CA2148544C - Conductive coatings - Google Patents
Conductive coatingsInfo
- Publication number
- CA2148544C CA2148544C CA002148544A CA2148544A CA2148544C CA 2148544 C CA2148544 C CA 2148544C CA 002148544 A CA002148544 A CA 002148544A CA 2148544 A CA2148544 A CA 2148544A CA 2148544 C CA2148544 C CA 2148544C
- Authority
- CA
- Canada
- Prior art keywords
- radical
- groups
- electroluminescent
- conductive
- optionally substituted
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 238000000576 coating method Methods 0.000 title claims abstract description 23
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 229920000123 polythiophene Polymers 0.000 claims abstract description 14
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 7
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
- 239000001257 hydrogen Substances 0.000 claims abstract description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 150000003951 lactams Chemical group 0.000 claims abstract description 4
- 230000007935 neutral effect Effects 0.000 claims abstract description 4
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims abstract 2
- 239000011248 coating agent Substances 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims 1
- 125000003368 amide group Chemical group 0.000 abstract description 3
- 125000004356 hydroxy functional group Chemical group O* 0.000 abstract description 3
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 abstract description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 2
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 41
- 239000000758 substrate Substances 0.000 description 15
- 239000000126 substance Substances 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 8
- 238000000137 annealing Methods 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- -1 silver halide Chemical class 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 239000010408 film Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 4
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- 239000000600 sorbitol Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 239000013065 commercial product Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 150000002739 metals Chemical group 0.000 description 3
- 229920000058 polyacrylate Polymers 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- SMNDYUVBFMFKNZ-UHFFFAOYSA-N 2-furoic acid Chemical compound OC(=O)C1=CC=CO1 SMNDYUVBFMFKNZ-UHFFFAOYSA-N 0.000 description 2
- IHCCAYCGZOLTEU-UHFFFAOYSA-N 3-furoic acid Chemical compound OC(=O)C=1C=COC=1 IHCCAYCGZOLTEU-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 2
- 229920002492 poly(sulfone) Polymers 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000011112 polyethylene naphthalate Substances 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000013047 polymeric layer Substances 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 2
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 description 1
- AXFYHFMCIXMZJM-UHFFFAOYSA-N 2-but-1-ynyl-1-hexoxy-3-methoxybenzene Chemical group CCCCCCOC1=CC=CC(OC)=C1C#CCC AXFYHFMCIXMZJM-UHFFFAOYSA-N 0.000 description 1
- GUBGYTABKSRVRQ-XLOQQCSPSA-N Alpha-Lactose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@H](O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-XLOQQCSPSA-N 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- 101000654316 Centruroides limpidus Beta-toxin Cll2 Proteins 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 description 1
- 102000006830 Luminescent Proteins Human genes 0.000 description 1
- 108010047357 Luminescent Proteins Proteins 0.000 description 1
- 229930195725 Mannitol Natural products 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- WPPOGHDFAVQKLN-UHFFFAOYSA-N N-Octyl-2-pyrrolidone Chemical compound CCCCCCCCN1CCCC1=O WPPOGHDFAVQKLN-UHFFFAOYSA-N 0.000 description 1
- ZWXPDGCFMMFNRW-UHFFFAOYSA-N N-methylcaprolactam Chemical compound CN1CCCCCC1=O ZWXPDGCFMMFNRW-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 206010037660 Pyrexia Diseases 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 229920000109 alkoxy-substituted poly(p-phenylene vinylene) Polymers 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000001913 cellulose Chemical class 0.000 description 1
- 229920002678 cellulose Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 230000005670 electromagnetic radiation Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000007646 gravure printing Methods 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical class C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000005525 hole transport Effects 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 239000008101 lactose Substances 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000447 polyanionic polymer Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000003586 protic polar solvent Substances 0.000 description 1
- 125000004309 pyranyl group Chemical group O1C(C=CC=C1)* 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 239000006120 scratch resistant coating Substances 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229920000638 styrene acrylonitrile Polymers 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 150000005846 sugar alcohols Chemical class 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 150000003577 thiophenes Chemical class 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 229920006163 vinyl copolymer Polymers 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
- H01B1/124—Intrinsically conductive polymers
- H01B1/128—Intrinsically conductive polymers comprising six-membered aromatic rings in the main chain, e.g. polyanilines, polyphenylenes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
- H01B1/124—Intrinsically conductive polymers
- H01B1/127—Intrinsically conductive polymers comprising five-membered aromatic rings in the main chain, e.g. polypyrroles, polythiophenes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/48—Conductive polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/56—Solid electrolytes, e.g. gels; Additives therein
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/80—Constructional details
- H10K59/805—Electrodes
- H10K59/8051—Anodes
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
- H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
- H10K85/1135—Polyethylene dioxythiophene [PEDOT]; Derivatives thereof
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1343—Electrodes
- G02F1/13439—Electrodes characterised by their electrical, optical, physical properties; materials therefor; method of making
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
- H05K3/188—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by direct electroplating
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
- H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
Abstract
Mixtures of A) neutral polythiophenes of formula (I),
Description
` 2~5~ 1 `_ Conductive coatinqs In the field of electronics there is a requirement for electrically conductive, transparent electrodes, for ex-ample, for LCD displays. Up to the present in most cases glasses or plastic sheets vapour-deposited with metal oxides are employed for these applications. Materials vapour-deposited or sputtered with ITO (indium tin oxide) have particularly good properties. The surface resistance of the ITO layers is of the order of magnitude of less than 500 ~
The production of such layers by sputtering under vacuum is very costly. There is therefore a need for a material which renders possible the production by simple application techniques of transparent coatings having good conductivity.
The production of conductive coatings based on organic conductive materials is known in principle. Thus for example coatings made of polypyrrole (EP-A 302 304) or of polythiophene derivatives (EP-A 440 957) have been described. These coatings can be produced using simple coating processes but they are not sufficiently conductive or transparent for many fields of application.
The present invention provides mixtures of A) neutral polythiophenes of the recurring structural unit of the formula I, R O OR
S
Le A 30 329-Eoreiqn Countries - 1 -2~54~
'_ wherein Rl and R2 independently of one another represent hydrogen or a Cl4 alkyl group or together form an optionally substituted Cl4 alkylene radical, preferably a methylene radical which is option-ally substituted by alkyl groups, an ethylene-1,2 radical optionally substituted by Cll2 alkyl or phenyl groups, or a cyclohexylene-1,2 radical, and B) organic compounds containing dihydroxy or poly-hydroxy and/or carboxyl groups or amide groups or lactam groups.
These mixtures can be applied in thin layers to the substrate and by drying and annealing can be converted into transparent and electrically conducting layers.
Suitable organic compounds cont~; n; ng dihydroxy or polyhydroxy and/or carboxyl groups or amide groups correspond to formula (II) /(H)n R \ (II) (COX)m wherein n and m independently of one another denote an integer from 1 to 20, preferably from 2 to 8 and R denotes a linear, branched or cyclic alkylene radical having 2 to 20 C atoms or an optionally substituted arylene radical having 6 to 14 C
atoms or a heterocyclic radical having 4 to 10 C
Le A 30 329-Forei~n Countries - 2 -i~148544 -atoms or a sugar radical or sugar alcohol radical and X denotes -OH or -NYZ, wherein Y, Z independently of one another represent hydrogen or alkyl, preferably hydrogen or Cl-Cl2-alkYl-Examples of suitable organic compounds containing lactam groups are N-methylpyrrolidone, pyrrolidone, caprolactam, N-methylcaprolactam, N-octylpyrrolidone.
Preferred radicals R are derived from the furan structure or the pyran structure.
Particularly preferred organic compounds corresponding to formula (II) are:
sugar and sugar derivatives such as sucrose, glucose, fructose, lactose; sugar alcohols such as sorbitol, mannitol; furan derivatives such as 2-furancarboxylic acid, 3-furancarboxylic acid; alcohols such as ethylene glycol, glycerol, di- or triethylene glycol.
In addition to water, other protic solvents can also be used as solvents for the polythiophene dispersions accord-ing to the invention, such as for example lower alcoholssuch as methanol, ethanol and isopropanol, as well as mix-tures of water with lower alcohols and other water-miscible organic solvents, such as acetone.
The average particle diameters of the particles in the dispersion can be up to 10 um, preferably up to 3 ,um and most preferably up to 1 ,um.
The polythiophenes of the recurring structural unit of the formula (I) are known (cf. EP-A 440,958 and 339,340). The preparation of the dispersions or solutions according to Le A 30 329-Eoreiqn Countries - 3 -21 18~4'1 -the invention is described in EP-A 440,958 and DE-OS 42 11 459.
The polythiophenes are preferably used in the dispersion or solution in a cationic form, i.e. in the form in which they are obtained for example by treating the neutral thiophenes with oxidising agents. Known oxidising agents, such as potassium peroxodisulphate are used for the oxidation. As a result of oxidation the polythiophenes acquire positive charges which are not shown in the formulae, since the number thereof and their positions cannot be accurately determined.
The number of recurring structural units of the formula (I) is generally >5.
The polythiophene dispersions or solutions according to the invention contain, based on the sum of polythiophene cations and polyanions, that is, based on the total solids content of the solution, from 1 to 100,000% by weight, preferably 10 to 1,000% by weight, of the compounds of formula (II) containing hydroxy and carboxyl groups.
Preferably compounds of formula (II) which are soluble in water are employed.
Organic, polymeric binders and/or organic, low-molecular cross-linking agents may also be added to the coating solutions according to the invention. Appropriate binders are described, for example, in EP-A 564 911.
Epoxysilanes, of the kind described in EP-A 564 911, can be added to the coating solutions according to the invention, particularly for the production of adhesive layers on glass.
The coatings according to the invention can be produced by known methods, for example, by spraying, application by a Le A 30 329-Foreiqn Countries - 4 -~148S4~
-doctor blade, dipping, application with roller applicator systems, by printing processes such as gravure printing, silk screen printing, curtain casting, and can be dried at room temperature or at temperatures of up to 300C, preferably up to 200C.
The coatings according to the invention can be annealed in order to increase electrical conductivity. Annealing can follow drying at temperatures of below 100C and can be combined with drying at temperatures of above 100C. This annealing is carried out at temperatures of from 100C to 400C, preferably at temperatures of up to 250C. The duration of the annealing is between 0.5 and 3600 seconds, and preferably 1 ànd 90 seconds.
The thickness of the coatings according to the invention, depending on the intended use and requirements as to transparency and conductivity, is from 0.025 to 250 um, preferably from 0.05 to 10 ~m; the surface resistance is generally from 0.1 to 2000 D / O, preferably from 1 to 300 D/O.
The coatings according to the invention are used in areas which require good electrical conductivities, for example, as electrodes in electroluminescent displays, in LCD
displays, in solid electrolyte capacitors, for the deposition of metals such as copper, nickel, for example, in the manufacture of printed circuits, in solar cells, in electrochromic displays or for the screening of electromagnetic radiation or for leading away electrical charges, for example, in picture tubes or as anticorrosive coatings on metals, for the production of touch screens.
Other areas of application are systems for picture production, for example, silver halide photography, dry-plate systems, electrophotography.
Le A 30 329-Forei~n Countries - 5 -2~485~
_ The conductive layers can optionally be coated with further layers, for example, W-curing coatings or organic or inorganic scratch-resistant coatings.
The layers according to the invention can be applied to organic and inorganic substrates. Examples of suitable inorganic substrates are glass, oxides or oxidic or non-oxidic ceramics such as aluminium oxide, silicon nitride.
Examples of suitable organic substrates are sheets or other mouldings of pure organic polymers, copolymers or mixtures of, for example, polycarbonate, polystyrene, polyacrylates, polyesters such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyamides, polyimides, optionally glass-fibre reinforced epoxy resins, cellulose derivatives such as cellulose triacetate, polyolefins such as polyethylene, polypropylene.
The invention also relates to electroluminescent systems which contain the polythiophene dispersions according to the invention in the form of a transparent conductive layer or electrode.
The electroluminescent systems according to the invention consist of an upper and a lower electrode, between which an electroluminescent layer and optionally other auxiliary layers, such as for example charge-injecting layers are inserted, and they are characterised in that they contain as the electrode a conductive layer consisting of the po-lythiophene mixtures according to the invention.
The electroluminescent system can contain one or more elec-trodes, the conductive layers of which contain the abovementioned polythiophene dispersions. The conductive layers are preferably transparent.
The conductive layer can be integrated in various positions in the structure of the electroluminescent systems. The Le A 30 329-Foreiqn Countries - 6 -~148544 conductive layer can be applied for example in the form of a transparent conductive electrode between a transparent substrate and an electroluminescent layer.
For this purpose the mixtures according to the invention are applied in the form of a film to a suitable substrate in the systems according to the invention.
Suitable substrates are transparent substrates such as glass or plastic films (e.g. polyesters, such as polye-thylene terephthalate or polyethylene naphthalate, poly-carbonate, polyacrylate, polysulphone or polyimide film).
The polythiophene mixture according to the invention is distributed evenly on the substrate by techniques such as spin-coating, casting, application by a doctor blade, prin-ting, curtain casting, etc.
After the film has dried the substrate thus coated can be subjected to a temperature of 150-250C for at least 1 sec, generally 30 secs. This annealing step increases the con-ductivity of the layer.
The thickness of the transparent conductive electrode is 5 nm to several ,um, preferably 10 nm to 1500 nm.
An electroluminescent layer is applied to this conductive transparent electrode in the form of a thin film. The substances described for example in EP-A 443,861 can be used as electroluminescent substances.
After the EL layer has dried it is coated with a counter-electrode. This consists of a conductive substance which can be transparent. Preferably metals such as Al, Au, Ag etc. or alloys or oxides thereof are suitable, which are applied by techniques such as vapour deposition, sputtering or platinisation.
Le A 30 329-Foreiqn Countries - 7 -2~ 48S4~
The system according to the invention is brought into con-tact with the two electrodes by two electrical supply leads (such as for example metal wires).
When direct voltage in the range of 2 to 100 volt is ap-plied the systems emit light of a wavelength of 400 to 700 nm. They display photoluminescence in the range from 400 to 700 nm.
The electroluminescent layer can contain one or more elec-trooptically active substances. It also optionally con-tains customary additives such as inert binders, charge-carrier-transporting substances and mixtures of inert bin-ders and charge-carrier-transporting substances. Charge-carrier-transporting substances increase the electrolumi-nescent intensity and reduce the inception voltages.
Suitable inert binders are preferably soluble, transparent polymers, such as for example polycarbonates, polystyrene and copolymers of polystyrene such as SAN, polysulphones, polyacrylates, polyvinylcarbazole, and vinyl acetate and vinyl alcohol polymers and copolymers, etc.
One or more intermediate layers can be additionally ar-ranged between the electroluminescent systems and the electrodes. These intermediate layers - charge-carrier-transporting substances - are known (for example from Appl.
Phys. Lett. 57 (1990)531) and are defined therein as HTL
(hole transport layer) and ETL (electron transport layer).
The conductive layers can also be applied as transparent conductive electrodes to form a covering layer on an elec-troluminescent layer.
Contrary to the arrangement described above, in which the mixture according to the invention is arranged between an electroluminescent layer and a transparent substrate, the Le A 30 329-Foreiqn Countries - 8 -214~54 1 substance according to the invention can also be used as a covering electrode.
In this use the electroluminescent substance is arranged on a conductive or conductively coated substrate, such as for example metal plates or metal coatings applied by vapour deposition. The substance according to the invention is applied to the electroluminescent layer in the manner des-cribed above.
The advantage of this structure is that it also allows electroluminescent layers which are exposed to high tempe-ratures during their production to be provided with a rea-dily applicable, transparent, conductive electrode.
Example: luminescent plates produced from a luminescent enamel based on ZnS.
The mixtures according to the invention can also be used as a charge-transporting intermediate layer in polymeric lumi-nescent diodes. This intermediate layer increases the efficiency of the systems.
The mixture according to the invention is applied in the abovementioned manner in the form of an intermediate layer.
The intermediate layer can be arranged:
- between the transparent conductive electrode and the electroluminescent polymeric layer, - between the electroluminescent polymeric layer and the 25covering electrode.
The thickness of the intermediate layer is about 3-200 nm, and generally between 10 - 100 nm, and most preferably about 10 nm.
Le A 30 329-Forei~n Countries - 9 -2148~44 -ExamPles A) Preparation of a 3,4-polyethylene dioxythiophene solution 20 g of free polystyrene sulphonic acid (Mn approx.
40,000), 13.0 g of potassium peroxydisulphate and 50 mg of iron(III) sulphate are stirred together in 2000 ml of water. 5.6 g of 3,4-ethylene dioxythiophene is added with stirring. The solution is stirred for 24 h at room temperature. Then 100 g of an anion exchanger (commercial product from Bayer AG, Lewatit MP 62) and 100 g of a cation exchanger (commercial product from Bayer AG, Lewatit S
100), both moistened by water, are added and stirred for 8 hours.
The ion exchangers are removed by filtration. A solution having a solids content of approximately 1.2% by weight is obtained, which is ready for use.
Exam~le 1:
10.0 g of the solution prepared in Example A) together with 10 g of isopropanol are mixed with each of the quantities of sorbitol and 3-glycidoxypropyltrimethoxysilane (com-mercial product A 187 Union Carbide) given in the Table.
The mixture is applied to glass plates and dried in air (approx. 400 mg/m2 dry).
The surface resistance of the dried layers is determined.
The coated glass plates are then placed for 90 seconds on a hot plate at a temperature of 200C and the surface resistance is again determined after cooling.
Le A 30 329-Foreign Countries - 10 -2148~44 -Table:
A 187 Sorbitol Surface resistance [Q/O]
[g] [g] beforeafter annealing 0.2 _ 3500 3500 0.1 0.2 3400 120 0.2 0.2 3500 180 0.4 0.2 3300 300 0.1 0.6 4000 90 0.2 0.6 3800 105 0.4 0.6 3950 125 It is apparent from the Table that the process according to the invention results in significantly superior conductive coatings than does the 3,4-polyethylene dioxythiophene solution without additives and annealing.
Example 2: An electroluminescent system B) Preparation of the coating solution 3.0 g of sorbitol are dissolved with stirring in 50 g of solution A. Then 50 g of isopropanol are added dropwise with stirring and 0.5 g of glycidoxypropyl trimethoxysilane (A 187 = a trade product of Union Carbide) is added.
C) Preparation of the 3,4-polyethylenedioxythiophene electrode Solution B is applied to a glass slide (20 X 30 mm2). The substrate is then rotated in a coating centrifuge for 10 seconds at 500 r.p.m. The substrate coated with the film is placed on a heating plate of a temperature of 180C for 60 seconds, during which the surface resistance is reduced to 80 Q/O. The layer thickness of the film is 1.3 ~m. The film is transparent in the visible region of the spectrum.
Le A 30 329-Foreign Countries - 11 -2~8541 -The electroluminescent polymer is then applied to this layer.
D) Application of an electroluminescent layer to the 3,4-polyethylenedioxythiophene electrode The electroluminescent material used is MEH-PPV (methoxy-ethylhexyloxy phenylenevinylene) known from the literature.
A 0.75% solution of the polymer in chloroform is distributed on the polythiophene-coated substrate of Ex-ample 2C) for 10 seconds at 2000 r.p.m. using a coating centrifuge. Al point contacts are then applied to the polymer film of a thickness of 130 nm by vapour deposition.
E) Use of the flexible polymeric luminescent diodes When the positive contact of a voltage source is connected to the PEDT layer and the negative contact with the Al, a current flows through the electroluminescent polymer. At the same time electroluminescence occurs. The luminescent intensity is proportional to the diode current and increa-ses as the voltage increases.
Le A 30 329-Foreiqn Countries - 12 -
The production of such layers by sputtering under vacuum is very costly. There is therefore a need for a material which renders possible the production by simple application techniques of transparent coatings having good conductivity.
The production of conductive coatings based on organic conductive materials is known in principle. Thus for example coatings made of polypyrrole (EP-A 302 304) or of polythiophene derivatives (EP-A 440 957) have been described. These coatings can be produced using simple coating processes but they are not sufficiently conductive or transparent for many fields of application.
The present invention provides mixtures of A) neutral polythiophenes of the recurring structural unit of the formula I, R O OR
S
Le A 30 329-Eoreiqn Countries - 1 -2~54~
'_ wherein Rl and R2 independently of one another represent hydrogen or a Cl4 alkyl group or together form an optionally substituted Cl4 alkylene radical, preferably a methylene radical which is option-ally substituted by alkyl groups, an ethylene-1,2 radical optionally substituted by Cll2 alkyl or phenyl groups, or a cyclohexylene-1,2 radical, and B) organic compounds containing dihydroxy or poly-hydroxy and/or carboxyl groups or amide groups or lactam groups.
These mixtures can be applied in thin layers to the substrate and by drying and annealing can be converted into transparent and electrically conducting layers.
Suitable organic compounds cont~; n; ng dihydroxy or polyhydroxy and/or carboxyl groups or amide groups correspond to formula (II) /(H)n R \ (II) (COX)m wherein n and m independently of one another denote an integer from 1 to 20, preferably from 2 to 8 and R denotes a linear, branched or cyclic alkylene radical having 2 to 20 C atoms or an optionally substituted arylene radical having 6 to 14 C
atoms or a heterocyclic radical having 4 to 10 C
Le A 30 329-Forei~n Countries - 2 -i~148544 -atoms or a sugar radical or sugar alcohol radical and X denotes -OH or -NYZ, wherein Y, Z independently of one another represent hydrogen or alkyl, preferably hydrogen or Cl-Cl2-alkYl-Examples of suitable organic compounds containing lactam groups are N-methylpyrrolidone, pyrrolidone, caprolactam, N-methylcaprolactam, N-octylpyrrolidone.
Preferred radicals R are derived from the furan structure or the pyran structure.
Particularly preferred organic compounds corresponding to formula (II) are:
sugar and sugar derivatives such as sucrose, glucose, fructose, lactose; sugar alcohols such as sorbitol, mannitol; furan derivatives such as 2-furancarboxylic acid, 3-furancarboxylic acid; alcohols such as ethylene glycol, glycerol, di- or triethylene glycol.
In addition to water, other protic solvents can also be used as solvents for the polythiophene dispersions accord-ing to the invention, such as for example lower alcoholssuch as methanol, ethanol and isopropanol, as well as mix-tures of water with lower alcohols and other water-miscible organic solvents, such as acetone.
The average particle diameters of the particles in the dispersion can be up to 10 um, preferably up to 3 ,um and most preferably up to 1 ,um.
The polythiophenes of the recurring structural unit of the formula (I) are known (cf. EP-A 440,958 and 339,340). The preparation of the dispersions or solutions according to Le A 30 329-Eoreiqn Countries - 3 -21 18~4'1 -the invention is described in EP-A 440,958 and DE-OS 42 11 459.
The polythiophenes are preferably used in the dispersion or solution in a cationic form, i.e. in the form in which they are obtained for example by treating the neutral thiophenes with oxidising agents. Known oxidising agents, such as potassium peroxodisulphate are used for the oxidation. As a result of oxidation the polythiophenes acquire positive charges which are not shown in the formulae, since the number thereof and their positions cannot be accurately determined.
The number of recurring structural units of the formula (I) is generally >5.
The polythiophene dispersions or solutions according to the invention contain, based on the sum of polythiophene cations and polyanions, that is, based on the total solids content of the solution, from 1 to 100,000% by weight, preferably 10 to 1,000% by weight, of the compounds of formula (II) containing hydroxy and carboxyl groups.
Preferably compounds of formula (II) which are soluble in water are employed.
Organic, polymeric binders and/or organic, low-molecular cross-linking agents may also be added to the coating solutions according to the invention. Appropriate binders are described, for example, in EP-A 564 911.
Epoxysilanes, of the kind described in EP-A 564 911, can be added to the coating solutions according to the invention, particularly for the production of adhesive layers on glass.
The coatings according to the invention can be produced by known methods, for example, by spraying, application by a Le A 30 329-Foreiqn Countries - 4 -~148S4~
-doctor blade, dipping, application with roller applicator systems, by printing processes such as gravure printing, silk screen printing, curtain casting, and can be dried at room temperature or at temperatures of up to 300C, preferably up to 200C.
The coatings according to the invention can be annealed in order to increase electrical conductivity. Annealing can follow drying at temperatures of below 100C and can be combined with drying at temperatures of above 100C. This annealing is carried out at temperatures of from 100C to 400C, preferably at temperatures of up to 250C. The duration of the annealing is between 0.5 and 3600 seconds, and preferably 1 ànd 90 seconds.
The thickness of the coatings according to the invention, depending on the intended use and requirements as to transparency and conductivity, is from 0.025 to 250 um, preferably from 0.05 to 10 ~m; the surface resistance is generally from 0.1 to 2000 D / O, preferably from 1 to 300 D/O.
The coatings according to the invention are used in areas which require good electrical conductivities, for example, as electrodes in electroluminescent displays, in LCD
displays, in solid electrolyte capacitors, for the deposition of metals such as copper, nickel, for example, in the manufacture of printed circuits, in solar cells, in electrochromic displays or for the screening of electromagnetic radiation or for leading away electrical charges, for example, in picture tubes or as anticorrosive coatings on metals, for the production of touch screens.
Other areas of application are systems for picture production, for example, silver halide photography, dry-plate systems, electrophotography.
Le A 30 329-Forei~n Countries - 5 -2~485~
_ The conductive layers can optionally be coated with further layers, for example, W-curing coatings or organic or inorganic scratch-resistant coatings.
The layers according to the invention can be applied to organic and inorganic substrates. Examples of suitable inorganic substrates are glass, oxides or oxidic or non-oxidic ceramics such as aluminium oxide, silicon nitride.
Examples of suitable organic substrates are sheets or other mouldings of pure organic polymers, copolymers or mixtures of, for example, polycarbonate, polystyrene, polyacrylates, polyesters such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyamides, polyimides, optionally glass-fibre reinforced epoxy resins, cellulose derivatives such as cellulose triacetate, polyolefins such as polyethylene, polypropylene.
The invention also relates to electroluminescent systems which contain the polythiophene dispersions according to the invention in the form of a transparent conductive layer or electrode.
The electroluminescent systems according to the invention consist of an upper and a lower electrode, between which an electroluminescent layer and optionally other auxiliary layers, such as for example charge-injecting layers are inserted, and they are characterised in that they contain as the electrode a conductive layer consisting of the po-lythiophene mixtures according to the invention.
The electroluminescent system can contain one or more elec-trodes, the conductive layers of which contain the abovementioned polythiophene dispersions. The conductive layers are preferably transparent.
The conductive layer can be integrated in various positions in the structure of the electroluminescent systems. The Le A 30 329-Foreiqn Countries - 6 -~148544 conductive layer can be applied for example in the form of a transparent conductive electrode between a transparent substrate and an electroluminescent layer.
For this purpose the mixtures according to the invention are applied in the form of a film to a suitable substrate in the systems according to the invention.
Suitable substrates are transparent substrates such as glass or plastic films (e.g. polyesters, such as polye-thylene terephthalate or polyethylene naphthalate, poly-carbonate, polyacrylate, polysulphone or polyimide film).
The polythiophene mixture according to the invention is distributed evenly on the substrate by techniques such as spin-coating, casting, application by a doctor blade, prin-ting, curtain casting, etc.
After the film has dried the substrate thus coated can be subjected to a temperature of 150-250C for at least 1 sec, generally 30 secs. This annealing step increases the con-ductivity of the layer.
The thickness of the transparent conductive electrode is 5 nm to several ,um, preferably 10 nm to 1500 nm.
An electroluminescent layer is applied to this conductive transparent electrode in the form of a thin film. The substances described for example in EP-A 443,861 can be used as electroluminescent substances.
After the EL layer has dried it is coated with a counter-electrode. This consists of a conductive substance which can be transparent. Preferably metals such as Al, Au, Ag etc. or alloys or oxides thereof are suitable, which are applied by techniques such as vapour deposition, sputtering or platinisation.
Le A 30 329-Foreiqn Countries - 7 -2~ 48S4~
The system according to the invention is brought into con-tact with the two electrodes by two electrical supply leads (such as for example metal wires).
When direct voltage in the range of 2 to 100 volt is ap-plied the systems emit light of a wavelength of 400 to 700 nm. They display photoluminescence in the range from 400 to 700 nm.
The electroluminescent layer can contain one or more elec-trooptically active substances. It also optionally con-tains customary additives such as inert binders, charge-carrier-transporting substances and mixtures of inert bin-ders and charge-carrier-transporting substances. Charge-carrier-transporting substances increase the electrolumi-nescent intensity and reduce the inception voltages.
Suitable inert binders are preferably soluble, transparent polymers, such as for example polycarbonates, polystyrene and copolymers of polystyrene such as SAN, polysulphones, polyacrylates, polyvinylcarbazole, and vinyl acetate and vinyl alcohol polymers and copolymers, etc.
One or more intermediate layers can be additionally ar-ranged between the electroluminescent systems and the electrodes. These intermediate layers - charge-carrier-transporting substances - are known (for example from Appl.
Phys. Lett. 57 (1990)531) and are defined therein as HTL
(hole transport layer) and ETL (electron transport layer).
The conductive layers can also be applied as transparent conductive electrodes to form a covering layer on an elec-troluminescent layer.
Contrary to the arrangement described above, in which the mixture according to the invention is arranged between an electroluminescent layer and a transparent substrate, the Le A 30 329-Foreiqn Countries - 8 -214~54 1 substance according to the invention can also be used as a covering electrode.
In this use the electroluminescent substance is arranged on a conductive or conductively coated substrate, such as for example metal plates or metal coatings applied by vapour deposition. The substance according to the invention is applied to the electroluminescent layer in the manner des-cribed above.
The advantage of this structure is that it also allows electroluminescent layers which are exposed to high tempe-ratures during their production to be provided with a rea-dily applicable, transparent, conductive electrode.
Example: luminescent plates produced from a luminescent enamel based on ZnS.
The mixtures according to the invention can also be used as a charge-transporting intermediate layer in polymeric lumi-nescent diodes. This intermediate layer increases the efficiency of the systems.
The mixture according to the invention is applied in the abovementioned manner in the form of an intermediate layer.
The intermediate layer can be arranged:
- between the transparent conductive electrode and the electroluminescent polymeric layer, - between the electroluminescent polymeric layer and the 25covering electrode.
The thickness of the intermediate layer is about 3-200 nm, and generally between 10 - 100 nm, and most preferably about 10 nm.
Le A 30 329-Forei~n Countries - 9 -2148~44 -ExamPles A) Preparation of a 3,4-polyethylene dioxythiophene solution 20 g of free polystyrene sulphonic acid (Mn approx.
40,000), 13.0 g of potassium peroxydisulphate and 50 mg of iron(III) sulphate are stirred together in 2000 ml of water. 5.6 g of 3,4-ethylene dioxythiophene is added with stirring. The solution is stirred for 24 h at room temperature. Then 100 g of an anion exchanger (commercial product from Bayer AG, Lewatit MP 62) and 100 g of a cation exchanger (commercial product from Bayer AG, Lewatit S
100), both moistened by water, are added and stirred for 8 hours.
The ion exchangers are removed by filtration. A solution having a solids content of approximately 1.2% by weight is obtained, which is ready for use.
Exam~le 1:
10.0 g of the solution prepared in Example A) together with 10 g of isopropanol are mixed with each of the quantities of sorbitol and 3-glycidoxypropyltrimethoxysilane (com-mercial product A 187 Union Carbide) given in the Table.
The mixture is applied to glass plates and dried in air (approx. 400 mg/m2 dry).
The surface resistance of the dried layers is determined.
The coated glass plates are then placed for 90 seconds on a hot plate at a temperature of 200C and the surface resistance is again determined after cooling.
Le A 30 329-Foreign Countries - 10 -2148~44 -Table:
A 187 Sorbitol Surface resistance [Q/O]
[g] [g] beforeafter annealing 0.2 _ 3500 3500 0.1 0.2 3400 120 0.2 0.2 3500 180 0.4 0.2 3300 300 0.1 0.6 4000 90 0.2 0.6 3800 105 0.4 0.6 3950 125 It is apparent from the Table that the process according to the invention results in significantly superior conductive coatings than does the 3,4-polyethylene dioxythiophene solution without additives and annealing.
Example 2: An electroluminescent system B) Preparation of the coating solution 3.0 g of sorbitol are dissolved with stirring in 50 g of solution A. Then 50 g of isopropanol are added dropwise with stirring and 0.5 g of glycidoxypropyl trimethoxysilane (A 187 = a trade product of Union Carbide) is added.
C) Preparation of the 3,4-polyethylenedioxythiophene electrode Solution B is applied to a glass slide (20 X 30 mm2). The substrate is then rotated in a coating centrifuge for 10 seconds at 500 r.p.m. The substrate coated with the film is placed on a heating plate of a temperature of 180C for 60 seconds, during which the surface resistance is reduced to 80 Q/O. The layer thickness of the film is 1.3 ~m. The film is transparent in the visible region of the spectrum.
Le A 30 329-Foreign Countries - 11 -2~8541 -The electroluminescent polymer is then applied to this layer.
D) Application of an electroluminescent layer to the 3,4-polyethylenedioxythiophene electrode The electroluminescent material used is MEH-PPV (methoxy-ethylhexyloxy phenylenevinylene) known from the literature.
A 0.75% solution of the polymer in chloroform is distributed on the polythiophene-coated substrate of Ex-ample 2C) for 10 seconds at 2000 r.p.m. using a coating centrifuge. Al point contacts are then applied to the polymer film of a thickness of 130 nm by vapour deposition.
E) Use of the flexible polymeric luminescent diodes When the positive contact of a voltage source is connected to the PEDT layer and the negative contact with the Al, a current flows through the electroluminescent polymer. At the same time electroluminescence occurs. The luminescent intensity is proportional to the diode current and increa-ses as the voltage increases.
Le A 30 329-Foreiqn Countries - 12 -
Claims (6)
1. A mixture of (A) a neutral polythiophene having a recurring structural unit of the formula (I), wherein R1 and R2 independently of one another represent hydrogen or a C1-4 alkyl group or together form an optionally substituted C1-4 alkylene radical, or a cyclohexylene-1,2 radical, and B) an organic compound containing a dihydroxy, polyhydroxy, carboxyl, amide or lactam group.
2. A mixture according to claim 1, wherein B) is an organic compound of the formula (II) wherein n and m independently of one another denote an integer from 1 to 20, and R denotes a linear, branched or cyclic alkylene radical having 2 to 20 C atoms or an optionally substituted arylene radical having 6 to 14 C atoms or a heterocyclic radical having 4 to 10 C atoms or a sugar radical or sugar alcohol radical and X denotes -OH or -NYZ, wherein Y, Z independently of one another represent hydrogen or alkyl.
3. A use of a mixture according to claim 1 in the preparation of a conductive coating.
4. A conductive coating containing a mixture according to claim 1, which has been annealed to increase the conductivity thereof.
5. A conductive coating according to claim 4, wherein the surface resistance is less than 300.OMEGA./?.
6. An electroluminescent system comprising an upper and a lower electrode, having an intermediate electroluminescent layer wherein the electrode comprises a conductive layer formed from a mixture according to claim 1.
Applications Claiming Priority (4)
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DE4416117 | 1994-05-06 | ||
DEP4416117.4 | 1994-05-06 | ||
DE19507413A DE19507413A1 (en) | 1994-05-06 | 1995-03-03 | Conductive coatings |
DE19507413.0 | 1995-03-03 |
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CA2148544A1 CA2148544A1 (en) | 1995-11-07 |
CA2148544C true CA2148544C (en) | 1999-10-26 |
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CA002148544A Expired - Fee Related CA2148544C (en) | 1994-05-06 | 1995-05-03 | Conductive coatings |
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EP (1) | EP0686662B2 (en) |
JP (1) | JP2916098B2 (en) |
AT (2) | ATE287929T1 (en) |
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JP6311355B2 (en) * | 2014-01-27 | 2018-04-18 | 東ソー株式会社 | Conductive polymer aqueous solution and conductive polymer film |
KR102348804B1 (en) | 2015-04-14 | 2022-01-10 | 주식회사 엘엠에스 | Novel compound and light-emitting diode containing the same |
KR102111576B1 (en) | 2015-08-20 | 2020-05-20 | 주식회사 엘엠에스 | Novel compound and light-emitting diode containing the same |
EP3477718A1 (en) | 2017-10-26 | 2019-05-01 | InnovationLab GmbH | Screen printable pedot containing printing paste for producing thermoelectric generators |
KR102174374B1 (en) * | 2018-02-21 | 2020-11-04 | 고려대학교 세종산학협력단 | A composition for an organic electroluminescent device, a hole injecting layer material produced therefrom and an organic electroluminescent device comprising the same |
EP3587506B1 (en) | 2018-06-28 | 2023-04-05 | Heraeus Deutschland GmbH & Co. KG | Liquid compositions comprising particles of a conductive polymer and an organic solvent forming an azeotrope with water |
US10790072B2 (en) * | 2018-08-01 | 2020-09-29 | Industrial Technology Research Institute | Conductive polymer composite material and capacitor |
EP4299647A1 (en) | 2022-06-30 | 2024-01-03 | Friedrich-Alexander-Universität Erlangen-Nürnberg | Method for producing doped organic nanoparticles, method for producing a functional layer, functional layer, and organic semiconductor device |
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JPS6411128A (en) * | 1987-07-03 | 1989-01-13 | Agency Ind Science Techn | 3,4-dialkoxythiophene polymer film |
DE3929691A1 (en) * | 1989-09-07 | 1991-03-14 | Hoechst Ag | ELECTROCHEMICAL METHOD FOR THE PRODUCTION OF ELECTRICALLY CONDUCTIVE POLY (ALKOXYTHIOPHENES) WITH THE ADDITION OF BROENSTED ACID |
DE59010247D1 (en) * | 1990-02-08 | 1996-05-02 | Bayer Ag | New polythiophene dispersions, their preparation and their use |
DE4211461A1 (en) * | 1992-04-06 | 1993-10-07 | Agfa Gevaert Ag | Antistatic plastic parts |
TW247319B (en) * | 1992-06-17 | 1995-05-11 | Japat Ltd |
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- 1995-04-24 AT AT01121781T patent/ATE287929T1/en active
- 1995-04-24 AT AT95106073T patent/ATE228545T1/en active
- 1995-04-24 EP EP95106073A patent/EP0686662B2/en not_active Expired - Lifetime
- 1995-05-01 JP JP7128804A patent/JP2916098B2/en not_active Expired - Fee Related
- 1995-05-03 CA CA002148544A patent/CA2148544C/en not_active Expired - Fee Related
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JP2916098B2 (en) | 1999-07-05 |
EP0686662A2 (en) | 1995-12-13 |
EP0686662B2 (en) | 2006-05-24 |
CA2148544A1 (en) | 1995-11-07 |
ATE287929T1 (en) | 2005-02-15 |
ATE228545T1 (en) | 2002-12-15 |
EP0686662A3 (en) | 1997-11-12 |
EP0686662B1 (en) | 2002-11-27 |
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