WO2013010661A1 - Couches sam avec une fonction htl - Google Patents

Couches sam avec une fonction htl Download PDF

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Publication number
WO2013010661A1
WO2013010661A1 PCT/EP2012/002989 EP2012002989W WO2013010661A1 WO 2013010661 A1 WO2013010661 A1 WO 2013010661A1 EP 2012002989 W EP2012002989 W EP 2012002989W WO 2013010661 A1 WO2013010661 A1 WO 2013010661A1
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Prior art keywords
layer
layered body
tetraarylbenzidine
polythiophene
general formula
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PCT/EP2012/002989
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English (en)
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Wilfried LÖVENICH
Timo Meyer-Friedrichsen
Stephan Kirchmeyer
Andreas Elschner
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Heraeus Precious Metals Gmbh & Co. Kg.
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Publication of WO2013010661A1 publication Critical patent/WO2013010661A1/fr

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    • 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
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/57—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton
    • C07C211/58—Naphthylamines; N-substituted derivatives thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/48—Conductive polymers
    • H—ELECTRICITY
    • 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
    • H10K85/633—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising polycyclic condensed aromatic hydrocarbons as substituents on the nitrogen atom
    • 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
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1007—Non-condensed systems
    • 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
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1011—Condensed systems
    • 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
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1014—Carbocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
    • 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]
    • H10K50/17—Carrier injection layers
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to ⁇ , ⁇ , ⁇ ', ⁇ '-tetraarylbenzidine derivatives, a layered body, a process for the production of a layered body, the layered body obtainable by this process, electronic components comprising a layered body and the use of an ⁇ , ⁇ , ⁇ ', ⁇ '-tetraarylbenzidine derivative.
  • An electroluminescent arrangement is characterized in that when an electrical voltage is applied, it emits light with a flow of current.
  • Such arrangements have been known for a long time by the name “light-emitting diodes” (LEDs).
  • LEDs light-emitting diodes
  • the emission of light arises by positive charges (holes) and negative charges (electrons) recombining with the emission of light.
  • LEDs customary in the art are all made predominantly of inorganic semiconductor materials.
  • EL arrangements of which the essential constituents are organic materials have been known for some years.
  • OLED organic light-emitting diode
  • the main layer configuration of an EL arrangement is e.g. as follows:
  • an EL arrangement consists of two electrodes, between which is an organic layer which fulfils all the functions - including the emission of light.
  • the polymerization of EDOT is carried out in an aqueous solution of the polyanion, and a polyelectrolyte complex is formed.
  • Cationic polythiophenes which contain polymeric anions as counter-ions for charge compensation are also often called polythiophene/polyanion complexes in the technical field. Due to the polyelectrolyte properties of PEDOT as a polycation and PSS as a polyanion, this complex in this context is not a true solution, but rather a dispersion.
  • NPB bis(l-naphthyl)-N,N'-diphenylbenzidine
  • the present invention was based on the object of overcoming the disadvantages resulting from the prior art in connection with OLEDs, in particular in connection with OLEDs which include hole injection layers comprising conductive polymers, in particular hole injection layers comprising polythiophenes and polyanions functional ized with acid groups.
  • the present invention was based on the object of providing compounds which are suitable as a hole transport or electron blocking layer, in particular on a hole injection layer comprising PEDOT/PSS, and which as far as possible are not washed off from this PEDOT/PSS layer when further layers, for example an emitter layer, are deposited on this hole transport or electron blocking layer from aqueous or organic solutions.
  • the present invention was furthermore based on the object of providing a layered body comprising a hole injection layer and a hole transport and/or electron blocking layer, the hole injection layer comprising conductive polymers, in particular conductive polymers comprising polythiophenes and polyanions functionalized with acid groups.
  • the hole transport and/or electron blocking layer should as far as possible not be washed off from the hole injection layer when further layers, for example an emitter layer, are deposited on this hole transport or electron blocking layer from aqueous or organic solutions.
  • the present invention was also based on the object of providing a process for the production of a layered body which renders possible the production of hole injection layers comprising conductive polymers, in particular conductive polymers including polythiophenes and polyanions functionalized with acid groups, followed by a hole transport and/or electron blocking layer by means of process measures which are as simple as possible.
  • a contribution towards achieving the abovementioned objects is made by ⁇ , ⁇ , ⁇ ', ⁇ '-tetraarylbenzidine derivatives of the general formula (I)
  • R can in each case be identical or different and in each case represents a hydrogen atom, a halogen atom, or an optionally substituted, straight-chain or branched Ci-C3o-alkyl group,
  • Ar can in each case be identical or different and represents an optionally mono- or polysubstituted aryl radical, wherein at least one of the aryl radicals is substituted by at least one radical -R -NR 2 R 3 , in which — R 1 represents a straight-chain or branched C 2 -C 20 -alkylene radical, particularly preferably a straight-chain or branched C 3 -Ci5-alkylene radical and most preferably a straight-chain or branched C4-C 10 - alkylene radical and R and R can be identical or different and in each case represent a hydrogen atom or a d-Cs-alkyl group, but particularly preferably a hydrogen atom.
  • ⁇ , ⁇ , ⁇ ', ⁇ '-tetraarylbenzidine derivatives of the general formula (I) can form a self-assembled monolayer (SAM) on a surface of a conductive polymer, in particular on a surface of a conductive polymer comprising a polythiophene and a polymer functionalized with acid groups, for example on a PEDOT : PSS surface, and an SAM layer of these ⁇ , ⁇ , ⁇ ', ⁇ '- tetraarylbenzidine derivatives can be employed, for example, as a hole transport layer in an OLED.
  • SAM self-assembled monolayer
  • ⁇ , ⁇ , ⁇ ', ⁇ '-tetraarylbenzidine derivatives according to the invention, these have the general formula (II) in which R 4 and R 5 correspond to the radical R, as defined above, with the proviso that at least one of the radicals R 4 represents a radical -R'-NR 2 R 3 , as likewise defined above.
  • R 4 and R 5 correspond to the radical R, as defined above, with the proviso that at least one of the radicals R 4 represents a radical -R'-NR 2 R 3 , as likewise defined above.
  • R 4 and R 5 correspond to the radical R, as defined above, with the proviso that at least one of the radicals R 4 represents a radical -R'-NR 2 R 3 , as likewise defined above.
  • R 4 and R 5 correspond to the radical R, as defined above, with the proviso that at least one of the radicals R 4 represents a radical -R'-NR 2 R 3 , as likewise defined above.
  • R 4 and R 5 correspond
  • R represents a radical -R -NR R as defined above.
  • R 4 represents a radical -R ! -NR 2 R 3 as defined above.
  • R 1 represents a C 2 -Ci 0 - alkylene group, in particular -(C H ]2 )-, and for R and R to represent a hydrogen atom.
  • a contribution towards achieving the abovementioned objects is also made by a layered body comprising at least - a first layer comprising a conductive polymer; a further layer following the first layer, comprising an ⁇ , ⁇ , ⁇ ', ⁇ '- tetraarylbenzidine derivative according to the invention.
  • the layered body according to the invention comprises a first layer which comprises a conductive polymer and which preferably serves as a hole injection layer.
  • a conductive polymer in this context are all polymers which have an electrical conductivity, such as, for example, conductive polymers based on optionally substituted polyanilines, optionally substituted polypyrroles or optionally substituted polythiophenes, conductive polymers based on optionally substituted polythiophenes being particularly preferred.
  • the conductive polymer in the first layer comprises a preferably cationic polythiophene and a preferably anionic polymer functionalized with acid groups.
  • the polythiophene is preferably a polythiophene with recurring units of the general formula (i) or (ii) or a combination of units of the general formulae (i) and (ii), preferably a polythiophene with recurring units of the general formula (ii) wherein
  • A represents an optionally substituted Ci-Cs-alkylene radical
  • R represents a linear or branched, optionally substituted Q-ds-alkyl radical, an optionally substituted C 5 -C 12 -cycloalkyl radical, an optionally substituted C 6 -C 14 -aryl radical, an optionally substituted C 7 -C 18 -aralkyl radical, an optionally substituted C 1 -C 4 -hydroxyalkyl radical or a hydroxyl radical, x represents an integer from 0 to 8 and in the case where several radicals R are bonded to A, these can be identical different.
  • Polythiophenes with recurring units of the general formula (ii) wherein A represents an optionally substituted C 2 -C 3 -alkylene radical and x represents 0 or 1 are particularly preferred.
  • Poly(3,4-ethylenedioxythiophene), which is optionally substituted, is very particularly preferred as the polythiophene.
  • the prefix poly- is to be understood as meaning that the polymer or polythiophene contains more than one identical or different recurring units of the general formulae (i) and (ii).
  • the polythiophenes can optionally also comprise other recurring units, but it is preferable for at least 50%, particularly preferably at least 75% and most preferably at least 95% of all recurring units of the polythiophene to have the general formula (i) and/or (ii), preferably the general formula (ii).
  • the polythiophenes contain a total of n recurring units of the general formula (i) and/or (ii), preferably of the general formula (ii), wherein n is an integer from 2 to 2,000, preferably 2 to 100.
  • the recurring units of the general formula (i) and/or (ii), preferably of the general formula (ii), can in each case be identical or different within a polythiophene.
  • Polythiophenes with in each case identical recurring units of the general formula (ii) are preferred.
  • the polythiophenes preferably in each case carry H on the end groups.
  • Cj-Cs-alkylene radicals A are preferably methylene, ethylene, n-propylene, n-butylene or n-pentylene.
  • C]-C 18 -alkyl radicals preferably represent linear or branched Ci-Ci 8 -alkyl radicals, such as methyl, ethyl, n- or iso-propyl, n-, iso-, sec- or tert-butyl, n-pentyl, 1 -methyl butyl, 2-methylbutyl, 3-methylbutyl, 1 -ethylpropyl, 1,1-dimethylpropyl, 1,2- dimethylpropyl, 2,2-dimethylpropyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n- nonyl, n-decyl, n-undecyl, n-do
  • radicals A and/or of the radicals R for example alkyl, cycloalkyl, aryl, aralkyl, alkoxy, halogen, ether, thioether, disulphide, sulphoxide, sulphone, sulphonate, amino, aldehyde, keto, carboxylic acid ester, carboxylic acid, carbonate, carboxylate, cyano, alkylsilane and alkoxysilane groups and carboxamide groups.
  • the polythiophenes can be neutral or cationic. In preferred embodiments they are cationic, "cationic" relating only to the charges on the polythiophene main chain.
  • the polythiophenes can carry positive and negative charges in the structural unit, depending on the substituent on the radicals R, the positive charges being on the polythiophene main chain and the negative charges optionally being on the radicals R substituted by sulphonate or carboxylate groups.
  • the positive charges of the polythiophene main chain can be partly or completely satisfied by the anionic groups optionally present on the radicals R. Overall, in these cases the polythiophenes can be cationic, neutral or even anionic.
  • the positive charges on the polythiophene main chain are the deciding factor.
  • the positive charges are not shown in the formulae, since their precise number and position cannot be determined absolutely. However, the number of positive charges is at least 1 and at most n, where n is the total number of all recurring units (identical or different) within the polythiophene.
  • the first layer furthermore comprises a polyanion based on polymers functionalized with acid groups.
  • Anions of polymeric carboxylic acids such as polyacrylic acids, polymethacrylic acid or polymaleic acids, or of polymeric sulphonic acids, such as polystyrenesulphonic acids and polyvinylsulphonic acids, are possible in particular as the polyanion.
  • These polycarboxylic and -sulphonic acids can also be copolymers of vinylcarboxylic and vinylsulphonic acids with other polymerizable monomers, such as acrylic acid esters and styrene.
  • the first layer contains an anion of a polymeric carboxylic or sulphonic acid for compensation of the positive charge of the polythiophene.
  • PSS polystyrenesulphonic acid
  • a polythiophene which, if a polythiophene is used, in particular poly(3,4-ethylenedioxythiophene), is preferably present bonded as a complex in the form of the PEDOT : PSS complexes known from the prior art, is particularly preferred as the polyanion.
  • Such complexes are obtainable by polymerizing the thiophene monomers, preferably 3,4-ethylenedioxythiophene, oxidatively in aqueous solution in the presence of polystyrenesulphonic acid.
  • the molecular weight of the polymers functionalized with acid groups which supply the polyanions is preferably 1,000 to 2,000,000, particularly preferably 2,000 to 500,000.
  • the polymers functionalized with acid groups or their alkali metal salts are commercially obtainable, e.g. polystyrenesulphonic acids and polyacrylic acids, or can be prepared by known processes (see e.g. Houben Weyl, Methoden der organischen Chemie, vol. E 20 Makromolekulare Stoffe, part 2, (1987), p. 1 141 et seq.).
  • Polymers functionalized with acid groups (polyanions) and polythiophenes, in particular polystyrenesulphonic acid and poly(3,4-ethylenedioxythiophene), can be present in the first layer in a weight ratio of from 0.5 : 1 to 50 : 1, preferably from 1 : 1 to 30 : 1, particularly preferably 2 : 1 to 20 : 1.
  • the weight of the electrically conductive polymers here corresponds to the weight of the monomers employed for the preparation of the conductive polymers, assuming that complete conversion takes place during the polymerization.
  • the polystyrenesulphonic acid is present in an excess by weight compared with the polythiophene, in particular compared with poly(3,4-ethylenedioxythiophene).
  • the first layer consists of the polythiophene and the polymer functionalized with acid groups, particularly preferably PEDOT : PSS, to the extent of at least 40 wt.%, particularly preferably to the extent of at least 55 wt.% and most preferably to the extent of at least 70 wt.%, in each case based on the total weight of the first layer.
  • the layer thickness of the first layer is preferably in a range of from 1 nm to 10 ⁇ , particularly preferably in a range of from 10 nm to 500 nm and most preferably in a range of from 20 nm to 200 nm.
  • the layered body according to the invention comprises a further layer which follows the first layer and comprises the ⁇ , ⁇ , ⁇ ', ⁇ '-tetraarylbenzidine derivative according to the invention described above, it being particularly preferable according to the invention for this further layer to be a layer which forms a self-assembled monolayer (SAM).
  • SAM self-assembled monolayer
  • a self- assembled monolayer in general forms spontaneously when a substrate is immersed in a fluid comprising the ⁇ , ⁇ , ⁇ ', ⁇ '-tetraarylbenzidine derivative. It is an organized layer of amphiphilic molecules, one end of the particular molecules having a specific, reversible affinity for a substrate.
  • SAMs have a defined layer thickness, conventionally a layer thickness in the range of from approximately 0.5 to 3 nm.
  • a contribution towards achieving the abovementioned objects is also made by a process for the production of a layered body, comprising the process steps i) application of a conductive polymer to a substrate to obtain a first layer; ii) application of an ⁇ , ⁇ , ⁇ ', ⁇ '-tetraarylbenzidine derivative according to the invention.
  • a conductive polymer is applied to a substrate to obtain a first layer.
  • Possible substrates in this context are all layers which can be employed in electronic components, such as, for example, an OLED.
  • the substrate can thus be in particular a substrate which is provided with a preferably transparent base electrode and is preferably likewise transparent.
  • the transparent substrate which can be employed in this context is glass, PET or other transparent plastics, for example, on to which a transparent electrically conductive electrode, such as e.g. an electrode of indium tin oxide (ITO), doped zinc oxide or tin oxide or a conductive polymer, is then applied.
  • a transparent electrically conductive electrode such as e.g. an electrode of indium tin oxide (ITO), doped zinc oxide or tin oxide or a conductive polymer
  • transparent substrates of plastic are, for example, polycarbonates, polyesters, such as e.g.
  • PET and PEN polyethylene terephthalate or polyethylene-naphthalene dicarboxylate
  • copolycarbonates polyacrylates, polysulphones, polyether sulphones (PES), polyimides, polyethylene, polypropylene, cyclic polyolefins or cyclic olefin copolymers (COC), hydrogenated styrene polymers or hydrogenated styrene copolymers.
  • Suitable polymer substrates can also be, for example, films, such as polyester films, PES films from Sumitomo or polycarbonate films from Bayer AG (Makrofol ® ). Glass coated with ITO is particularly preferred according to the invention as the substrate.
  • the conductive polymer is applied to such a substrate or also the electrode layer applied to such a substrate to obtain the first layer of the layered body according to the invention, those conductive polymers which have already been mentioned above as the preferred conductive polymer in connection with the layered body according to the invention being particularly preferred as the conductive polymer.
  • a conductive polymer comprising a polythiophene, particularly preferably PEDOT, and a polymer fiinctionalized with acid groups, particularly preferably PSS is accordingly particularly preferred according to the invention, here also the use of PEDOT : PSS complexes as the conductive polymer being very particularly preferred.
  • the conductive polymer is applied to the substrate in the form of a dispersion comprising the conductive polymer and a dispersing agent, particularly preferably in the form of a dispersion comprising a polythiophene, a polymer fiinctionalized with acid groups and a dispersing agent, very particularly preferably in the form of a PEDOT : PSS dispersion, and the dispersing agent is then at least partially removed to obtain the first layer.
  • a dispersing agent particularly preferably in the form of a dispersion comprising a polythiophene, a polymer fiinctionalized with acid groups and a dispersing agent, very particularly preferably in the form of a PEDOT : PSS dispersion
  • the application of the dispersions can be carried out, for example, by known processes, e.g.
  • the at least partial removal of the dispersing agent is preferably carried out by drying at a temperature in a range of from 20 °C to 200 °C, it possibly being advantageous to at least partially remove the supernatant dispersion from the substrate before the drying process, for example by spinning off.
  • dispersions comprising a polythiophene, a polymer fiinctionalized with acid groups and a dispersing agent is described in principle in EP-A 1 122 274 or US 5, 1 11 ,327.
  • the polymerization of the corresponding monomelic compounds is carried out in the presence of the polymers fiinctionalized with acid groups with suitable oxidizing agents in suitable solvents.
  • suitable oxidizing agents are iron(III) salts, in particular FeCl 3 und iron(III) salts of aromatic and aliphatic sulphonic acids, H 2 0 2 , K 2 Cr 2 0 7 , K 2 S 2 0 8 , Na 2 S 2 0 8 , ⁇ 0 4 , alkali metal perborates and alkali metal or ammonium persulphates or mixtures of these oxidizing agents.
  • iron(III) salts in particular FeCl 3 und iron(III) salts of aromatic and aliphatic sulphonic acids, H 2 0 2 , K 2 Cr 2 0 7 , K 2 S 2 0 8 , Na 2 S 2 0 8 , ⁇ 0 4 , alkali metal perborates and alkali metal or ammonium persulphates or mixtures of these oxidizing agents.
  • suitable oxidizing agents are described, for example, in Handbook of Conducting Polymers (ed. Skotheim, T.A.), Marcel Dekker: New York,
  • Particularly preferred oxidizing agents are FeCl 3 , Na 2 S 2 0 8 and 2 S 2 0 8 or mixtures of these.
  • the polymerization is preferably carried out at a reaction temperature of from -20 to 100 °C. Reaction temperatures of from 20 to 100 °C are particularly preferred. If appropriate, the reaction solution is then treated with at least one ion exchanger.
  • Suitable solvents are e.g. polar solvents, such as, for example, water, alcohols, such as methanol, ethanol, 2-propanol, n-propanol, n-butanol, diacetone alcohol, ethylene glycol, glycerol or mixtures of these.
  • polar solvents such as, for example, water, alcohols, such as methanol, ethanol, 2-propanol, n-propanol, n-butanol, diacetone alcohol, ethylene glycol, glycerol or mixtures of these.
  • Aliphatic ketones such as acetone and methyl ethyl ketone, aliphatic nitriles, such as acetonitrile, aliphatic and cyclic amides, such as N,N-dimethylacetamide, ⁇ , ⁇ -dimethylformamide (DMF) and 1- methyl-2-pyrrolidone (NMP), ethers, such as tetrahydrofuran (THF), and sulphoxides, such as dimethylsulphoxide (DMSO), or mixtures of these with one another or with the abovementioned solvents are likewise suitable.
  • aliphatic ketones such as acetone and methyl ethyl ketone
  • aliphatic nitriles such as acetonitrile
  • aliphatic and cyclic amides such as N,N-dimethylacetamide, ⁇ , ⁇ -dimethylformamide (DMF) and 1- methyl-2-pyrrolidone (NMP)
  • the dispersions have a solids content in a range of from 0.01 to 20 wt.% and particularly preferably in a range of from 0.2 to 5 wt.%, i.e. they contain in total 0.01 to 20 wt.%, particularly preferably 0.2 to 5 wt.% of polythiophene(s), preferably PEDOT, of polymer functionalized with acid groups, preferably PSS, and optionally further components, such as e.g. binders, crosslinking agents and/or surfactants, in dissolved and/or dispersed form.
  • the viscosity at 20 °C of the dispersions employed for the preparation of the first layer is preferably between the viscosity of the dispersing agent and 200 mPas, preferably between the viscosity of the dispersing agent and 100 mPas.
  • the desired amount of dispersing agent can be removed from the dispersions by distillation, preferably in vacuo, or by other processes, e.g. ultrafiltration.
  • Organic, polymeric binders and/or organic, low molecular weight crosslinking agents or surfactants can moreover be added to the dispersions.
  • Corresponding binders are described e.g. in EP-A 564 91 1. There may be mentioned here by way of example polyvinylcarbazole, silanes, such as Silquest ® A 187 (OSi Specialities), or surfactants, such as the fluoro-surfactant FT 248 (Bayer AG).
  • an ⁇ , ⁇ , ⁇ ', ⁇ '- tetraarylbenzidine derivative according to the invention is then applied to the first layer to obtain a further layer, it being particularly preferable for an SAM to be formed on application of the ⁇ , ⁇ , ⁇ ', ⁇ '-tetraarylbenzidine derivative to the first layer in process step ii).
  • Preferred ⁇ , ⁇ , ⁇ ', ⁇ '-tetraarylbenzidine derivatives in this context are those ⁇ , ⁇ , ⁇ ', ⁇ '-tetraarylbenzidine derivatives which have already been described above as preferred ⁇ , ⁇ , ⁇ ', ⁇ '-tetraarylbenzidine derivatives in connection with the ⁇ , ⁇ , ⁇ ', ⁇ '-tetraarylbenzidine derivative according to the invention.
  • the ⁇ , ⁇ '- bis(l-naphthyl)-N,N'-diphenylbenzidine derivatives of the general formula (III) or (IV) are accordingly very particularly preferred in this connection.
  • the application of the ⁇ , ⁇ , ⁇ ', ⁇ '-tetraarylbenzidine derivatives to the first layer is preferably carried out by a procedure in which the ⁇ , ⁇ , ⁇ ', ⁇ '-tetraarylbenzidine derivatives are dissolved in a suitable, preferably polar solvent, for example water, an alcohol, such as, for example, methanol, ethanol, n-propanol, isopropanol, ethylene glycol or glycerol, a sulphoxide, such as, for example, dimethylsulphoxide, an ester, such as, for example, ⁇ -butyrolactone, methyl acetate or ethyl acetate, an ether, such as, for example, tetrahydrofuran or 1,4- dioxane, a ketone, such as, for example, acetone or methyl ethyl ketone, an amide, such as, for example, formamide, dimethylformamide, N-methylformamide or
  • the coating is also washed once or several times with suitable solvents after the spinning off, in order to ensure that a monolayer of the ⁇ , ⁇ , ⁇ ', ⁇ '-tetraarylbenzidine derivative remains.
  • the process conditions during application of the ⁇ , ⁇ , ⁇ ', ⁇ '-tetraarylbenzidine derivative to the first layer should preferably be chosen such that an SAM layer of the ⁇ , ⁇ , ⁇ ', ⁇ '-tetraarylbenzidine derivative is formed on the first layer comprising the conductive polymer, preferably on the layer comprising PEDOT : PSS.
  • the concentration of ⁇ , ⁇ , ⁇ ', ⁇ '-tetraarylbenzidine derivative in the solution which is employed for application of the ⁇ , ⁇ , ⁇ ', ⁇ '-tetraarylbenzidine derivative to the first layer is preferably in a range of from 0.1 to 20 wt.%, particularly preferably in a range of from 1 to 10 wt.%, in each case based on the total weight of the solution.
  • process step ii) can be followed by still further process steps, such as, for example, iii) application of an emitter layer to the hole transport layer; iv) application of an electron injection layer to the emitter layer; v) application of a cathode layer to the electron injection layer.
  • the hole transport layer or the hole injection layer can also be called an electron blocking layer. If the electron injection layer has the ability to block the hole transport, the electron injection layer can also be called a hole blocking layer.
  • Suitable materials for the emitter layer are conjugated polymers, such as polyphenylenevinylenes and/or polyfluorenes, for example the polyparaphenylenevinylene derivatives and polyfluorene derivatives described in WO-A-90/13148, or emitters from the class of low molecular weight emitters, also called "small molecules" in technical circles, such as aluminium complexes, such as, for example, tris(8-hydroxyquinolinato)aluminium (Alq 3 ), fluorescent dyestuffs, e.g. quinacridones, or phosphorescent emitters, such as, for example, Ir(ppy) 3 .
  • Further suitable materials for the emitter layer are described e.g. in DE- A-196 27 071. Tris(8-hydroxyquinolinato)aluminium (Alq 3 ) is particularly preferred according to the invention as the emitter layer.
  • metals of group IA of the periodic table which have an exit work of from 1.5 to 3.0 eV and of oxides, halides and carbonates thereof are lithium, lithium fluoride, sodium oxide, lithium oxide and lithium carbonate.
  • Examples of metals of group IIA of the periodic table, excluding Ca, which have an exit work of from 1.5 to 3.0 eV and of oxides, halides and carbonates thereof are strontium, magnesium oxide, magnesium fluoride, strontium fluoride, barium fluoride, strontium oxide and magnesium carbonate.
  • Suitable materials for the cathode layer are, in particular, transparent or translucent materials with a relatively low exit work (of preferably less than 4.0 eV).
  • metals such as, for example, lithium (Li), sodium (Na), potassium (K), rubidium (Rb), caesium (Cs), Be, magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), aluminium (Al), scandium (Sc), vanadium (V), Zn, yttrium (Y), indium (In), cerium (Ce), samarium (Sm), Eu, Tb, and ytterbium (Yb); alloys which consist of two or more of these metals; alloys which consist of one or more of these metals and one or more metals which are chosen from Au, Ag, Pt, Cu, manganese (Mn), titanium (Ti), cobalt (Co), nickel (Ni), tungsten (W) and tin (Sn); graphite
  • a contribution towards achieving the abovementioned objects is also made by a layered body, particularly preferably an OLED or an OPV element, which is or are obtainable by the process according to the invention.
  • an electronic component comprising a layered body according to the invention or a layered body obtainable by the process according to the invention, wherein this component is preferably an OLED or an OPV element, particularly preferably an
  • the layer configuration of the OLED can have all the configurations known to the person skilled in the art, but preferably the layer sequence of hole injection layer/hole transport layer is replaced by the layered body according to the invention such that further layers of ⁇ , ⁇ , ⁇ ', ⁇ '-tetraarylbenzidine derivatives according to the invention, preferably the further SAM layer of ⁇ , ⁇ , ⁇ ', ⁇ '- tetraarylbenzidine derivatives according to the invention, face the emitter layer.
  • the OLED according to the invention can have any of the following layer configurations (a) to (d) as desired:
  • the anode is arranged on the side of the substrate, for example glass or a transparent film of plastic, or an embodiment in which the cathode is arranged on the side of the substrate is used.
  • the electron transport layer can be made of materials such as, for example, oxadiazole derivatives, anthraquinodimethane or derivatives thereof, benzoquinone or derivatives thereof, naphthoquinone or derivatives thereof, anthraquinone or derivatives thereof, tetracyanoanthraquinodimethane or derivatives thereof, fluorenone derivatives, diphenyldicyanoethylene or derivatives thereof, diphenoquinone derivatives and metal complexes of 8- hydroxyquinoline or derivatives thereof, polyquinoline or derivatives thereof, polyquinoxaline or derivatives thereof or polyfluorene or derivatives thereof.
  • materials such as, for example, oxadiazole derivatives, anthraquinodimethane or derivatives thereof, benzoquinone or derivatives thereof, naphthoquinone or derivatives thereof, anthraquinone or derivatives thereof, tetracyanoanthraquinodimethane or derivatives thereof, fluor
  • an OLED which is built up from the following layers is particularly preferred according to the invention: anode layer/first layer of the layered body according to the invention or of the layered body obtainable by the process according to the invention/further layer of the layered body according to the invention or of the layered body obtainable by the process according to the invention/optionally emitter layer/optionally electron injection layer/cathode layer.
  • a contribution towards achieving the abovementioned objects is also made by the use of the ⁇ , ⁇ , ⁇ ', ⁇ '-tetraarylbenzidine derivatives of the general formula (I) according to the invention, in particular the use of the N,N'-bis(l-naphthyl)-N,N'- diphenylbenzidine derivatives of the general formula (III) or (IV) according to the invention, for the formation of an SAM in an electronic component.
  • the electronic component is preferably an OLED, very particularly preferably an OLED which is built up from the following layers: anode/hole injection layer/layer of the N,N,N',N'-tetraarylbenzidine derivative according to the invention, preferably SAM layer of the ⁇ , ⁇ , ⁇ ', ⁇ '-tetraarylbenzidine derivative according to the invention/emitter layer/electron injection layer/cathode.
  • the hole injection layer preferably comprises a conductive polymer, particularly preferably complexes of PEDOT : PSS.
  • Example 2 The combined organic phases were washed with water, dried over MgS0 4 and filtered and the solvent was stripped off in vacuo.
  • the crude product obtained (20.5 g) was purified by chromatography (silica gel 60, eluent: toluene). Yield: 10.3 g (60 % of theory); slightly reddish oil with a product content according to GC-MS analysis of 79.5 %.
  • the product was employed in Example 2 without further purification.
  • Example 2
  • Aluminium chloride (12.66 g, 94.9 mmol) was added in portions to a suspension of l-(6-bromohexano)naphthone (9.06 g, 29.7 mmol) and sodium borohydride (6.47 g, 171 mmol) in anhydrous THF (200 ml) at 0-4 °C. Then, heating under reflux was carried out for 3 hours. After cooling, water (100 ml) was slowly metered in. Ethyl acetate (100 ml) was then added, the organic phase was separated off and the aqueous phase was extracted with ethyl acetate (30 ml). The combined organic phases were dried with sodium sulphate and filtered and the solvent was evaporated.
  • N-Bromosuccinimide (2.93 g, 16.5 mmol) was added in one portion to a solution of r-(6-bromohexyl)naphthene (4.37 g, 15 mmol) in acetonitrile (45 ml). The solution was stirred for 16 hours with exclusion of light. The reaction solution was added to water (100 ml) and extracted with 3 x 50 ml of methylene chloride. The combined organic phases were dried over Na 2 S0 4 and filtered and the solvent was evaporated. The crude product obtained (4.08 g, brown oil) was purified by chromatography (silica gel, eluent: hexane).
  • 0.326 g of potassium phthalimide was added to a solution of 0.54 g of ⁇ , ⁇ '- diphenyl-N,N'-di-4-(6-bromohexyl)naphthylbenzidine in 15 ml of anhydrous DMF. The solution was stirred at 100 °C for 16 hours. After cooling, the solvent was stripped off in vacuo, water was added to the residue and the residue was filtered off, rinsed with water and dried in vacuo at 40 °C. The intermediate product was suspended in 20 ml of ethylene glycol, 0.165 g of hydrazine hydrate (98 % pure) were added and it was stirred at 175 °C for 18 hours.
  • the solution was degassed and a solution, prepared under argon, of 0.03 g (0.1 mmol) of bis(dibenzylideneacetone)palladium(0) and 0.01 g (0.05 mmol) of tri-tert- butylphosphine in 15 ml of anhydrous toluene was then injected at 1 10 °C.
  • the reaction solution was boiled under reflux for 19.5 h. After cooling, 250 ml of methylene chloride were added and extracted with 2 x 40 ml of water. The organic phase was dried over Na 2 S0 4 , filtered and concentrated.
  • the crude product obtained was purified by chromatography (silica gel, mobile phase: hexane/toluene 1 : 1).
  • N,N'-Diphenyl-N-4-(6-bromohexyl)naphthyl-N'-4-naphthylbenzidine is reacted in accordance with Example 7 to give the product.

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Abstract

La présente invention concerne des dérivés de Ν,Ν,Ν',Ν'-tétraarylbenzidine de formule générale (I) dans laquelle R peut dans chaque cas être identique ou différent et dans chaque cas représente un atome d'hydrogène, un atome d'halogène, ou un groupe alkyle éventuellement substitué, à chaîne linéaire ou ramifié en C1 à C30, Ar peut dans chaque cas être identique ou différent et représente un radical aryle éventuellement mono- ou poly-substitué, au moins un des radicaux aryle étant substitué par au moins un radical -R1-NR2R3, où R1 représente un radical alkylène à chaîne linéaire ou ramifié en C2 à C20 et R2 et R3 peuvent être identiques ou différents et dans chaque cas représentent un atome d'hydrogène ou un groupe alkyle en C1 à C5. L'invention concerne également un corps en couches, un procédé pour la production d'un corps en couches, le corps en couches pouvant être obtenu par le présent procédé, des composants électroniques comprenant un corps en couches et l'utilisation d'un dérivé de Ν,Ν,Ν',Ν'-tétraarylbenzidine.
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