DE19837390A1 - New complexes of conjugated organic polymer with ionic side chains and ionic surfactant are used as electroluminescent material, e.g. in opto-electronic device, including blue luminescent diode - Google Patents

Abstract

Complexes of a conjugated organic polymer (I) with several ionic groups as side chains and ionic surfactant molecule (II) with the opposite charge are claimed. An Independent claim is also included for the preparation of the complexes by bringing an aqueous (I) solution into contact with an aqueous (II) solution and recovering the resultant precipitate.

Description

The invention relates to complexes of conjugated polyelectrolytes for optoelectronic applications, especially for manufacturing optoelectronic components such as semiconductor components.

There is a high demand for large-area solid-state light sources with a variety of applications, especially in the field of Screen technology, lighting technology and display elements. The requirements placed on these light sources can, however, e.g. Zt. cannot be solved completely satisfactorily by any existing technology.

Since the discovery of the first polymeric electroluminescent material from Burroughes et al. (Nature 347 (1990), 539-541) is used in numerous Research institutions are intensively involved in the development of light emitting diodes Based on conjugated organic polymers. In Sixl et, al. (Phys. Bl. 54: 225-230 (1998), Kraft et al., Angew. Chem. 110 (1998), 416-443) and Heeger (Current Opinion in Solid State & Material Science 3 (1998), 16-22) there are summaries of the development status on this Territory. Common to all known electroluminescent materials organic basis that they contain conjugated polymers, such as Polyparaphenylene, polyparavinylene and polyparaethinylene. These materials are in an unmodified form, however, at very low levels Degrees of polymerization are infusible, insoluble and cannot be vaporized, see above that they are very difficult to process. For coating They are therefore substrates in a modified soluble form used by incorporating flexible, covalently bound Side chains to the conjugated polymer backbone is obtained. Are there however negative effects on the optical properties  unavoidable. Therefore, numerous efforts have been made through suitable selection and positioning of the side chain groups to keep such effects low. For example, Hoechst and Philipps dialkoxy-poly-phenylene-vinylene systems, as the current one Optimization maximum are called (Sixl et al., DE-A 196 15 128). However, these dialkoxy-substituted poly-phenylene-vinylene systems have an undesirable red shift in light emission compared to one unsubstituted poly-phenylene-vinylene polymer. Such However, redshift is the rule with side chain substitution.

Another problem lies in the high voltages that operate of single-layer LEDs are necessary. The operational tension (gymnastic On point), d. H. the lowest voltage in electroluminescence is observed for a typical ITO / polymer / Al Single layer light emitting diode 10 to 20 V (Son et al., Science 269 (1995), 376-378; Gho et al., Adv. Mater. 9: 326-328 (1997); Garten et. al., Adv. Mater. 9: 127-138 (1997). The operating voltages can be Structures (DE-A-44 28 450, Stapffet. Al., Liquid Chrystals 23 (1997), 613-617; Romero et al., Adv. Mater. 9 (1997), 1158-1161) or / and Use of oxygen or moisture sensitive Ca or Mg Electrodes (Romero et al. (1997), supra; Cacialli et al., Synthetic Metals 76 (1996), 145-148) can be reduced. Compared to multilayer structures single-layer light emitting diodes have the advantage, however significantly shorter switching times (time differences between switching on the Voltage and the onset of electroluminescence) and they are too far easier to manufacture.

There is therefore a great need to find Electroluminescent materials in which the disadvantages of the prior art Technology are at least partially eliminated and particularly easy are processable, no red shift towards unsubstituted Polymers have a low threshold voltage for electroluminescence  possess good solution and film formation properties and not for Tend to crystallize.

It was surprisingly found that by complexing Polyelectrolytes with ionic surfactant compounds are obtained which are outstandingly suitable as electroluminescent materials. These complexes can be both simple and inexpensive to manufacture and can be easily varied for product optimizations. For example the emission spectrum by simply varying the amphiphilic counterions be deliberately influenced so that with a single conjugate Polyelectrolyte LEDs of different colors are accessible. It was also surprisingly found that the threshold voltage is one LED with a complex according to the invention as an active layer e.g. B. is 2 to 3 V far below an otherwise identical diode, in which Prior art polymers act as an active release layer. In addition, the emission maximum of the invention Complexes strongly compared to known side chain-modified polymers shifted to shorter wavelengths, e.g. 469 nm (blue) against 557 nm (yellow). Since the manufacture of blue LEDs so far was very problematic, this blue shift represents another essential advantage of the complexes according to the invention classic side chain modified polymers.

Yet another advantage of the complexes according to the invention is that they are in filmed state can have highly ordered layer structures that periodically from alternating semiconducting and insulating layers are built up. The thickness of the layers is less Nanometers and the application can be done in a single step respectively.

An object of the invention is thus a complex of a conjugate organic polymer with several ionic groups as side chains  (Polyelectrolyte with a conjugated polymer backbone) and oppositely charged ionic surfactant molecules. The complex is preferably electroluminescent, d. H. he can create one Voltage emit light.

A conjugated organic polymer in the sense of the present invention contains an alternating sequence of single bonds and Multiple bonds, e.g. B. C = C, C ∼ C, C = N and / or atoms with free Electron pairs such as N, S or O. Preferred examples of conjugated organic polymers are poly-phenylenes, e.g. B. polyp-phenylene, poly Phenylene vinylenes, such as polypphenylene vinylene, polyphenylene Ethynylenes such as poly (p-phenylene-ethynylene) or polythiophenes. The polymers preferably have a degree of polymerization (number of Monomer units) between 5 and 1000, particularly preferably between 10 and 100 on. The polymers are preferably linear.

A conjugated polymer used for the preparation of the complex contains several ionic groups or groups which can be ionized under the conditions prevailing in the preparation of the complex as side chains, for example negatively charged anionic groups or positively charged cationic groups. Examples of negatively charged ionic groups are carboxylate, sulfonate, sulfate, phosphate, phosphinate and phosphonate groups or combinations thereof. Carboxylate (COO ^- , sulfonate (-SO ₃ ^- and sulfate (-OSO ₃ ^- ) - groups as well as combinations thereof are particularly preferred. Examples of positively charged cationic groups are iminium, hydrazinium, guanidinium, ammonium groups, e.g. B. primary, secondary, tertiary and quaternary ammonium groups, or combinations thereof, preference is given to ammonium groups, in particular quaternary ammonium groups.

The ionic groups can be attached to the polymer backbone directly or via be bound a spacer. The binding preferably takes place via a  Spacer z. B. via an unbranched or branched, if necessary Heteroatoms such as O-containing alkylene group of 1 to 12 Carbon atoms.

Each monomer unit of the polymer can have one or more ionic ones Groups included. If necessary, however, the polymer can also nonionic monomers, for example, in a proportion of up to 80 mol% contain. The proportion of the nonionic monomer units is preferred ≦ 50 mol%, particularly preferably 30 mol% and most preferred ≦ 10 mol%.

The conjugated organic polymer, which has more than one ionic group Contains side chains, is with oppositely charged ionic Complexed surfactant molecules. The number of surfactant molecules is such that overall an essentially neutral molecule (at least 90% and preferably at least 99% charge balance), the remaining charges by low molecular weight groups, for example inorganic or organic ions can be balanced. The Complex can consist of the polymer and each the same or different Be formed surfactant molecules.

Surfactant molecules according to the present invention have at least one Charge carriers, preferably one or two charge carriers and especially preferably a charge carrier and at least one hydrophobic portion on. The hydrophobic part is formed by organic residues, particularly preferred of saturated or unsaturated, branched or straight chain, linear or cyclic hydrocarbon residues, the optionally non-polar substituents such as halogen atoms, e.g. B. fluorine or chlorine, can wear, with perhalogenated, for. B. perfluorinated Hydrocarbon radicals can be particularly preferred. Especially the hydrophobic portion preferably comprises one or more flexible, optionally halogen-substituted hydrocarbon chains. The  The hydrophobic portion is preferably such that the Accumulate surfactant molecules at interfaces and / or micelle formation be able to show. To ensure sufficient hydrophobicity, contain the hydrophobic components of unsubstituted hydrocarbons preferably at least 6 and preferably at least 10 Carbon atoms. In the case of halogen-substituted hydrocarbons, the The number of carbon atoms in the hydrophobic portions is also lower his. The total molecular weight of the surfactant is preferably ≦ 4000 and particularly preferably ≦ 2000.

To prepare complexes with a polymer which contains negatively charged ionic groups, surfactant molecules are used which contain positively charged cationic groups, ie groups which may be present as cationic groups during the preparation of the complex. Examples of such groups are iminium, hydrazinium, guanidinium and ammonium groups, e.g. B. primary, secondary, tertiary and quaternary ammonium groups, with quaternary ammonium groups being particularly preferred. Particularly preferred examples of positively charged surfactant molecules are dialkyl dimethyl ammonium surfactants R ₂ Me ₂ NX, where R in this case represents an optionally halogenated organic radical with mit 3 and preferably ≧ 5 carbon atoms and X stands for a counter ion or perfluoroalkylethyl trialkyl ammonium surfactants R _f CH ₂ -CH ₂ -NR ₃ X, where R _{f is} a perfluorinated radical having ≧ 1 and preferably ≧ 4 carbon atoms, R is a C ₁ -C ₄ alkyl radical and X is a counter ion. Specific examples of such compounds are dihexadecyl-dimethylammonium bromide or F (CF ₂ CF ₂ ) ₁₉ N ^⊕ (CH ₃ ) ₃ CH ₃ SO ₄ ^⊖ (HOE-L-3658-1®, Hoechst AG).

To prepare complexes with a polymer which contains positively charged groups as side groups, surfactant molecules with negatively charged anionic groups are used, ie groups which may be present as anionic groups when the complex is prepared. Examples of such negatively charged groups are carboxylate, sulfonate, sulfate, phosphate; Phosphinate and phosphonate groups, with carboxylate, sulfonate and sulfate groups being particularly preferred. Examples of such surfactants are carboxylic acids and carboxylic acid salts with preferably more than 8 carbon atoms, organic sulfonic acids and their salts; organic sulfuric acid and its salts or organic phosphinic, phosphonic or phosphoric acid and its salts, which may optionally be halogenated, for example fluorinated. Particularly preferred examples of anionic surfactants are perfluoroalkylethylsulfonic acids and their salts, R _f CH ₂ -CH ₂ -SO ₃ M, where R _{f is} a perfluorinated radical with ≧ 1 carbon atom and preferably ≧ 4 carbon atoms and M is a counter ion, e.g. B. H ⁺ or NH ₄ ⁺ means, such as F (CF ₂ CF ₂ ) ₁₉ CH ₂ CH ₂ SO ₃ ^⊖ NH ₄ ^⊕ (Zonyl TBS®; DuPont), phosphoric acid perfluoroalkyl ethyl ester or its salts (R _f CH ₂ CH ₂ O) _X PO (OM) _Y , where R _f and M are as previously defined, X = 1, 2, Y = 2, 1 and X + Y = 3 such as [F (CF ₂ CF ₂ ) _1-7 O] _X PO (ONH ₄ ) _Y (ZonylFSP®, DuPont), perfluoroalkylethyl hydroxyethyl phosphoric acids and their salts (R _f CH ₂ CH ₂ O) _X PO (OM) _Y (OCH ₂ CH ₂ OH) _Z , where R _f and M are as previously defined and X + Y + Z = 3, such as [F (CF ₂ CF ₂ ) _3-8 O] _X PO (ONH ₄ ) _Y (OCH ₂ CH ₂ OH) _Z (Zonyl FSE® , DuPont), 3 [(1H, 1H, 2H, 2H-fluoroalkyl) thio] propionic acids and their salts R _f CH ₂ CH ₂ SCH ₂ CH ₂ CO ₂ M, where R _f and M are as previously defined, e.g. . B. F (CF ₂ CF ₂ ) _1-9 CH ₂ CH ₂ SCH ₂ CH ₂ CO ₂ Li (Zonyl FSA®, DuPont) and succinic acid-diperfluoroalkylethyl diester-2-sulfonic acids and their salts, such as Fluowet SB® ( Maximum).

The complexes according to the invention have several extremely interesting ones Properties on. So they essentially have one at room temperature non-crystalline, e.g. B. mesomorphic or amorphous structure such as determined by wide-angle X-ray scattering. They are also preferably located at 0 ° C, particularly preferably at -10 ° C in non-crystalline form.  

Furthermore, the complexes according to the invention have an optical one Anisotropy and preferably have an ordered, several structure comprising different domains, e.g. Legs Nanostructuring, which alternately isolating and semiconducting Layers. These structural features can be and small-angle x-ray examinations can be determined.

In addition, the complexes of the invention show excellent Electroluminescent properties. So they have z. B. when installed in a Single-layer electroluminescent device with ITO and Al as electrodes Threshold voltage of the electroluminescence of preferably ≦ 15 V and particularly preferred ≦ 10 V. Most preferred are complexes with a threshold voltage ≦ 5 V, for example in the range from 0.5 to 5 V. The complexes according to the invention have an electroluminescence preferably in the visible range. With a suitable selection of Polymer and surfactant are found even in short electroluminescence Wavelengths, e.g. B. a maximum of electroluminescence at one Wavelength ≦ 525 nm. The maximum of the is particularly preferred Electroluminescence at a wavelength ≦ 500 nm and most preferably at a wavelength ≦ 480 nm.

The complexes according to the invention can easily be obtained from aqueous Solutions are made. For this purpose, an aqueous solution of a conjugated organic polymer with more ionic groups than Side chains with an aqueous solution of oppositely charged ionic surfactant molecules contacted. By complexing the Polymer with the surfactant becomes an ionic, sparingly soluble in water Complex formed, which can be obtained as a precipitate. In doing so the polymer and the surfactant preferably in the form of water-soluble Salts with suitable counterions, e.g. B. inorganic or / and low molecular weight organic ions used.  

Scheme 1 shows a preferred embodiment of this method. The conjugated polymer 1 consists of monomers A, one or have several ionic groups x, as well as low molecular counterions y. Polymer 1 is charged with a surfactant that is oppositely charged to x 2 complexed. The surfactant 2 consists of a surface-active Component B and a low molecular counterion z. By Complexation of 1 with 2 forms an ionic, difficult in water soluble complex of composition AB. The complexation is ongoing preferably by precipitation from aqueous solution and removal of the low molecular weight salt yz. The resulting complex can be in one dissolved organic solvents such as chloroform and then to be processed further.

Scheme 1:

The symbols in scheme 1 preferably have the following meanings:
A is a monomer unit of the conjugated polymer, which can be the same or different.
n is the degree of polymerization of the conjugated polymer and is preferably between 5 and 1000, particularly preferably between 10 and 100.
x is a charged anionic or cationic group as previously defined, which via a spacer, e.g. B. an unbranched or branched alkylene group having 1 to 12 carbon atoms, where one or more CH ₂ groups can be replaced by heteroatoms such as -O- or can be bonded directly to the polymer backbone.
y is a low molecular ion charged opposite to x, e.g. B. NR ₄ ⁺ , SO ₄ ^- , Cl ^- , Br ^- or I ^- .
B is an amphiphilic ionic molecule, for example an alkyl dimethyl ammonium surfactant or an organic carboxylic acid.
z is an ion charged opposite to B, e.g. B. a low molecular weight ion such as Br ^- .

The complexes according to the invention can be used as electroluminescent materials can be used, for example as an active layer in a Electroluminescent device. As an active layer in the sense of the invention apply electroluminescent materials that are capable of being applied to emit light from an electric field (light-emitting layer), as well as materials for the injection and / or the transport of improve positive or negative charges (charge injection layers and charge transport layers).

The general structure of electroluminescent devices is known and for example in Sixl et al. (1998), supra. Usually contain electroluminescent devices one or more active, for example electroluminescent layers that are between an anode  and a cathode are arranged, at least one of these Electrodes is transparent. You can also choose between the electroluminescent layer and the cathode an electron injection or / and electron transport layer can be arranged and / or between the electroluminescent layer and the anode a hole injection or / and hole transport layer can be arranged. Metals can be used as cathode such as calcium, magnesium, indium or magnesium / aluminum. Films such as Au or ITO can be used as the anode (indium oxide / tin oxide) on a transparent substrate or a serve transparent polymer. In operation, the cathode turns negative Potential set against the anode so that electrodes from the cathode into the electron injection layer / electron transport layer or directly into the light emitting layer is transported. Be simultaneous Holes from the anode into the hole injection / hole transport layer or injected directly into the light emitting layer. The injected Charge carriers move under the influence of the applied voltage through the active layers towards each other. This leads to the interface between charge transport layer and light emitting layer or within the emissive layer to electron-hole pairs, the under Recombine emission of light. The color of the emitted light can varies by the compound used as the light-emitting layer become. In particular, with the same conjugated polyelectrolyte by simply varying the surfactant used as the counter ion Change in the light wavelength and thus a color change achieved become.

The device according to the invention is preferably an electroluminescent Light-emitting diode and particularly preferably as a single-layer light-emitting diode formed, the thickness of the active layers, for example in Range of 3 nm-100 µm can be.  

The lateral extent of individual domains when manufactured after Solvent-cast process (slow evaporation of the solvent) is depending on the conditions, preferably 100 nm to 5 mm. The Layer thickness is preferably in the range of 1 to 10 microns. At Production of layers with thicknesses in the range of preferably 5 to 20 nm in the spin-coating process (film production on a rotating disc however, with rapid evaporation of the solvent) none are formed such nanostructured domains. So you can choose one Equilibrium structure (mesomorphic) or a non-equilibrium structure (amorphous) can be obtained. The latter is preferred for LED.

Yet another object of the present invention is that Use of the complexes described above as Electroluminescent materials, for example, for installation in optoelectronic components, in particular in semiconductor components. The Electroluminescent layers according to the invention can be used as LEDs serve, for. B. in screens, in display elements such as Displays, signs, optoelectronic couplers and alphanumeric displays.

The invention is further illustrated by the following figures and Examples explained. Show it:

Fig. 1 shows a comparison of the electroluminescence of a complex (A) according to the invention which has a maximum electroluminescence at 469 nm and a threshold voltage at 2 to 3 V with a complex of the prior art (B) with a maximum wavelength of 557 nm and a threshold voltage from 20 to 21 V.

Fig. 2 shows the current density-voltage curve of a light emitting diode according to the invention.

Fig. 3 shows the schematic representation of a nanostructured domain with a lamellar structure, as can be found in films produced from complexes according to the invention by solvent casting. Semiconductor layers (A) with a thickness of 1.16 nm alternate periodically with non-conductive layers (B) with a thickness of 1.86 nm. The lateral extent of individual domains is 100 nm to 5 mm, depending on the filming conditions.

Fig. 4 shows the DSC curve obtained by differential calorimetry of a film from a complex according to the invention. The diagram shows a glass point at -41 ° C and a melting point at -16 ° C. There are no further phase transitions above -16 ° C to 200 ° C.

Fig. 5 shows the tension-elongation curve of a film from a complex according to the invention.

Examples example 1

For complexation, 370 mg (2.55 mmol) of poly (1,4-phenylene-ethynylene carboxylic acid) 1, finely ground, were dissolved in 100 ml of 2% aqueous NaOH at 40 ° C. Immediately after the polymer had dissolved, the polymer solution was added dropwise to 200 ml of 1% NaOH at 70 ° C. in which 1759 mg (3.06 mmol) of dihexadexyl-dimethyl-ammonium bromide 2 were dissolved within 5 min. A fine brown precipitate of dihexadecyl-dimethylammonium poly (1,4-phenylene-ethynylene carboxylate) 3 formed immediately, which was filtered off and washed with NaOH and NaBr by repeated washing with hot water at 70 ° C. The yield was 1.45 g (90%) of brown-red powder. The results of the elementary analysis show a stoichiometric 1: 1 complexation.

Scheme 2

Example 2

A 1% w / w solution of the complex dihexadecyl-dimethylammonium poly (1,4-phenylene-ethynylene carboxylate) (preparation according to Example 1) in tetrahydrofuran (HPLC quality) was spin-coated on ITO glass (Merck ) applied at a rotation speed of 1800 rpm. The coated glass support was then tempered at 50 ° C. for 15 minutes and at 100 ° C. for 30 minutes. The determination of the layer thickness of the complex with a surface profile analyzer (DecTac) gave a value of approx. 100 nm. Then a final aluminum layer (typically 150 nm) was applied at a pressure of P <10 ^-6 mbar.

If the positive pole on ITO and the negative pole on aluminum If the voltage source is connected, a voltage of 2-3 V is shown Electroluminescence with a maximum in the blue light range at 469 nm.

A structurally identical diode with the non-ionic, ie an ester substituted poly (phenyleneethynylene) (poly (2-ethylhexyl) -oxycarbonyl-1,4-phenyleneethynylene) as the active layer only shows detectable electroluminescence from 20-21 volts, with a maximum at 557 nm (see Fig. 1).

Example 3

The current-voltage characteristic of a diode according to Example 2 shows three areas. No measurable current flow can be observed in area 1, below the threshold voltage of 2 to 3 V for the electroluminescence. Range 2 lies between the threshold voltage and a value of 6 V. Here the current flow increases disproportionately with the voltage. In area 3, between 6 V and the short-circuit voltage of 21 to 25 V, the current increases approximately linearly with the voltage. The maximum current thickness is 1600 A m ^-2 . For the conductivity, values between 1 and 2.10 ^-4 Siemens result at a temperature of 20 ° C.

Example 4

In the area of X-ray wide-angle scattering between 10 and 80 ° C at 20 ° C for a complex according to Example 1, no sharp reflections found. It just becomes an amorphous halo with a Bragg distance of  0.43 nm found. In the absence of crystalline reflections, one can Crystallinity can be excluded.

Example 5

A film of approximately 10 μm thick, produced from complex 3 according to example 1, shows a strong one between crossed polarizers of a light microscope Birefringence. The size of individual domains can be up to 5 mm. This optical anisotropy together with the absence proves crystalline reflexes (see Example 4) that the complex of the invention has a structure ordered on the mesoscopic length scale. This is structurally comparable to that found in liquid crystals becomes.

Example 6

The small-angle X-ray diffractogram of a complex 3 according to Example 1 has an intense scattering maximum at s = 3.3 nm ^-1 (s = scatter vector, s = 2 / λ sin θ, λ = wavelength of the X-ray radiation used, θ = scattering angle) and at higher scattering angles a pronounced area in which the scattering intensity drops with the third power of the scattering vector (measurement with a Kratky camera). This scattering behavior is interpreted as a nanostructured material with sharp phase boundaries. The phase boundary is below 0.5 nm. From the detailed evaluation of the scattering curve using the formalism of the interfacial distribution function (Ruland, Colloid and Polymer Sci. 255 (1977), 417-427 and Wolff et al., Macromolecules 27 (1994), 3301 -3309) a lamellar nanostructuring with a long period (repeat unit) of 3.02 nm can be derived. Each repeating unit consists of a lamella type 1 with a thickness of d ₁ = 1.16 nm and a lamella type 2 with a thickness of d ₂ = 1.86 nm. Lamella type 1 is assigned to the conjugated polyelectrolytes, including the ionic groups of the surfactants. Lamella type 2 consists of saturated hydrocarbon chains. The lamellar arrangement is shown schematically in Fig. 3. There is great interest in miniaturized semiconductor components in such alternating insulating and semiconducting layers.

Example 7

The investigation using differential calorimetry provides information about the thermal behavior of a film from a complex according to Example 1. A corresponding diagram is shown in Fig. 4. The material has a glass point of -41 ° C and a melting peak at -16 ° C. The melting peak is caused by the melting of crystalline alkyl side groups. From the enthalpy of fusion, the proportion of crystalline methylene units below -16 ° C is less than 1%. Above -16 ° C the material is mesomorphic as shown in Fig. 3.

Example 8

Films from complex 3 according to example 1 are very flexible and can be produced in any size. Tensile strain measurements were carried out on free-standing films to qualify the mechanical properties. Fig. 5 shows a typical measurement curve. Up to a relative elongation of approx. 28%, a dependency according to Hooke's law is found, ie the elongation is linear and reversible. The tensile modulus is 3 MPa, the maximum reversible tension is approximately 0.55 MPa. Above an elongation of 28%, the deformation is irreversible, recognizable by the step-like drop in tension.

Claims (26)

1. Complex of a conjugated organic polymer with several ionic groups as side chains and oppositely charged ionic surfactant molecules. 2. Complex according to claim 1, characterized, that the ionic polymer is selected from polyphenylenes, poly Vinylenes, poly-phenylene-vinylenes, poly-phenylene-ethynylenes and Polythiophenes. 3. Complex according to claim 1 or 2, characterized, that the degree of polymerisation of the polymer is between 5 and 1000 lies. 4. Complex according to one of claims 1 to 3, characterized, that the polymer negatively charged anionic groups as Side chains contains selected from carboxylate, sulfonate, sulfate, Phosphate, phosphinate and phosphonate groups or combinations from that. 5. Complex according to one of claims 1 to 3, characterized, that the polymer positively charged cationic groups as Side chains contains selected from iminium, hydrazinium, Guanidinium and ammonium groups or combinations thereof.   6. Complex according to one of the preceding claims, characterized, that the ionic surfactant molecules have at least one charge carrier and comprise at least one hydrophobic organic portion. 7. Complex according to claim 6, characterized, that the hydrophobic organic portion is at least 6 Contains carbon atoms. 8. Complex according to claim 4, characterized, that the surfactant positively charged cationic groups selected from Iminium, hydrazinium, guanidinium and ammonium groups contains. 9. Complex according to claim 8, characterized, that the surfactant is a dialkyl dimethyl ammonium surfactant. 10. Complex according to claim 9, characterized, that the surfactant negatively charged anionic groups selected from Carboxylate, sulfonate, sulfate, phosphate, phosphinate and Contains phosphonate groups. 11. Complex according to one of the preceding claims, characterized, that it is non-crystalline at room temperature.   12. Complex according to one of the preceding claims, characterized, that it has an optical anisotropy. 13. Complex according to one of the preceding claims, characterized, that it is an ordered, several different domains has extensive structure. 14. Complex according to claim 13, characterized, that it alternately includes insulating and semiconducting layers. 15. Complex according to one of the preceding claims, characterized, that it has a threshold voltage of electroluminescence ≦ 15 V having. 16. Complex according to one of the preceding claims, characterized, that it has a maximum of electroluminescence at a wavelength ≦ 525 nm. 17. Process for the preparation of a complex according to one of the preceding claims 1 to 16, characterized, that an aqueous solution of a conjugated organic Polymers with multiple ionic groups as side chains with one aqueous solution of oppositely charged ionic Contacting surfactant molecules and the resulting precipitate wins.   18. electroluminescent device, characterized, that it has one or more active layers that one Contain complex according to one of claims 1 to 16. 19. The apparatus of claim 18, characterized, that the active layers are selected from light emitting Layers, charge injection layers and Charge transport layers. 20. The apparatus of claim 18 or 19, characterized, that the active layers between a cathode and an anode are arranged. 21. Device according to one of claims 18 to 20, characterized, that it includes an electroluminescent light emitting diode. 22. The apparatus according to claim 21, characterized, that it comprises a single-layer light-emitting diode. 23. The device according to one of claims 18 to 22, characterized, that the thickness of the active layers is in the range of 5 to 200 nm. 24. Use of complexes according to one of claims 1 to 16 as Electroluminescent materials.   25. Use according to claim 24 for installation in optoelectronic Components, especially in semiconductor components. 26. Use according to claim 25 for installation in screens, Display elements, signs, optoelectronic couplers and alphanumeric displays.