EP2547737A1 - Sulphonated polyketones as a counter-ion of conductive polymers - Google Patents

Abstract

The present invention relates to a complex comprising at least one optionally substituted conductive polymer and at least one functionalized polyketone, characterized in that the polyke- tone is a polymer which comprises a (-CO-) group in its recurring units and in which this (- CO-) group is linked with two aromatic groups. The present invention also relates to 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 substrate, a process for the production of a coated substrate, the coated substrate obtainable by this process and an electronic component.

Description

SULPHONATED POLYKETONES AS A COUNTER-ION OF CONDUCTIVE POLYMERS

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 π-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. optionally substituted thiophenes, pyrroles and anilines and the particular optionally oligomeric derivatives thereof. In particular, 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. An overview of numerous poly(alkylene-3,4-dioxythiophene) derivatives, in particular poly(ethylene-3,4- dioxythiophene) derivatives and their monomer units, syntheses and uses is given by L. Groenendaal, F. Jonas, D. Freitag, H. Pielartzik & J. R. Reynolds, Adv. Mater. 12, (2000) p. 481-^94.

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. 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. In this context, 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. No distinction is therefore made in the fol- lowing between the terms "dispersed" and "dissolved". Similarly little distinction is made between "dispersing" and "solution" or between "dispersing agent" and "solvent". Rather, these terms are used as being equivalent in the following.

Complexes of PEDOT and PSS have found a diversity of uses, as described above. Neverthe- less, these complexes are distinguished by an intrinsic high acidity. This is based on the high acidity of PSS. The equivalent weight of PSS is 184 g/mol. The pH of PEDOT : PSS dispersions is correspondingly low. A typical PEDOT : PSS dispersion which is used as a hole injection layer in OLEDs thus has a pH of 1.5. This low pH can lead, for example, to etching of the transparent electrode of indium tin oxide (ITO) in OLEDs. As a result, In and Sn ions are mo- bilized and can diffuse into adjacent layers (M. P. de Jong et al., Appl. Phys. Lett. 77, (2000), 2255-2257) and therefore have an adverse effect on the life of the OLEDs. Si-Jeon Kim et al, Chem. Phys. Lett. 386, (2004), 2-7 and Jaengwan Chung et al, Organic Electronics 9, (2009), 869-872 have reported that PSS decomposes thermally and thereby splits off sulphate, i.e. PSS is not stable. This sulphate can, for example, have an adverse effect on the life in OLEDs.

In EP 1 564 250 A1 and WO 2004/032306 A2, mixtures of perfluonnated sulphonic acid polymers with conductive polymers have been described by Elschner et al. as a hole injection layer in OLEDs. Using these mixtures for the production of hole injection layers in OLEDS, it has been possible to demonstrate that the presence of the fluorinated polymer leads to an improvement in the lives of the OLED. Layers which comprise fluorinated polymers, however, are distinguished by a high contact angle. This makes it difficult to deposit further solvent- based layers, since the high contact angle makes film formation difficult. There was thus a need for novel complexes comprising conductive polymers and polyanions. In particular, there was a need for complexes in which the polyanions are distinguished by a lower acidity compared with PSS and an increased stability. There was furthermore a need for complexes which are suitable for the production of hole injection layers for OLEDs, the layers being distinguished by a low contact angle and the OLEDs being distinguished by long lives.

It has now been found, surprisingly, that 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. In a preferred embodiment of the complex according to the invention, the functionalized poly- ketone comprises recurring units of the general formula (I)

(I),

wherein

Aii and Ar₂ 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

(-CO-) group or an oxygen atom and

n is an integer from 5 to 5,000, preferably from 10 to 3,000, particularly preferably from 20 to 2,000. In the context of the invention, 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.

Furthermore, in the context of the invention 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.

Unless expressly mentioned otherwise, "substituted" here and in the following means substitution by a group chosen from the series consisting of an alkyl groups, preferably a CrC₂₀-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|₄-aryl group, a halogen atom, preferably CI, Br or I, an ether group, a thioether group, a disulphide group, a sulphoxide group, a sulphone group, a sulphonate group, an amino group, an aldehyde group, a keto group, a carboxylic acid ester group, a carboxylic acid group, a carbonate group, a carboxylate group, a phosphonic acid group, a phosphonate group, a cyano group, an alkylsilane group, an alkoxysilane group and a carboxylamide group.

The term "Ci-C₂o-alkyl" represents linear or branched d-C₂o-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, n-heptadecyl, n-octadecyl, n- nonadecyl or n-eicosyl. The term "C₃-Ci₂-cycloalkyl" represents cycloalkyl radicals, such as, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyc- lononyl or cyclodecyl, and the term "C -C₁₄-aryl" represents C₆-C₁₄-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. 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. Zhang and Y. Wang, J. Membrane Sci. 226 (2003), 159-167; B. Bauer, D. J. Jones, J. Roziere, L. Tchicaya, G. Alberti, M. Casciola, L. Massinelli, A. Peraio, S. Besse and E. Ramunni, J. New Mater. Electrochem. Systems, 3, 93-98 (2000); F. Trotta, E. Drioli, G. Moraglio and E. B. Poma, J. Appl. Polym. Sci. 70, 477-482 (1998); S. M. J. Zaidi, S. D. Mik- hailenko, G. P. Robertson, M. D. Guiver and S. Kaliaguine, J. Membrane Sci. 173 (2000), 17- 34; C. Bailly, D. J. Williams, F. E. Kharasz and W. J. MacKnight, Polymer 1987 (28), 1009- 1016; X. Jin, M. T. Bishop, T. S. Ellis and F. E. Kharasz, Br. Polymer J. 17(1), 4-10 (1985)) In a preferred embodiment of the complex according to the invention, the functionalized poly- ketones comprise recurring units of the general formula (II)

wherein can be identical or different, and represent an optionally substituted aromatic, can be identical or different and each represent a sulphonic acid, sulphonate, phosphonic acid, phosphonate, carboxylic acid or carboxylate group, can be identical or different, and each independently of each other represent an integer or non-integer in a range of from 0 to 2, non-integers meaning that the acid mentioned does not occur in every recurring unit, but only in the corresponding fraction of the recurring units,

has the same meaning as Rj, and

is an integer from 5 to 5,000, preferably from 10 to 3,000, particularly preferably from 20 to 2,000. 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 X₂ mentioned does not occur in every recurring unit, but only in the corresponding fraction of the recurring units.

Very particularly preferably, the functionalized polyketones are sulphonated polyketones (Xi and X₂ = sulphonic acid or sulphonate group), the preparation of which is described, for example, by Schuster et al. (Macromolecules 2009, 42(8), p. 3129-3137). In a very particularly preferred embodiment of the complex according to the invention, the functionalized polyketones comprise recurring units of the general formula (Ila), in which the aromatic Ai_\ and Ar₂ in each case represents a benzene ring:

(Ila), wherein a, b and R₂ have the meaning given for the general formula (II), and

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 S0₃M group, it being possible in particular for methyl or ethyl groups to be present as substituents (not shown in the formulae (II) and (Ila)). In a further very particularly preferred embodiment of the complex according to the invention, 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:

(HI), wherein c has the same meaning as a and b and

a and b have the meaning given for the general formula (II),

M represents a metal cation or H, preferably Na, K, Li or H, particularly preferably H.

In the context of the invention, the sulphonated polyketones according to the general formula (III) are also called sulphonated polyether ether ketones (s-PEE ).

Here also, 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 S0₃M group, it being possible in particular for methyl or ethyl groups to be present as substituents (not shown in the formula (III)).

In a further very particularly preferred embodiment of the complex according to the invention, 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:

(IV), wherein has the same meaning as a, b and c and

a, b, c and M have the meaning given for the general formula (II) or (III).

Here also, 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)).

In yet a further very particularly preferred embodiment of the complex according to the inven- tion, 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:

(V),

have the meaning given for the general formula (II) and M represents a metal cation or H, preferably Na, K, Li or H, particularly preferably H.

In the context of the present invention, 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)).

In a further very particularly preferred embodiment of the complex according to the invention, 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:

(VI), and wherein a, b, c and M have the meaning given for the general formula (II) or (III).

In the context of the present invention, the sulphonated polyketones according to the general formula (VI) are also called sulphonated polyether ketone ketones (s-PEKK).

Here also, 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 S0₃M group, it being possible in particular for methyl or ethyl groups to be present as substituents (not shown in the formula (VI)).

In the context of the invention, functionalized polyketones are also understood as meaning mixtures or copolycondensates of the functionalized polyketones described above.

In addition to the functionalized polyketones described above which are present as a polyan- ion, the complex according to the invention comprises at least one optionally substituted conductive polymer as a polycation. Such conductive polymers are, for example, optionally substituted polyanilines, optionally substituted polypyrroles and optionally substituted polythio- phenes.

In a preferred embodiment of the complex according to the invention, the conductive polymers are optionally substituted polythiophenes comprising recurring units of the general formula (VII)

(VII) wherein

R4 and R5 independently of each other each represent H, an optionally substituted C - C₁₈-alkyl radical or an optionally substituted CpQs-alkoxy radical, R4 and R₅ together represent an optionally substituted Q-C₈-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-C₈-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.

Particularly preferably, these are those polythiophenes comprising recurring units of the general formula (Vll-a) and/or (Vll-b)

(Vll-a) (Vll-b) wherein

A represents an optionally substituted CrC₅-alkylene radical, preferably an optionally substituted C₂-C₃-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 C₆- Cn-aryl radical, an optionally substituted C₇-C₁₈-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

0 or 1 , and wherein in the case where several radicals ¾ are bonded to A, these can be identical or different. The general formula (Vll-a) is to be understood as meaning that the substituent R₆ can be bonded y times to the alkylene radical A.

In further very particularly preferred embodiments of the complex according to the invention, 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)

(VII-aa) (Vll-ab) wherein Rs and y have the abovementioned meaning.

In still further extremely preferred embodiments of the complex according to the invention, 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)

(Vll-aaa) (Vll-aba) In the context of the invention, the prefix "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. In particularly preferred embodiments, 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, i.e. a homopolythiophene of recurring units of the formula (VII- aaa), (Vll-aba) or (Vll-b), in which Y = S. In further particularly preferred embodiments of the complex according to the invention, 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-aaa) and (Vll-aba) as well as (VII-aaa) and (Vll-b) being preferred.

In the context of the invention, Ci-C₅-alkylene radicals A are preferably methylene, ethylene, n-propylene, n-butylene or n-pentylene, and C]-C₈-alkylene radicals moreover are n-hexylene, n-heptylene and n-octylene. In the context of the invention, Ci-Cs-alkylidene radicals are preferably abovementioned Q-Q-alkylene radicals comprising at least one double bond. In the context of the invention, CpQ-dioxyalkylene radicals, CrQ-oxyfhiaalkylene radicals and C_\- C₈-dithiaalkylene radicals preferably represent the Q-Q-dioxyalkylene radicals, Q-C₈- oxythiaalkylene radicals and Cj-Q-dithiaalkylene radicals corresponding to the abovementioned CrC₈-alkylene radicals. Q-Qs-Alkyl, C]-Ci4-alkyl and C₅-Ci₂-cycloalkyl represent the corresponding selection from the Q-Cao-alkyl and C3-C₁₂-cycloalkyl radicals mentioned in connection with the substituents of the groups Arj, Ar₂ and R_\ in the formula (I). In the context of the invention, Ci-C₁ -alkoxy radicals represent the alkoxy radicals corresponding to the abovementioned Ci-Cjs-alkyl radicals, and C₆-Ci₄-aryl has the meaning given in connection with the substituents of the groups Ai_\, Ar₂ and R] in the formula (I). Furthermore, in the context of the invention C₇-Ci₈-aralkyl preferably represents C7-Ci₈-aralkyl radicals, such as, for example, benzyl, or alkylbenzyl radicals, such as o-, rn-, p-methylbenzyl, C₇-Ci₈-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 C₁-C₄-hydroxyalkyl is preferably understood as meaning a Ci-C₄-alkyl radical which comprises a hydroxyl group as a substituent, and wherein the Ci-C₄-alkyl radical can represent, for example, methyl, ethyl, n- or iso-propyl, n-, iso-, sec- or tert-butyl. The preceding list serves to illustrate the present invention by way of example and is not to be considered conclu- sive.

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. In this context, 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. Nevertheless, in the context of the invention they are all re- garded as cationic polythiophenes, since 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. To compensate the positive charge, if this is not already done by the optionally sulphonate- or carboxylate-substituted and therefore negatively charged radicals R or R₅, 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. According to a quite particular embodiment of the complex according to the invention, 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).

It is furthermore preferable according to the invention for the complex according to the inven- tion described above to 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, such as methylacetamide, dimethylacetamide, dimethylformamide or N-methylpyrrolidone; and aliphatic and araliphatic ethers, such as diethyl ether and anisole. 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. of 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, for example, 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. Alternatively, the particle size can also be reduced by ultrasound treatment.

Processes for the preparation of the monomelic precursors for the preparation of the polythio- phenes comprising recurring units of the general formula (VII) and derivatives thereof are known to the person skilled in the art and are described, for example, in L. Groenendaal, F. Jonas, D. Freitag, H. Pielartzik & J. R. Reynolds, Adv. Mater. 12 (2000) 481-494 and the literature cited therein. Mixtures of various precursors can also be used.

In the context of the invention, 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. In the context of the invention, 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.

Particularly suitable monomeric precursors for the preparation of optionally substituted polythiophenes comprising recurring units of the general formula (VII) are optionally substi- . tuted 3,4-alkylenedioxythiophenes, which can be represented by way of example by the general formula (VIII)

(VIII) wherein A, R and y have the meaning given in connection with the formula (Vll-a) and wherein in the case where several radicals R are bonded to A, these can be identical or different.

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, polyurethanes, polyamides, polyimides, non-functionalized polyke- tones, polysulphones, melamine-formaldehyde resins, epoxy resins, silicone resins or celluloses. 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.

In the context of the present invention, 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).

For production of the transparent conductive coatings, 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 μπι to 250 μπι, preferably in a wet film thickness of from 2 μπι to 50 μιτι, and are then dried at a temperature of at least from 20 °C to 200 °C.

Organic light-emitting diodes (OLEDs) are increasingly gaining importance in uses such as displays and flat antennae. 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 unserer Zeit, 39 (2005), pages 336-347. The complexes according to the invention can be employed as intermediate layers in these uses. Thus, for example, the following construction is conceivable: a transparent electrically conductive electrode, such as e.g. of indium tin oxide (ITO), doped zinc or tin oxide or a conductive polymer, for example a conductive polymer comprising recurring units of the structure (VII), is applied to the transparent substrate of glass, poly( ethylene terephthalate) (PET) or other transparent plastics. The complexes according to the invention are deposited thereon as a thin layer. One or more organic functional layers are then applied thereto. These can be 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 unserer Zeit, 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. On application of 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 advantages of polymeric intermediate layers in OLEDs are:

1. ) Simple deposition of the polymeric intermediate layer from solution without a time- consuming and costly vacuum process.

2. ) The polymeric intermediate layer is highly transparent and allows efficient decoupling of light.

3.) 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.

4) Improved electrical properties of the OLEDs due to improved injection of the charge carriers from the transparent electrode into the subsequent organic layers.

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. In OSCs, 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;

ii) coating of the substrate with a composition comprising the complex according to the invention.

In process step i) of the process according to the invention for the production of a coated sub- strate, a substrate is first provided, the substrate preferably being one of the abovementioned substrates.

In process step ii), this substrate is then coated with a composition comprising the complex according to the invention. In this connection, it is particularly preferable for 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. In an organic light-emitting diode, the coating applied to the substrate can function in particular as a hole injection layer or hole transport layer. However, the use of the complex according to the invention in other electronic components, such as, for example, capacitors, is also conceivable.

The following examples serve merely to illustrate the invention by way of example and are not to be interpreted as a limitation.

EXAMPLES

Example 1 : Preparation of a dispersion from PEDOT and s-PEE 25.0 g of the polyether ether ketone Victrex^® PEEK™ 150 PF (supplier: Victrex Europa

GmbH, Hofheim/Ts.) were metered into 250.0 g of 95 % strength sulphuric acid. The mixture was heated at 100 °C for 5 h with intensive stirring. Thereafter, the reaction mixture was cooled to 0 °C and stirred at this temperature into a mixture of 650 ml of water and 325 ml of n-butanol, while cooling. The aqueous phase was discarded. The butanol phase was washed twice with 200 ml of water each time and the wash water was discarded. Thereafter, 150 ml of water were added to the butanol phase and the mixture was neutralized to a pH of approx. 6 with 12 ml of 30 % strength NaOH. 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. 57 g of anion exchanger (Lewatit^® MP 62, Lanxess AG, Leverkusen, Germany) and 1 1 1 g of cation exchanger (Lewatit^® S 100 H, Lanxess AG, Leverkusen, Germany) were then added. The mixture was stirred for 2 h. The ion exchanger was then separated off over a filter paper and the dispersion was passed over a 0.2 μη filter. Solids content: 0.61 %

Viscosity: 2 mPas (Haake RV 1 , 20 °C, 700 s^"1)

Example 2: Production of layers based on the complex PEDOT/s-PEE

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. Example 3: Storage at elevated temperature

50 g of the dispersion from Example 1 were stored at 50 °C for 16 days. The sulphate content after the storage was 7 ppm. The sulphate concentration therefore remained unchanged in the context of measurement accuracy. The complex produced splits off no sulphate under exposure to a temperature of 50 °C.

Comparison Example 1 : Storage of a conventional dispersion at elevated temperature

A 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 %

Sulphate content 5 ppm

pH 1.5

50 g of this material were likewise stored at 50 °C for 16 days. The sulphate content after the storage was 22 ppm and had thus increased significantly.

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.

Example 4: Production of an OLED

The dispersion according to the invention from Example 1 was used for construction of organic light-emitting diodes (OLED). The procedure was as follows for the production of the OLEDs:

1. Preparation of the ITO-coated substrate

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).

2. Application of the hole-injecting layer

About 5 ml of the dispersion according to the invention from Example 1 were filtered (Milli- pore HV, 0.45 μτή). 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).

3. Application of the hole transport and the emitter layer

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 A1Q₃ (tris-(8-hydroxyquinoline)aluminium) were vapour-deposited in succession at a vapour deposition rate of 1 A/sec.

4. Application of the metal cathode

The layer system was then transferred into a glove box with an N₂ atmosphere and an inte- grated vapour deposition unit (Edwards), and metal electrodes were vapour-deposited. For this, 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. A 0.5 nm thick LiF layer and then a 200 nm thick Al layer were vapour-deposited successively from two vapour deposition boats under a pressure of p = 10^"3 Pa. 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 mm².

5. Characterization of the OLED The two electrodes of the organic LED were connected (contacted) to a voltage source via electrical leads. The positive pole was connected to the ITO electrode and the negative pole was connected to the metal electrode. The dependency of the OLED current and the electroluminescence intensity (detection is with a photodiode (EG&G C30809E)) on the voltage was plotted. The life was then determined by allowing a constant current of I = 3.84 mA to flow through the arrangement and monitoring the voltage and light intensity as a function of time. Comparison Example 2: Production of an OLED by means of a conventional dispersion

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. For this, 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

The procedure is as in Example 4 and 5, with the difference that the polymeric intermediate layer was omitted completely and process step 2 was absent. Example 5: Comparison of the OLEDs from Example 4 and Comparison Example 2 and 3

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. On the other hand, the constructions produced in accordance with Comparison Example 3 all showed electrical short circuits.

In the life measurements, the voltage and luminance at time t = 0, U0 and L0, the current efficiency as the quotient LO/1, the time taken for the luminance to fall to 50 % of L0, t @ LO/2, and the voltage at time t @ LO/2 are evaluated. Life of the ITO//HlL// PB//ALQ//LiF//Al OLEDs

@ I = 96 mA/cm²

UO L0 Efficiency t @ LO/2 U(t@L0/2)

[V] [cd/m²] [cd/A] [h] [V] Example 4

(according 5.8 2,200 2.3 225 6.3

to the invention)

OLED from

Comparison 6.0 2,400 2.5 15 6.2

Example 2

OLED from

Comparison No life measurements possible because of electrical short circuits Example 3

It has thus been demonstrated that a polymeric intermediate layer is necessary for OLEDs free from short circuits. The dispersion according to the invention from Example 1 as an intermediate layer in OLEDs has the clear advantage of a more than 10-fold life with a reduced increase in voltage with respect to time compared with the standard material Clevios^® P AI 4083.

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

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

Analogously to Example 6, the contact angle of a layer of the reference material corresponding to EP 1 564 250 Al , i.e. a mixture of perfluorinated sulphonic acid polymers with conductive polymers, was determined: a = 48°. It follows from Example 6 and Comparison Examples 4 and 5 that the wetting of layers comprising the formulation according to the invention with toluene-based solutions is similarly as good as that for Clevios^® P AI 4083, but on the other hand is significantly better than that for the reference material corresponding to EP 1 564 250 Al . Example 7: Preparation of a dispersion from PEDOT and s-PEKK

25 g of a polyether ketone ketone (Oxpekk^® C, supplier: Polytron Kunststofftechnik GmbH & Co. KG, Bergisch Gladbach, Germany) were added to a mixture of 62.5 g of 95 % strength sulphuric acid and 187.5 g of oleum (S0₃ content 20 %). The mixture was stirred at 120 °C for 30 h and then at 140 °C for 15 h. The cooled reaction mixture was then introduced into 1,800 ml of water and 500 ml of butanol were added to the solution formed. After separation of the phases, the aqueous phase was extracted twice with 100 ml of butanol each time. The butanol phase was washed with water. 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.

4.92 g of the sulphonated polyether ketone ketone, 0.5 g of a 10 % strength solution of iron(III) sulphate in water and 1.91 g of 3,4-ethylenedioxythiophene (Clevios^® M V2, H. C. Starck Clevios GmbH, Germany) were stirred thoroughly in 248 g of water in a 500 ml flask with a stirrer and thermometer at 25 °C for 30 min until a clear solution was present. Thereafter, 0.94 g of sodium peroxodisulphate was added and the mixture was stirred at 25 °C for 24 h. 18 g of anion exchanger (Lewatit MP^® 62, Lanxess AG, Leverkusen, Germany) and 30 g of cation exchanger (Lewatit^® S 100 H, Lanxess AG, Leverkusen, Germany) were then added. The mixture was stirred for 2 h. The ion exchanger was then separated off over a filter paper and the dispersion was passed over a 0.45 pm filter. A blue dispersion of the PEDOT : s- PEKK complex was obtained, from which it was possible to produce conductive layers by knife coating.

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). The procedure is as follows for the production of the OSC.

1. Preparation of the ITO-coated substrate

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).

2. Application of the hole-extracting layer (HEL)

About 1 ml of the formulation according to the invention from Example 1 are filtered (MiUipore HV, 0.45 μπι). 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).

3. Application of the light- absorbing layer (LAL) 50 mg of the polymer P3HT (BASF, Sempiolid P 200) and 50 mg of the fullerene PCBM (So- lenne [60] PCBM) are dissolved in 5 ml of dichlorobenzene at room temperature. To achieve complete dissolution of the material in the solution, the solution is agitated with a stirring fish for approx. 10 h. The solution is then filtered over a syringe filter (Millipore HV, 0.45 pm) and then distributed on the substrate, which is on a lacquer whirler coater, and the excess solution is 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 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. A 25 nm thick Ca layer and then an 80 nm thick Ag layer are vapour-deposited from two thermal vaporizers under a pressure of p = 10^" Pa. 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.

5. Characterization of the OSC

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

The construction of a reference cell without an HEL is carried out analogously to Example 8, with the difference that process step 2 "Application of the hole-extracting layer" is omitted. Example 10: OSC reference cell with an alternative HEL

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 μπι). 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. In the table of results, 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_max), fill factor (FF) and conversion efficiency

(η)·

Table of results:

From the table of results it follows that 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.

Claims

Complex comprising at least one optionally substituted conductive polymer and at least one functionalized polyketone, characterized in that the polyketone is a polymer which comprises a (-CO-) group in its recurring units and in these recurring units this (-CO-) group is linked with two aromatic groups.

Complex according to claim 1 , characterized in that the functionalized polyketone comprises recurring units of the general formula (I)

(I) wherein

ATI and Ar₂ can be identical or different, and are optionally substituted aromatics, Ri is an optionally substituted organic radical with 1 to 80 carbon atoms, a (-CO-) group or an oxygen atom and

n is an integer from 5 to 5,000.

Complex according to claim 1 or 2, characterized in that the functionalized polyketone comprises recurring units of the general formula (II)

(Π) wherein Ατ ι and Ar₂ can be identical or different and represent an aromatic,

X_! and X₂ can be identical or different and each represent a sulphonic acid, sulphonate, phosphonic acid, phosphonate, carboxylic acid or car- boxylate group,

a and b can be identical or different and each independently of each other represent an integer or non-integer in a range of from 0 to 2, non- integers meaning that the acid mentioned does not occur in every recurring unit, but only in the corresponding fraction of the recurring units,

R₂ has the same meaning as R_\ in claim 2, and

n is an integer from 5 to 5,000.

Complex according to at least one of claims 1 to 3, characterized in that the function- alized polyketone comprises recurring units of the general formula (Ila)

(Ila) wherein

a, b and R₂ have the meaning given in claim 3,

M represents a metal cation or H.

Complex according to at least one of claims 1 to 4, characterized in that the function- alized polyketone comprises recurring units of the general formula (III)

(HI), of the general formula (IV)

(IV), of the general formula (V) or of the general formula (VI)

wherein

a, b, c and d can be identical or different and each represent an integer or non- integer in a range of from 0 to 2, non-integers meaning that the acid mentioned does not occur in every recurring unit, but only in the corresponding fraction of the recurring units,

M represents a metal cation or H,

and

n is an integer from 5 to 5,000.

Complex according to at least one of claims 1 to 5, characterized in that the conductive polymer comprises optionally substituted polythiophenes comprising recurring units of the general formula (VII)

wherein

R and R₅ independently of each other each represent H, an optionally substituted C_t-Cis-alkyl radical or an optionally substituted Q-Cis-alkoxy radical, R4 and R₅ together represent an optionally substituted Q- C₈-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-Cs-dioxyalkylene radical, an optionally substituted C]-C₈-oxythiaalkylene radical or an optionally substituted C_\- C₈-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.

Complex according to claim 6, characterized in that the polythiophene comprises recurring units of the general formula (Vll-a) and/or (Vll-b)

(Vll-a) (Vll-b) wherein

A represents an optionally substituted Q-Cs-alkylene radical, preferably an optionally substituted C₂-C₃-alkylene radical,

Y represents O or S,

R6 represents a linear or branched, optionally substituted CrQs-alkyl radical, preferably linear or branched, optionally substituted Ci-C)₄- alkyl radical, an optionally substituted C5-C₁₂-cycloalkyl radical, an optionally substituted C6-C₁₄-aryl radical, an optionally substituted C7-Ci₈-aralkyl radical, an optionally substituted C₇-C₁8-alkaryl radical, an optionally substituted Q-Crhydroxyalkyl radical or a hy- droxyl radical, and

represents an integer from 0 to 8, preferably 0, 1 or 2, particularly preferably 0 or 1 , and

wherein in the case where several radicals ¾ are bonded to A, these can be identical or different.

8. Complex according to claim 7, characterized in that the polythiophene is poly(3,4- ethylenedioxythiophene).

9. Complex according to at least one of claims 1 to 8, characterized in that the complex is dispersed or dissolved in one or more dispersing agents.

10. Complex according to claim 9, characterized in that the dispersion has a pH in a range of from 1 to 8.

11. Process for the preparation of complexes from electrically conductive polymers, as defined in one of claims 6 to 8, and functionalized polyketones, as defined in one of claims 2 to 5, in which precursors for the preparation of the electrically conductive polymers are polymerized in the presence of the sulphonated polyketones.

12. Complexes obtainable by the process according to claim 11.

13. Use of a complex according to at least one of claims 1 to 10 and 12 for the production of transparent conductive coatings.

14. Use of a complex according to at least one of claims 1 to 10 and 12 for the production of hole injection or hole transport layers in organic light-emitting diodes or organic solar cells.

15. Use of sulphonated polyketones, as defined in one of claims 2 to 5, as a polyanion in complexes with electrically conductive polymers, as defined in one of claims 6 to 8.

16. Coated substrate on which a coating comprising a complex according to at least one of claims 1 to 10 and 12 is applied.

17. Process for the production of a coated substrate, comprising the process steps: i) provision of a substrate;

ii) coating of the substrate with a composition comprising a complex according to at least one of claims 1 to 10 and 12.

18. Coated substrate obtainable by a process according to claim 17.

19. Electronic component comprising a coated substrate according to claim 16 or 18.

20. Electronic component according to claim 19, wherein the electronic component is an organic light-emitting diode or an organic solar cell.