EP1114474A1 - Ensembles electroluminescents comportant des complexes metalliques a base de thiophenecarboxylate - Google Patents

Ensembles electroluminescents comportant des complexes metalliques a base de thiophenecarboxylate

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Publication number
EP1114474A1
EP1114474A1 EP99942899A EP99942899A EP1114474A1 EP 1114474 A1 EP1114474 A1 EP 1114474A1 EP 99942899 A EP99942899 A EP 99942899A EP 99942899 A EP99942899 A EP 99942899A EP 1114474 A1 EP1114474 A1 EP 1114474A1
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EP
European Patent Office
Prior art keywords
alkyl
electroluminescent
optionally substituted
hole
hydrogen
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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EP99942899A
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German (de)
English (en)
Inventor
Helmut-Werner Heuer
Rolf Wehrmann
Andreas Elschner
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Bayer AG
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Bayer AG
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Publication of EP1114474A1 publication Critical patent/EP1114474A1/fr
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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/18—Light sources with substantially two-dimensional radiating surfaces characterised by the nature or concentration of the activator
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D215/20—Oxygen atoms
    • C07D215/24—Oxygen atoms attached in position 8
    • C07D215/26—Alcohols; Ethers thereof
    • C07D215/30—Metal salts; Chelates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
    • C07D333/24—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D333/38—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/06—Aluminium compounds
    • C07F5/069—Aluminium compounds without C-aluminium linkages
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
    • C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/321—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3]
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
    • H10K85/1135—Polyethylene dioxythiophene [PEDOT]; Derivatives thereof
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/917—Electroluminescent

Definitions

  • An electroluminescent (EL) arrangement is characterized in that it emits light when an electrical voltage is applied under current flow.
  • LEDs light emitting diodes
  • the emission of light occurs because positive charges ("holes”, holes) and negative charges (“electrons”, electrons) recombine while emitting light.
  • 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.
  • 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-A 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.
  • 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:
  • Layers 3 to 7 represent the electroluminescent element.
  • 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 described, for example, in application 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.
  • zone is synonymous with layer.
  • the present invention therefore relates to an electroluminescent arrangement composed of a substrate, an 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, each of the zones present also being able to take on tasks of the other zones mentioned, characterized in that the electroluminescent element contains a thiophene carboxylate metal complex.
  • the hole-injecting zone preferably contains a neutral or cationic polythiophene of the formula (I)
  • Ql and Q ⁇ independently of one another represent hydrogen, optionally substituted (Cl-C2 ⁇ ) - Alkvl > CH2OH or (Cg-Ci ⁇ -aryl or
  • n is 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.
  • 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, 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)
  • R 2 represents hydrogen, optionally substituted alkyl or halogen
  • R3 and R ⁇ independently of one another represent optionally substituted (C J -C J Q) alkyl, alkoxycarbonyl-substituted (C] -C] o) alkyl, each optionally substituted aryl, aralkyl or cycloalkyl.
  • R ⁇ and R ⁇ independently of one another preferably represent (Cj-Cg) alkyl, in particular methyl, ethyl, n- or iso-propyl, n-, iso-, sec- or tert-butyl, (Cj-C4) - Alkoxycarbonyl- (C ⁇ -C6) -alkyl, such as, for example, methoxy-, ethoxy-, propoxy-, butoxycarbonyl- (C ⁇ -C4) -alkyl, in each case optionally by (C1-C4) -alkyl and / or (C] - C4) alkoxy substituted phenyl- (C 1 -C 4 ) alkyl, naphthyl- (C 1 -C 4 ) alkyl, cyclopentyl, cyclohexyl, phenyl or naphthyl.
  • Cj-Cg alkyl, in particular methyl, ethyl,
  • R-3 and R ⁇ are particularly preferably independently of one another unsubstituted phenyl or naphthyl or in each case monosubstituted to triple by methyl, ethyl, n-, iso-propyl, methoxy, ethoxy, n- and / or iso-propoxy-substituted phenyl or naphthyl.
  • R2 preferably represents hydrogen, (Ci-Cg) alkyl, such as methyl, ethyl, n- or isopropyl, n-, iso-, sec- or tert-butyl, or chlorine.
  • the tris-nitrophenyl compound can be converted into the tris-aminophenyl compound, for example by generally known catalytic hydrogenation, for example in the presence of Raney nickel (Houben-Weyl 4 / IC, 14-102, Ullmann (4) 13 , 135-148).
  • the amino compound is reacted in a generally known manner with substituted halogenobenzenes.
  • further hole conductors e.g. in the form of a mixture with the tertiary amino compound, used to build up the electroluminescent element.
  • it can be one or more compounds of the formula (II), mixtures of isomers being included, on the other hand, it can also be mixtures of hole-transporting compounds with compounds of tertiary amino compounds - with the general formula (II) - with different structures.
  • the compounds can be used in any ratio.
  • Materials which have hole-conducting properties and can be used in pure form or as mixing partners with the tertiary amino compounds are, for example, the following compounds, where X 1 to X 6 independently of one another represent H, halogen, alkyl, aryl, alkoxy, aryloxy.
  • X 1 to X 6 independently of one another preferably represent hydrogen, fluorine, chlorine, bromine, (C ] -C 10 ) -, 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 unit of the 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 11 459.
  • the polythiophenes in the dispersion or solution are preferably in cationic form, as described e.g. obtained by treating the neutral thiophenes with oxidizing agents.
  • 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.
  • Preferred cationic or neutral polydioxythiophenes are composed of structural units of the formula (Ia) or (Ib)
  • Q 3 and Q 4 independently of one another for hydrogen, optionally substituted (C 1 -C 18 ) alkyl, preferably (C] -C 10 ), in particular (CC 6 ) alkyl, (C 1 -C 2 ) alkenyl, preferably ( C -C 8 ) alkenyl, (C 3 -C 7 ) cycloalkyl, preferably cyclopentyl, cyclohexyl, (C 7 -Cj 5 ) aralkyl, preferably phenyl (C j - C) alkyl, (C 6 -C 10 ) aryl, preferably phenyl, naphthyl, (C r C 18 ) alkoxy, preferably (-C-C ⁇ o) alkoxy, for example methoxy, ethoxy, n- or iso-propoxy or (C 2 -Ci8) alkyloxy ester and
  • Q 5 and Q 6 independently of one another for hydrogen, each substituted with at least one sulfonate group (-CC 8 ) -alkyl, preferably (C Cjo) -, in particular (C r 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 phenyl (C 1 -C 4 ) alkyl, (C 6 -C 10 ) aryl, preferably
  • 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.
  • the cationic form of the polythiophenes contains anions, preferably polyanions.
  • 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.
  • 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 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).
  • free polyacids 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.
  • 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 such as, for example, 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 described, for example, in Encyclopedia of Polymer Science and Engineering, 2 nc Ed. a 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 thiophene carboxylate metal complex is preferably a compound of the general formula (III) a to (III) g
  • V j , V 2 , V 3 and V 4 represent an optionally substituted and / or optionally branched alkylene radical or an optionally substituted thiophene or oligothiophene radical,
  • V 5 represents an alkylene radical or a single bond
  • Z stands independently in both forms for atoms which complete a part of the molecule which consists of at least 2 condensed rings
  • R j to R 20 independently of one another represent hydrogen or optionally substituted (-CC 16 ) alkyl or (-C-C ] 0 ) - alkoxy, where in the case of alkoxy substitution adjacent substituents can be linked to form a ring,
  • Trivalent metals which are known to form chelates can generally be used.
  • the metal can be aluminum, gallium, indium or a lanthanoid.
  • Z completes a heterocyclic moiety that consists of at least two fused rings, one of which is an azole or azine ring, with additional additional aliphatic or aromatic rings attached to the two fused rings.
  • the component is particularly preferably a compound of the general formulas (I ⁇ I) h to (I ⁇ I) n
  • R 2 stands for particularly preferred (C 1 -C jg) alkyl
  • R 22 to R 26 independently of one another for hydrogen optionally substituted (C ] -C ⁇ 6 ) alkyl or acyl or halogen or optionally substituted Aryl or cyano or sulfonamide or an optionally substituted amino group,
  • R 27 to R 40 independently of one another are hydrogen or optionally substituted or (Cj-Cj 0 ) - alkoxy, where in the case of alkoxy substitution adjacent substituents can be linked to form a ring,
  • a compound of the general formulas (III) h to (III) n very particularly preferably stands for the thiophene carboxylate metal complex
  • R 1 is very particularly preferably (C 1 -C 10 ) -alkyl 1
  • R 22 to R 26 independently of one another very particularly preferably represent hydrogen, optionally substituted (C] -C] o) - alkyl- or acyl or sulfonamide
  • R 27 to R 40 are independently hydrogen or optionally substituted or (C J-CJ O) - alkoxy, where in the case of alkoxy substitution adjacent substituents can be linked to form a ring,
  • V3 and V 4 very particularly represent an alkylene radical
  • V 5 stands especially for a direct link
  • Examples include:
  • One or more compounds of the formulas B1 to B13 can be used.
  • 8-hydroxyquinoline ligands are commercially available or can be prepared by known organic chemical processes (R.G.W. Hallingshead, Voll, Chap. 6, Butterworths, London (1954)).
  • the metal complexes can also be prepared by known processes (L.S. Sapachak et al., J. Phys. Chem. 100, 177766 (1996) and H. Schmidbauer et al., Z. Naturforsch. 46b, 1065 (1991)).
  • the thiophene derivatives are commercially available or can be prepared by known organic chemical processes.
  • the thiophene carboxylate 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.
  • the metal complex can optionally also be applied separately as a layer by means of a vapor deposition process.
  • the base can be, for example, glass or a plastic material that is provided with a transparent electrode.
  • a film made of polycarbonate, polyester such as polyethylene terephthalate or polyethylene naphthalate, polysulfone or polyimide can be used as the plastic material.
  • metal oxides e.g. Indium tin oxide (ITO), tin oxide (NESA), zinc oxide, doped tin oxide, doped zinc oxide, etc.
  • ITO Indium tin oxide
  • NESA tin oxide
  • zinc oxide doped tin oxide
  • doped zinc oxide etc.
  • conductive polymer films such as polyanilines, polythiophenes, etc.
  • the metal oxide and semi-transparent metal film electrodes are made by
  • the conductive polymer films are applied from the solution using techniques such as spin coating, casting, knife coating etc.
  • the thickness of the transparent electrode is 3 nm to approximately several ⁇ m, 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
  • a further charge-transporting layer can be inserted on the electroluminescent layer before a counterelectrode is applied.
  • EP-A 0 532 798 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 can be varied in the range 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 can also contain a binder in addition to low molecular weight compounds, can be obtained from a solution e.g. be deposited by means of spin coating, casting, knife coating.
  • emitting and / or electron-conducting substances can be applied 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 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. Al, 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).
  • the arrangements When a direct voltage is applied in the range from 0J to 100 volts, the arrangements emit light of the wavelength from 200 to 2000 nm. They show photoluminescence in the range from 200 to 2000 nm.
  • the arrangements according to the invention are suitable for producing units for lighting and for displaying information.
  • Substance B4 according to the invention is used to build up an organic light emitting diode
  • OLED used.
  • the OLED is manufactured as follows:
  • 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 mucasol 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.
  • 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).
  • a third organic layer namely the substance B4 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 ⁇ sec.
  • the total layer thickness of the 3 organic layers is 200 nm.
  • a metal electrode is vaporized onto the organic layer system.
  • 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 ⁇ / sec.
  • the thickness of the vapor-deposited metal contacts is 500 nm.
  • the two electrodes of the organic LED are connected to a voltage source via electrical fillings.
  • the positive pole is connected to the ITO electrode, the negative pole is connected to the MgAg electrode.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Electroluminescent Light Sources (AREA)
  • Heterocyclic Compounds Containing Sulfur Atoms (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)

Abstract

L'invention concerne un ensemble électroluminescent constitué d'un substrat, d'une anode, d'un élément électroluminescent et d'une cathode, au moins une des deux électrodes étant transparentes dans le domaine spectral visible et l'élément électroluminescent contenant une ou plusieurs zones, dans l'ordre suivant, du groupe comportant une zone d'injection de trous, une zone de transport de trous, une zone électroluminescente, une zone de transport d'électrons et une zone d'injection d'électrons. Chacune des zones présentes peut prendre en charge les fonctions des autres zones. L'ensemble électroluminescent présenté se caractérise en ce que l'élément électroluminescent contient un complexe métallique à base de thiophènecarboxylate.
EP99942899A 1998-09-02 1999-08-23 Ensembles electroluminescents comportant des complexes metalliques a base de thiophenecarboxylate Withdrawn EP1114474A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19839947 1998-09-02
DE19839947A DE19839947A1 (de) 1998-09-02 1998-09-02 Elektrolumineszierende Anordnungen mit Thiophencarboxylat-Metallkomplexen
PCT/EP1999/006151 WO2000014815A1 (fr) 1998-09-02 1999-08-23 Ensembles electroluminescents comportant des complexes metalliques a base de thiophenecarboxylate

Publications (1)

Publication Number Publication Date
EP1114474A1 true EP1114474A1 (fr) 2001-07-11

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EP99942899A Withdrawn EP1114474A1 (fr) 1998-09-02 1999-08-23 Ensembles electroluminescents comportant des complexes metalliques a base de thiophenecarboxylate

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US (1) US6503643B1 (fr)
EP (1) EP1114474A1 (fr)
JP (1) JP2002524830A (fr)
KR (1) KR20010079716A (fr)
AU (1) AU5623699A (fr)
DE (1) DE19839947A1 (fr)
TW (1) TW515836B (fr)
WO (1) WO2000014815A1 (fr)

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Publication number Publication date
WO2000014815A1 (fr) 2000-03-16
TW515836B (en) 2003-01-01
AU5623699A (en) 2000-03-27
KR20010079716A (ko) 2001-08-22
US6503643B1 (en) 2003-01-07
JP2002524830A (ja) 2002-08-06
DE19839947A1 (de) 2000-03-09

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