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  • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
  • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
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  • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
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  • C07F15/0086—Platinum compounds
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  • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
  • C07F15/02—Iron compounds
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  • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
  • C07F15/04—Nickel compounds
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  • H10K71/30—Doping active layers, e.g. electron transporting layers
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  • H10K85/30—Coordination compounds
  • H10K85/331—Metal complexes comprising an iron-series metal, e.g. Fe, Co, Ni
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  • H10K85/30—Coordination compounds
  • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
• • H—ELECTRICITY
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  • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
  • H10K85/30—Coordination compounds
  • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
  • H10K85/346—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising platinum
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  • 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
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  • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
  • H10K85/60—Organic compounds having low molecular weight
  • H10K85/649—Aromatic compounds comprising a hetero atom
• • 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
  • Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
  • Y02B10/00—Integration of renewable energy sources in buildings
  • Y02B10/10—Photovoltaic [PV]
• • 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

• the present invention relates to the use of a square planar transition metal complex as a dopant for doping an organic semiconductive matrix material, as a charge injection layer, as an electrode material and as a memory material in electronic or optoelectronic components.
• Inorganic dopants such as alkali metals (eg cesium) or Lewis acids (eg FeCl 3 ) are usually disadvantageous in organic matrix materials because of their high diffusion coefficients, since the function and stability of the electronic components is impaired. Furthermore, these materials are volatile and thus lead to increasing contamination of the evaporation apparatus. Further, it is known to release dopants via chemical reactions in the semiconductive matrix material to provide dopants. However, the reduction potential of the dopants released in this way is often insufficient for various applications, in particular for organic light-emitting diodes (OLEDs). Furthermore, upon release of the dopants, further compounds and / or atoms, for example atomic hydrogen, are generated, whereby the properties of the doped layer or of the corresponding electronic component are impaired.
• alkali metals eg cesium
• Lewis acids eg FeCl 3
• the acceptor-like material can also be used as a hole injection layer.
• a layer structure anode / acceptor / hole transporter can be produced.
• the hole transporter can be a pure layer or a mixed layer.
• the hole transporter may also be doped with an acceptor.
• the anode may be, for example, ITO.
• the acceptor layer may, for example, be 0.5-100 nm thick.
• Square planar transition metal complexes are known, for example, from WO 2005/123754 A2, which can be used in a wide variety of electronic applications, for example in active electronic components, passive electronic components, in electroluminescent devices (eg organic light emitting diodes), photovoltaic cells, light emitting diodes, Field effect transistors, phototransistors, etc ..
• electroluminescent devices eg organic light emitting diodes
• photovoltaic cells eg.g., light emitting diodes
• light emitting diodes e.g., Field effect transistors, phototransistors, etc .
• the use of the described square planar transition metal complexes is given as a charge transport material.
• the compounds used as dopants should lead to sufficiently high reduction potentials without interfering influences for the matrix material itself and should provide an effective increase in the number of charge carriers in the matrix material and be comparatively easy to handle.
• the first object is achieved in that the square planar transition metal complex has one of the following structures (I) or (II): - -
• M is a transition metal selected from Groups 8 to 11 of the Periodic Table of the Elements
• Xi, X 2 , X 3 and X 4 are independently selected from S, NR 5 and PR 5 , wherein R 5 is selected from, substituted or unsubstituted, linear or branched alkyl, cycloalkyl, aryl, heteroaryl, fused aromatic rings, donor groups and acceptor groups,
• Ri and R 2 are independently selected from, substituted or unsubstituted, aromatics, heteroaromatics, aliphatic hydrocarbons, cycloaliphatic hydrocarbons and nitrile,
• Li and L 2 are independently selected from aromatic amine, aromatic phosphine, halogen, pseudohalogen, NCS, SCN and CN.
• M is selected from nickel, copper, palladium, platinum, iron, ruthenium and osmium, preferably nickel, cobalt and iron.
• R 1 and R 2 are selected from substituted phenyl, preferably trifluoromethylphenyl, anisyl, tolyl, 2-pyridyl, methyl, propyl, isopropyl, trifluoromethyl, pentafluoroethyl and trichloromethyl. - -
• the disclosed transition-metal complexes a significantly stronger and / or more stable dopant is present than with previously known acceptor compounds, the square planar transition metal complexes being used here in neutral form as a p-dopant over an organic semiconductive matrix material.
• the conductivity of charge transport layers in the case of use according to the invention is substantially increased and / or the transfer of the charge carriers between the contacts and the organic layer is substantially improved in applications as an electronic component.
• CT complexes are formed in a doped layer according to the invention when the disclosed transition metal complexes are used, in particular by the transfer of at least one electron from the respective surrounding matrix material.
• cations of the matrix material are formed, which have movable holes on the matrix material.
• the matrix material acquires a conductivity that is increased compared to the conductivity of the undoped matrix material.
• Conductivities of undoped matrix materials are as a rule ⁇ 10 "8 S / cm, in particular frequently ⁇ 10 " 10 S / cm. It is important to ensure that the matrix materials have a sufficiently high purity. Such purities can be achieved by conventional methods, for example gradient sublimation. By doping the conductivity of such matrix materials can be increased to greater than 10 "8 S / cm, often> 10 " 5 S / cm. This is especially true for matrix materials that have an oxidation potential greater than -0.5 V vs.
• Fc / Fc + preferably greater than 0 V vs. Fc / Fc + , in particular greater +0.2 V vs. Have Fc / Fc +.
• the term Fc / Fc + refers to the redox couple ferrocene / ferrocenium, which is used as reference in an electrochemical determination of potential, for example cyclic voltammetry.
• the described square planar transition metal complexes can be used as an injection layer in electronic components, preferably between an electrode and a semiconductor layer, which can also be doped, in electronic components.
• Transition metal complexes can also be used according to the invention as part of a charge carrier generation layer, for example by use in a layer adjacent to another p- or n-doped layer.
• the described planar transition compounds preferably represent isolated molecules which are thus preferably present in the respective semiconducting layer as isolated molecules which are not fixed by chemical bonds to one another and / or to a matrix or to another component.
• the complexes have surprisingly high stability with respect to their reactivity with the atmosphere.
• Transition metal complexes as described herein can be synthesized by known methods, and in part they are also commercially available. The synthesis of such compounds is described, for example, in the following references, which are hereby incorporated by reference in the application in their entirety. It is understood that the cited references are given by way of example only. According to Schrauzer et al. Such transition metal complexes can be prepared from 1,2-diketones or 2-hydroxyketones, phosphorus pentasulfide and a suitable transition metal salt, J. Am. Chem. Soc. (1965) 87/7 1483-9. The reaction of transition metal carbonyls with sulfur and acetylenes also leads to the complexes according to the invention, A. Davonon et al.
• transition metal carbonyls instead of the transition metal carbonyls, it is also possible to use other formally 0-valent transition metal compounds, such as, for example, corresponding cyclooctadienyls, phosphines, etc., but also pure transition metals. G.N. Schrauzer et al. Z. Naturforschg. (1964) 19b, 192-8.
• phthalocyanine complexes for example of Zn (ZnPc), Cu (CuPc), Ni (NiPc) or other metals, where the phthalocyanine ligand may also be substituted, may be used as p-dopable matrix materials.
• Other metal complexes of naphthocyanines and porphyrins may optionally be used.
• arylated or heteroarylated amines or benzidine derivatives which may be substituted or unsubstituted, in particular spiro-linked, can also be used as the matrix material.
• NPD can be used as the matrix material.
• heteroaromatics in particular imidazole, thiophene, thiazole derivatives, heterotriphenylenes, but also others, may also be used as the matrix material, optionally also dimeric, oligomeric or polymeric heteroaromatics.
• the heteroaromatics are preferably substituted, in particular aryl-substituted, for example phenyl or naphthyl-substituted. They can also be present as spiro compounds.
• matrix materials mentioned can also be used with one another or mixed with other materials in the context of the invention. It is understood that suitable other organic matrix materials can be used which have semiconducting, in particular hole-conducting properties. doping concentration
• the dopant is present in a doping concentration of ⁇ 1: 1 to the matrix molecule or the monomeric unit of a polymeric matrix molecule, such as in a doping concentration of 1: 2 or smaller, more preferably 1: 5 or less or 1: 10 or smaller ,
• the doping concentration may be in the range of 20: 1 to 1: 100,000, more preferably in the range of 10: 1 to 1: 1000, preferably in the range of 1: 1 to 1: 100, without being limited thereto.
• the doping of the respective matrix material with the compounds to be used according to the invention can be carried out by one or a combination of the following processes:
• the electron-deficient compounds according to the invention as p-dopants used may cm, for example in the use of spiro-TTB or ZnPc as the matrix semiconducting layers with conductivities at room temperature in the range of 10 "5 S / or be achieved higher, for example from 10 -3 S / cm or higher.
• spiro-TTB or ZnPc as the matrix semiconducting layers with conductivities at room temperature in the range of 10 "5 S / or be achieved higher, for example from 10 -3 S / cm or higher.
• cyanine zinc as the matrix a conductivity scored by higher 10 -8 S / cm, for example 10 -6 S / cm. it has not been possible to dope this matrix with organic acceptors since the oxidation potential of the matrix was too low, the conductivity of undoped phthalocyanine-zinc is not more than 10 -10 S / cm.
• the dopant layer or formation may each contain one or more different such electron-poor transition metal complex compounds.
• the described compounds for producing p-doped organic semiconducting materials which can be arranged in particular in the form of layers or electrical conduction paths, a multiplicity of electronic components or devices containing them can be produced with a p-doped organic semiconductor layer.
• the term "electronic components” also encompasses optoelectronic components.
• the described connections can be used to determine the electronic properties of an electronically functionally effective region of the component, such as its electrical conductivity, light-emitting properties or the like, are advantageously changed.
• the conductivity of the doped layers can be improved and / or the improvement of the charge carrier injection of contacts into the doped layer can be achieved.
• the invention comprises in particular organic light-emitting diodes (OLED), organic solar cells, field-effect transistors, organic diodes, in particular those with a high rectification ratio such as 10 3 -10 7 , preferably 10 4 -10 7 or 10 5 -10 7 , and organic field-effect transistors, which are produced by means of the electron-poor transition metal complex compounds.
• OLED organic light-emitting diodes
• organic solar cells organic solar cells
• field-effect transistors organic diodes, in particular those with a high rectification ratio such as 10 3 -10 7 , preferably 10 4 -10 7 or 10 5 -10 7
• organic field-effect transistors which are produced by means of the electron-poor transition metal complex compounds.
• a p-doped layer based on an organic matrix material may be present, for example, in the following layer structures, wherein preferably the base materials or matrix materials of the individual layers are each organic:
• p-i-M p-doped semiconductor insulator metal
• p-i-n p-doped semiconductor-insulator-n-doped semiconductor
• n-i-p n-doped semiconductor-insulator-p-doped semiconductor.
• i is an undoped layer
• p is a p-doped layer.
• the contact materials are here hole injecting, wherein on the p-side, for example, a layer or a contact of ITO or Au may be provided, or electron-injecting, n-side, a layer or a contact of ITO, Al or Ag can be provided.
• the i-layer may also be omitted, whereby layer sequences with pn or np junctions can be obtained.
• the use of the compounds described is not limited to the abovementioned exemplary embodiments; in particular, the layer structures can be supplemented or modified by introducing additional suitable layers.
• OLEDs with such layer sequences, in particular with pin or with an inverse structure with them, can be constructed with the compounds described.
• organic diodes of the metal-insulator-p-doped semiconductor type (mip) or optionally of the pin type, for example on the basis of phthalocyanine zinc. These diodes show a rectification ratio of 10 5 and higher.
• dopants according to the invention it is possible to produce electronic components with pn junctions, in which case the same semiconductor material can be used in particular for the p- and n-doped sides (homo-pn junction), and where doped semiconductor material, a described electron-poor transition metal complex compound is used.
• the electron-poor transition metal complex compounds can be used according to the invention in the electronic components but also in layers, conductance paths, point contacts or the like, if these predominate over another component, for example as an injection layer in pure or substantially pure form.
• An extremely electron-poor transition metal complex compound of high purity is provided.
• the presented electron-poor transition metal complex compound is evaporated simultaneously with the matrix material.
• the matrix material eg spiro-TTB or ⁇ -NPD.
• the p-type dopant and the matrix material can be evaporated in such a way that the layer deposited on a substrate in a vacuum evaporation system has a doping ratio of p-dopant to matrix material of 1:10.
• Each doped with the p-dopant layer of the organic semiconductor material is applied to an ITO layer (indium tin oxide), which is arranged on a glass substrate.
• ITO layer indium tin oxide
• a metal cathode is deposited, for example, by vapor deposition of a suitable metal to produce an organic light emitting diode.
• the organic light-emitting diode can also have a so-called inverted layer structure, wherein the layer sequence is: glass substrate - metal cathode -p-doped organic layer - transparent conductive cover layer (for example ITO). It is understood that depending on the application, further layers can be provided between the individual layers mentioned.
• the neutral nickel complex bis (cw-l, 2-bis [trifluoromethyl] ethylene-l, 2-dithiolato) nickel was used for the doping of spiro-TTB as a matrix material.
• Doped layers with a doping ratio dopant: matrix material of 1:10 were prepared by mixed evaporation of matrix and dopant with spiro-TTB.
• the conductivity was 2xlO ⁇ 4 S / cm.
• the neutral nickel complex bis (cw-l, 2-bis [trifluoromethyl] ethylene-l, 2-dithiolato) nickel was used for doping ⁇ -NPD as a matrix material.
• Doped layers with a doping ratio of dopant: matrix material of 1:10 were prepared by mixed evaporation of matrix and dopant with ⁇ -NPD. 2xlO '7, the conductivity was S / cm. - -
• the neutral cobalt complex bis (c / 5-l, 2-bis [trifluoromethyl] ethylene-l, 2-dithiolato) cobalt was used for doping ZnPc as a matrix material.
• Doped layers with a doping ratio of dopant: matrix material of 1:10 were prepared by mixed evaporation of matrix and dopant with ZnPc.
• the conductivity was 2XW 4 SlCm.
• the neutral iron complex bis (c / 5-l, 2-bis [trifluoromethyl] ethylene-l, 2-dithiolato) iron was used for doping ZnPc as a matrix material.
• Doped layers with a doping ratio of dopant: matrix material of 1:10 were prepared by mixed evaporation of matrix and dopant with ZnPc.
• the conductivity was 3 ⁇ 10 -3 S / cm.
• the neutral nickel complex Bis (c / sl, 2-bis [2,2'-pyridyl] ethylene-l, 2-dithiolato) nickel was used for doping ZnPc as a matrix material.
• Doped layers with a doping ratio of dopant: matrix material of 1:10 were prepared by mixed evaporation of matrix and dopant with ZnPc.
• the conductivity was 4x10 "5 S / cm.

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