to 9 A/sec. In one embodiment, the material is deposited at a rate of 9 to 10 A/sec. In one embodiment, the final layer thickness is between 0.1 and 3 nm. In one embodiment, the final layer thickness is between 0.1 and 1 nm. In one embodiment, the final layer thickness is between 1 and 2 nm. In one embodiment, the final layer thickness is between 2 and 3 nm. [0051] The cathode can be deposited by any vapor deposition method. In one embodiment, it is deposited by thermal evaporation under vacuum. In one embodiment, the vacuum is less than 10-6 torr. In one embodiment, the vacuum is less than 10-7 torr. In one embodiment, the vacuum is less than 10-8 torr. In one embodiment, the material is heated to a temperature in the range of 100oC to 400oC; 150oC to 350oC peferrably. In one embodiment, the material is deposited at a rate of 0.5 to 10 A/sec. In one embodiment, the material is deposited at a rate of 0.5 to 1 A/sec. In one embodiment, the material is deposited at a rate of 1 to 2 A/sec. In one embodimentm, the material is deposited at a rate of 2 to 3 A/sec. In one embodiment, the material is deposited at a rate of 3 to 4 A/sec. In one embodiment, the material is deposited at a rate of 4 to 5 A/sec. In one embodiment, the material is deposited at a rate of 5 to 6 A/sec. In one embodiment, the material is deposited at a rate of 6 to 7 A/sec. In one embodiment, the material is deposited at a rate of 7 to 8 A/sec. In one embodiment, the material is deposited at a rate of 8 to 9 A/sec. In one embodiment, the material is
In one embodiment, the final layer thickness is between 10 and 10000 nm. In one embodiment, the final layer thickness is between 10 and 1000 nm. In one embodiment, the final layer thickness is between 10 and 50 nm. In one embodiment, the final layer thickness is between 50 and 100 nm. In one embodiment, the final layer thickness is between 100 and 200 nm. In one embodiment, the final layer thickness is between 200 and 300 nm. In one embodiment, the final layer thickness is between 300 and 400 nm. In one embodiment, the final layer thickness is between 400 and 500 nm. In one embodiment, the final layer thickness is between 500 and 600 nm. In one embodiment, the final layer thickness is between 600 and 700 nm. In one embodiment, the final layer thickness is between 700 and 800 nm. In one embodiment, the final layer thickness is between 800 and 900 nm. In one embodiment, the final layer thickness is between 900 and 1000 nm. In one embodiment, the final layer thickness is between 1000 and 2000 nm. In one embodiment, the final layer thickness is between 2000 and 3000 nm. In one embodiment, the final layer thickness is between 3000 and 4000 nm. In one embodiment, the final layer thickness is between 4000 and 5000 nm. In one embodiment, the final layer thickness is between 5000 and 6000 nm. In one embodiment, the final layer thickness is between 6000 and 7000 nm. In one embodiment, the final layer thickness is between 7000 and 8000 nm. In one embodiment, the final layer thickness is between 8000 and 9000 nm. In one embodiment, the final layer thickness is between 9000 and 10000 nm. In one embodiment, the device is fabricated by vapor deposition of the buffer layer, the hole transport layer, and the photoactive layer, the electron transport layer, the electron injection layer, and the cathode.
[0052] In one embodiment, the buffer layer is applied by vapor deposition. In one embodiment, it is deposited by thermal evaporation under vacuum. In one embodiment, the vacuum is less than 10-6 torr. In one embodiment, the vacuum is less than 10-7 torr. In one embodiment, the vacuum is less than 10-8 torr. In one embodiment, the material is heated to a temperature in the range of 100oC to 400oC; 150oC to 350oC peferrably. In one embodiment, the material is deposited at a rate of 0.5 to 10 A/sec. In one embodiment, the material is deposited at a rate of 0.5 to 1 A/sec. In one embodiment, the material is deposited at a rate of 1 to 2 A/sec. In one embodiment, the material is deposited at a rate of 2 to 3 A/sec. In one embodiment, the material is deposited at a rate of 3 to 4 A/sec. In one embodiment, the material is deposited at a rate of 4 to 5 A/sec. In one embodiment, the material is deposited at a rate of 5 to 6 A/sec. In one embodiment, the material is deposited at a rate of 6 to 7 A/sec. In one
emSόSfmentHii mlbπafϊl'dijjillted at a rate of 7 to 8 A/sec. In one embodiment, the material is deposited at a rate of 8 to 9 A/sec. In one embodiment, the material is deposited at a rate of 9 to 10 A/sec. In one embodiment, the final layer thickness is between 5 and 200 nm. In one embodiment, the final layer thickness is between 5 and 30 nm. In one embodiment, the final layer thickness is between 30 and 60 nm. In one embodiment, the final layer thickness is between 60 and 90 nm. In one embodiment, the final layer thickness is between 90 and 120 nm. In one embodiment, the final layer thickness is between 120 and 150 nm. In one embodiment, the final layer thickness is between 150 and 280 nm. In one embodiment, the final layer thickness is between 180 and 200 nm.
[0053] In one embodiment, the hole transport layer is applied by vapor deposition. In one embodiment, it is deposited by thermal evaporation under vacuum. In one embodiment, the vacuum is less than 10-6 torr. In one embodiment, the vacuum is less than 10-7 torr. In one embodiment, the vacuum is less than 10-8 torr. In one embodiment, the material is heated to a temperature in the range of 100oC to 400oC; 150oC to 350oC peferrably. In one embodiment, the material is deposited at a rate of 0.5 to 10 A/sec. In one embodiment, the material is deposited at a rate of 0.5 to 1 A/sec. In one embodiment, the material is deposited at a rate of 1 to 2 A/sec. In one embodimentm, the material is deposited at a rate of 2 to 3 A/sec. In one embodiment, the material is deposited at a rate of 3 to 4 A/sec. In one embodiment, the material is deposited at a rate of 4 to 5 A/sec. In one embodiment, the material is deposited at a rate of 5 to 6 A/sec. In one embodiment, the material is deposited at a rate of 6 to 7 A/sec. In one embodiment, the material is deposited at a rate of 7 to 8 A/sec. In one embodiment, the material is deposited at a rate of 8 to 9 A/sec. In one embodiment, the material is deposited at a rate of 9 to 10 A/sec. In one embodiment, the final layer thickness is between 5 and 200 nm. In one embodiment, the final layer thickness is between 5 and 30 nm. In one embodiment, the final layer thickness is between 30 and 60 nm. In one embodiment, the final layer thickness is between 60 and 90 nm. In one embodiment, the final layer thickness is between 90 and 120 nm. In one embodiment, the final layer thickness is between 120 and 150 nm. In one embodiment, the final layer thickness is between 150 and 280 nm. In one embodiment, the final layer thickness is between 180 and 200 nm.
[0054] In one embodiment, the photoactive layer is applied by vapor deposition. In one embodiment, it is deposited by thermal evaporation under vacuum. In one embodiment, the photoactive layer consists essentially of a single electroluminescent
evaporation under vacuum. In one embodiment, the vacuum is less than 10-6 torr. In one embodiment, the vacuum is less than 10-7 torr. In one embodiment, the vacuum is less than 10-8 torr. In one embodiment, the material is heated to a temperature in the range of 100oC to 400oC; 150oC to 350oC peferrably. In one embodiment, the material is deposited at a rate of 0.5 to 10 A/sec. In one embodiment, the material is deposited at a rate of 0.5 to 1 A/sec. In one embodiment, the material is deposited at a rate of 1 to 2 A/sec. In one embodimentm, the material is deposited at a rate of 2 to 3 A/sec. In one embodiment, the material is deposited at a rate of 3 to 4 A/sec. In one embodiment, the material is deposited at a rate of 4 to 5 A/sec. In one embodiment, the material is deposited at a rate of 5 to 6 A/sec. In one embodiment, the material is deposited at a rate of 6 to 7 A/sec. In one embodiment, the material is deposited at a rate of 7 to 8 A/sec. In one embodiment, the material is deposited at a rate of 8 to 9 A/sec. In one embodiment, the material is deposited at a rate of 9 to 10 A/sec. In one embodiment, the final layer thickness is between 5 and 200 nm. In one embodiment, the final layer thickness is between 5 and 30 nm. In one embodiment, the final layer thickness is between 30 and 60 nm. In one embodiment, the final layer thickness is between 60 and 90 nm. In one embodiment, the final layer thickness is between 90 and 120 nm. In one embodiment, the final layer thickness is between 120 and 150 nm. In one embodiment, the final layer thickness is between 150 and 280 nm. In one embodiment, the final layer thickness is between 180 and 200 nm.
[0055] In one embodiment, the photoactive layer comprises two electroluminescent materials, each of which is applied by thermal evaporation under vacuum. Any of the above listed vacuum conditions and temperatures can be used. Any of the above listed deposition rates can be used. The relative deposition rates can be from 50:1 to 1 :50. In one embodiment, the relative deposition rates are from 1 :1 to 1 :3. In one embodiment, the relative deposition rates are from 1 :3 to 1 :5. In one embodiment, the relative deposition rates are from 1 :5 to 1 :8. In one embodiment, the relative deposition rates are from 1 :8 to 1 :10. In one embodiment, the relative deposition rates are from 1 :10 to 1 :20. In one embodiment, the relative deposition rates are from 1 :20 to 1 :30. In one embodiment, the relative deposition rates are from 1 :30 to 1 :50. The total thickness of the layer can be the same as that described above for a single-component photoactive layer.
[0056] In one embodiment, the photoactive layer comprises one electroluminescent material and at least one host material, each of which is applied by thermal evaporation
vacuum conditions and temperatures can be used. Any of the above listed deposition rates can be used. The relative deposition rate of electroluminescent material to host can be from 1 :1 to 1 :99. In one embodiment, the relative deposition rates are from 1 :1 to 1 :3. In one embodiment, the relative deposition rates are from 1 :3 to 1 :5. In one embodiment, the relative deposition rates are from 1 :5 to 1 :8. In one embodiment, the relative deposition rates are from 1 :8 to 1 :10. In one embodiment, the relative deposition rates are from 1 :10 to 1 :20. In one embodiment, the relative deposition rates are from 1 :20 to 1 :30. In one embodiment, the relative deposition rates are from 1 :30 to 1 :40. In one embodiment, the relative deposition rates are from 1 :40 to 1 :50. In one embodiment, the relative deposition rates are from 1 :50 to 1 :60. In one embodiment, the relative deposition rates are from 1 :60 to 1 :70. In one embodiment, the relative deposition rates are from 1 :70 to 1 :80. In one embodiment, the relative deposition rates are from 1 :80 to 1 :90. In one embodiment, the relative deposition rates are from 1 :90 to 1 :99. The total thickness of the layer can be the same as that described above for a single-component photoactive layer. [0057] In one embodiment, the electron transport layer is applied by vapor deposition. In one embodiment, it is deposited by thermal evaporation under vacuum. In one embodiment, the vacuum is less than 10-6 torr. In one embodiment, the vacuum is less than 10-7 torr. In one embodiment, the vacuum is less than 10-8 torr. In one embodiment, the material is heated to a temperature in the range of 100oC to 400oC; 150oC to 350oC peferrably. In one embodiment, the material is deposited at a rate of 0.5 to 10 A/sec. In one embodiment, the material is deposited at a rate of 0.5 to 1 A/sec. In one embodiment, the material is deposited at a rate of 1 to 2 A/sec. In one embodimentm, the material is deposited at a rate of 2 to 3 A/sec. In one embodiment, the material is deposited at a rate of 3 to 4 A/sec. In one embodiment, the material is deposited at a rate of 4 to 5 A/sec. In one embodiment, the material is deposited at a rate of 5 to 6 A/sec. In one embodiment, the material is deposited at a rate of 6 to 7 A/sec. In one embodiment, the material is deposited at a rate of 7 to 8 A/sec. In one embodiment, the material is deposited at a rate of 8 to 9 A/sec. In one embodiment, the material is deposited at a rate of 9 to 10 A/sec. In one embodiment, the final layer thickness is between 5 and 200 nm. In one embodiment, the final layer thickness is between 5 and 30 nm. In one embodiment, the final layer thickness is between 30 and 60 nm. In one embodiment, the final layer thickness is between 60 and 90 nm. In one embodiment, the final layer thickness is between 90 and 120 nm. In one embodiment, the final layer thickness is between 120 and 150 nm. In one embodiment, the final layer
thiclϊϋnέsl is
In one embodiment, the final layer thickness is between 180 and 200 nm.
[0058] In one embodiment, the electron injection layer is applied by vapor deposition, as described above.
[0059] In one embodiment, the cathode is applied by vapor deposition, as describe above. In one embodiment, the device is fabricated by vapor deposition of some of the organic layers, and liquid deposition of some of the organic layers. In one embodiment, the device is fabricated by liquid deposition of the buffer layer, and vapor deposition of all of the other layers.
[0060] In operation, a voltage from an appropriate power supply (not depicted) is applied to the device 100. Current therefore passes across the layers of the device
100. Electrons enter the organic polymer layer, releasing photons. In some OLEDs, called active matrix OLED displays, individual deposits of photoactive organic films may be independently excited by the passage of current, leading to individual pixels of light emission. In some OLEDs, called passive matrix OLED displays, deposits of photoactive organic films may be excited by rows and columns of electrical contact layers.
[0061] Devices can be prepared employing a variety of techniques. These include, by way of non-limiting exemplification, vapor deposition techniques and liquid deposition.
Devices may also be sub-assembled into separate articles of manufacture that can then be combined to form the device.
Definitions
[0062] The use of "a" or "an" are employed to describe elements and components of the invention. This is done merely for convenience and to give a general sense of the invention. This description should be read to include one or at least one and the singular also includes the plural unless it is obvious that it is meant otherwise. [0063] The term "active" when referring to a layer or material is intended to mean a layer or material that exhibits electronic or electro-radiative properties. An active layer material may emit radiation or exhibit a change in concentration of electron-hole pairs when receiving radiation. Thus, the term "active material" refers to a material which electronically facilitates the operation of the device. Examples of active materials include, but are not limited to, materials which conduct, inject, transport, or block a charge, where the charge can be either an electron or a hole. Examples of inactive materials include, but are not limited to, planarization materials, insulating materials,
anf SKmSaI iaff'iMiϊlrtak
[0064] As used herein, the terms "comprises," "comprising," "includes," "including," "has," "having" or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Further, unless expressly stated to the contrary, "or" refers to an inclusive or and not to an exclusive or. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).
[0065] The term "layer" is used interchangeably with the term "film" and refers to a coating covering a desired area. The area can be as large as an entire device or a specific functional area such as the actual visual display, or as small as a single sub- pixel. Films can be formed by any conventional deposition technique, including vapor deposition and liquid deposition. Liquid deposition techniques include, but are not limited to, continuous deposition techniques such as spin coating, gravure coating, curtain coating, dip coating, slot-die coating, spray-coating, and continuous nozzle coating; and discontinuous deposition techniques such as ink jet printing, gravure printing, and screen printing.
[0066] The term "organic electronic device" is intended to mean a device including one or more semiconductor layers or materials. Organic electronic devices include, but are not limited to: (1 ) devices that convert electrical energy into radiation (e.g., a light- emitting diode, light emitting diode display, diode laser, or lighting panel), (2) devices that detect signals through electronic processes (e.g., photodetectors photoconductive cells, photoresistors, photoswitches, phototransistors, phototubes, infrared ("IR") detectors, or biosensors), (3) devices that convert radiation into electrical energy (e.g., a photovoltaic device or solar cell), and (4) devices that include one or more electronic components that include one or more organic semiconductor layers (e.g., a transistor or diode). The term device also includes coating materials for memory storage devices, antistatic films, biosensors, electrochromic devices, solid electrolyte capacitors, energy storage devices such as a rechargeable battery, and electromagnetic shielding applications.
[0067] The term "substrate" is intended to mean a workpiece that can be either rigid or flexible and may include one or more layers of one or more materials, which can include, but are not limited to, glass, polymer, metal, or ceramic materials, or
coAHΪo'ήlϊifia-
[0068] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of embodiments of the present invention, suitable methods and materials are described below. All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety, unless a particular passage is cited. In case of conflict, the present specification, including definitions, will control. In addition, the materials, methods, and examples are illustrative only and not intended to be limiting. [0069] To the extent not described herein, many details regarding specific materials, processing acts, and circuits are conventional and may be found in textbooks and other sources within the organic light-emitting diode display, photodetector, photovoltaic, and semiconductive member arts.
EXAMPLES
[0070] The concepts described herein will be further described in the following examples, which do not limit the scope of the invention described in the claims.
Example 1 Preparation of an aluminum complex of 4-(4-t-butylphenyl)-phenol
[0071] A degassed solution of K2CO3 (31.52 g, 22.8 mmol) in H2O (400 ml_) was added to a mixture of 4-bromophenol (5.19 g, 30 mmol), 4-(t-butylphenyl)boronic acid (10.38 g, 66 mmol) and Pd(PPh3) 4 (2.00 g, 1.72 mmol) in monoglyme (400 ml_) and then heated to 800C for two days. Upon cooling, the mixture was diluted with diethylether and 1 M HCI (~100mL) was added. After neutralization with a saturated solution of NaHCO3, the organic layer was separated and dried over MgSO4. Upon evaporation of the solvent a yellow solid was obtained which was purified by chromatography on silica (hexane) to obtain the desired product as a white powder (13.1 g, 96%).
1b Preparation of the aluminum complex containing ligand prepared in 1a [0072] In glove box, 1.6Og of quinaldine (2-methyl-8-hydroxyquinoline) was dissolved into 25ml_ toluene with stirring in a 30OmL RB flask. 2.75 ml_ of 1.9M triethylaluminum in toluene solution (Aldrich) was added by syringe with rapid stirring. Addition must be done slowly to prevent overflow, as solution foams. The solution became cloudy and eventually a dense yellow fibrous ppt formed. The solution was refluxed in a heating mantle and the solid redissolved as the solution became clear yellow. 1.13g of the ligand prepared in 1 a was added as a solution in 5ml_ toluene to yield a pale orange clear solution after heat and stirring. The solution was refluxed for 30mins. [0073] Addition of hexanes leads to a ppt of white crystals of the desired product in moderate yield of ~1.4g. The crystals were collected by filtration and suction dried. The resulting material is blue photoluminescent and has the 1-H nmr in methylene chloride shown. Product Tg: 1210C. The material was sublimed in high vacuum prior to device fabrication.
1 PPM
1-H nmr spectrum of product 1 b
35 80 75 70 65 60 55 PPM
1-H nmr spectrum of product 1b (aromatic region)
Example 2 Preparation of an aluminum complex of 6-(4-t-butylphenyl)-naphth-2-oI
C40H35AlN2O3
Exact Mass: 618.25
MoI Wt.: 618.70
C, 77.65; H, 5.70; Al, 4.36; N, 4.53; O, 776
2a
[0074] A degassed solution of K2CO3 (8.2 g, 5.9 mmol) in H2O (100 ml_) was added to a mixture of 6-bromo-2-naphthol (3.43 g, 1.54 mmol), 4-(t-butylphenyl)boronic acid (3.21 g, 1.80 mmol) and Pd(PPh3)4 (0.89 g, 0.77 mmol) in monoglyme (100 ml_) and then heated to 800C for two days. Upon cooling, the mixture was diluted with diethylether and 1M HCI (~20mL) was added. After neutralization with a saturated solution of NaHCO3, the organic layer was separated and dried over MgSO4. Upon evaporation of the solvent a yellow solid was obtained which was purified by chromatography on silica (hexane) to obtain the desired product as a tan powder (3.8 g, 89%).
2b Preparation of aluminum complex containing ligand prepared in 2a [0075] In a glove box, 1.6Og of quinaldine (2-methyl-8-hydroxyquinoline) was dissolved into 25ml_ toluene with stirring in a 30OmL RB flask. 2.65 mL of 1.9M triethylaluminum in toluene solution (Aldrich) was added via syringe and rapid stirring. There is much foaming and addition must be done slowly to prevent overflow. The solution becomes cloudy and eventually a dense yellow fibrous ppt forms. The solution is brought to reflux in a heating mantle and the solid redissolves as the solution becomes clear yellow. 1.4g of the ligand prepared in 2a was added as a solid with heat and stirring. Reflux with an air condensor in the glove box for 2 hrs then cool. [0076] The initial solution is yellow orange and clear. As the solution cools there is a slight ppt and hexanes is added to enhance pptn. The desired product material crystallizes from hot toluene as a pale yellow solid when a little hexanes is added. Yield 2.9g. 1-H nmr in methylene chloirde reveals the expected product contaminated with a minor second isomer. Melting Point 264°C, Tg 1310C. The material was sublimed in high vacuum prior to device fabrication.
PPM -H nmr spectrum of product 2b
85 B O 75 70 PPM -H nmr spectrum of product 2b (aromatic region)
complex of 4-(3,5-dimethylphenyl)-phenol
3a Preparation of the phenolic ligand
[0077] A mixture of 4.9g of 4-Br-phenol, 4.5 g of 3,5-dimethylphenylboronic acid, 19.5 g of potassium carbonate, 0.3 g of tetrakis(triphenylphosphine)-palladium, 150 mL of water and 150 mL of 1 ,2-dimethoxyethane was refuxed (85-9O0C) for 12hrs. The reaction mixture was diluted with 600 mL of water, extracted with dichloromethane (75 mlx3), and the combined organic layer was dried over MgSO4. Solvent was removed under vacuum and the residue was distilled under reduced pressure to give 1.5 g of 3a >95%purity, b.p. 125-1330C /0.1 mm Hg.
3b Preparation of the aluminum complex of ligand prepared in 3a [0078] In a glove box, 1.6g of quinaldine (2-methyl-8-hydroxyquinoline) was dissolved into 25mL toluene with stirring in a 30OmL RB flask. 2.65 mL of 1.9M triethylaluminum in toluene solution (Aldrich) was added via syringe and with rapid stirring. The addition must be done slowly to prevent overflow. The solution becomes cloudy and eventually a dense yellow fibrous ppt forms. The solution is brought to reflux in a heating mantle and it becomes clear bright yellow. 1.Og phenol prepared in 3a was added as a solution in 5mL toluene and the solution was heated and stirred as a bright yellow solution. Reflux for 30mins then cool and add methanol and hexanes. A pale yellow crystalline solid precipitates on standing and is collected by filtration, washed well with methanol and suction dried to yield a material having the 1-H nmr spectrum shown below. The material contains a small amount of a second isomeric material. Melting Point 265°C, Tg 1050C The material was sublimed in hiqh vacuum prior to device fabrication.
PPM
1 -H nmr spectrum of product 3b
B 5 80 75 70 85 PPM
1-H nmr spectrum of product 3b (aromatic region)
Example 4 Preparation of an aluminum complex of 6-(3,5-dimethylphenyl)-naphth- 2-ol
[0079] Similar to the synthesis given in example 3a, 11.6 g of 6-bromonaphthol, 8.2 g of 3,5-dimethylphenylboronic acid, 300 mL of deionized water, 36 g of potassium carbonate, 0.3 g of tetrakis(triphenylphosphine)palladium, and 250 mL of 1 ,2- dimethoxyethane was refluxed (85-90° C) for 12hr. The reaction mixture was then diluted with 600 mL of 10% hydrochloric acid, extracted with dichloromethane (75 mlx3), and the combined organic layer was washed with water (300 mL) and dried over MgSO4. The solvent was removed under vacuum and the residue was redissolved into hot hexane and the hot solution was put through a short silica gel plug. The solvent was removed and the solid residue was dried under vacuum to afford 6 g (65%) of 4a. 1H NMR (CDCI3): 2.50 (6H,s), 7.10(1 H,s), 7.22(2H,m), 7.38(2H,s), 7.75(2H,s), 7.85(1 H,d), 8.05 (1 H,s) ppm.
4b Preparation of the aluminum complex of ligand prepared in 4a [0080] In a glove box, 3.2g of quinaldine (2-methyl-8-hydroxyquinoline) was dissolved into 25mL toluene with stirring in a 30OmL RB flask. 5.3 mL of 1.9M triethylaluminum in toluene solution (Aldrich) was added via syringe and with rapid stirring. There is much foaming and addition must be done slowly to prevent overflow. The solution becomes cloudy and eventually a dense yellow fibrous ppt forms. The solution is brought to reflux in a heating mantle and it becomes clear yellow. 2.5g phenol prepared in 4a was added as a solution in 5mL toluene and then heated and stirred as a pale orange solution. Reflux for 30mins and then cool to room temperature whereupon a very pale yellow crystalline precipitate begins to deposit. The crystals were collected by filtration and washed well with methanol and suction dried. Yield of 5.3g of pale yellow powder. Tg 117°C. The solid is blue photoluminescent and has the 1-H nmr spectrum shown below
1 PPM -H nmr spectrum of product 4b
B O 75 70 B 5 PPM -H nmr spectrum of product 4b (aromatic region)
5a Preparation of the phenolic ligand
[0081] 6-bromo-2-naphthol 6.1 g, 0.0273 mol; 3,5-trifluoromethylphenylboronic acid 7.6g, 0.0295 mol; potassium carbonate 18.6 g, 0.1346 mol; water 18OmL; ethyleneglycoldimethylether 18OmL were combined and sparged with nitrogen for 45 minutes. Tetrakistriphenylphosphine Pd(O) (1.2g, 0.001 mol) was then added and the mixture was refluxed overnight. Upon cooling to room temperature 50OmL of acidic water was added and extracted with dichloromethane. The organic layer was preabsorbed onto silica gel and eluted down a silica column with hexanes 80%/ethylacetate 20%. The eluted organic material was concentrated and taken up in ethanol and stirred with activated carbon, filtered and concentrated_to precipitate the desired phenolic ligand in 75% yield.
5b Preparation of the aluminum complex of ligand prepared in 5a [0082] In a glove box, 3.2g of quinaldine (2-methyl-8-hydroxyquinoline) was dissolve into 25mL toluene with stirring in a 30OmL RB flask. 5.3 mL of 1.9M triethylaluminum in toluene solution (Aldrich) was added via syringe with rapid stirring. There is much foaming and addition must be done slowly to prevent overflow. The solution becomes cloudy and eventually a dense yellow fibrous ppt forms. The solution is brought to reflux in a heating mantle and it becomes clear yellow. 3.6g phenol prepared in 5a was added as a solution in 5mL toluene then "~ Bated and stirred as a pale orange solution.
methanol. Evaporation and additional methanol additions deposits a pale yellow crystalline material which was collected by filtration, washed well with methanol and suction dried. 5.5g of pale yellow crystals were collected with MPt 2470C and Tg 114°C. The crystals were blue green photoluminescent and highly soluble in toluene, >2.8wt%. 1-H nmr spectra of the material in methylene chloride are shown below
1-H nmr spectrum of product 5b
B O 7 5 7 0 65 PPM
1-H nmr spectrum of product 5b (aromatic region)
complex of 4-(4-trifluoromethylphenyl)-
6a Preparation of the phenolic ligand
[0083] Under an atmosphere of nitrogen, 4-bromophenol (5.00 g, 2.91 x10'2 mol), 4- CF3-I -phenyl boronic acid (6.075 g, 3.20x10"2 mol), KF (5.57 g, 9.60x10"2 mol), Pd2(dba)3 (0.133 g, 1.45x10"4 mol) were mixed in THF (100 ml_). After a few minutes of stirring a THF (1OmL) solution of P(4Bu)3 (0.059 g, 2.91 x10"4 mol). The resulting mixture was stirred at room temperature for 48 hours. Dilution of this solution with 200 ml_ of Et2O followed by filtration through a silica plug and evaporation of the volatiles yielded a dark brown thick oil. Upon addition of hexane to this oil, a light brown powder formed, which was further purified by column chromatography (1 :5 EtOAc/hexane) to give a white powder. Yield = 4.86 g (70%). The 1H NMR (in CD2Cl2) spectrum of phenol 6a is shown below.
75 7 0 65 B O 55 50 PPM
6b Preparation of the aluminum complex of ligand prepared in 6a [0084] In a glove box, 3.2g of quinaldine (2-methyl-8-hydroxyquinoline) was dissolve into 25mL toluene with stirring in a 30OmL RB flask. 5.3 ml_ of 1.9M triethylaluminum in toluene solution (Aldrich) was added via syringe with rapid stirring. There is much foaming and addition must be done slowly to prevent overflow. The solution becomes cloudy and eventually a dense yellow fibrous ppt forms. The solution is brought to reflux in a heating mantle and it becomes clear yellow. 2.4g phenol prepared in 6a was added as a solution in 5mL toluene then heated and stirred as a pale orange solution. Reflux for 30mins then cool and add methanol. Evaporation and additional methanol additions deposits an off-white crystalline material which was collected by filtration, washed well with methanol and suction dried. 2.5g of white crystals were collected with MPt 2020C and Tg 92°C. The crystals were blue green photoluminescent and highly soluble in toluene, >2.8wt%. 1-H nmr spectra of the material in methylene chloride are shown below. The material was sublimed under high vacuum prior to device evaluations.
1 PPM
1-H nmr spectrum of product 6b
85 8 0 75 70 6 5 PPM
1-H nmr spectrum of product 6b (aromatic region)
Example 7 Preparation of an aluminum complex of 4-(3-cyanophenyI)-phenoI
[0085] Under an atmosphere of nitrogen, 4-bromophenol (5.30 g, 3.08x10"2 mol), 3- CN-1 -phenyl boronic acid (4.986 g, 3.39x10"2 mol), KF (5.91 g, 1.02x10"1 mol), Pd2(dba)3 (0.141 g, 1.54x10"4 mol) were mixed in THF (100 ml_). After a few minutes of stirring a THF (1OmL) solution of P(1Bu)3 (0.062 g, 3.08x10"4 mol). The resulting mixture was stirred at room temperature for 48 hours. Dilution of this solution with 200 ml_ of Et2O followed by filtration through a silica plug and evaporation of the volatiles yielded a dark brown thick oil. Upon addition of hexane to this oil, a light brown powder formed, which was further purified by column chromatography (1 :5 EtOAc/hexane) to give a white powder. Yield = 3.9 g (65%). The 1H NMR (in CD2CI2) spectrum of phenol 7a is shown below.
7 5 70 B 5 60 55 PPM
7b Preparation of the aluminum complex of ligand prepared in 7a [0086] In a glove box, 3.2g of quinaldine (2-methyl-8-hydroxyquinoline) was dissolve into 25mL toluene with stirring in a 30OmL RB flask. 5.3 mL of 1.9M triethylaluminum in toluene solution (Aldrich) was added via syringe with rapid stirring. There is much foaming and addition must be done slowly to prevent overflow. The solution becomes cloudy and eventually a dense yellow fibrous ppt forms. The solution is brought to reflux in a heating mantle and it becomes clear yellow. 1.96g phenol prepared in 7a was added as a solution in 5mL toluene then heated and stirred as a pale orange solution.
methanol. Evaporation and additional methanol additions deposits a cream colored crystalline material which was collected by filtration, washed well with methanol and suction dried. 5.Og of cream crystals were collected with MPt 219°C and Tg 1060C. The crystals were blue green photoluminescent and quite soluble in toluene, ~1.6wt%. 1-H nmr spectra of the material in methylene chloride are shown below. The material was sublimed in high vacuum prior to device evaluation
1 PPM
1-H nmr spectrum of product 7b
8 5 80 75 70 65 60 PPM
1-H nmr spectrum of product 7b (aromatic region)
δa Preparation of the phenolic ligand
[0087] Under an atmosphere of nitrogen, 4-bromophenol (5.30 g, 3.08x10'2 mol), A- CN-1 -phenyl boronic acid (4.986 g, 3.39x10'2 mol), KF (5.91 g, 1.02x10"1 mol), Pd2(dba)3 (0.141 g, 1.54x10'4 mol) were mixed in THF (100 ml_). After a few minutes of stirring a THF (1OmL) solution of P(1Bu)3 (0.062 g, 3.08x10'4 mol). The resulting mixture was stirred at room temperature for 48 hours. Dilution of this solution with 200 mL of Et2O followed by filtration through a silica plug and evaporation of the volatiles yielded a dark brown thick oil. Upon addition of hexane to this oil, a light brown powder formed, which was further purified by column chromatography (1 :5 EtOAc/hexane) to give a white powder. Yield = 3.3 g (55%). The 1H NMR (in CD2CI2) spectrum of phenol 8a is shown below.
7.5 7.0 6.5 6.0 5.5 PPM
8b Preparation of the aluminum complex of ligand prepared in 8a [0088] In a glove box, 3.2g of quinaldine (2-methyl-8-hydroxyquinoline) was dissolve into 25ml_ toluene with stirring in a 30OmL RB flask. 5.3 ml_ of 1.9M triethylaluminum in toluene solution (Aldrich) was added via syringe with rapid stirring. There is much foaming and addition must be done slowly to prevent overflow. The solution becomes cloudy and eventually a dense yellow fibrous ppt forms. The solution is brought to reflux in a heating mantle and it becomes clear yellow. 1.96 phenol prepared in 8a was added as a solution in 5ml_ toluene then heated and stirred as a pale orange solution. Reflux for 30mins then cool and add methanol. Evaporation and additional methanol additions deposits a cream colored crystalline material which was collected by filtration, washed well with methanol and suction dried. 1.6g of cream colored crystals were collected with MPt 1800C and Tg 123°C. The crystals were blue green photoluminescent and quite soluble in toluene, ~1.6wt%. 1-H nmr spectra of the material in methylene chloride are shown below. The material was sublimed in high vacuum prior to device evaluations.
LJIUIVLL Jb A
PPM
1-H nmr spectrum of product 8b
8 5 B O 7 5 7 0 65 PPM
1-H nmr spectrum of product 8b (aromatic region)
Example 9. Device fabrication and characterization data [0089] OLED devices were fabricated by a combination of solution processing and thermal evaporation techniques. Patterned indium tin oxide (ITO) coated glass substrates from Thin Film Devices, lnc were used. These ITO substrates are based on Corning 1737 glass coated with 1400 A of ITO having a sheet resistance of 30 ohms/square and 80% light transmission. The patterned ITO substrates were cleaned ultrasonically in aqueous detergent solution and rinsed with distilled water. The patterned ITO was subsequently cleaned ultrasonically in acetone, rinsed with isopropanol, and dried in a stream of nitroαen. Immediately before device fabrication
the cfeaned"! pifeernlciifiluBityies were treated with O2 plasma for 5 minutes. Immediately after cooling, an aqueous dispersion of Buffer 1 was spin-coated over the ITO surface and heated to remove solvent. After cooling, the substrates were then spin-coated with a solution of Hole Transport 1 , and then heated to remove solvent. After cooling the substrates were spin-coated with the emissive layer solution, and heated to remove solvent. The substrates were masked and placed in a vacuum chamber. A ZrQ layer was deposited by thermal evaporation, followed by a layer of LiF. Masks were then changed in vacuo and a layer of Al was deposited by thermal evaporation. The chamber was vented, and the devices were encapsulated using a glass lid, dessicant, and UV curable epoxy. [0090] In Example 9.1 , the host was a mixture of the material of Example 3 and Host
A. The emitter was Red emitter 2.
[0091] In Example 9.2, the host was a mixture of the material of Example 5 and Host
B. The emitter was Red emitter 1.
[0092] The OLED samples were characterized by measuring their (1 ) current-voltage
(I-V) curves, (2) electroluminescence radiance versus voltage, and
(3) electroluminescence spectra versus voltage. All three measurements were performed at the same time and controlled by a computer. The current efficiency of the device at a certain voltage is determined by dividing the electroluminescence radiance of the LED by the current density needed to run the device. The unit is a cd/A. The power efficiency is the current efficiency divided by the operating voltage. The unit is
Im/W.
[0093] The materials used in device fabrication are listed below:
Buffer 1 was an aqueous dispersion of poly(3,4-dioxythiophene) and a polymeric fluorinated sulfonic acid. The material was prepared using a procedure similar to that described in Example 3 of published U.S. patent application no. 2004/0254297.
Hole Transport 1 was a crosslinkable polymeric hole transport material.
Host A:
Red emitter 1 :
Red emitter 2:
ZrQ: Tetrakis-(δ-hydroxyquinoline) zirconium
Table 9.1 Device characterization data
[0094] OLED devices were fabricated by the thermal evaporation technique. The base vacuum for all of the thin film deposition was in the range of 10~8 torr. Patterned indium tin oxide coated glass substrates from Thin Film Devices, lnc were used. These ITO's are based on Coming 1737 glass coated with 1400A ITO coating, with sheet resistance of 30 ohms/square and 80% light transmission. The patterned ITO substrates were then cleaned ultrasonically in aqueous detergent solution. The substrates were then rinsed with distilled water, followed by isopropanol, and then degreased in toluene vapor. Immediately after cleaning, an aqueous dispersion of Buffer 1 was spin-coated over the ITO surface and heated to remove solvent.
[0095] The substrate was then loaded into the vacuum chamber and multiple layers of thin films were then deposited sequentially onto the buffer layer by thermal evaporation. Patterned layers of LiF and Al were deposited through a mask. The completed OLED device was then taken out of the vacuum chamber, encapsulated with a cover glass using epoxy, and characterized. The device layers are given in Table 10.1 below. The OLED samples were characterized by measuring their (1 ) current-voltage (I-V) curves, (2) electroluminescence radiance versus voltage, and (3) electroluminescence spectra versus voltage. All three measurements were performed at the same time and controlled by a computer. The current efficiency of the device at a certain voltage is determined by dividing the electroluminescence radiance of the LED by the current density needed to run the device. The unit is a cd/A. The power efficiency is the current efficiency divided by the operating voltage. The unit is Im/W. [0096] The materials used in device fabrication are listed below: NPB: N,N'-Bis(naphthalen-1 -yl)-N,N'-bis-(phenyl)benzidine TDATA: 4,4',4"-Tris-(N,N-diphenyl-amino)-triphenylamine
Table 10.1 Device summary:
[0097] In the foregoing specification, the concepts have been described with reference to specific embodiments. However, one of ordinary skill in the art appreciates that various modifications and changes can be made without departing from the scope of the invention as set forth in the claims below. Accordingly, the specification and figures are to be regarded in an illustrative rather than a restrictive sense, and all such modifications are intended to be included within the scope of invention. [0098] Many aspects and embodiments have been described above and are merely exemplary and not limiting. After reading this specification, skilled artisans appreciate that other aspects and embodiments are possible without departing from the scope of the invention.
[0099] Benefits, other advantages, and solutions to problems have been described above with regard to specific embodiments. However, the benefits, advantages, solutions to problems, and any feature(s) that may cause any benefit, advantage, or solution to occur or become more pronounced are not to be construed as a critical, required, or essential feature of any or all the claims.
[0100] It is to be appreciated that certain features are, for clarity, described herein in the context of separate embodiments, may also be provided in combination in a single embodiment. Conversely, various features that are, for brevity, described in the context of a single embodiment, may also be provided separately or in any subcombination. Further, reference to values stated in ranges include each and every value within that range.
Claims
1. A ligand for a metal, the ligand comprising Formula I or II:
wherein Ri is alkyl or aryl.
2. The ligand of claim 1 , wherein Ri is in the para-position.
3. The ligand of claim 1 , wherein Ri is a C4-C5 alkyl.
4. The ligand of claim 1 , wherein Ri is t-butyl.
5. The ligand of claim 1 , wherein Ri is aryl.
6. An organometallic complex comprising formula:
[Y]nMZ wherein: n is 1 , 2, or 3;
M is a metal in a +2, +3, or +4 oxidation state;
Y is a ligand comprising 8-hydroxyquinoline or alkyl-substituted 8- hydroxyquinoline at each occurrence; and
Z is a ligand comprising Formula I or II:
wherein Ri is alkyl or aryl.
7. The complex of claim 6, wherein M is Al, Zn, Zr, or Ga.
8. The complex of claim 6, wherein the alkyl-substituted 8-hydroxyquinoIine is substituted at the 2 position.
9. The complex of claim 6, wherein the alkyl-substituted 8-hydroxyquinoline is 2- methyl-8-hydroxyquinoline.
10. The complex of claim 6 that is:
11. The complex of claim 6 that is:
12. An organometallic complex having the formula:
MYnZ wherein: n is 1 , 2, or 3;
M is a metal in a +2, +3, or +4 oxidation state;
Y is selected from 8-hydroxyquinolate and substituted 8-hydroxyquinolate; and Z is a compound of formula III or IV:
IV
wherein:
R'i is one or more solvent-solubilizing or Tg enhancing groups;
R2, R3, and R4 are independently one or more selected from the group consisting of H, alkyl, substituted alkyl, aryl, substituted aryl, F, CN, a solvent-solubilizing group, and a Tg enhancing group.
13. The complex of claim 12, wherein M is Al, Zn, Zr, In, or Ga.
14. The complex of claim 12, wherein R'I is an alkyl group.
15. The complex of claim 12, wherein R'I is cyano, alkyl, fluoroalkyl, aryl, fluoroaryl, alkylaryl, alkoxy, aryloxy, fluoroalkoxy, or fluoroaryloxy, or their hetero-analogs.
16. The complex of claim 12, wherein R'-i is phenyl, fluorophenyl, alkylphenyl, fluoroalkylphenyl, alkoxy phenyl, or fluoroalkoxyphenyl.
17. A composition comprising the complex of claim 6 and at least one solvent, processing aid, charge transporting material, or charge blocking material.
18. An organic electronic device comprising an active layer and the complex of claim 6.
19. The device of claim 18, wherein the active layer is a photoactive layer, and the complex is in or adjacent to the photoactive layer.
20. An article useful in the manufacture of an organic electronic device, comprising the complex of claim 6.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US11/722,129 US20090216018A1 (en) | 2004-12-30 | 2005-12-29 | Organometallic complexes |
| JP2007549665A JP2008526768A (en) | 2004-12-30 | 2005-12-29 | Organometallic complex |
| CN2005800446717A CN101088178B (en) | 2004-12-30 | 2005-12-29 | Organometallic complexes |
| EP05855983A EP1834363A4 (en) | 2004-12-30 | 2005-12-29 | Organometallic complexes |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US64049304P | 2004-12-30 | 2004-12-30 | |
| US60/640,493 | 2004-12-30 | ||
| US69494305P | 2005-06-28 | 2005-06-28 | |
| US60/694,943 | 2005-06-28 |
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| Publication Number | Publication Date |
|---|---|
| WO2006072015A2 true WO2006072015A2 (en) | 2006-07-06 |
| WO2006072015A3 WO2006072015A3 (en) | 2006-11-02 |
Family
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/US2005/047501 WO2006072015A2 (en) | 2004-12-30 | 2005-12-29 | Organometallic complexes |
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| Country | Link |
|---|---|
| US (1) | US20090216018A1 (en) |
| EP (1) | EP1834363A4 (en) |
| JP (1) | JP2008526768A (en) |
| KR (1) | KR20070110279A (en) |
| CN (1) | CN101088178B (en) |
| TW (1) | TW200641091A (en) |
| WO (1) | WO2006072015A2 (en) |
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| WO2007079101A2 (en) | 2005-12-29 | 2007-07-12 | E. I. Du Pont De Nemours And Company | Compositions comprising novel compounds and electronic devices made with such compositions |
| JP2010528426A (en) * | 2007-05-18 | 2010-08-19 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Method for forming organic light-emitting diode and device manufactured by the method |
| JP2010537975A (en) * | 2007-08-31 | 2010-12-09 | エルジー・ケム・リミテッド | Organometallic complex derivative and organic light emitting device using the same |
| US8440324B2 (en) | 2005-12-27 | 2013-05-14 | E I Du Pont De Nemours And Company | Compositions comprising novel copolymers and electronic devices made with such compositions |
| US8617720B2 (en) | 2009-12-21 | 2013-12-31 | E I Du Pont De Nemours And Company | Electroactive composition and electronic device made with the composition |
| US8648333B2 (en) | 2009-10-19 | 2014-02-11 | E I Du Pont De Nemours And Company | Triarylamine compounds for use in organic light-emitting diodes |
| US8937300B2 (en) | 2009-10-19 | 2015-01-20 | E I Du Pont De Nemours And Company | Triarylamine compounds for use in organic light-emitting diodes |
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| US8470208B2 (en) * | 2006-01-24 | 2013-06-25 | E I Du Pont De Nemours And Company | Organometallic complexes |
| US8524381B2 (en) * | 2006-03-07 | 2013-09-03 | Sfc Co., Ltd. | Organometallic complex for organic light-emitting layer and organic light-emitting diode using the same |
| TW201245408A (en) * | 2011-04-08 | 2012-11-16 | Du Pont | Electronic device |
| CN103992342B (en) * | 2013-02-16 | 2016-07-06 | 清华大学 | Metallic aluminium coordination compound and application in an organic light emitting device thereof |
| KR101721229B1 (en) * | 2015-06-19 | 2017-03-29 | 경북대학교 산학협력단 | Electric double layer capacitor using aqueous solution-processable organic-metal chelate complex |
| EP3549944B1 (en) | 2018-04-02 | 2021-12-29 | Samsung Electronics Co., Ltd. | Organometallic compound, organic light-emitting device including the same, and diagnostic composition including the organometallic compound |
| CN110343136B (en) * | 2018-04-02 | 2023-08-11 | 三星电子株式会社 | Organometallic compound, organic light emitting device and diagnostic composition including the same |
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- 2005-12-29 KR KR1020077017437A patent/KR20070110279A/en not_active Application Discontinuation
- 2005-12-29 CN CN2005800446717A patent/CN101088178B/en not_active Expired - Fee Related
- 2005-12-29 EP EP05855983A patent/EP1834363A4/en not_active Withdrawn
- 2005-12-29 WO PCT/US2005/047501 patent/WO2006072015A2/en active Application Filing
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8440324B2 (en) | 2005-12-27 | 2013-05-14 | E I Du Pont De Nemours And Company | Compositions comprising novel copolymers and electronic devices made with such compositions |
| WO2007079101A2 (en) | 2005-12-29 | 2007-07-12 | E. I. Du Pont De Nemours And Company | Compositions comprising novel compounds and electronic devices made with such compositions |
| EP1976822A2 (en) * | 2005-12-29 | 2008-10-08 | E.I. Du Pont De Nemours And Company | Compositions comprising novel compounds and electronic devices made with such compositions |
| EP1976822A4 (en) * | 2005-12-29 | 2010-12-15 | Du Pont | Compositions comprising novel compounds and electronic devices made with such compositions |
| JP2010528426A (en) * | 2007-05-18 | 2010-08-19 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Method for forming organic light-emitting diode and device manufactured by the method |
| JP2010537975A (en) * | 2007-08-31 | 2010-12-09 | エルジー・ケム・リミテッド | Organometallic complex derivative and organic light emitting device using the same |
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| US8937300B2 (en) | 2009-10-19 | 2015-01-20 | E I Du Pont De Nemours And Company | Triarylamine compounds for use in organic light-emitting diodes |
| US8617720B2 (en) | 2009-12-21 | 2013-12-31 | E I Du Pont De Nemours And Company | Electroactive composition and electronic device made with the composition |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20070110279A (en) | 2007-11-16 |
| EP1834363A2 (en) | 2007-09-19 |
| CN101088178A (en) | 2007-12-12 |
| JP2008526768A (en) | 2008-07-24 |
| EP1834363A4 (en) | 2010-10-06 |
| US20090216018A1 (en) | 2009-08-27 |
| WO2006072015A3 (en) | 2006-11-02 |
| CN101088178B (en) | 2010-09-29 |
| TW200641091A (en) | 2006-12-01 |
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