WO2000014814A1

WO2000014814A1 - Electro-luminescent arrangements with metal complexes that are bonded to fluorescent dyes

Info

Publication number: WO2000014814A1
Application number: PCT/EP1999/006150
Authority: WO
Inventors: Helmut-Werner Heuer; Rolf Wehrmann; Andreas Elschner
Original assignee: Bayer Aktiengesellschaft
Priority date: 1998-09-02
Filing date: 1999-08-23
Publication date: 2000-03-16
Also published as: KR20010073071A; JP2002524829A; DE19839948A1; EP1133802A1; AU5738599A

Abstract

An electro-luminescent arrangement comprising a substrate, an anode, an electro-luminescent element and a cathode, whereby at least one of the two electrodes is transparent in the visible spectral range and the electro-luminescent element contains one or several zones from the following group in the following order: a hole injection zone, a hole transportation zone, an electro-luminescent zone, an electron transportation zone and an electron injection zone. Each of the available zones can also handle tasks pertaining to the other zones thus indicated. The invention is characterized in that the electro-luminescent element contains a metal complex that is chemically bonded to a fluorescent dye.

Description

Electroluminescent devices with metal complexes with attached fluorescent dyes

An electroluminescent (EL) arrangement is characterized in that it emits light when an electrical voltage is applied under current flow. Such arrangements have long been known in the art under the name "light emitting diodes" (LEDs). The emission of light occurs because positive charges ("holes", holes) and negative charges ("electrons", electrons) recombine while emitting light.

In the development of light-emitting components for electronics or photonics, mainly inorganic semiconductors such as gallium arsenide are used today. Point-like display elements can be produced on the basis of such substances. Large-scale arrangements are not possible.

In addition to the semiconductor light-emitting diodes, electroluminescent arrangements based on evaporated low-molecular organic compounds are known (US Pat. Nos. 4,539,507, 4,769,262, 5,077,142, EP 0 406 762, EP 0 278 758, EP) -A 0 278 757).

Polymers such as poly (p-phenylene) and poly (p-phenylene vinylene (PPV)) are also described as electroluminescent polymers: G. Leising et al., Adv. Mater. 4 (1992) No. 1; Friend et al., J. Chem. Soc, Chem. Commun. 32 (1992); Saito et al., Polymer, 1990, Vol. 31, 1137; Friend et al., Physical Review B, Vol. 42, No.

18, 11670 or WO 90/13148. Further examples of PPV in electroluminescent displays are described in EP-A 0 443 861, WO-A 92/03490 and 92/03491.

EP-A 0 294 061 presents an optical modulator based on polyacetylene. For the production of flexible polymer LEDs, Heeger at al. Soluble conjugated PPV derivatives proposed (WO-A 92/16023).

Polymer blends of different compositions are also known: M. Stolka et al., Pure & Appt. Chem., Vol. 67, No. 1, pp 175-182, 1995; H. Bässler et al., Adv. Mater. 1995, 7, No. 6, 551; K. Nagai et al, Appl. Phys. Lett. 67 (16), 1995, 2281; EP-A 0 532 798.

The organic EL devices typically contain one or more layers of organic charge transport compounds. The basic structure in the order of the layers is as follows:

1 carrier, substrate

2 base electrode 3 hole injecting layer

4 hole transporting layer

5 light-emitting layer

6 electron transporting layer

7 electron-injecting layer 8 top electrode

9 contacts

10 wrapping, encapsulation.

Layers 3 to 7 represent the electroluminescent element.

This structure represents the most general case and can be simplified by omitting individual layers so that one layer performs several tasks. In the simplest case, an EL arrangement consists of two electrodes, between which there is an organic layer that fulfills all functions - including the emission of light. Such systems are e.g. in the registration

WO-A 90/13148 based on poly (p-phenylene vinylene). Multi-layer systems can be built up by vapor deposition processes, in which the layers are applied successively from the gas phase, or by casting processes. Casting processes are preferred due to the higher process speeds. However, the dissolving process of a layer that has already been applied can be difficult in certain cases when layering over with the next layer.

The object of the present invention is to provide electroluminescent arrangements with high luminance, novel metal complexes with improved solubility in common solvents being used as emitters and / or electron conductors. These new types of metal complexes should also be able to be applied by vapor deposition from the gas phase.

It has been found that electroluminescent devices, the below

Contain metal complexes that meet these requirements. In the following, the term zone is synonymous with layer.

The present invention therefore relates to an electroluminescent arrangement composed of a substrate, an anode and an electroluminescent device

Element and a cathode, wherein at least one of the two electrodes is transparent in the visible spectral range and the electroluminescent element contains one or more zones from the group of the hole-injecting zone, hole-transporting zone, electroluminescent zone, electron-transporting zone and electron-injecting zone in the order mentioned, wherein each of the existing zones can also take on tasks of the other zones mentioned, characterized in that the electroluminescent element contains a metal complex to which a fluorescent dye is chemically bound.

The hole-injecting zone preferably contains a neutral or cationic polythiophene of the formula (I)

in which

Ql and Q ^ independently of one another are hydrogen, optionally substituted (Cι-C2θ) -Al, CH2OH or (Cg-Ci ^ aryl or

Q ¹ and Q ² together mean - (CH2) _m -CH2- with m = 0 to 12, preferably 1 to 5, (Cg-C _] 4) -arylene, and

represents an integer from 2 to 10,000, preferably 5 to 5,000.

The hole-conducting zone adjoining the hole-injecting zone preferably contains one or more aromatic tertiary amino compounds, preferably optionally substituted triphenylamine compounds, particularly preferably tris, 3,5- (aminophenyl) benzene compounds of the formula (II).

The zones or zones located between the hole-injecting zone and the cathode can also perform several functions, i.e. a zone e.g. hole-injecting, hole-transporting, electroluminescent, electron-transporting and / or electron-injecting substances.

The electroluminescent element may further contain one or more transparent polymeric binders. The transparent binder is preferably selected from the group consisting of polycarbonates, polyester carbonates, copolymers of styrene such as SAN or styrene acrylates, polysulfones, polymers based on monomers containing vinyl groups, polyolefins, cyclic olefin copolymers and phenoxy resins. The optionally substituted tris-1,3,5- (aminophenyl) benzene compound preferably represents an aromatic tertiary amino compound of the general formula (II)

in which

R ^{2 represents} hydrogen, optionally substituted alkyl or halogen,

R3 and R ^ independently of one another are optionally substituted (CJ -CJO) alkyl, alkoxycarbonyl-substituted (C] -Cιo) alkyl, each optionally substituted aryl, aralkyl or cycloalkyl.

R ^ and R ^ independently of one another preferably represent (-C-Cg) -alkyl, in particular methyl, ethyl, n- or iso-propyl, n-, iso-, sec- or tert-butyl, (Cι-C4) - Alkoxycarbonyl- (C -C6) -alkyl, such as, for example, methoxy-, ethoxy-, propoxy-, butoxycarbonyl- (Cι-C4) -alkyl, in each case optionally by (Cι-C4) -alkyl and / or (Cj-C4) - Alkoxy substituted phenyl (C ₁ -C 4) alkyl, naphthyl (C ₁ -C 4) alkyl, cyclopentyl. Cyclohexyl. Phenyl or naphthyl.

R-> and R ^ are particularly preferably independently of one another unsubstituted phenyl or naphthyl or in each case one to three times by methyl, ethyl, n-, iso- Propyl, methoxy, ethoxy, n- and / or iso-propoxy substituted phenyl or naphthyl.

R ² preferably represents hydrogen, (-C -Cg) alkyl, such as methyl, ethyl, n- or iso-propyl, n-, iso-, sec- or tert-butyl, or chlorine.

Such compounds and their preparation are described in US Pat. No. 4,923,774 for use in electrophotography, which is hereby expressly incorporated as part of the description ("incorporated by reference"). The tris-nitrophenyl compound can, for example, be converted into the tris-aminophenyl compound by generally known catalytic hydrogenation, for example in the presence of Raney nickel (Houben-Weyl 4/1 C, 14-102, Ulimann (4) L3, 135-148). The amino compound is reacted in a generally known manner with substituted halogenobenzenes.

The following compounds may be mentioned by way of example:

In addition to the tertiary amino compound, further hole conductors, e.g. in the form of a mixture with the tertiary amino compound, used to build up the electroluminescent element. On the one hand, this can be one or more compounds of the formula (II). Mixtures of isomers are also included, on the other hand also mixtures of hole-transporting compounds with compounds of tertiary amino compounds - with the general formula (II) - with different structures.

A compilation of possible hole-injecting and hole-conducting materials is given in EP-A 0 532 798.

In the case of mixtures of the aromatic amines, the compounds can be used in any ratio.

Examples include:

Materials that have hole-conducting properties and that can be used in pure form or as mixing partners with the tertiary amino compounds for example the following compounds, where X ¹ to X ⁶ independently of one another are H, halogen, alkyl, aryl, alkoxy, aryloxy.

Me = methyl

These and other examples are described in J. Phys. Chem. 1993, 97, 6240-6248 and Appl. Phys. Lett., Vol. 66, No. 20, 2679-2681.

In general, different amines with different basic structures and / or different substitution patterns can be mixed.

X ¹ to X ⁶ independently of one another preferably represent hydrogen, fluorine, chlorine, bromine, (C, -C _{] 0} ) -, in particular (C _r C ₄ ) - alkyl or alkoxy, phenyl, naphthyl, phenoxy and / or naphthyloxy . The aromatic rings can be substituted one, two, three or four times, identically or differently, by at least one radical X ¹ to X ⁶ . The polythiophenes of the recurring structural formula (I) are known (cf. EP-A 0 440 958 and 0 339 340). The preparation of the dispersions or solutions according to the invention is described in EP-A 0 440 957 and DE-A 42 1 1 459.

The polythiophenes in the dispersion or solution are preferably in cationic form, as described e.g. can be obtained by treating the neutral thiophenes with oxidizing agents. Usual oxidizing agents such as potassium peroxodisulfate are used for the oxidation. The oxidation gives the polythiophenes positive charges, which are not shown in the formulas, since their number and their position cannot be determined properly. According to the information in EP-A 0 339 340, they can be produced directly on supports.

Q ¹ and Q ² in formula (I) are preferably - (CFI ₂ ) _n -CH ₇ - with m = 1 to 4, very particularly preferably ethylene.

Preferred cationic or neutral polydioxythiophenes are composed of structural units of the formula (Ia) or (Ib)

wherein

Q ³ and Q ⁴ independently of one another for hydrogen, optionally substituted (C _j -C _{] 8} ) alkyl, preferably (C 1 -C ₁₀ ) -, in particular (Ci-Cg) - alkyl, (C ₂ - C ₁₂ ) alkenyl , preferably (C ₂ -C ₈ ) alkenyl, (C ₃ -C ₇ ) cycloalkyl, preferably cyclopentyl, cyclohexyl, (C ₇ -C ₅ ) aralkyl, preferably phenyl (C 1 -C) alkyl, (C ₆ -C _{] 0} ) aryl, preferably phenyl, naphthyl, (C _j -C ₁₈ ) alkoxy, preferably (Cj-C ₁₀ ) alkoxy, for example methoxy, ethoxy, n- or iso-propoxy or (C ₂ - C _{] 8} ) alkyloxy ester and

Q ⁵ and Q ⁶ independently of one another for hydrogen, each with at least one sulfonate group substituted (C] -C ₁₈ ) alkyl, preferably (CC _j o) -, in particular (C _] -C ₆ ) -alkyl, (C ₂ -C ₁₂ ) alkenyl, preferably (C ₂ -C ₈ ) alkenyl, (C ₃ -C ₇ ) cycloalkyl, preferably cyclopentyl, cyclohexyl, (C ₇ -C ₅ ) aralkyl, preferably

(C ₆ -Cι ₀ ) aryl, preferably

Phenyl, naphthyl, (C _j -C _{] 8} ) alkoxy. preferably (C _r C ₁₀ ) alkoxy, for example methoxy, ethoxy, n- or iso-propoxy or (C ₂ -C ₁₈ ) alkyloxy ester, where Q ^{5 is} hydrogen, Q ^{6 is} different from hydrogen and vice versa,

n is an integer from 2 to 10,000, preferably 5 to 5,000.

Cationic or neutral polythiophenes of the formulas (Ia-1) and (Ib-I) are particularly preferred

wherein

Q ⁵ and n have the meaning given above.

To compensate for the positive charge, the cationic form of the polythiophenes contains anions, preferably polyanions.

The anions of polymeric carboxylic acids such as polyacrylic acids, polymethacrylic acid or polymaleic acids and polymeric sulfonic acids such as polystyrene sulfonic acids and polyvinyl sulfonic acids are preferably used as polyanions. These polycarbonic and sulfonic acids can also be copolymers of vinylcarbonic and vinylsulfonic acids with other polymerizable monomers, such as acrylic acid esters and styrene.

The anion of the polystyrene sulfonic acid is particularly preferred as the counter ion.

The molecular weight of the polyacids providing the polyanions is preferably 1,000 to 2,000,000, particularly preferably 2,000 to 500,000. The polyacids or their alkali metal salts are commercially available. e.g. Polystyrene sulfonic acids and

Polyacrylic acids, or can be prepared by known processes (see, for example, Houben-Weyl, Methods of Organic Chemistry, Vol. E 20 Macromolecular Substances, Part 2 (1987), p. 1 141 f). Instead of the free polyacids required for the formation of the dispersions from polydioxythiophenes and polyanions, it is also possible to use mixtures of alkali salts of the polyacids and corresponding amounts of monoacids.

In the case of formula (Ib) and (Ib-1), the polydioxythiophenes carry positive and negative charges in the monomer unit itself.

The arrangements according to the invention optionally contain polymers and / or copolymers such as e.g. Polycarbonates, polyester carbonates, copolymers of styrene such as SAN or styrene acrylates, polysulfones, polymers based on

Monomers containing vinyl groups, e.g. Poly (meth) acrylates, polyvinylpyrrolidone, polyvinylcarbazole, vinyl acetate and vinyl alcohol polymers and copolymers, polyolefins, cyclic olefin copolymers, phenoxy resins, etc. Mixtures of different polymers can also be used. The polymeric binders have molecular weights of 10,000 to 2,000,000 g / mol, are soluble and film-forming and are transparent in the visible spectral range. They are e.g. described in Encyclopedia of Polymer Science and Engineering, 2 ™ Ed., an I. Wiley Interscience publication. They are usually used in an amount of up to 95, preferably up to 80,% by weight, based on the total weight of the electroluminescent elements.

The metal complex to which a fluorescent dye is chemically bound is preferably a compound of the general formula (III) a and (I (I) b

and

wherein

Me stands for a metal

and

independently in both forms stands for atoms that complete a nucleus that consists of at least 2 condensed rings. Trivalent metals which are known to form chelates can generally be used.

The metal can be, for example, aluminum, gallium, indium or a lanthanoid.

Z completes a heterocyclic part of the molecule, which consists of at least two fused rings, one of which is an azole or azine ring, and further additional aliphatic or aromatic rings can be attached to the two amieled rings.

The component is particularly preferably a compound of the general formulas (III) c and (IΙI) d

in which

R _{j is} particularly preferred

and

R ₂ , R ₃ , R4, R ₅ , R independently of one another for hydrogen optionally substituted (Ci-Cig) - alkyl or acyl or halogen or optionally substituted aryl or cyano or sulfonamide or an optionally substituted amino group

and

Me stands for particularly preferred Al or Ga.

A compound of the general formulas (IIIc) and (IIld) very particularly preferably stands for the metal complex.

in which

R _] very particularly preferably represents methyl and

R, R ₃ , R ₄ , R ₅ , R, 5 independently of one another very particularly preferably represent hydrogen, optionally substituted (C _j -C _j o) alkyl or acyl or sulfonamide

and

Me very particularly preferably stands for Al, Ga.

Examples include:

One or more compounds of the formulas B1 to B8 can be used. Some of the 8-hydroxyquinoline ligands are commercially available or can be prepared by known organic chemical processes (RGW Hallingshead, Vol.l, Chap. 6, Butterworths, London (1954)). The metal complexes can also be produced by known processes (cf., for example, US Pat. No. 4,769,292).

Fluorescent dyes are generally known and some are commercially available.

To produce the electroluminescent element, the metal complex and, if appropriate, the tertiary amino compound and the binder are dissolved in a suitable solvent and applied to a suitable base by casting, knife coating or spin coating. However, the metal complex can optionally also be applied separately as a layer by means of a vapor deposition process. The underlay can e.g. are glass or a plastic material that is provided with a transparent electrode. As a plastic material e.g. a

Polycarbonate film, polyester such as polyethylene terephthalate or polyethylene naphthalate, polysulfone or polyimide can be used.

Suitable as transparent electrodes

a) metal oxides, e.g. Indium tin oxide (ITO), tin oxide (NESA), zinc oxide, doped tin oxide, doped zinc oxide, etc.,

b) semi-transparent metal films, e.g. Au, Pt, Ag, Cu etc.,

c) conductive polymer films such as polyanilines, polythiophenes, etc.

The metal oxide and semi-transparent metal film electrodes are applied in a thin layer using techniques such as vapor deposition, sputtering, platinum plating, etc. The conductive polymer films are made by techniques such as spin coating,

Casting. Squeegees etc. applied from the solution. The thickness of the transparent electrode is 3 nm to approximately several μm, preferably 10 nm to 500 nm.

The electroluminescent layer is applied directly to the transparent electrode or to a charge-transporting layer which may be present as a thin film. The thickness of the film is 10 to 500 nm, preferably 20 to 400 nm, particularly preferably 50 to 250 nm.

Another charge-transporting layer can be applied to the electroluminescent layer

Layer be inserted before a counter electrode is applied.

A compilation of suitable charge-transporting intermediate layers, which can be hole- and / or electron-conducting materials, which can optionally be present as a blend in polymeric or low molecular weight form, is listed in EP-A 0 532 798. Specially substituted polythiophenes which have hole-transporting properties are particularly suitable. They are described, for example, in EP-A 0 686 662.

The content of low molecular hole conductor in a polymeric binder is in

Range can be varied from 2 to 97% by weight; the content is preferably 5 to

95% by weight, particularly preferably 10 to 90% by weight, in particular 10 to 85% by weight.

The hole-injecting or hole-conducting zones can be deposited using various methods.

Film-forming hole conductors can also be used in pure form (100%).

If appropriate, the hole-injecting or hole-conducting zone can also contain portions of an electroluminescent substance.

Blends that consist exclusively of low molecular weight compounds can be evaporated; soluble and film-forming blends, which in addition to low molecular weight Compounds which can also contain a binder can be deposited from a solution, for example by means of spin coating, casting, or knife coating.

It is also possible to apply emitting and / or electron-conducting substances to the hole-conducting layer in a separate layer. An emitting substance can also be doped into the layer containing the compound (II) (“dopant”) and an electron-conducting substance can also be applied. An electroluminescent substance can also be added to the electron-injecting or electron-conducting layer.

The content of low molecular weight electron conductors in the polymeric binder can be varied in the range from 2 to 95% by weight; the content is preferably 5 to 90% by weight, particularly preferably 10 to 85% by weight. Film-forming electron conductors can also be used in pure form (100%).

The counter electrode consists of a conductive substance that can be transparent. Metals are preferably suitable, e.g. AI, Au. Ag, Mg, In, etc. or alloys and oxides thereof, which can be applied by techniques such as vapor deposition, sputtering, platinum plating.

The arrangement according to the invention is brought into contact with the two electrodes by means of two electrical leads (e.g. metal wires).

When a DC voltage is applied in the range from 0.1 to 100 volts, the arrangements emit light of the wavelength from 200 to 2000 nm. They show in the range from

200 to 2000 nm photoluminescence.

The arrangements according to the invention are suitable for producing units for lighting and for displaying information. Examples

example 1

2.387 g (15 mmol) of recrystallized 8-hydroxyquininaldine (commercially available from Aldrich), 1.32 g (7.5 mmol) of coumarin 4 (commercially available from ACROS) together with 1.53 g (7.5 mmol) of aluminum isopropylate in 200 ml absolute ethanol boiled under reflux under DC control. On cooling, a yellow precipitate precipitates out of the cloudy yellow solution and is washed with water and methanol.

2.72 g (5.2 mmol = 69.9% of theory) of an intensely blue-green fluorescent yellow solid are obtained. Example 2

2.387 g (15 mmol) of recrystallized 8-hydroxyquinoline, 1.32 g (7.5 mmol) of coumarin 4 are refluxed together with 1.536 g (7.5 mmol) of gallium ethoxide in 200 ml of absolute ethanol under TLC control. On cooling, a yellow precipitate precipitates out of the cloudy yellow solution and is washed with water and methanol.

2.58 g (4.59 mmol = 61.3% of theory) of an intensely green fluorescent yellow solid are obtained.

Example 3

2.387 g (15 mmol) of recrystallized 8-hydroxyquininaldine, 1.726 g (7.5 mmol) of 7-hydroxy-4- (trifluoromethyl) -coumarin (commercially available from Aldrich) together with 1.536 g (7.5 mmol) of aluminum isopropylate in 200 ml absolute ethanol boiled under reflux under DC control. On cooling, a yellow precipitate precipitates out of the cloudy yellow solution and is washed with water and methanol.

1.58 g (2.76 mmol = 36.8% of theory) of an intensely blue fluorescent lemon-yellow solid are obtained.

Examples, physical part:

example 1

The substance B1 according to the invention is used to build up an organic light emitting diode

(OLED) used. The OLED is manufactured as follows:

1. Cleaning the ITO substrate

ITO-coated glass (Merck Balzers AG, FL, Part No. 253 674 XO) is cut into 50 mm x 50 mm pieces (substrates). The substrates are then cleaned in a 3% aqueous Mukaso solution in an ultrasonic bath for 15 minutes. The substrates are then rinsed with distilled water and spun dry in a centrifuge. This rinsing and drying process is repeated 10 times.

2. Apply the ®Baytron P layer to the ITO

About 10 ml of the 1.3% polyethylene dioxythiophene / polysulphonic acid solution (Bayer AG, Baytron P) are filtered (Millipore HV, 0.45 μm). The substrate is then placed on a spin coater and the filtered solution is distributed on the ITO-coated side of the substrate.

The supernatant solution is then spun off by rotating the plate at 500 rpm over a period of 3 minutes. The substrate coated in this way is then dried on a hot plate at 110 ° C. for 5 minutes. The layer thickness is 60 nm (Tencor, Alphastep 200).

3. Application of the hole-conducting layer

5 ml of a 1.0% THF solution of the phenylamine (Agfa-Gevaert, compound AI) are filtered (Millipore HV, 0.45 μm) and distributed on the dried Baytron P layer. The supernatant solution is then spun off by rotating the plate at 500 rpm for 60 seconds. After that the substrate coated in this way was dried on a hot plate at 110 ° C. for 5 minutes. The total layer thickness is 130 nm.

4. Evaporation of the light-emitting / electron-injecting layer A third organic layer, namely the substance B1 according to the invention, is thermally evaporated onto the two organic layers thus produced. This is done in a vapor deposition system (Leybold, Univex 350). The pressure in the vapor deposition system is 10 ^{~ 3} Pa during the vapor deposition and the vapor deposition rate is 2 Å sec. The total layer thickness of the 3 organic layers is 200 nm.

5. Evaporation of the metal cathode

A metal electrode is vaporized onto the organic layer system. For this purpose, the substrate is placed with the organic layer system down on a shadow mask (hole diameter 5 mm). The elements Mg and Ag are evaporated in parallel from two evaporation boats at a pressure of 10 ^-3 Pa. The evaporation rates for Mg are: 28 Å sec. The thickness of the evaporated metal contacts is 500 nm.

The two electrodes of the organic LED are connected to a voltage source via electrical leads. The positive pole is connected to the ITO electrode, the negative pole is connected to the MgAg electrode.

Electroluminescence can be detected with a photodiode (EG&G C30809E) from a voltage of 3 volts. At a voltage of 10 volts, an area current of 35 mA / cm ^{2 flows} and the electroluminescence is clearly visible. The electroluminescent luminance, measured with a Minolta LS-100, is 250 cd / m ² . The color of the electroluminescence is green-blue with the color location: x = 0.283; y = 0.434 and the spectral curve shown in FIG. 1 (spectrometer: CDI-PDA, Sentronic GmbH).

Claims

claims

1. Electroluminescent arrangement, made up of a substrate, one

Anode, an electroluminescent element and a cathode, at least one of the two electrodes being transparent in the visible spectral range and the electroluminescent element being one or more zones from the group of the hole-injecting zone, hole-transporting zone, electroluminescent zone, electron-transporting zone and electron-injecting zone in the order mentioned contains, wherein each of the existing zones can also take on tasks of the other zones mentioned, characterized in that the electroluminescent element contains a metal complex to which a fluorescent dye is chemically bound.

2. Electroluminescent arrangement according to claim 1, characterized in that the hole-injecting zone contains a neutral or cationic polythiophene of the formula (I),

in which

Ql and Q ^ independently of one another represent hydrogen, optionally substituted (C1-C20) -alkyl, CH2OH or (Cg-C ^ -aryl) or

Q and Q ^ together represent - (CH2) _m -CH2- with m = 0 to 12, preferably 1 to 5, (C ₍ 5-Cj 4) - arylene, and n is an integer from 2 to 10,000, preferably 5 to 5,000.

3. Electroluminescent arrangements according to claim 1, characterized in that the hole-injecting zone contains a neutral or cationic polythiophene of the formula (Ia) or (Ib) or a mixture,

wherein

Q ³ and Q ⁴ independently of one another for hydrogen, optionally substituted (C _r C ₁₈ ) alkyl, (C ₂ -C ₁₂ ) alkenyl, (C ₃ -C ₇ ) cycloalkyl, (C ₇ - C ₁₅ ) aralkyl , (C ₆ -C ₁₀ ) aryl, (C _r C ₁₈ ) alkoxy or (C ₂ -C ₁₈ ) alkyloxy ester and

Q ⁵ and Q ^{6 are} independently hydrogen, each having at least one sulfonate group substituted (C _] -C ₁₈ ) alkyl, (C ₂ -C ₁₂ ) alkenyl, (C ₃ -C ₇ ) cycloalkyl, (C ₇ - C ₁₅ ) aralkyl, (C ₆ -C, ₀ ) aryl, (C, -C _lg ) alkoxy or (C ₂ -C _{] 8} ) alkyloxy ester, where Q ^{5 is} hydrogen, Q ^{6 is} different from hydrogen and vice versa, n represents an integer from 2 to 10,000.

4. Electroluminescent arrangements according to claim 3, characterized in that the cationic or neutral polythiophenes of the formulas (Ia-1) and (Ib-1) correspond,

wherein

Q ⁵ and n have the meaning given in claim 3.

Electroluminescent arrangements according to claims 1 to 4, characterized in that the anions of polymeric carboxylic acids and or polymeric sulfonic acids are contained as polyanions.

Electroluminescent arrangements according to claims 1 to 5, characterized in that polystyrene sulfonic acid and / or an alkaline earth salt thereof is contained as the counter ion.

Electroluminescent arrangement according to Claim 1, characterized in that the hole-injecting and / or hole-transporting zone contains an aromatic tertiary amino compound of the general formula (II)

R2 represents hydrogen, optionally substituted alkyl or halogen,

R ^ and R ^ independently of one another are optionally substituted (C 1 -C 8) -alkyl, alkoxycarbonyl-substituted (C 1 -C 1 C) -alkyl, in each case optionally substituted aryl, aralkyl or cycloalkyl.

8. Electroluminescent arrangement according to claim 7, characterized in that in formula (II)

R ^{2 represents} hydrogen or (C \ -Cg) -alky 1,

R3 and R ^ independently of one another for (C1-C5) -alkyl, (Cj-C4) -alkoxycarb- onyl- (Cι-Cg) -alkyl, in each case optionally through (Cj-C4) -alkyl and / or (C] - C4) - Alkoxy substituted phenyl, naphthyl, phenyl- (C _j -C4) alkyl. Naphthyl -CC -C4 alkyl, cyclopentyl or cyclohexyl.

9. Electroluminescent arrangement according to claim 7, characterized in that the tertiary amino compound is selected from the following compounds: 36

37 -

- 31

- 39

41

51

0. Electroluminescent arrangement according to claim 1, characterized in that the metal complex is a compound of the general formula (III) a and (III) b

and

wherein

Me stands for a metal

and

Z stands independently in both forms for atoms that complete a nucleus that consists of at least 2 condensed rings.

1 1. Electroluminescent arrangement according to claim 10, characterized in that Me stands for a trivalent metal that forms chelates.

12. Electroluminescent arrangement according to claim 1, characterized in that it contains one or more transparent polymeric binders and the transparent binder is selected from the group consisting of polycarbonates, polyester carbonates, copolymers of styrene such as SAN or styrene acrylates, polysulfones, polymers based on vinyl groups Monomers, polyolefins, cyclic olefin copolymers and phenoxy resins.

3. Electroluminescent arrangement according to claim 1, characterized in that the metal complex is selected from the following compounds: