EP2547737A1 - Polycétones sulfonées en tant que contre-ion de polymères conducteurs - Google Patents

Polycétones sulfonées en tant que contre-ion de polymères conducteurs

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Publication number
EP2547737A1
EP2547737A1 EP11712468A EP11712468A EP2547737A1 EP 2547737 A1 EP2547737 A1 EP 2547737A1 EP 11712468 A EP11712468 A EP 11712468A EP 11712468 A EP11712468 A EP 11712468A EP 2547737 A1 EP2547737 A1 EP 2547737A1
Authority
EP
European Patent Office
Prior art keywords
optionally substituted
radical
recurring units
general formula
complex according
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.)
Withdrawn
Application number
EP11712468A
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German (de)
English (en)
Inventor
Knud Reuter
Wilfried LÖVENICH
Arnulf Scheel
Andreas Elschner
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Heraeus Deutschland GmbH and Co KG
Original Assignee
Heraeus Precious Metals GmbH and Co KG
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Filing date
Publication date
Application filed by Heraeus Precious Metals GmbH and Co KG filed Critical Heraeus Precious Metals GmbH and Co KG
Publication of EP2547737A1 publication Critical patent/EP2547737A1/fr
Withdrawn legal-status Critical Current

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    • 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
    • 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
    • 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
    • C09D165/00—Coating compositions based on macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Coating compositions based on derivatives of such polymers
    • 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
    • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C09D179/02—Polyamines
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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, LIGHT-SENSITIVE OR TEMPERATURE-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
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/14—Side-groups
    • C08G2261/145—Side-chains containing sulfur
    • C08G2261/1452—Side-chains containing sulfur containing sulfonyl or sulfonate-groups
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
    • C08G2261/3223—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/34—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain
    • C08G2261/344—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain containing heteroatoms
    • C08G2261/3442—Polyetherketones
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/50—Physical properties
    • C08G2261/51—Charge transport
    • C08G2261/512—Hole transport
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/70—Post-treatment
    • C08G2261/79—Post-treatment doping
    • C08G2261/794—Post-treatment doping with polymeric dopants
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/90—Applications
    • C08G2261/91—Photovoltaic applications
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers

Definitions

  • the invention relates to novel polyelectrolyte complexes comprising a functionalized polyke- tone and a conductive polymer, a process for the preparation of a complex, a complex obtainable by this process, the use of the complex, the use of sulphonated polyketones, a coated sub- strate, a process for the production of a coated substrate, the coated substrate obtainable by this process and an electronic component.
  • Conductive polymers are increasingly gaining economic importance, since polymers have advantages over metals with respect to processability, weight and targeted adjustment of proper- ties by chemical modification.
  • Examples of known ⁇ -conjugated polymers are polypyrroles, polythiophenes, polyanilines, polyacetylenes, polyphenylenes and poly(p-phenylene- vinylenes).
  • Layers of conductive polymers are employed in diverse industrial uses, e.g. as polymeric counter-electrodes in capacitors or for throughplating of electronic circuit boards.
  • the preparation of conductive polymers is carried out chemically or electrochemically by oxi- dation from monomelic precursors, such as e.g.
  • thiophenes optionally substituted thiophenes, pyrroles and anilines and the particular optionally oligomeric derivatives thereof.
  • chemically oxidative polymerization is widely used, since it is easy to realize industrially in a liquid medium or on diverse substrates.
  • a particularly important polythiophene which is used industrially is poly(ethylene-3,4- dioxythiophene) (PEDOT or PEDT), which is described, for example, in EP 0 339 340 A2 and is prepared by chemical polymerization of ethylene-3,4-dioxythiophene (EDOT or EDT), and which has very high conductivities in its oxidized form.
  • PEDOT or PEDT poly(ethylene-3,4- dioxythiophene)
  • EDOT or EDT ethylene-3,4-dioxythiophene
  • the dispersions disclosed for example in EP 0 440 957 A2, of PEDOT with polyanions, such as e.g. polystyrenesulphonic acid (PSS), have acquired particular industrial importance.
  • polyanions such as polystyrenesulphonic acid (PSS)
  • PSS polystyrenesulphonic acid
  • Transparent, conductive films which have found a large number of uses, e.g. as an antistatic coating or as a hole injection layer in organic light-emitting diodes (OLEDS), as shown in EP 1 227 529 A2, can be produced from these dispersions.
  • the polymerization of EDOT is carried out in an aqueous solution of the poly- anion, and a polyelectrolyte complex is formed.
  • Cationic polythiophenes which comprise polymeric anions as counter-ions for charge compensation are also often called polythio- phene/polyanion complexes in the technical field. Due to the polyelectrolyte properties of PEDOT as a polycation and PSS as a polyanion, this complex in this context is not a true solu- tion, but rather a dispersion. The extent to which polymers or parts of the polymers are dissolved or dispersed in this context depends on the weight ratio of the polycation and the polyanion, on the charge density of the polymers, on the salt concentration of the environment and on the nature of the surrounding medium (V. Kabanov, Russian Chemical Reviews 74, 2005, 3-20). The transitions in this context can be fluid.
  • complexes of conductive polymers and functionalized polyketones are suitable as polyanions for the production of transparent conductive films and these complexes are distinguished by a high stability. It has furthermore been found that such conductive films are suitable as a hole injection layer in OLEDs, the life of such OLEDs being particularly long if the pH of the dispersion is increased by addition of base(s).
  • the present invention thus provides a complex comprising at least one optionally substituted conductive polymer and at least one functionalized polyketone, characterized in that the poly- ketone is a polymer which comprises at least one (-CO-) group (keto group) in its recurring units and in these recurring units this (-CO-) group is linked with two aromatic groups.
  • the functionalized poly- ketone comprises recurring units of the general formula (I)
  • Aii and Ar 2 can be identical or different, and are optionally substituted radicals of aro- matics,
  • Ri is an optionally substituted organic radical with 1 to 80 carbon atoms, a
  • n is an integer from 5 to 5,000, preferably from 10 to 3,000, particularly preferably from 20 to 2,000.
  • aromatics are cyclic conjugated systems, preferably benzene, naphthalene, anthracene and biphenyl, particularly preferably benzene, it being possible for the abovementioned compounds to be optionally substituted.
  • an organic radical having 1 to 80 carbon atoms is preferably a radical which, for example, is composed of one or more groups chosen from the group consisting of ether, ketone, sulphone, sulphide, ester, carbonate, amide, imide and aromatic groups - in particular phenylene, biphenylene and naphthalene - as well as aliphatic groups, in particular methylene, ethylene, propylene and isopropylidene, it also being possible for individual groups to occur repeatedly in the radical.
  • the aromatic and aliphatic groups can additionally be substituted.
  • substituted here and in the following means substitution by a group chosen from the series consisting of an alkyl groups, preferably a CrC 20 -alkyl group, very particularly preferably a methyl group or an ethyl group, a cycloalkyl group, pref- erably a C3-C !2 -cycloalkyl group, an aryl group, preferably a C6-C
  • Ci-C 2 o-alkyl represents linear or branched d-C 2 o-alkyl radicals, such as, for example, methyl, ethyl, n- or iso-propyl, n-, iso-, sec- or tert-butyl, n-pentyl, 1-methylbutyl, 2- methylbutyl, 3-methylbutyl, 1-ethylpropyl, 1,1-dimethylpropyl, 1 ,2-dimethylpropyl, 2,2- dimethylpropyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n- dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl,
  • C 3 -Ci 2 -cycloalkyl represents cycloalkyl radicals, such as, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyc- lononyl or cyclodecyl
  • C -C 14 -aryl represents C 6 -C 14 -aryl radicals, such as phenyl or naphthyl.
  • the functionalized polyketones which are comprised in the complex according to the invention are preferably distinguished by a molecular weight (Mw) of from 5,000 to 500,000 g/mol, par- ticularly preferably from 10,000 to 100,000 g/mol and still more preferably from 20,000 to 50,000 g/mol.
  • Mw molecular weight
  • These functionalized polyketones can be prepared by essentially known processes (S. Swier, Y. S. Chun, J. Gasa, M. T. Shaw and R. A. Weiss, Polym. Engin. Sci. 2005, p. 1081-1091; S. Vetter, B. Ruffmann, I. Buder and S. P. Nunes, J. Membrane Sci. 260 (2005), 181-186; L. Li, J.
  • the functionalized poly- ketones comprise recurring units of the general formula (II)
  • the functionalization of the polyketones comprising recurring units of the formula (II) can occur on all or, however, only on some of the corresponding recurring units, i.e. non-integers for a and b mean - including in the following - that the functional group X] or X 2 mentioned does not occur in every recurring unit, but only in the corresponding fraction of the recurring units.
  • the functionalized polyketones comprise recurring units of the general formula (Ila), in which the aromatic Ai ⁇ and Ar 2 in each case represents a benzene ring:
  • M represents a metal cation or H, preferably Na, K, Li or H, particularly preferably H.
  • One or both of the benzene rings in the recurring unit of the formulae (II) and (Ila) can be optionally mono- or polysubstituted by substituents which differ from the S0 3 M group, it being possible in particular for methyl or ethyl groups to be present as substituents (not shown in the formulae (II) and (Ila)).
  • the functionalized polyketones comprise recurring units of the general formula (III), in which the recurring unit comprises three benzene rings which are bridged via a keto group and two ether groups, it being possible for each benzene ring to carry sulphonic acid groups:
  • M represents a metal cation or H, preferably Na, K, Li or H, particularly preferably H.
  • the sulphonated polyketones according to the general formula (III) are also called sulphonated polyether ether ketones (s-PEE ).
  • one or two or all three of the benzene rings in the recurring unit of the formula (III) can be optionally mono- or polysubstituted by substituents which differ from the S0 3 M group, it being possible in particular for methyl or ethyl groups to be present as substituents (not shown in the formula (III)).
  • the functionalized polyketones comprise recurring units of the general formula (IV), in which the recurring unit includes four benzene rings which are bridged by a keto group and three ether groups, it being possible for each benzene ring to carry sulphonic acid groups:
  • one or two, three or all four of the benzene rings in the recurring unit of the formula (IV) can be optionally mono- or polysubstituted by substituents which differ from the SO3M group, it being possible in particular for methyl or ethyl groups to be present as substituents (not shown in the formula (IV)).
  • the functionalized polyketones comprise recurring units of the general formula (V), in which the recurring unit comprises two benzene rings which are bridged by a keto group and ether group, it being possible for each benzene ring to carry sulphonic acid groups:
  • M represents a metal cation or H, preferably Na, K, Li or H, particularly preferably H.
  • the sulphonated polyketones according to the general formula (V) are also called sulphonated polyether ketones (s-PE ).
  • One or both of the benzene rings in the recurring unit of the formula (V) can be optionally mono- or polysubstituted by substituents which differ from the SO3M group, it being possible in particular for methyl or ethyl groups to be present as substituents (not shown in the formula (V)).
  • the functionalized polyketones comprise recurring units of the general formula (VI), in which the recurring unit includes three benzene rings, one of which can be bridged in the meta or para position with the two adjacent carbonyl substituents corresponding to that shown in formula (VI), it being possible for each benzene ring to carry sulphonic acid groups:
  • sulphonated polyketones according to the general formula (VI) are also called sulphonated polyether ketone ketones (s-PEKK).
  • one or two or all three of the benzene rings in the recurring unit of the formula (VI) can be optionally mono- or polysubstituted by substituents which differ from the S0 3 M group, it being possible in particular for methyl or ethyl groups to be present as substituents (not shown in the formula (VI)).
  • functionalized polyketones are also understood as meaning mixtures or copolycondensates of the functionalized polyketones described above.
  • the complex according to the invention comprises at least one optionally substituted conductive polymer as a polycation.
  • conductive polymers are, for example, optionally substituted polyanilines, optionally substituted polypyrroles and optionally substituted polythio- phenes.
  • the conductive polymers are optionally substituted polythiophenes comprising recurring units of the general formula (VII)
  • R4 and R5 independently of each other each represent H, an optionally substituted C - C 18 -alkyl radical or an optionally substituted CpQs-alkoxy radical, R4 and R 5 together represent an optionally substituted Q-C 8 -alkylene radical, wherein one or more C atom(s) can be replaced by one or more identical or different hetero atoms chosen from O or S, preferably a Ci-C 8 -dioxyalkylene radical, an optionally substituted Cj-Cs-oxythiaalkylene radical or an option- ally substituted Ci-Cs-dithiaalkylene radical, or represent an optionally substituted Ci-C8-alkylidene radical, wherein optionally at least one C atom is replaced by a hetero atom chosen from O or S.
  • these are those polythiophenes comprising recurring units of the general formula (Vll-a) and/or (Vll-b)
  • A represents an optionally substituted CrC 5 -alkylene radical, preferably an optionally substituted C 2 -C 3 -alkylene radical,
  • Y represents O or S
  • R $ represents a linear or branched, optionally substituted Q-Cis-alkyl radical, preferably linear or branched, optionally substituted Q-Cn-alkyl radical, an optionally substituted Cs-Cn-cycloalkyl radical, an optionally substituted C 6 - Cn-aryl radical, an optionally substituted C 7 -C 18 -aralkyl radical, an optionally substituted CrQs-alkaryl radical, an optionally substituted C]-C4- hydroxyalkyl radical or a hydroxyl radical, and
  • y represents an integer from 0 to 8, preferably 0, 1 or 2, particularly preferably
  • polythiophenes comprising recurring units of the general formula (VII) are those comprising recurring units of the general formula (Vll-aa) and/or of the general formula (Vll-ab)
  • polythiophenes comprising recurring units of the general formula (VII) are those comprising recurring units of the general formula (Vll-aaa) and/or of the general formula (VII-aba)
  • poly- is to be understood as meaning that the polythiophene comprises more than one identical or different recurring unit.
  • the polyfhio- phenes comprise n recurring units of the general formula (VII) in total, wherein n can be an integer from 2 to 2,000, preferably 2 to 100.
  • the recurring units of the general formula (VII) can in each case be identical or different within one polythiophene.
  • Polythiophenes comprising in each case identical recurring units of the general formula (VII) are preferred.
  • the polythiophenes preferably carry H on each of the end groups.
  • the polythiophene with recurring units of the general formula (VII) is a copolymer of recurring units of the formula (VII-aaa) and (Vll-aba), (Vll-aaa) and (Vll-b), (Vll-aba) and (Vll-b) or (Vll-aaa), (Vll-aba) and (Vll-b), copolymers of recurring units of the formula (VII-aa) and (Vll-aba) as well as (VII-aaa) and (Vll-b) being preferred.
  • Ci-C 5 -alkylene radicals A are preferably methylene, ethylene, n-propylene, n-butylene or n-pentylene, and C]-C 8 -alkylene radicals moreover are n-hexylene, n-heptylene and n-octylene.
  • Ci-Cs-alkylidene radicals are preferably abovementioned Q-Q-alkylene radicals comprising at least one double bond.
  • CpQ-dioxyalkylene radicals, CrQ-oxyfhiaalkylene radicals and C ⁇ - C 8 -dithiaalkylene radicals preferably represent the Q-Q-dioxyalkylene radicals, Q-C 8 - oxythiaalkylene radicals and Cj-Q-dithiaalkylene radicals corresponding to the abovementioned CrC 8 -alkylene radicals.
  • Q-Qs-Alkyl, C]-Ci4-alkyl and C 5 -Ci 2 -cycloalkyl represent the corresponding selection from the Q-Cao-alkyl and C3-C 12 -cycloalkyl radicals mentioned in connection with the substituents of the groups Arj, Ar 2 and R ⁇ in the formula (I).
  • Ci-C 1 -alkoxy radicals represent the alkoxy radicals corresponding to the abovementioned Ci-Cjs-alkyl radicals
  • C 6 -Ci 4 -aryl has the meaning given in connection with the substituents of the groups Ai ⁇ , Ar 2 and R] in the formula (I).
  • C 7 -Ci 8 -aralkyl preferably represents C7-Ci 8 -aralkyl radicals, such as, for example, benzyl, or alkylbenzyl radicals, such as o-, rn-, p-methylbenzyl, C 7 -Ci 8 -aralkyl repre- sents 0-, m-, p-tolyl, 2,3-, 2,4-, 2,5-, 2,6-, 3,4-, 3,5-xylyl or mesityl, and in the context of the invention C 1 -C 4 -hydroxyalkyl is preferably understood as meaning a Ci-C 4 -alkyl radical which comprises a hydroxyl group as a substituent, and wherein the Ci-C 4 -alkyl radical can represent, for example, methyl, ethyl, n- or iso-propyl, n-, iso-, sec- or tert-butyl.
  • the optionally substituted polythiophenes are cationic, "cationic” relating only to the charges on the polythiophene main chain.
  • the polythiophenes can carry positive and negative charges in the structural unit, depending on the substituent on the radicals R4 and R5, the positive charges being on the polythiophene main chain and the negative charges optionally being on the radicals R substituted by sulphonate or carboxylate groups.
  • the positive charges of the polythiophene main chain can be partly or completely satisfied by the anionic groups optionally present on the radicals R. Overall, in these cases the polythiophenes can be cationic, neutral or even anionic.
  • the positive charges on the polythiophene main chain are decisive.
  • the positive charges are not shown in the formulae, since they are mesomerically delocalized. However, the number of positive charges is at least 1 and at most n, wherein n is the total number of all recurring units (identical or different) within the polythiophene.
  • the cationic polythiophenes require anions as counter-ions, in the context of the invention this role being at least partly assumed by the functionalized polyketones.
  • the polythiophene with recurring units of the general formula (VII) is poly(3,4- ethylenedioxythiophene), poly(3,4-ethylenoxythiathiophene) or poly(thieno[3,4-b]thiophene), very particularly preferably poly(3,4-ethylenedioxythiophene), and the polyketone is a sulpho- nated polyketone with recurring units of the formula (II), very particularly preferably a sul- phonated polyether ether ketone with recurring units of the formula (III), a sulphonated poly- ketone with recurring units according to the formula (IV), a sulphonated polyether ketone with recurring units of the formula (V) or a sulphonated polyether ketone ketone with recurring units according to the formula (VI).
  • the polyketone is a sulpho- nated polyketone with recurring units of the formula (II), very particularly preferably
  • the complex according to the inven- tion described above prefferably be dissolved or dispersed in one or more solvents or dispersing agents and therefore to be present in the form of a solution or dispersion.
  • the solids content of conductive polymer, in particular of an optionally substituted polythio- phene comprising recurring units of the general formula (VII), in the dispersion or solution is preferably between 0.05 and 20.0 per cent by weight (wt.%), particularly preferably between 0.1 and 5.0 wt.% and most preferably between 0.3 and 4.0 wt.%, in each case based on the total weight of the solution or dispersion.
  • Solvents and dispersing agents which may be mentioned are, for example, the following liq- uids: aliphatic alcohols, such as methanol, ethanol, i-propanol and butanol; aliphatic ketones, such as acetone and methyl ethyl ketone; aliphatic carboxylic acid esters, such as ethyl acetate and butyl acetate; aromatic hydrocarbons, such as toluene and xylene; aliphatic hydrocarbons, such as hexane, heptane and cyclohexane; chlorohydrocarbons, such as methylene chloride, chloroform and 1 ,2-dichloroethane; aliphatic nitriles, such as acetonitrile; aliphatic sulphoxides and sulphones, such as dimethyl sulphoxide and sulpholane; aliphatic carboxylic acid amides
  • Water or a mixture of water with the abovementioned organic solvents can furthermore also be used as a solvent or dispersing agent.
  • Preferred solvents or dispersing agents are water or other protic solvents, such as alcohols, e.g. methanol, ethanol, i-propanol and butanol, and mixtures of water with these alcohols, water being particularly preferred as the solvent or dispersing agent.
  • the total content of the complex according to the invention i.e.
  • the conductive polymer in particular of the optionally substituted polythiophenes comprising recurring units of the general formula (VII), and of the functionalized polyketone in the solution or in the dispersion is, for example, between 0.05 and 10 wt.%, preferably between 0.1 and 5 wt.%, in each case based on the total weight of the solution or dispersion.
  • the solution or dispersion can comprise the conductive polymer, in particular the optionally substituted polythiophene comprising recurring units of the general formula (VII), and the functionalized polyketone in a weight ratio in a range of from 1 : 0.3 to 1 : 100, preferably in a range of from 1 : 1 to 1 : 40, particularly preferably in a range of from 1 : 2 to 1 : 20 and ex- tremely preferably in a range of from 1 : 2 to 1 : 15.
  • the weight of the conductive polymer here approximately corresponds to the weight of the monomers employed, assuming that complete conversion takes place during the polymerization.
  • the preparation of the abovementioned solution or dispersion is carried out by first preparing from the corresponding precursors for the preparation of conductive polymers solutions or dispersions of electrically conductive polymers in the presence of counter-ions, preferably in the presence of the functionalized polyketones described above, for example analogously to the conditions mentioned in EP 0 440 957 A2.
  • An improved variant for the preparation of this solution or dispersion is the use of ion exchangers for removal of the inorganic salt content or of a part thereof. Such a variant is described, for example, in DE 196 27 071 Al .
  • the ion exchanger can be stirred with the product, for example, or the product is conveyed over a column filled with ion exchanger.
  • Low metal contents can be achieved by using the ion exchanger.
  • the size of the particles in the dispersion can be reduced after the desalination, for example by means of a high pressure homogenizer. This operation can also be repeated in order to increase the effect. Particularly high pressures of between 100 and 2,000 bar have proved to be particularly advantageous here for greatly reducing the particle size.
  • the particle size can also be reduced by ultrasound treatment.
  • derivatives of the thiophenes described above are understood as meaning, for example, dimers or trimers of these thiophenes.
  • Higher molecular weight derivatives, i.e. tetramers, pentamers etc., of the monomelic precursors are also possible as derivatives.
  • the derivatives can be built up from either identical or different monomer units and can be employed in the pure form and in a mixture with one another and/or with the abovemen- tioned thiophenes.
  • oxidized or reduced forms of these thiophenes and thiophene derivatives are also included in the term "thiophenes" and "thiophene derivatives" as long as the same conductive polymers are formed in their polymerization as in the case of the abovementioned thiophenes and thiophene derivatives.
  • Very particularly preferred monomelic precursors are optionally substituted 3,4- ethylenedioxythiophenes, and in a preferred embodiment unsubstituted 3,4- ethylenedioxythiophene.
  • the solution or dispersion can comprise further polymers in addition to the complex of conductive polymer and functionalized polyketone, for example polystyrenesulphonic acid, fiuori- nated or perfluorinated sulphonic acids, polyvinyl alcohols, polyvinylpyrrolidones, polyvinyl chlorides, polyvinyl acetates, polyvinyl butyrates, polyacrylic acid esters, polyacrylic acid amides, polymethacrylic acid esters, polymethacrylic acid amides, polyacrylonitriles, sty- rene/acrylic acid ester, vinyl acetate/acrylic acid ester and ethyl ene/vinyl acetate copolymers, polyethers, polyesters, polyurethane
  • the solution or dispersion can moreover comprise further components, such as surface-active substances, e.g. ionic and nonionic surfactants, or adhesion promoters, such as e.g. organo- functional silanes or hydrolysates thereof, e.g. 3-glycidoxypropyltrialkoxysilane, 3- aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3- methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane or octyltriethoxysilane.
  • surface-active substances e.g. ionic and nonionic surfactants
  • adhesion promoters such as e.g. organo- functional silanes or hydrolysates thereof, e.g. 3-glycidoxypropyltrialkoxysilane, 3- aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3- me
  • the solution or dispersion can furthermore have a pH in the range of from 1 to 8, preferably in the range of from 2 to 7, particularly preferably in the range of from 4 to 7.
  • Bases for example, such as amines, ammonium hydroxides or metal hydroxides, preferably ammonia or alkali metal hydroxides, can be added to the dispersions to adjust the corresponding pH.
  • the pH is determined here at 25 °C with the aid of a pH electrode (Knick Labor pH-meter 766).
  • the present invention thus also relates to a process for the preparation of complexes from electrically conductive polymers, preferably from electrically conductive polythiophenes comprising recurring units of the general formula (VII) and functionalized, preferably sulphonated polyketones, particularly preferably sulphonated polyketones with recurring units of the structure (III), (IV), (V) or (VI), in which precursors for the preparation of the conductive polymers, preferably optionally substituted 3,4-ethylenedioxythiophenes, very particularly preferably 3,4-ethylenedioxythiophene, are polymerized in the presence of the sulphonated polyketones.
  • the complexes according to the invention are surprisingly suitable for the production of hole- injecting or hole-transporting layers in OLEDs or organic solar cells (OSCs), or for the production of transparent conductive coatings.
  • the present invention thus also provides the use of the complexes according to the invention for the production of transparent conductive coatings or for the production of hole injection layers or hole transport layers in organic light-emitting diodes (OLEDs) or organic solar cells (OSCs).
  • OLEDs organic light-emitting diodes
  • OSCs organic solar cells
  • the abovementioned solutions or disper- sions are applied, for example, by known processes, e.g. by spin coating, impregnation, pouring, dripping on, spraying, misting, knife coating, brushing or printing, for example by ink-jet, screen, gravure, offset or tampon printing, to a suitable substrate in a wet film thickness of from 0.5 ⁇ to 250 ⁇ , preferably in a wet film thickness of from 2 ⁇ to 50 ⁇ , and are then dried at a temperature of at least from 20 °C to 200 °C.
  • OLEDs Organic light-emitting diodes
  • OLEDs Organic light-emitting diodes
  • the construction and functioning of OLEDs is known to the person skilled in the art and has been frequently described, such as e.g. in D. Hertel and . Meerholz, Chemie in j Zeit, 39 (2005), pages 336-347.
  • the complexes according to the invention can be employed as intermediate layers in these uses.
  • a transparent electrically conductive electrode such as e.g.
  • ITO indium tin oxide
  • a conductive polymer for example a conductive polymer comprising recurring units of the structure (VII)
  • PET poly( ethylene terephthalate)
  • the complexes according to the invention are deposited thereon as a thin layer.
  • organic functional layers are then applied thereto.
  • conjugated polymers such as polyphenylenevinylene or polyfluorenes, or layers of vapour-deposited molecules, such as are known to the person skilled in the art and such as are described e.g. by D. Hertel and K. Meerholz, Chemie in 102, 39 (2005), pages 336-347.
  • the OLED is finished by deposition of a final metal electrode, such as e.g. metallic barium or LiF//Al.
  • a final metal electrode such as e.g. metallic barium or LiF//Al.
  • a direct voltage of 2 - 20 V a current flows through the arrangement, and electroluminescence is generated in at least one of the functional layers.
  • the polymeric intermediate layer is highly transparent and allows efficient decoupling of light.
  • a polymeric intermediate layer smoothes the layer underneath. This means fewer short circuits in the finished processed OLED and therefore higher yields in component production.
  • the complexes according to the invention can also be used analogously for the production of organic solar cells (OSCs) and lead to similar advantages there.
  • OSCs organic solar cells
  • a voltage is generated by absorption of light at the electrodes.
  • the construction is known to the person skilled in the art and has frequently been described, such as e.g. in S. Sensfuss et al., Kunststoffe 8 (2007), page 136.
  • the present invention furthermore relates to the use of functionalized, preferably sulphonated polyketones, particularly preferably of sulphonated polyketones with recurring units of the structure (III), (IV), (V) or (VI), as a polyanion in complexes with electrically conductive polymers as a polycation, preferably with electrically conductive polymers with recurring units of the structure (VII).
  • the present invention furthermore relates to a coated substrate, on which a preferably transparent, conductive coating comprising the complex according to the invention is applied.
  • Possible substrates are, in particular, films, particularly preferably polymer films, very particularly preferably polymer films of thermoplastic polymers, or glass plates.
  • the present invention furthermore relates to a process for the production of a coated substrate, comprising the process steps: i) provision of a substrate;
  • a substrate is first provided, the substrate preferably being one of the abovementioned substrates.
  • this substrate is then coated with a composition comprising the complex according to the invention.
  • a composition comprising the complex according to the invention.
  • a solution or a dispersion comprising one or more solvents or dispersing agents and the complexes according to the invention to be applied to the substrate or to certain areas of the substrate and then for at least some of the solvent or dispersing agent to be evaporated, it being possible for this evaporation to be carried out, for example, by simple drying in air or optionally in an oven.
  • the present invention furthermore relates to a coated substrate obtainable by this process.
  • the present invention also relates to an electronic component comprising a coated substrate according to the invention or a coated substrate obtainable by the process according to the invention for the production of a coated substrate, this electronic component preferably being an organic light-emitting diode or an organic solar cell.
  • this electronic component preferably being an organic light-emitting diode or an organic solar cell.
  • the coating applied to the substrate can function in particular as a hole injection layer or hole transport layer.
  • the use of the complex according to the invention in other electronic components, such as, for example, capacitors, is also conceivable.
  • Example 1 Preparation of a dispersion from PEDOT and s-PEE 25.0 g of the polyether ether ketone Victrex ® PEEKTM 150 PF (supplier: Victrex Europa
  • Butanol was then distilled off on a rotary evaporator and replaced stepwise by water, the volume having been concentrated to approx. 1/3 at the end. 300 ml of methanol were added to this aqueous solution and the sodium sulphate which had precipitated out was filtered off. The filtrate was treated 3 x with ion exchanger (Lewatit MP 62 and Lewatit ® Monoplus S 100, supplier: Lanxess AG) to remove sulphate and sodium ions and was then evaporated to dryness and the residue was after-dried under 0.5 mbar. The yield was 23.6 g of s-PEEK. The degree of sulphonation per recurring unit of the polymer was 1.09 (determined by titration with 0.1 N sodium hydroxide solution), which corresponds to an equivalent weight of 286 g/mol.
  • a 1.5 1 glass vessel was equipped with a stirrer and a thermometer.
  • 1 ,338 g of water, 10 g of the sulphonated polyether ether ketone, 2.36 g of a 10 % strength solution of iron(III) sulphate in water and 1.91 g of ethylenedioxythiophene, EDT (Clevios M V2, H. C. Starck Clevios GmbH, Germany) were stirred thoroughly in the glass vessel at 25 °C for 15 min. Thereafter, 4.66 g of sodium peroxodi sulphate were added, and the mixture was stirred at 25 °C for 24 h.
  • Viscosity 2 mPas (Haake RV 1 , 20 °C, 700 s "1 )
  • Example 2 Production of layers based on the complex PEDOT/s-PEE
  • Example 1 The dispersion from Example 1 is concentrated to a solids content of 1.36 % on a rotary evaporator.
  • a cleaned glass substrate was laid on a lacquer whirler coater and 5 ml of the concentrated dispersion were distributed on the substrate. The excess dispersion was then spun off by rotating the plate at 500 revolutions/minute for 30 sec. Thereafter, the substrate coated in this way was dried on a hot-plate at 200 °C for 3 min.
  • the layer thickness was 65 nm (Tencor, Al- phastep 500).
  • the conductivity was determined by vapour deposition of Ag electrodes of 2.5 cm length at a distance of 0.5 mm via a shadow mask.
  • the surface resistance determined with an electrometer was multiplied by the layer thickness in order to obtain the specific resistance.
  • the specific resistance of the layer was 1,760 Ohm-cm.
  • the layer was transparent.
  • Comparison Example 1 Storage of a conventional dispersion at elevated temperature
  • PEDOT PSS dispersion (Clevios ® P VP AI 4083, H.C. Starck Clevios GmbH) with the following properties was employed for a reference experiment: Solids content 1 .6 %
  • Example 3 shows that the dispersion according to the invention from Example 1 splits off no sulphate at elevated temperature, in contrast to the known PEDOT : PSS complex.
  • the dispersion according to the invention from Example 1 was used for construction of organic light-emitting diodes (OLED).
  • OLED organic light-emitting diodes
  • ITO-coated glass was cut into pieces 50 mm x 50 mm in size (substrates) and was structured with photolacquer to four parallel lines - each 2 mm in width and 5 cm in length. Thereafter, the substrates were cleaned in 0.3 % strength Mucasol solution in an ultrasound bath, rinsed with distilled water and spin-dried in a centrifuge. Immediately before coating, the ITO-coated sides were cleaned for 10 min in a UV/ozone reactor (PR- 100, UVP Inc., Cambridge, GB).
  • PR- 100 UV/ozone reactor
  • Example 2 About 5 ml of the dispersion according to the invention from Example 1 were filtered (Milli- pore HV, 0.45 ⁇ ). The cleaned ITO-coated substrate was laid on a lacquer whirler coater and the filtered solution was distributed on the ITO-coated side of the substrate. The excess solution was then spun off by rotating the plate at 600 rpm over a period of 30 sec. Thereafter, the substrate coated in this way was dried on a hot-plate at 200 °C for 5 min. The layer thickness was approx. 50 ran, measured with a profilometer (Tencor, Alphastep 500).
  • the ITO substrates coated with the dispersion from Example 1 were transferred into a vapour deposition unit (Univex 350, Leybold). Under a pressure of 10 ⁇ 3 Pa, first 60 nm of a hole transport layer of NPB (N,N'-bis(naphthalen-l-yl)-N,N'-bis(phenyl)benzidine) and then 50 nm of an emitter layer of A1Q 3 (tris-(8-hydroxyquinoline)aluminium) were vapour-deposited in succession at a vapour deposition rate of 1 A/sec.
  • NPB N,N'-bis(naphthalen-l-yl)-N,N'-bis(phenyl)benzidine
  • A1Q 3 tris-(8-hydroxyquinoline)aluminium
  • the layer system was then transferred into a glove box with an N 2 atmosphere and an inte- grated vapour deposition unit (Edwards), and metal electrodes were vapour-deposited.
  • the substrate was laid on a shadow mask with the layer system downwards.
  • the shadow mask comprised rectangular slots of 2 mm width which intersected the ITO strips and were orientated perpendicular to these.
  • the vapour deposition rates were 1 A/s for LiF and 10 A/s for Al.
  • the area of the individual OLEDs was 4.0 mm 2 .
  • Example 5 The procedure is as in Example 5, with the difference that in the 2nd process step the intermediate layer used was not the dispersion according to the invention from Example [sic], but the Clevios ® P VP AI 4083 (H.C. Starck Clevios GmbH) often used as the standard in OLED construction.
  • AI 4083 was filtered, whirler coated on at 700 rpm for 30 sec and then dried on a hot-plate at 200 °C for 5 min.
  • the layer thickness was 50 nm, the spec, resistance was 1,290 Ohm-cm.
  • Comparison Example 3 Production of an OLED without a polymeric intermediate layer
  • Example 5 Comparison of the OLEDs from Example 4 and Comparison Example 2 and 3
  • Example 4 In order to demonstrate the improvement of the OLEDs comprising the dispersion according to the invention from Example 1 compared with the standard material Clevios P VP AI 4083, in each case 1 substrate from Example 4 and Comparison Example 2 and 3 were processed in parallel, i.e. the vapour deposition layers and cathodes were deposited on all the substrates under identical conditions.
  • the OLEDs produced in accordance with Example 4 and Comparison 2 showed the typical diode properties of organic light-emitting diodes.
  • the constructions produced in accordance with Comparison Example 3 all showed electrical short circuits.
  • Example 6 Determination of the contact angle employing a dispersion according to the invention Analogously to Example 4, point 2, layers of the dispersion according to the invention from Example 1 were deposited on glass substrates with the aid of a lacquer whirler coater and were dried on a hot-plate at 200 °C for 5 min. The contact angle of a drop of toluene deposited on the layer with the layer was then determined (Kriiss MicroDrop). The wetting was so good that the contact angle was ⁇ 3° and therefore was not measurable.
  • Comparison Example 4 Determination of the contact angle employing a conventional dispersion
  • Example 6 Analogously to Example 6, the contact angle of a layer of the reference material Clevios P VP AI 4083 with toluene was determined. The wetting was so good that the contact angle was ⁇ 3° and therefore was not measurable.
  • Comparison Example 5 Determination of the contact angle employing a conventional dispersion based on perfluorinated sulphonic acid polymers
  • Example 7 Preparation of a dispersion from PEDOT and s-PEKK
  • the butanol phases were then combined, 20 ml of 30 % strength sodium hydroxide solution was added and the mixture was then adjusted further to a pH of 6.3 with 30 % strength sodium hydroxide solution.
  • the aqueous phase was concentrated to 100 ml and 250 ml of methanol were added. The supernatant solution was decanted off from the so- dium sulphate which had precipitated out and was evaporated.
  • the residue was dissolved in 200 ml of water and the solution was treated 3 x with ion exchanger (Lewatit MP ® 62 and Lewatit ® Monoplus S 100, supplier: Lanxess AG) to remove sulphate and sodium ions and was then evaporated to dryness and the residue was after-dried under 0.5 mbar.
  • the yield was 17 g of s-PEKK with a degree of sulphonation per recurring unit of the polymer of 0.97, detennined by titration with 0.1 N sodium hydroxide solution, corresponding to an equivalent weight of 389 g/mol.
  • Example 8 Organic solar cell comprising a formulation according to the invention
  • the formulation according to the invention from Example 1 is used for construction of an organic solar cell (OSC).
  • OSC organic solar cell
  • ITO-coated glass (Merck Balzers AG, FL, part no. 253 674 XO) is cut into pieces 25 mm x 25 mm in size (substrates). The substrates are then cleaned in 3 % strength Mucasol solution in an ultrasound bath for 15 min. Thereafter, the substrates are rinsed with distilled water and spin- dried in a centrifuge. Immediately before coating, the lTO-coated sides are cleaned for 10 min in a UV/ozone reactor (PR- 100, UVP Inc., Cambridge, GB).
  • PR- 100 UV/ozone reactor
  • Example 2 About 1 ml of the formulation according to the invention from Example 1 are filtered (MiUipore HV, 0.45 ⁇ ). The cleaned lTO-coated substrate is laid on a lacquer whirler coater and the filtered solution is distributed on the ITO-coated side of the substrate. The excess solution is then spun off by rotating the plate at 500 rpm over a period of 30 s. Thereafter, the substrate coated in this way is dried on a hot-plate at 200 °C for 5 min. The layer thickness is about 50 nm (Tencor, Alphastep 500).
  • the substrate coated in this way is dried on a hot-plate at 130 °C for 10 min.
  • the layer thickness is 100 nm (Tencor, Alphastep 500). This work and all the following work is carried out in a glove box system in a pure nitrogen atmosphere. 4. Application of the metal cathode
  • Metal electrodes are vapour-deposited as cathodes on the substrate with the layer system ITO//HEL//LAL.
  • a vacuum apparatus (Edwards) equipped with two thermal vaporizers is used for this.
  • the layer system is covered with a shadow mask which has holes of 2.5 mm and 5 mm diameter.
  • the substrate is laid on the rotating sample holder with the mounted shadow mask downwards. The dimensions of the sample holder are such that four substrates can be accommodated at the same time.
  • the vapour deposition rates are 10 A/s for Ba [sic] and 20 A/s for Ag.
  • the metal electrodes isolated have an area of 4.9 mm 2 and 28 mm 2 respectively.
  • the OSC is likewise characterized in the glove box system filled only with nitrogen, in the base of which is inserted a solar simulator (Atlas, Solar Celltest 575) and the homogeneous light of which is directed upwards.
  • a holder with the OSC is located in the cone of light.
  • the distance from the sample plane to the base is about 10 cm.
  • the light intensity can be attenuated with inserted grating filters.
  • the intensity at the sample plane is determined with a pyranome- ter (Kipp & Zonen, CM10) and is about 500 W/m .
  • the temperature of the sample holder is determined with a heat sensor (PT100) and is max. 40 °C.
  • the OSC is contacted electrically by connecting the ITO electrode to an Au contact pin (+ pole) and pressing a thin flexible Au wire on to one of the metal electrodes (- pole). Both contacts are connected via a cable to a current/voltage source (Keithley 2800). The light source is first covered and the dark characteristic line is measured. For this, a voltage is applied to the sample and varied in the range of from -2 to +2 V and the current is recorded. The current/voltage characteristic line is then plotted analogously under illumination. From these data, the parameters relevant to the solar cell, such as conversion efficiency, open circuit voltage, short circuit current and fill factor, are determined in accordance with ONORM EN 60904-3.
  • Example 9 OSC reference cell without an HEL
  • Example 10 OSC reference cell with an alternative HEL
  • Example 8 The construction of a reference cell without an HEL is carried out analogously to Example 8, with the difference that in process step 2 an alternative material, namely Clevios P AI4083 (H.C. Starck Clevios GmbH, Leverkusen), is used instead of the formulation according to the invention.
  • the conditions in process step 2 are: About 1 ml of the solution of Clevios ® P AI4083 is filtered (Millipore HV, 0.45 ⁇ ). The cleaned ITO-coated substrate is laid on a lacquer whirler coater and the filtered solution is distributed on the ITO-coated side of the substrate. The excess solution is then spun off by rotating the plate at 750 rpm over a period of 30 s. Thereafter, the substrate coated in this way is dried on a hot-plate at 200 °C for 5 min. The layer thickness is about 50 nm (Tencor, Alphastep 500).
  • Example 11 Comparison of the results from Example 8 - 10:
  • the current/voltage characteristic lines of the OSCs from Example 1 - 3 were plotted under the same experimental conditions.
  • the parameters relevant to the evaluation are extracted; cell area (A), irradiance (P0), short circuit current (Isc), open circuit voltage (Voc), electrical output at the working point (P m ax), fill factor (FF) and conversion efficiency
  • the formulation according to the invention is particu- larly suitable as an intermediate layer for OSCs and improves the resistance of the arrange- ments to short circuits.
  • the comparison with the reference Clevios P AI4083 shows that in principle similar OSC properties are achieved, the open circuit voltage and the fill factor being improved.
  • a further advantage of the formulation according to the invention compared with Clevios P AI4083 is that the material has a higher heat stability, and as expected this leads to longer OSC lives.

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Abstract

La présente invention concerne un complexe comportant au moins un polymère conducteur éventuellement substitué et au moins une polycétone fonctionnalisée, caractérisé en ce que la polycétone est un polymère comportant un groupe (-CO-) dans ses unités de répétition et dans lequel le groupe (-CO-) est lié à deux groupes aromatiques. La présente invention concerne également un procédé pour la préparation d'un complexe, un complexe capable d'être obtenu par ce procédé, l'utilisation du complexe, l'utilisation de polycétones sulfonées, un substrat revêtu, un procédé pour la production d'un substrat revêtu, le substrat revêtu capable d'être obtenu par ce procédé et un composant électronique.
EP11712468A 2010-03-19 2011-03-18 Polycétones sulfonées en tant que contre-ion de polymères conducteurs Withdrawn EP2547737A1 (fr)

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US33161910P 2010-05-05 2010-05-05
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CN105489264B (zh) * 2015-12-08 2017-08-29 李烈熊 一种复合聚苯胺导电材料及其制备方法
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JP2013522401A (ja) 2013-06-13
CN102892850A (zh) 2013-01-23
TW201139506A (en) 2011-11-16
KR20130018436A (ko) 2013-02-22
DE102010012180A1 (de) 2011-09-22

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