EP1984964A1 - Composant electronique, son procede de fabrication et d'utilisation - Google Patents

Composant electronique, son procede de fabrication et d'utilisation

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Publication number
EP1984964A1
EP1984964A1 EP07703163A EP07703163A EP1984964A1 EP 1984964 A1 EP1984964 A1 EP 1984964A1 EP 07703163 A EP07703163 A EP 07703163A EP 07703163 A EP07703163 A EP 07703163A EP 1984964 A1 EP1984964 A1 EP 1984964A1
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EP
European Patent Office
Prior art keywords
layer
organic
component according
derivatives
atoms
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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Application number
EP07703163A
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German (de)
English (en)
Inventor
Frank Meyer
Aurélie LUDEMANN
René SCHEURICH
Heinrich Becker
Klaus Meerholz
David Christoph Mueller
Nina Riegel
Anne Koehnen
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Merck Patent GmbH
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Merck Patent GmbH
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Publication date
Application filed by Merck Patent GmbH filed Critical Merck Patent GmbH
Publication of EP1984964A1 publication Critical patent/EP1984964A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • 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
    • 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
    • H10K50/171—Electron injection layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/191—Deposition of organic active material characterised by provisions for the orientation or alignment of the layer to be deposited
    • 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
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/115—Polyfluorene; 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
    • H10K85/10—Organic polymers or oligomers
    • H10K85/151—Copolymers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
    • H10K2102/301—Details of OLEDs
    • H10K2102/351—Thickness
    • 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

Definitions

  • Organic-based charge transport materials for example triarylamine-based hole transports
  • OLEDs or PLEDs organic or polymeric light-emitting diodes
  • O-SC organic solar cells
  • O-FET organic field effect transistors
  • O-TFT organic thin-film transistors
  • O-IC organic switching elements
  • O-lasers organic optical amplifiers or organic laser diodes
  • Electrode often metallic or inorganic, but also of organic or polymeric conductive materials
  • planarization layer possibly of a conductive, doped polymer
  • Pixels (pixels) with high resolution next to each other The same applies to electronic circuits with different switching elements. While with low-molecular vapor-deposited molecules, the individual pixels can be generated by the vapor deposition of the individual colors through shadow masks, this is not possible for polymeric and solution-processed materials.
  • One way out of this is to apply the active layer (for example, the light-emitting layer in OLEDs / PLEDs, analogously, for charge transport layers in all applications) directly structured.
  • various printing techniques have been considered, such as inkjet printing (e.g., EP 0880303), off-set printing, and gravure coating.
  • inkjet printing e.g., EP 0880303
  • off-set printing e.g., off-set printing
  • gravure coating e.g., the development of ink-jet printing processes is being intensively pursued and significant progress has recently been made, so that the first commercial products thus produced may be expected in the near future.
  • an intermediate layer of a conductive, doped polymer which acts as a charge injection layer is frequently introduced between the electrode (in particular the anode) and the organic semiconductor ⁇ Appl. Phys. Lett. 1997, 70, 2067-2069).
  • the most common of these polymers are polythiophene derivatives (e.g., poly (3,4-ethylenedioxy-2,5-thiophene), PEDOT) and polyaniline (PANI), which are typically doped with polystyrene sulfonic acid or other polymer-bound Bronsted acids, and are thus described in U.S. Pat be brought to a conductive state. It is believed that from the acidic groups when operating the device protons or other impurities diffuse into the functional layer, which are suspected there to disturb the functionality of the device significantly. So it is believed that this Impurities reduce the efficiency as well as the lifetime of the devices.
  • a material is selected for the buffer layer whose glass transition temperature is lower than that of the conductive doped polymer and anneals at a temperature above the glass transition temperature of the buffer layer, but below the glass transition temperature of the conductive doped polymer, in order not to damage it by the tempering process.
  • a thin part of the buffer layer generally becomes insoluble, generally of the order of 1 to 25 nm.
  • a material having a relatively low molecular weight is required for a relatively low molecular weight.
  • such a material can not be applied by ink-jet printing since the molecular weight should be higher for good printing properties.
  • the organic semiconductor By applying the organic semiconductor by spin coating, the soluble part of the buffer layer is then rinsed off and the organic semiconductor layer is formed on the insoluble part of the buffer layer.
  • a multi-layer structure can be produced.
  • the application of the organic semiconductor to the buffer layer by a printing or coating process is not possible in this way since the soluble part of the buffer layer is then dissolved by the solvent and an undefined blend of the material of the buffer layer and the organic semiconductor results.
  • the production of structured multi-layer devices is therefore not possible.
  • the production of a device with buffer layer only by ink jet printing is so far not yet possible, since on the one hand, the buffer layer not because of the low molecular weight
  • the solution of the organic semiconductor when applied by printing techniques partially dissolves the buffer layer. Since printing techniques, in particular ink jet printing, are regarded as a very important method for producing structured devices, but on the other hand, the use of buffer layers also has much potential for further developments, there is therefore an even greater need for improvement.
  • EP 0637899 proposes electroluminescent arrangements with one or more layers in which at least one layer is crosslinked, which also contains at least one emitter layer and at least one charge transport unit per layer.
  • the crosslinking can take place radically, anionically, cationically or via a photoinduced ring closure reaction. Thus, several layers can be built on top of each other and the layers can also be patterned radiation-induced.
  • the versatile crosslinking reactions a suitable device can be prepared and how the crosslinking reaction is best performed. It is merely mentioned that radically crosslinkable units or groups capable of photocycloaddition are preferred, that auxiliaries of various types, such as for example initiators, can be present and that the film is preferably crosslinked by means of actinic radiation.
  • Semiconductor layer is introduced at least one crosslinkable polymeric buffer layer, preferably a cationic crosslinkable polymeric buffer layer.
  • the crosslinking is induced thermally, ie by increasing the temperature to 50 to 250 0 C.
  • the crosslinking can be initiated but also, for example, the addition of a photo-acid by irradiation.
  • a buffer layer can also be advantageously applied by printing or coating techniques, in particular ink jet printing, since here the ideal temperature for the thermal treatment is independent of the glass transition temperature of the material. This does not rely on low molecular weight materials, which in turn allows the coating to be applied by printing techniques.
  • the buffer layer becomes insoluble by the crosslinking, the following layer (the organic semiconductor layer) can also be printed by various printing techniques, in particular
  • US 2005/0088079 describes a light-emitting device in which a light-emitting material is accumulated in one region and a polymer in another region.
  • the polymer is characterized by selective Crosslinking of a monomer prepared from a mixture of the two materials, so that an accumulation of the light-emitting material in the first and the polymer in the second region occurs.
  • the light-induced crosslinking results in a solid polymer in which light-emitting regions are embedded in the polymer (microcapsules). This process is initiated by a chemical
  • Device can be constructed so that a blend of two materials with significantly different molecular weights by means of a coating process can be applied to an electrode and then directed and segregated parallel to the electrode surface. In this way, a plurality of layers can be formed only by physical phase separation. As described in the document, but it is desirable that this segregation does not take place completely, but rather remains a transition zone of the blend.
  • a solution is applied, which includes at least two materials, of which at least one can be made insoluble by a chemical reaction.
  • the reaction of the reactive material preferably a cationic crosslinkable, is thermally induced, ie by a temperature increase to 50 to 250 ° C. It is assumed that in the course of the chemical reaction a directional phase separation takes place, starting from the charge injection layer, which leads to the formation of a multi-layer structure.
  • This multilayer structure can be detected are by washing away the non-involved in the chemical reaction material by the previously used solvent, but is not limited to this.
  • the washing off of the material not involved in the reaction leads to the formation of a very homogeneous surface of the crosslinked layer; which is significantly more homogeneous than that achievable by the surface coating method described in WO 05/024971, in particular ink jet printing.
  • the formation of the multilayer structure by means of the chemical reaction initiated directional phase separation leads to a very homogeneous boundary layer between the two layers, which leads to a significant reduction of interface defects, as in a separate layer structure by the formation of black spots and high voltage rise during operation is observed.
  • the invention relates to an electronic component which has at least one anode, at least one cathode, at least one charge injection layer, at least one layer of an organic semiconductor and at least one layer located between the charge injection layer and the organic semiconductor layer, wherein the between the charge injection layer and the organic Semiconductor- layer and the organic semiconductor layer by coating the charge injection layer with a mixture comprising at least one material which can be made insoluble by a chemical reaction, and at least one organic semiconductor, are available.
  • the chemical reaction leading to the formation of the insoluble material is induced or initiated by the charge injection layer.
  • the onset of chemical reaction achieves complete and directed segregation of the organic semiconductor.
  • the material which can be made insoluble by a chemical reaction is a correspondingly modified organic semiconductor.
  • the material forming the charge injection layer is suitable for initiating a chemical reaction.
  • a further subject of the present invention is thus a process for producing organic electronic devices, characterized in that it comprises at least one layer A which is suitable for initiating a chemical reaction and contains at least one layer B of an organic semiconductor or conductor characterized in that said layer B consists of at least two materials, of which at least one material has the property of becoming insoluble by a chemical reaction, thereby separating from the other materials and forming a separate layer on the initiating layer.
  • Insoluble in the sense of the present invention is understood to mean that the chemical reaction of the material leads to a layer which can no longer be appreciably dissolved with the solvent with which the material was originally applied.
  • Another object of the present invention are organic electronic devices, which have been prepared by the methods described above and are characterized by improved interfacial properties.
  • Directed separation of two or more components from a mixture in the sense of this invention is a process which begins in a defined manner on the surface of the layer A and continues at an arbitrary rate constant through the volume of the overlying primary layer B. After completion of the segregation, ideally a component of the primary layer B has completely accumulated on the surface of the layer A, thus forming a further separate layer B1.
  • the residual components of the primary layer B form a third separate layer B2 following the layers A and B1.
  • the nature of the chemical reaction inducing layer A is not limited to conductive, doped polymeric charge injection layers, but also includes semiconducting and / or non-conducting layers of inorganic or organic nature, characterized merely by the chemical reaction in the layer B and the subsequent directed phase separation can trigger.
  • the application of the layer A to a substrate can be carried out by means of any conventional coating method.
  • coating processes of organic or nonorganic solution such as ink jet printing, classical printing techniques, spin coating, dip drawing or coating processes using physical vaporization techniques in a high vacuum or in a carrier gas stream.
  • the layer A consists of a conductive organic polymer, which is applied from a liquid phase, preferably an aqueous, to a carrier.
  • the polymer is doped with an acid, preferably a polymeric acid, and this acid initiates the chemical reaction and the resulting directional segregation of the materials in layer B.
  • the layer A consists of polymers which, depending on the application, have a conductivity of> 10 -8 S / cm. Particularly preferred here are polymers having a conductivity of> 10 -6 S / cm and in particular with a conductivity of> 10 "3 S / cm.
  • the potential of the layer is preferably from -4 to -6 eV against vacuum.
  • the layer thickness is preferably between 10 and 500 nm, particularly preferably between 20 and 250 nm. Particular preference is given to derivatives of polythiophene (in particular poly (3,4-ethylenedioxy)
  • the doping is usually carried out by acids or by oxidizing agents.
  • the doping is preferably carried out by polymer-bound Brönsted acids.
  • Particularly preferred for this purpose are polymer-bound sulfonic acids, in particular poly (styrenesulfonic acid), Nafion TM, poly (vinylsulfonic acid) and PAMPSA (poly (2-acrylamido-2-methylpropanesulfonic acid)).
  • the conductive polymer is typically applied from an aqueous solution or dispersion and is insoluble in organic solvents. As a result, the follow-up layer of organic solvents can be applied without problems.
  • the composition of the layer B applied by a printing or coating process may consist of soluble polymeric as well as soluble low molecular compounds or mixtures thereof, at least however, two components.
  • Polymers, oligomers and high molecular weight compounds can be linear or branched, highly branched or dendritic.
  • the prerequisite is that at least one of the components is capable of a chemical reaction, which leads to a directional separation of the layer.
  • This component can be both a low molecular weight and a high molecular weight component. It is particularly preferred if the chemical reaction is a crosslinking which leads to at least one of the directionally segregated layers.
  • all suitable chemical reactions such as, for example, free-radical, anionic or cationic initiated polymerization reactions, metathesis or Diels-Alder reactions, can be used as crosslinking reactions.
  • Particularly preferred is the cationic polymerization, which both photochemically optionally with the addition of an initiator (eg., A photoacid) as well as thermally can be initiated.
  • Particularly preferred here is the thermally initiated cationic polymerization.
  • the directional segregation of the components of the layer B resulting from the chemical reaction leads to a layer structure where the layer B forming the chemical reaction initiating layer A for the operation of the organic electronic device follows by way of example but not exclusively Functions can perceive:
  • Electronic blocking layer to hold charges in the functional layer B of the organic electronic device or to slow down the entry or transition of electrons in the layer A.
  • Reaction is capable in their physical properties of the materials as in ChemPhys 2000, 207 and WO 05/024971 and M. Leadbeater, N. Patel, B. Tierney, S. O'Connor, I. Grizzi, C. Towns, SID Digest, SID Seattle, 2004, an organic electronic device incorporating a hole-conducting layer that does not need to be applied in a separate area-coating step can be realized.
  • the resulting buffer layer leads to a comparable improvement in the electronic properties of the device with significantly lower technical complexity.
  • protons or other cationic impurities contained in the conductive doped polymer are problematic and their diffusion from the doped polymer is suspected, limiting the life of the electronic To be device.
  • hole injection from the doped polymers into the organic semiconductor is often unsatisfactory.
  • Layer B1 developed between the conductive, doped polymer and the other components of the organic semiconductor. It is particularly advantageous if this layer B1 contains crosslinked units, in particular cationically crosslinked units, so that they can take up low molecular weight, cationic species and also intrinsic cationic charge carriers which can diffuse out of the conductive, doped polymer.
  • crosslinkable groups for example anionic or free-radically crosslinkable groups are possible and according to the invention.
  • This layer B1 can further serve for an improved hole injection and as an electron blocking layer without being limited to this function.
  • Crosslinkable polymers, particularly preferably conjugated or partially conjugated crosslinkable polymers, in particular conjugate crosslinkable are preferably used for the directed separation for forming this layer B1.
  • the molecular weight of the polymers used for the layer B1 before crosslinking is preferably in the range from 50 to 500 kg / mol, particularly preferably in the range from 200 to 300 kg / mol. This range of molecular weights has been found to be particularly suitable for application by ink jet printing. However, other molecular weight ranges may be preferred for other printing techniques.
  • the layer thickness of the resulting layer B1 is preferably in the range from 1 to 300 nm, particularly preferably in the range from 10 to 200 nm, and in particular in the range from 15 to 100 nm.
  • the setting of the desired layer thickness of the layer B1 is effected by the quantitative fraction of
  • the layer B before the chemical reaction has a layer thickness of 100 nm and consists of 50% reaction-capable materials
  • the layer B1 resulting from the directional segregation has a Layer thickness of about 50 nm.
  • the potential of the layer B1 lies between the potential of the conductive, doped polymer and that of the organic semiconductor in order to possibly improve the charge injection. This can be achieved by suitable choice of the materials for the layer B1 as well as suitable substitution of the materials.
  • crosslinkable low molecular weight compounds may also be preferred to admix further crosslinkable low molecular weight compounds to the polymeric material which leads to the formation of the layer B1. This can be useful, for example, to reduce the glass transition temperature of the mixture and thus to enable crosslinking at a lower temperature.
  • the materials capable of forming the layer B1 are constructed solely from low-molecular-weight materials, provided that the remaining components of the layer B, if necessary, help to set the necessary physical parameters for the surface application method.
  • Preferred materials for the layer B1 are derived from hole-conducting materials. Particularly suitable for this purpose are cationically crosslinkable materials based on triarylamine, based on thiophene, based on triarylphosphine or combinations of these systems, wherein copolymers thereof with other structures, for example
  • the proportion of hole-conducting units in the polymer is particularly preferably at least 10 mol%. It is particularly preferred if the proportion of hole-conducting units is between 40 and 60 mol%. By suitable substitution, the potentials of these compounds can be adjusted.
  • a cationically crosslinkable layer B absorbs diffusing cationic species, in particular protons can. This initiates the crosslinking reaction.
  • a layer B1 is simultaneously formed by the crosslinking, which is insoluble, so that after washing away the soluble layer B2 then applying a further organic semiconductor from the usual organic solvents no problems.
  • the crosslinked layer B1 represents another barrier to diffusion.
  • Preferred polymerizable groups are therefore cationically crosslinkable groups, in particular:
  • Electron-rich olefin derivatives and compounds having heteronuclear multiple bonds with heteroatoms or hetero moieties are preferred, as described in H.-G. Elias, Macromolecules, Volume 1.
  • cationic ring-opening polymerization see, for example, EJ Goethals et al., "Cationic Ring Opening Polymerization” ⁇ New Methods Polym., Synth., 0, 1992, 67-109.]
  • non-aromatic cyclic systems in which or several ring atoms identical or different are O, S, N, P, Si, etc.
  • ring atoms Systems are unsubstituted or substituted 5-cyclic amines (eg, aziridine, azeticin, tetrahydropyrrole, Piperidine), cyclic ethers (eg oxirane, oxetane, tetrahydrofuran, pyran, dioxane), as well as the corresponding sulfur derivatives, cyclic acetals (eg 1, 3-dioxolane, 1, 3-dioxepane, trioxane) , Lactones, cyclic carbonates, but also cyclic structures containing different heteroatoms in the cycle (eg, oxazolines, dihydrooxazines, oxazolones). Preference is furthermore given to cyclic siloxanes having 4 to 8 ring atoms.
  • 5-cyclic amines eg, aziridine, azeticin, tetrahydropyrrole, Piperidine
  • R 1 is on each occurrence, identically or differently hydrogen, a straight-chain, branched or cyclic alkyl, alkoxy or thioalkoxy group having 1 to 20 carbon atoms, an aromatic or heteroaromatic ring system having 4 to 24 aromatic ring atoms or an alkenyl group having 2 to 10 C atoms in which one or more hydrogen atoms may be replaced by halogen, such as Cl and F, or CN and one or more non-adjacent C atoms by -O-, -S-, -CO-, -COO - or -O-CO- may be replaced; also several radicals R 1 with one another or with R 2 , R 3 and / or R 4 form a mono- or polycyclic, aliphatic or aromatic ring system,
  • R 2 is the same or different hydrogen on each occurrence, a straight-chain, branched or cyclic alkyl group with 1 to 20 carbon atoms, an aromatic or heteroaromatic ring system having 4 to 24 aromatic ring atoms or an alkenyl group having 2 to 10 carbon atoms, in which one or more hydrogen atoms may be replaced by halogen, such as Cl and F, or CN and CN or several non-adjacent C atoms may be replaced by -O-, -S-, -CO-, -COO- or -O-CO-; in this case also a plurality of radicals R 2 with one another or with R 1 , R 3 and / or R 4 can form a monocyclic or polycyclic, aliphatic or aromatic ring system,
  • x is the same or different at each occurrence -O-, -S-, -CO-,
  • Z is the same or different at each occurrence as a bivalent
  • R is the same or different hydrogen on each occurrence, a straight-chain, branched or cyclic alkyl, alkoxy, alkoxyalkyl or thioalkoxy group having 1 to 20 carbon atoms, an aromatic or heteroaromatic ring system having 4 to 24 aromatic ring atoms or an alkenyl group with 2 to
  • n is identical or different at each occurrence an integer between 0 and 20, preferably between 1 and 10, and particularly preferably between 1 and 6,
  • the crosslinking of these units can be initiated, for example, by thermal treatment of the device.
  • the thermal crosslinking is preferably without the addition of a photoacid.
  • further auxiliaries for example salts or acids, which are added to the buffer layer and / or to the conductive polymer layer.
  • this crosslinking takes place at a temperature of 80 to 200 ° C. and for a period of 0.1 to 120 minutes in an inert atmosphere.
  • This crosslinking particularly preferably takes place at a temperature of 100 to 180 ° C. and for a period of 30 to 120 minutes in an inert atmosphere.
  • the component of the organic semiconductor capable of chemical reaction and directed segregation is a light-emitting material in its physical properties
  • a device can be realized which in principle permits the construction of multicolor layer systems in one process step.
  • a device may be constructed in which the component capable of chemical reaction and directional segregation exerts a light-emitting function, while the other component is selected in electronic properties to be a barrier to holes in order to reduce power losses at the cathode avoid.
  • a device can be realized, where on the directionally segregated layer B1, a layer B2 is formed, without being limited to only one layer, which represents a barrier layer for holes and electrons in their physical properties.
  • the design principle always applies that the components of the layer B always form a layer B1 following the chemical reaction on the layer A which initiates the chemical reaction, which layers are chemically reactive.
  • the components not capable of the chemical reaction in the sense of the invention then form the third layer B2.
  • Preferred materials for such a construction of the layer B1 of an organic electronic device are cationically crosslinkable low molecular weight, oligomeric or polymeric organic materials in which at least one H atom has been replaced by a group of the formula (A),
  • R is a straight-chain, branched or cyclic alkyl, alkoxyalkyl,
  • Z is -O-, -S-, -CO-, -COO-, -O-CO- or a divalent group
  • X is -O-, -S-, -CO-, -COO-, -O-CO- or a divalent group
  • R 1 and R 2 independently of one another, are hydrogen, a straight-chain, branched or cyclic alkyl, alkoxy, alkoxyalkyl or thioalkoxy group having 1 to 20 C Atoms, C 4 -Cis-aryl, C 2 -C 10 -alkenyl, in which one or more hydrogens may be replaced by halogen, such as Cl and F 1 or CN, and
  • n is an integer between 1 and 20, preferably between 3 and 10, and particularly preferably 3 or 6,
  • the chemically reactive materials used according to the invention are electroluminescent or laser materials, preferably
  • Hole conductor materials preferably K) polystyrenes, polyacrylates, polyamides, polyesters bearing derivatives of tetra-aryl-benzidine in the side chain,
  • Layer structure may be used in applications other than optical organic electronic devices, such as optical devices.
  • the directional segregation of the materials in layer B is not bound by the sequence of the layer structure.
  • the layer A can be coated on the layer B.
  • a directed separation takes place in this case as well, in which the chemically reacting component in the layer B segregates in the direction of the layer A applied above and forms a layer B1.
  • a nonconductive layer can be produced by two methods:
  • the non-conductive component in layer B is chemically reactive and thus forms a layer B1 after the chemical reaction.
  • the non-reacting layer B2 can lie on the substrate-side or on the side facing away from the substrate from the layer A.
  • the non-conductive component in the layer B is not chemically active and forms a layer B2 after the chemical reaction, which leads to the formation of the layer B1.
  • the non-conductive layer B2 on the substrate on the substrate side or the side facing away from the layer A lie.
  • the oxetane content is defined by the molar ratio of oxetane rings relative to the total of organic rings, i. including the oxetane rings in the respective structure. This can generally be determined by analytical methods.
  • One of the preferred methods besides IR spectroscopy is nuclear spin resonance spectroscopy (NMR).
  • Rings in the context of the invention are cyclic structural elements formed from at least three ring atoms with the proviso that at least two
  • the oxetane content can be varied within wide ranges from 0.01 to 0.6. At the bottom, low levels of crosslinking are achieved, resulting in relatively soft, rubber-elastic to gel-like layers. In the upper, high crosslink densities are achieved with thermoset-like properties, e.g. Bakelite.
  • the homopolymers and copolymers of the PPV contain one or more structural units of the formula (B), where at least one hydrogen atom in the polymer is replaced by a substituent of the formula (A) and / or according to
  • R 'to R “"” are the same or different H, CN, F, Cl or a straight-chain, branched or cyclic alkyl or alkoxy group having 1 to 20 C atoms, wherein one or more non-adjacent CH 2 Groups can be replaced by -O-, -S-, -CO-, -COO-, -O-CO-, -NR 1 -, - (NR 2 R 3 J + -A " or -CONR 4 - and wherein one or more H atoms may be replaced by F, or an aryl group having 4 to 14 C atoms, which may be substituted by one or more non-aromatic radicals R 1 ,
  • R 1 , R 2 , R 3 , R 4 are the same or different aliphatic or aromatic hydrocarbon radicals having 1 to 20 C atoms or H,
  • A- is a singly charged anion or its equivalent.
  • Preferred here are PPVs according to WO 98/27136, which are given in formula (C).
  • Aryl is an aryl group with 4 to 14 C atoms
  • Aryl group having 4 to 14 C atoms which may be substituted by one or more non-aromatic radicals R 1 ,
  • R 1 , R 2 , R 3 T R 4 are identical or different aliphatic or aromatic hydrocarbon radicals having 1 to 20 carbon atoms or H,
  • a " is a singly charged anion or its equivalent
  • n O, 1 or 2
  • n 1, 2, 3, 4 or 5.
  • polymers consisting mainly of repeating units of the formula (C).
  • copolymers consisting essentially of, preferably consisting of repeating units of the formula (I) and further repeating units, which preferably also contain poly (arylenevinylene) structures, more preferably 2,5-dialkoxy-1, 4-phenylenevinylene structures, wherein the alkoxy groups are preferably straight-chain or branched and contain 1 to 22 C atoms.
  • Copolymers in the context of the present invention include random, alternating, regular and block-like structures. Likewise preferred are polymers containing recurring units of the formula (C) in which the symbols and indices have the following meanings:
  • Aryl is phenyl, 1- or 2-naphthyl, 1-, 2- or 9-anthracenyl, 2-, 3- or 4-pyridinyl, 2-, 4- or 5-pyrimidinyl, 2-pyrazinyl, 3 or 4-pyridazinyl, 2-, 3-, 4-, 5-, 6-, 7- or 8-quinoline, 2- or 3-thiophenyl, 2- or 3-pyrrolyl, 2- or 3-furanyl and 2- (1, 3,4-
  • R ' is identical or different, CN, F, Cl, CF 3 or a straight-chain or branched alkoxy group having 1 to 12 C atoms,
  • R is, identically or differently, a straight-chain or branched alkyl or alkoxy group having 1 to 12 C atoms,
  • n 0, 1, 2 or 3, preferably 0, 1 or 2.
  • Polymers can be prepared by copolymerizing corresponding monomers which carry the substituents of the formula (A) and / or of the formula (I), (II) and / or (III).
  • the homopolymers and copolymers of polyfluorene contain one or more structural units of the formula (D) where at least one hydrogen atom in the polymer is replaced by a substituent according to formula (A) and / or according to formula (I), (II) and / or (III) is replaced.
  • R 1 to R "" are identical or different H, CN, F, Cl or a straight-chain, branched or cyclic alkyl or alkoxy group having 1 to 20 C atoms, wherein one or more non-adjacent CH 2 groups -O-, -S-, -CO-, -COO-, -O-CO-, -NR 1 -, - (NR 2 R 3) + -A or -CONR 4 ⁇ - may be replaced and where one or several H atoms may be replaced by F, or an aryl group having 4 to 14 C atoms, which may be substituted by one or more non-aromatic radicals R 1 ,
  • R 3 , R 4 are the same or different aliphatic or aromatic
  • Hydrocarbon radicals having 1 to 20 carbon atoms or else H Hydrocarbon radicals having 1 to 20 carbon atoms or else H,
  • a ' is a singly charged anion or its equivalent
  • n, m is the same or different, 0, 1, 2, or 3, preferably 0 or 1.
  • R 1 and R 2 are both identical and unlike hydrogen or chlorine; furthermore preferred are compounds in which R 1 and R 2 are different from one another and also different from hydrogen;
  • R 5 , R 6, identical or different, denote H, C 1 -C 22 -alkyl, C 2 -C 20 -heteroaryl or C 5 -C 2 o-aryl; while the alkyl radicals may be branched or unbranched or represent cycloalkyls; and individual, non-adjacent CH 2 groups of the alkyl radical to be replaced by O, S, C O, COO, NR 5 or C 2 -Ci 0 -Aryle, wherein the abovementioned aryls substituted with one or more non-aromatic substituents R 3 can be, and
  • n are identical or different, in each case an integer O, 1, 2 or 3, preferably O or 1,
  • Ar 1 , Ar 2 are mono- or polycyclic aromatic conjugated systems of 2 to 40 carbon atoms in which one or more carbon atoms are represented by nitrogen, oxygen or sulfur
  • ⁇ Q can be replaced, and those with one or more
  • Substituents R 3 may be substituted. It is quite possible or sometimes even preferred that the aromatics Ar 1 and Ar 2 by a bond or another substituted or unsubstituted carbon atom or heteroatom with each other
  • R 7 are identical or different -C 22 alkyl, C 2 -C 2 o-heteroaryl, or C 5 -
  • alkyl radicals may be branched or unbranched or represent cycloalkyls
  • O, S, C O, COO, NR 5 or even simple aryls may be replaced, wherein the abovementioned aryls / heteroaryls may be substituted with a odedeerr mmeehhrreerreen non-aromatic substituent R 3 .
  • the structural units of the formula (E2) are very particularly preferably derived from the following basic structures:
  • Diphenylamine derivatives in the 4,4'-position into the polymer incorporated 30 are -
  • Phenothiazine or phenoxazine derivatives which are incorporated into the polymer in the 3,7-position
  • R 1 R represent two different substituents from the group Cs-C ⁇ o-aryl or C 2 -C 4 o-heteroaryl; wherein the abovementioned aryls or heteroaryls may be substituted by one or more substituents R 3 ;
  • the aryls or heteroaryls for the purposes of this invention should already be various if they differ in the nature or position of substituents.
  • Aryls may be replaced, wherein the abovementioned aryls may be substituted by one or more non-aromatic substituents R 3 , and
  • n are the same or different, each an integer 0, 1, 2 or 3, preferably 0 or 1, is.
  • R 1 , R 2 are two different substituents from the group C 5 -C 4 o-aryl, C 2 -C 4 o-heteroaryl; where the abovementioned aryls or heteroaryls can be substituted by one or more nonaromatic substituents R 3 .
  • Preference is furthermore given to compounds in which R 1 and R 2 are different from one another and also different from hydrogen;
  • O, S, C O, COO, NR 5 or even simple aryls may be replaced, wherein the abovementioned aryls may be substituted by one or more non-aromatic substituents R 3 , and
  • n are the same or different, each is an integer 0, 1, 2 or 3, preferably O or 1,
  • Aromatic is a mono- or polycyclic aromatic conjugated system of 5 to 20 carbon atoms in which one or more carbon atoms may be replaced by nitrogen, oxygen or sulfur, and their attachment sites are selected so as to form an angle along the polymer backbone not equal to 180 °, preferably less than 120 °, particularly preferably less than 90 °.
  • Preparation of corresponding polymers according to the invention can be carried out by copolymerizing corresponding monomers which carry the substituents of the formula (A) and / or of the formula (I), (II) and / or (III).
  • the homo- and copolymers of poly-spiro contain one or more structural units of the formula (H), where at least one hydrogen atom in the polymer is represented by a substituent according to formula (A) and / or according to formula (I), (II) and / or (III) is replaced.
  • R 1 to R "" are identical or different H, CN, F, Cl or a straight-chain, branched or cyclic alkyl or alkoxy group having 1 to 20 C atoms, wherein one or more non-adjacent CH 2 groups -O-, -S-, -CO-, -COO-, -O-CO-, -NR 1 -, - (NR 2 R 3 ) + -A " or -CONR 4 - may be replaced, and wherein a or several H atoms may be replaced by F, or an aryl group with
  • R 1 , R 2 , R 3 , R 4 are the same or different aliphatic or aromatic hydrocarbon radicals having 1 to 20 C atoms or H,
  • a " is a singly charged anion or its equivalent
  • n, m, o, p are the same or different 0, 1, 2, or 3, preferably 0.1 or 2.
  • Preferred embodiments of the poly spiros are contained in US-A-5621131.
  • the homopolymers and copolymers of poly-dihydrophenanthrene contain one or more structural units of the formula (1) where at least one hydrogen atom in the polymer is replaced by a substituent according to formula (A) and / or according to formula (I), (II) and / or (III) is replaced,
  • X is identical or different at each occurrence C (R 3 ) (R 4 ) or
  • R 3 , R 4 is the same or different at each occurrence H, with the
  • R 1 to R 4 simultaneously describe H, a straight-chain, branched or cyclic alkyl or alkoxy chain having 1 to 22 C atoms, in which also one or more nonadjacent C atoms is represented by NR 6 , O, S or
  • O-CO-O may be replaced, wherein also one or more H atoms may be replaced by fluorine, an aryl or aryloxy group having 5 to 40 carbon atoms, in which also one or more C atoms by O, S or N, which may also be replaced by one or more non-aromatic radicals
  • R 1 may be substituted, it also being possible for two or more of the radicals R 1 to R 4 to form a ring system with one another; with the proviso that not two substituents on a C atom (ie R 1 and R 2 or R 3 and R 4 ) simultaneously correspond to an alkoxy or aryloxy side chain and that not all
  • Substituents R 1 to R 4 simultaneously describe a methyl group, or fluorine, chlorine, bromine, iodine, CN, N (R 6 ) 2 , Si (R 6 ) 3 or B (R 6 ) 2 , R 5 is the same or different H, a straight-chain, branched or cyclic alkyl or alkoxy chain having 1 to 22 C atoms in each occurrence, in which also one or more nonadjacent C atoms are represented by O, S 1 -CO-O- or O-CO-O may be replaced, wherein one or more H atoms may be replaced by fluorine, an aryl or aryloxy group having 5 to 40
  • R 6 is the same or different H 1 is a straight-chain, branched or cyclic alkyl chain having 1 to 22 C atoms in each occurrence, in which also one or more nonadjacent C atoms by O, S, -CO-O- or O- CO-O may be replaced, it also being possible for one or more H atoms to be replaced by fluorine, an aryl group having 5 to 40 C atoms, in which one or more C atoms may also be replaced by O, S or N, which may also be substituted by one or more non-aromatic radicals R 1 .
  • Preferred embodiments of the poly-dihydrophenanthrenes are those mentioned in WO 05/014689.
  • Polymer can be carried out by copolymerizing corresponding monomers which carry the substituents according to formula (A) and / or according to formula (I), (II) and / or (III).
  • the homo- and copolymers of poly-phenanthrene contain one or more structural units of the formula (I), where at least one hydrogen atom in the polymer is replaced by a substituent according to formula (A) and / or according to formula (I), (II) and / or (III) is replaced,
  • Phenanthrene unit are bound, and in which one or more H atoms may be replaced by F, Cl, Br, I or CN, or an aromatic or heteroaromatic ring system having 2 to 40 carbon atoms, which also by a
  • radicals R 1 may be substituted; while the two radicals R can also form another mono- or polycyclic, aromatic or aliphatic ring system; with the proviso that at least one of the two radicals R is not H,
  • 25 X is the same or different at each instance -CR 1 -CR 1 -,
  • Y is the same or different bivalent at each occurrence
  • R 2 is identical or different at each occurrence, H or an aliphatic or aromatic hydrocarbon radical having 1 to 20 C atoms,
  • Ar is the same or different at each occurrence, a monovalent aromatic or heteroaromatic
  • Ring system with 2 to 40 carbon atoms which may be substituted by R 1 or unsubstituted,
  • n is the same or different 0 or 1 for each occurrence
  • n is the same or different 0, 1 or 2 at each occurrence
  • Preferred embodiments of the poly-phenanthrenes are those mentioned in DE 102004020298.
  • the preparation of such polymers is described in detail in DE 102004020298.
  • the preparation of corresponding polymers according to the invention can be carried out by copolymerizing corresponding monomers which carry the substituents according to formula (A) and / or according to formula (I), (II) and / or (III).
  • B) The low molecular weight compounds having a 3-dimensional spirobifluorene structure preferably consist of structural units of the formula (K1)
  • benzo groups can be substituted and / or fused independently of one another and wherein at least one H atom is replaced by a substituent according to formula (A) and / or according to formula (I), (II) and / or (III).
  • K, L, M, N are the same or different
  • R the same or different, may have the same meanings as K, L, M, N or is -H, a linear or branched alkyl, alkoxy or ester group having 1 to 22 C atoms, -CN, -NO 2 , -NR 2 R 3 , -Ar or -O-Ar,
  • Ar is phenyl, biphenyl, 1-naphthyl, 2-naphthyl, 2-thienyl, 2-furanyl, where each of these groups may carry one or two radicals R,
  • n, p are the same or different 0, 1, 2 or 3,
  • X, Y are the same or different CR or N,
  • R> 1 1 D R4 may, identically or differently, have the same meanings as R,
  • R 3 2, R D 3 are identical or different H, a linear or branched alkyl group having 1 to 22 C atoms, -Ar or 3-methylphenyl.
  • the preparation of such compounds is described in detail in EP 676461.
  • the preparation of corresponding compounds according to the invention can be carried out by replacing corresponding substituents or H atoms with the substituents according to formula (A) and / or according to formula (I), (II) and / or (III).
  • the low molecular weight compounds having a 3-dimensional triptycene structure preferably consist of structural units of the formula (L)
  • benzo groups can be substituted and / or fused independently of one another and wherein at least one hydrogen atom is replaced by a substituent according to formula (A) and / or according to formula (I), (M) and / or (III).
  • the low molecular weight compounds having a 2-dimensional triphenylene structure preferably consist of structural units of the formula (M)
  • benzo groups can be substituted and / or fused independently of one another and wherein at least one H atom is replaced by a substituent according to formula (A) and / or according to formula (I) 1 (II) and / or (III).
  • R 1 R "denote a straight-chain, branched or cyclic alkyl or alkoxy group having 1 to 20 C atoms, one or more non-adjacent CH 2 groups represented by -O-, -S- , -CO-, -COO-, -O-CO-, -NR 1 -, - (NR 2 R 3 ) + -A " or -CONR 4 - may be replaced, and wherein one or more H atoms by F may be replaced, or an aryl group having 4 to 14 carbon atoms, which may be substituted by one or more non-aromatic radicals R 1 , mean.
  • benzo groups can be substituted independently of one another and wherein at least one hydrogen atom is replaced by a substituent according to formula (A) and / or according to formula (I), (II) and / or (III).
  • the substituents may be identical or different to a straight-chain, branched or cyclic alkyl or alkoxy group having 1 to 20 C atoms, analogously to R ', R ", where one or more nonadjacent CH 2 groups is represented by -O-, -S- , -CO-, -COO-, -O-CO-, -NR 1 -, - (NR 2 R 3 J + -A " or -CONR 4 - may be replaced, and wherein one or more H atoms by F may be replaced, or an aryl group having 4 to 14 carbon atoms, which may be substituted by one or more non-aromatic radicals R ' can mean.
  • the substituents other than R 1 and R " may also denote CN 1 F and Cl.
  • the organic lanthanoid complexes preferably consist of structural units of the formula (P)
  • the substituents R ' may be, identically or differently, carboxylates, ketonates, 1,3-diketonates, imides, amides or alcoholates, at least one H atom being represented by a substituent of the formula (A) and / or of the formula (I), (II ) and / or (III).
  • the number of ligands depends on the metal. Preference is given here to the organic complexes of europium, gadolinium and terbium, particularly preferably those of europium.
  • M is aluminum, zinc, gallium or indium, preferably aluminum; n stands for an integer 0, 1, 2 or 3.
  • the substituents of the benzo group R ' may be, identically or differently, a straight-chain, branched or cyclic alkyl or alkoxy group having 1 to 20 C atoms, where one or more nonadjacent CH 2 groups is represented by -O-, -S-, - CO-, -COO-, -O-CO-, -NR 1 -, - (NR 2 R 3 J + -A " or -CONR 4 - can be replaced, and wherein one or more H atoms are replaced by F. may mean, or an aryl group having 4 to 14 C atoms, which may be substituted by one or more non-aromatic radicals R 1. Furthermore, the substituents other than R 1 and R "may also denote CN, F and Cl.
  • the substituents according to formula (A) and / or according to formula (I), (II) and / or (III) can either replace one H atom on one of the quinoxaline rings or also on another ligand R ' , which is one of quinoxaline Ligands replaced.
  • Ar 'and Ar may be, identically or differently, a substituted or unsubstituted aromatic or heteroaromatic compound having 4 to 14 C atoms, where at least one H atom is substituted by a substituent according to formula (A) and / or according to formula (I), (II ) and / or (III).
  • Ar 1 and Ar are particularly preferably phenyl, 1- or 2-naphthyl, 1-, 2- or 9-anthracenyl, 2-, 3- or 4-pyridinyl, 2-, 4- or 5-pyrimidinyl, 2-pyrazinyl, 3- or 4-pyridazinyl, 2-, 3-, 4-, 5-, 6-, 7- or 8-quinoline, 2- or 3-thiophenyl, 2- or 3-pyrrolyl or 2- or 3-furanyl.
  • the possible substituents are the same or different, CN, F, Cl, CF 3 or a straight-chain, cyclic or branched alkyl or alkoxy group having 1 to 12 C atoms, where one or more non-adjacent CH 2 - groups are represented by -O-, -S-, -CO-, -COO-, -O-CO-, -NR 1 -, - (NR 2 R 3 ) + -A- or -CONR 4 - may be replaced, and wherein one or more H- Atoms can be replaced by F.
  • the substituents according to formula (A) and / or according to formula (I), (II) and / or (III) can either replace an H atom on one of the aryl rings or also on one of the substituents of the aryl rings.
  • Organometallic complexes capable of phosphorescence are characterized by emission from the triplet state.
  • Suitable materials are described, for example, in M.A. Baldo et al. Appl. Phys. Lett. 1999, 75, 4-6 and WO 02/068435, WO 04/026886 and WO 03/000661.
  • Other organometallic complexes which are capable of phosphorescence have compounds according to formula (T)
  • M is at each occurrence an element of the first to ninth subgroup of the Periodic Table of the Elements, preferably iridium, rhodium, platinum, palladium, gold, tungsten, rhenium, ruthenium or osmium,
  • D is the same or different on each occurrence, a sp - hybridized heteroatom with a non-bonding pair of electrons coordinated to M,
  • Cy1 is identical or different at each occurrence a homo- or heterocycle optionally substituted by R, which binds to M via an sp 2 -hybridised carbon atom; Cy1 may be both a monocycle and an oligocycle,
  • Cy2 is identical or different at each occurrence a heterocycle optionally substituted by R, which coordinates to M via the atom D; Cy2 may be both a monocycle and an oligocycle,
  • Radicals R 1 may be substituted, wherein a plurality of substituents R 1 , both on the same ring and on different rings together can in turn span another mono- or polycyclic, aliphatic or aromatic ring system, R 'is identical or different at each occurrence H or an aliphatic hydrocarbon radical having 1 to 20 C atoms or aromatic hydrocarbon radical having 6 to 20 C atoms or a heteroaromatic hydrocarbon radical having 2 to 30 C atoms,
  • the ligands L 'and L "in formula (T) are bidentate chelating ligands, m and o are the same or different at each occurrence 0, 1 or 2.
  • Cy2 cycle may also be a carbene which coordinates to the metal, as described, for example, in WO 05/019373.
  • Polystyrenes which carry tetraarylbenzidine units in the side chain consist of structural units of the formula (S) or analogous compounds in other polymer backbones (polyacrylates, polyamides, polyesters)
  • Ar 1 , Ar “, Ar” 1 and Ar “” may be, identically or differently, a substituted or unsubstituted aromatic or heteroaromatic having 4 to 14 C atoms.
  • Ar 1 , Ar “, Ar 1 " and Ar “” are each, identically or differently, phenyl, 1- or 2-naphthyl, 1-, 2- or 9-anthracenyl, 2-, 3- or 4-pyridinyl, 2-, 4- or 5-pyrimidinyl, 2-pyrazinyl, 3- or 4-pyridazinyl, 2-, 3-, 4-, 5-, 6-, 7- or 8-quinoline, 2- or 3-thiophenyl, 2- or 3-pyrrolyl or 2- or 3-furanyl.
  • the possible substituents are identical or different, CN 1 F, Cl, CF 3 or a straight-chain, cyclic or branched alkyl or alkoxy group having 1 to 12 C atoms, where one or more non-adjacent CH 2 - groups are represented by -O-, -S-, -CO-, -COO-, -O-CO-, -NR 1 -, - (NR 2 R 3 J + -A " or -CONR 4 - may be replaced and wherein one or more H atoms be replaced by F.
  • This tetraaryl-benzidine group is now connected to the polymer main chain via a spacer, preferably a C1 to C6 alkyl, alkoxy or ester grouping.
  • the substituents according to formula (A) and / or according to formula (I), (II) and / or (III) can either replace an H atom on one of the aryl rings, or sit on one of the substituents of the aryl rings, or on one another copolymerized monomer which carries no tetraaryl benzidine unit.
  • the other components of layer B not participating in the chemical reaction for the purposes of the invention are electroluminescent or laser materials, preferably
  • nonreactive materials which produce a nonconductive layer B2 on the layer B1 or which have no fluorescent properties.
  • the components which form the layer B2 and further layers forming B1 are not limited to organic or organic semiconducting materials. It is particularly preferred if the composition of the organic semiconductive layer consists of at least two components, one of which is capable of chemical reaction.
  • the composition of layer B can also consist of three or more organic as well as inorganic materials, two of which are capable of chemical reactions and directed segregation, as long as these chemical reactions are different in nature and / or the same nature, but at a significantly different speed , This is it in another
  • Embodiment possible to obtain multi-layer devices. It is also possible to repeat the procedure to get to more complex layer structures.
  • a photoacid is a compound that releases a protic acid upon irradiation with actinic radiation by photochemical reaction.
  • Examples of photoacids are 4- (thiophenoxyphenyl) -diphenylsulfonium hexafluoroantimonate, ⁇ 4 - [(2-hydroxy-tetradecyl) -oxyl] -phenyl ⁇ -phenyl-iodonium hexafluoroantimonate, and others, e.g. described in EP 1308781.
  • the photoacid may be added for the crosslinking reaction, preferably with a content of about 0.5 to 3 wt%, but need not necessarily be added. It is particularly preferred if one of the initiation methods is thermal in nature.
  • OLEDs organic or polymeric light emitting diodes
  • PLEDs organic solar cells
  • O-SC organic solar cells
  • O-FET organic field-effect transistors
  • O-TFT organic thin-film transistors
  • O-IC organic switching elements
  • FQD organic field quench elements
  • O-lasers organic Laser diodes
  • Organic in the sense of this invention means that at least one layer of an organic conductive doped polymer or at least one conductive or semiconductive polymeric buffer layer or at least one layer containing at least one organic semiconductor is present; there may also be other organic layers (for example electrodes, etc.). But there may also be layers that are not based on organic materials, such as other intermediate layers or electrodes.
  • the electronic device is constructed in the simplest case of substrate (usually glass or plastic film), electrode, inventive intermediate layers and counter electrode.
  • This device can be structured accordingly (depending on the application), contacted and finally hermetically sealed because the life of such devices in the presence of water and / or air can be drastically shortened.
  • the structure except for the electrode and counterelectrode (source and drain) contain yet another electrode (gate) through an insulator layer with a generally high (or less low ) Dielectric constant of the organic Semiconductor is separated.
  • the electrodes are chosen so that their potential matches as closely as possible the potential of the adjacent organic layer to ensure the most efficient electron or hole injection possible.
  • low work function metals, metal alloys, or multi-layered structures of various metals are preferred, e.g. Alkaline earth metals, alkali metals, main group metals or lanthanides (eg Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.).
  • Alkaline earth metals alkali metals
  • main group metals or lanthanides eg Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.
  • Metals which have a relatively high work function, such. Ag, which then usually combinations of metals, such as Ca / Ag or Ba / Ag are used.
  • a thin intermediate layer of a high dielectric constant material between a metallic cathode and the organic semiconductor may also be preferred to introduce a thin intermediate layer of a high dielectric constant material between a metallic cathode and the organic semiconductor.
  • Suitable examples of these are alkali metal or alkaline earth metal fluorides, but also the corresponding oxides (for example LiF, Li 2 O, BaF 2 , MgO, NaF, etc.).
  • the layer thickness of this dielectric layer is preferably between 1 and 10 nm.
  • the anode high workfunction materials are preferred.
  • the anode has a potential greater than 4.5 eV against vacuum.
  • metals with a high redox potential such as Ag, Pt or Au, are suitable for this purpose.
  • Metal / metal oxide electrodes eg Al / Ni / NiO x , Al / Pt / PtO x ) may also be preferred.
  • At least one of the electrodes must be transparent to either irradiate the organic material
  • O-SC organic light-semiconductor
  • O-LASER the extraction of light
  • a preferred construction uses a transparent anode.
  • Preferred anode materials here are conductive mixed metal oxides.
  • ITO indium tin oxide
  • IZO indium zinc oxide
  • the organic semiconductor layer B may preferably be applied by various printing methods, in particular by ink-jet printing methods. Under an organic material in the sense of this
  • Invention should be understood not only purely organic compounds, but also organometallic compounds and metal coordination compounds with organic ligands. In the case of luminescent compounds, these can either fluoresce or phosphoresce, ie emit light from the singlet or from the triplet state.
  • the polymeric materials may be conjugated, partially conjugated or non-conjugated. Preferred are conjugated materials.
  • Conjugated polymers in the context of this invention are polymers which contain in the main chain mainly sp 2 -hybridized carbon atoms, which may also be replaced by corresponding heteroatoms.
  • conjugated if in the main chain, for example arylamine units and / or certain heterocycles (ie conjugation of N, O or S atoms) and / or organometallic complexes (ie, conjugation via the metal atom) , typical
  • conjugated polymers such as those used in PLEDs or O-SCs, are poly-para-phenylenevinylenes (PPV), polyfluorenes, poly-spirobifluorenes, poly-dihydrophenanthrenes, poly-phenanthrenes, poly-indenofluorenes, systems which are the furthest Based on poly-p-phenylene (PPP), and derivatives of these structures.
  • PPP poly-para-phenylenevinylenes
  • PPP poly-para-phenylenevinylenes
  • the layer thickness of the organic semiconductor is, depending on the application, preferably 10 to 500 nm, more preferably 20 to 250 nm.
  • any ratio of the unmixed layers are adjusted to each other.
  • the actually set layer thicknesses of the separated layers depend on the function of the layer in the organic electronic device.
  • the adjustment of the desired layer thickness of the segregated layers to each other is determined by the ratio of the reactive materials to the non-reactive in the mixture B before the directed segregation.
  • Another object of the present invention is the use of the directed segregation of the organic semiconductor layer for the production of films with a homogeneous surface profile.
  • soluble polymeric systems When soluble polymeric systems are applied to a substrate by a printing process, preferably inkjet printing, evaporation of the solvent results in directional transport of dissolved material towards the drop edge to form a non-homogeneous layer thickness, the layer thickness being higher at the edge of the drop than in the drop Center.
  • layers according to the invention are brought to a directed separation of the components of the layer by chemical reaction, preferably thermally initiated cationic polymerization, a very homogeneous layer thickness distribution of the crosslinked layer is formed, regardless of how homogeneous or inhomogeneous the surface of the overall layer is.
  • a layer which has only a small variation in the layer thickness By bringing the unvemetzt layer in solution can be obtained in this way a layer which has only a small variation in the layer thickness.
  • these layer thickness variations in the range between 0.1 and 3 nm; especially in the range between 0.5 and 1 nm.
  • a substrate eg glass or even a plastic
  • the anode for example indium tin oxide, ITO
  • the anode eg photolithographically
  • the pre-cleaned substrate coated with the anode is treated with ozone or with oxygen plasma or irradiated for a short time with an excimer lamp.
  • a conductive polymer e.g. a doped polythiophene (PEDOT) or polyaniline derivative (PANI) in a thin layer A on the ITO substrate by spincoating or others
  • the layer B according to the invention is applied to this layer.
  • the corresponding mixture is first dissolved in a solvent or solvent mixture, preferably under protective gas, and filtered.
  • Suitable solvents are aromatic liquids (e.g., toluene, xylene, anisole, chlorobenzene), cyclic ethers (e.g., dioxane,
  • Separation can then be done (using cationic crosslinkable groups) by heating the device at this stage in an inert atmosphere.
  • the crosslinking can be initiated in different ways.
  • a solvent for example
  • charge injection or transport layers or hole blocking layers can be applied to these polymer layers, for example from solution, but also by vapor deposition. • Then a cathode is applied. This is done according to the prior art by a vacuum process and can be done for example by both thermal vapor deposition and by plasma spraying (sputtering).
  • the structure described above is adapted and optimized for the individual applications without any further inventive step and can generally be applied to various applications, such as e.g. organic and polymeric light emitting diodes, organic solar cells, organic field effect transistors, organic thin film transistors, organic switching elements, organic optical amplifiers or organic laser diodes can be used.
  • organic and polymeric light emitting diodes organic solar cells, organic field effect transistors, organic thin film transistors, organic switching elements, organic optical amplifiers or organic laser diodes can be used.
  • Example 1 The present invention will be further illustrated by the following examples without wishing to be limited thereto. In these examples, only organic and polymeric light emitting diodes will be discussed. However, the person skilled in the art can represent other electronic devices from the listed examples without inventive step, such as O-SC, O-FETs, O-TFTs, O-LETs, O-FQDs, O-ICs, organic optical amplifiers and O-lasers, just to name a few more applications.
  • Example 1 Example 1 :
  • the invention is described by way of example by using the polymer 1 as described below (WO 2005/024971 A1) and a blue polymer of the formula 2.
  • PEDOT / PSSH available from HC Starck as Baytron ® P 4083 by means of spin coating on a glass substrate in a Layer thickness of about 80 nm coated, which is coated with ITO (indium tin oxide) (layer A).
  • the substrate is annealed for 2 hours at 150 0 C.
  • the substrate can now be rinsed with THF.
  • a check of the total layer thickness gives 105 nm (80 nm PEDOT + 20 nm crosslinked material 1), which proves that the crosslinkable component 1 has become insoluble.
  • the soluble component 2 can be removed by rinsing with THF. 6) In case no rinsing step is performed, now becomes
  • Emerson & Cuming® Emerson & Cuming® .
  • a device is prepared analogously to steps 1, 2, 3, 4, 6 and 7 of Example 1.
  • step 2 only the polymer 2 is weighed in the specified concentration and spin coated in step 3 only 65 nm layer thickness, which the layer thickness of Polymer 2 in the layer B2 in Example 1 corresponds.
  • the resulting device shows the following characteristics:

Abstract

La présente invention concerne un composant électronique qui comporte au moins une anode, au moins une cathode, au moins une couche d'injection de charge, au moins une couche d'un semi-conducteur organique et au moins une couche insérée entre la couche d'injection de charge et la couche semi-conductrice organique, qui est caractérisé en ce que la couche insérée entre la couche d'injection de charge et la couche semi-conductrice organique est obtenue par revêtement de la couche d'injection de charge avec un mélange comportant au moins un matériau qui peut être réalisé de façon insoluble au moyen d'une réaction chimique, et au moins un semi-conducteur organique, ainsi que ses procédés de fabrication et d'utilisation.
EP07703163A 2006-02-13 2007-01-31 Composant electronique, son procede de fabrication et d'utilisation Withdrawn EP1984964A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102006006412A DE102006006412A1 (de) 2006-02-13 2006-02-13 Elektronisches Bauteil, Verfahren zu dessen Herstellung und dessen Verwendung
PCT/EP2007/000820 WO2007093282A1 (fr) 2006-02-13 2007-01-31 Composant électronique, son procédé de fabrication et d'utilisation

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EP1984964A1 true EP1984964A1 (fr) 2008-10-29

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US (2) US20090026448A1 (fr)
EP (1) EP1984964A1 (fr)
JP (1) JP5096378B2 (fr)
KR (1) KR101379991B1 (fr)
CN (1) CN101385157B (fr)
DE (1) DE102006006412A1 (fr)
WO (1) WO2007093282A1 (fr)

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CN101385157B (zh) 2011-03-30
CN101385157A (zh) 2009-03-11
US20110065222A1 (en) 2011-03-17
KR20080102391A (ko) 2008-11-25
WO2007093282A1 (fr) 2007-08-23
US20090026448A1 (en) 2009-01-29
KR101379991B1 (ko) 2014-04-11
JP2009527110A (ja) 2009-07-23
DE102006006412A1 (de) 2007-08-16
JP5096378B2 (ja) 2012-12-12

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