WO2024002424A1 - Élément de construction électronique organique avec un composé chimique de formule générale i, et utilisation d'un tel composé chimique en tant que dopant n dans un élément de construction électronique organique - Google Patents

Élément de construction électronique organique avec un composé chimique de formule générale i, et utilisation d'un tel composé chimique en tant que dopant n dans un élément de construction électronique organique Download PDF

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WO2024002424A1
WO2024002424A1 PCT/DE2023/100489 DE2023100489W WO2024002424A1 WO 2024002424 A1 WO2024002424 A1 WO 2024002424A1 DE 2023100489 W DE2023100489 W DE 2023100489W WO 2024002424 A1 WO2024002424 A1 WO 2024002424A1
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chemical compound
layer
alkyl
aryl
group
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PCT/DE2023/100489
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German (de)
English (en)
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Andre Weiss
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Heliatek Gmbh
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/04—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • 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
    • 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
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/30—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/50—Photovoltaic [PV] devices
    • 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]
    • H10K50/14—Carrier transporting layers
    • H10K50/16—Electron transporting layers
    • H10K50/165—Electron transporting layers comprising dopants
    • 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

Definitions

  • Organic electronic component with a chemical compound of the general formula I and use of such a chemical compound as an n-dopant in an organic electronic component
  • the present invention relates to an organic electronic component with an electrode, a counterelectrode and a layer system between the electrode and the counterelectrode, at least one layer of the layer system having a chemical compound of the general formula I, a use of a chemical compound of the general formula I as n -Dopant for doping at least one layer in a layer system of an organic electronic component, as well as a chemical compound of the general formula II.
  • Organic electronic components can convert electromagnetic radiation into electrical current using the photoelectric effect. For such a conversion of electromagnetic radiation, absorber materials are required that exhibit good absorption properties for light. Other organic electronic components are light-emitting components that emit light when an electrical current flows through them.
  • Organic electronic components include at least two electrodes, one electrode being applied to a substrate and the other functioning as a counter electrode. Between the electrodes there is at least one photoactive layer and transport layers for charge carriers, in particular electron transport layers and hole transport layers.
  • photoactive compounds are typically used in a donor/acceptor system, a heterojunction, with at least the donor and/or the acceptor absorbing electromagnetic radiation.
  • the donor/acceptor system can be designed as a planar hetero union or as a bulk hetero union.
  • the absorbers absorb electromagnetic radiation of a specific wavelength, where photons are converted into excitons that contribute to a photocurrent.
  • the compounds in the donor/acceptor system must have high charge carrier mobility in order to minimize loss of photocurrent due to recombination of the excitons within the donor/acceptor system.
  • the excitons must be separated into charge carriers at an interface and the charge carriers must leave the photoactive layer before recombination.
  • the layers In order to minimize the recombination of charge carriers, the layers must have high conductivity.
  • the transport layers are doped with dopants.
  • a structure of an organic solar cell known from the prior art consists of a pin or nip diode (Martin Pfeiffer, "Controlled doping of organic vacuum deposited dye layers: basics and applications", PhD thesis TU-Dresden, 1999, and W02011/ 161108A1 ). Substrate with an adjoining mostly transparent base contact, n-layer(s), i-layer(s), p-layer(s) and a cover contact.
  • doped organic layers or layer systems in organic components, in particular in organic solar cells and organic light-emitting diodes, is known.
  • Various materials have been proposed as dopants, such as aryl- and/or heteroaryl-substituted main group element halides (DE102007018456B4), metal complexes (02005086251A2), transition metal complexes (DE102008051737), boratetetraazapentalenes (W02007115540A1), and organic ones Phosphoranes (EP2724388B1).
  • dopants such as alkali metals (e.g.
  • the n-doping of an electron transport layer made of the matrix material PCBM with the n-dopant trimethyltriazine is known from the prior art (Li et al., N-doping of fullerene using 1, 3, 5-trimethylhexahydro-1, 3, 5-triazine as an electron transport layer for nonfullerene organic solar cells", Sustainable Energy Fuels, 2020, 4, 1984).
  • the conductivity described here is moderate and decreases significantly at higher temperatures, which significantly limits its technical usability.
  • dopants disclosed in the prior art are suitable for transport layers in electronic components, there is a need to improve the conductivity of transport layers obtained through doping. Furthermore, dopants are required that lead to increased conductivity at higher temperatures.
  • the present invention is therefore based on the object of providing dopants for doping organic layers of organic electronic components, the disadvantages mentioned being overcome, and in particular the dopants having sufficiently high redox potentials, without a disruptive influence on the matrix material, and an effective increase the number of charge carriers in the matrix material to increase the conductivity.
  • the loss due to recombination of charge carriers in particular should be minimized.
  • an organic electronic component with an electrode, a counterelectrode and a layer system between the electrode and the counterelectrode, the layer system has at least one photoactive layer.
  • At least one layer of the layer system has at least one chemical compound of the general formula I, with Xi, X2, X3, X4, X5 and Heteroatom selected from 0, S or N, the substituent being selected in each case from the group consisting of halogen, amino, alkyl, alkenyl, alkynyl, alkoxy, thioalkoxy, aryl, heteroaryl, and an alkyl group la wherein R41, R42, and R43 are each independently selected from the group consisting of H, unsubstituted or substituted alkyl, unsubstituted or substituted aryl, and unsubstituted or substituted heteroaryl having a heteroatom selected from 0, S or N, preferably H and alkyl, where the substituent is each selected from the group consisting of
  • a substituent is in particular the exchange of H understood by another group.
  • a substituent is understood to mean in particular all atoms and atom groups other than H, preferably a halogen, an alkyl group, the alkyl group can be linear or branched, an alkenyl group, an alkynyl group, an alkoxy group, an Thioalkoxy group, an aryl group, or a heteroaryl group.
  • a halogen is understood to mean in particular F, CI or Br, preferably F.
  • At least one transport layer, preferably an electron transport layer, of the layer system has the at least one chemical compound as a dopant, preferably as an n-dopant.
  • the electrodes are made of a metal, preferably Al, Ag, Au or a combination thereof, a conductive oxide, preferably ITO, ZnO:Al or another TCO (Transparent Conductive Oxide), a conductive polymer, preferably PEDOT /PSS Poly (3, 4-ethylenedioxythiophene) poly (styrenesulfonate) or PANI (polyaniline), or formed from a combination of these materials.
  • a metal preferably Al, Ag, Au or a combination thereof
  • a conductive oxide preferably ITO, ZnO:Al or another TCO (Transparent Conductive Oxide)
  • a conductive polymer preferably PEDOT /PSS Poly (3, 4-ethylenedioxythiophene) poly (styrenesulfonate) or PANI (polyaniline), or formed from a combination of these materials.
  • the at least one chemical compound is present in a matrix material.
  • the organic electronic component with the chemical compound according to the invention has advantages compared to the prior art.
  • the chemical compounds are advantageously suitable for doping a matrix material, preferably for doping transport materials, in particular electron transport materials.
  • the chemical compounds are advantageously suitable for doping organic transport layers in electronic components; in particular, the chemical compounds have sufficiently high redox potentials for this.
  • the chemical compounds advantageously contribute to an increase in the number of charge carriers in a matrix material. High conductivities can be achieved, especially in a range from ICh 2 to I Ch 6 S/cm at a doping concentration of 2% to 25% [w/w], while this is often the case for undoped matrix materials below I CH 8 S/cm or even below ICb 10 S/cm.
  • the conductivity of matrix material doped with a chemical compound according to the invention increases significantly at higher temperatures.
  • the conductivity achieved at higher temperatures of a layer doped with a chemical compound according to the invention is at least largely retained even after cooling.
  • the chemical compounds have no disruptive influence on the matrix material, in particular on fullerenes.
  • the dopants are easily accessible due to their relatively simple synthesis and can therefore be produced inexpensively.
  • the chemical compounds are air-stable and can be used under atmospheric conditions.
  • the chemical compounds are sufficiently thermally stable and can be evaporated in a vacuum, for example with vacuum thermal evaporation (VTE) or organic vapor phase deposition (OVPD); in particular, the chemical compounds do not decompose when evaporating in a vacuum.
  • VTE vacuum thermal evaporation
  • OVPD organic vapor phase deposition
  • the chemical compounds do not decompose when evaporating in a vacuum.
  • the chemical compounds are colorless, which at least largely does not lead to a reduction in the efficiency of photovoltaic elements due to parasitic absorption.
  • the chemical compound has the general formula II with Xi, X2, alkyl, and unsubstituted or substituted aryl, the substituent in each case being selected from the group consisting of halogen, amino, alkyl, alkenyl, alkynyl, alkoxy, thioalkoxy, aryl, and heteroaryl with a heteroatom selected from 0, S or N, where Ri and R2, R3 and R4, and / or R5 and Re can each form a homocyclic or a heterocyclic aromatic or aliphatic ring.
  • Ri or R2, and R3 or R4, and R5 or Re are each independently an unsubstituted or substituted aryl or an unsubstituted or substituted heteroaryl with a heteroatom selected from 0, S or N, where the Each substituent is selected from the group consisting of halogen, amino, alkyl, alkoxy, thioalkoxy, aryl, and heteroaryl with a heteroatom selected from 0, S or N.
  • Ri and R2, R3 and R4, and/or R5 and Re each form a homocyclic or a heterocyclic aromatic or aliphatic ring.
  • Ri and R2, R3 and R4, and/or R5 and Re each independently form a homocyclic or a heterocyclic aliphatic ring, preferably a homocyclic or a heterocyclic aromatic 5 ring or a homocyclic or a heterocyclic aromatic 6-ring, with a heteroatom selected from 0, S or N, preferably H atoms in the ring are independently substituted with a substituent selected from the group consisting of halogen, amino, alkyl, alkenyl, alkynyl, alkoxy, thioalkoxy, aryl , and heteroaryl with a heteroatom selected from 0, S or N.
  • Ri, R3, and Rs are each an unsubstituted or substituted cyclic alkyl, preferably cyclopentanyl or cyclohexanyl.
  • Ri and R2, R3 and R4, and R5 and Re are the same, particularly preferably Ri, R2, R3, R4, Rs, and Re are the same.
  • Xi, X2, X3, X4, X5 and Xe are H.
  • the chemical compound has the general formula III with Xi, X2, X3, X4, X5 and preferably F, amino, alkyl, alkenyl, alkynyl, alkoxy, thioalkoxy, aryl, preferably phenyl, and heteroaryl with a heteroatom selected from 0, S or N, where H can each be further substituted, preferably with a substituent selected from the group consisting from halogen, amino, alkyl, alkoxy, aryl, and heteroaryl with a heteroatom selected from 0, S or N.
  • Rn to Rn, R21 to R25, and R31 to R35 are each H, or are each at least one Rn to Rn, R21 to R25, or R31 to R35 an Arnino group each with at least one alkyl, aryl or heteroaryl, preferably with two alkyl, aryl or heteroaryl.
  • At least one Rn to R, R21 to R25, or R31 to R35 is an arnino group each with at least one alkyl or aryl, preferably with two alkyl or aryl.
  • Rn to Rn, R21 to R25, and R31 to R35 are each independently selected from the group consisting of H, halogen, preferably F, amino, alkyl, alkenyl, alkynyl, alkoxy, thioalkoxy, aryl, preferred phenyl, and Heteroaryl with a heteroatom selected from 0, S or N, where H can each be further substituted, with the proviso that at least one Rn to Rn, R21 to R25, and R31 to R35 is not H, preferably the substituent is selected from the group consisting of halogen, amino, alkyl, alkoxy, aryl, and heteroaryl with a heteroatom selected from 0, S or N.
  • Rn to Rn, R21 to R25, and R31 to R35 are each independently selected from the group consisting of halogen, preferably F, amino, alkyl, alkoxy, aryl, preferably phenyl, and heteroaryl with a heteroatom from 0, S or N, where H can each be independently substituted with a substituent selected from the group consisting of halogen, amino, alkyl, alkoxy, aryl, and heteroaryl with a heteroatom selected from 0, S or N.
  • two of Rn to R15, R21 to R25, and R31 to R35 each form a homocyclic or a heterocyclic aromatic or aliphatic ring.
  • Xi, X2, X3, X4, X5 and Xg are H.
  • Xi, X2, X3, X4, X5 and Xe are independently selected from H and CH3, and/or Xi, X3 X4, X5 and Heteroaryl can be substituted with a heteroatom selected from 0, S or N.
  • Y2 and Y3 for the alkyl group la at least one R41, R42 or R43 is an H.
  • Yi, Y2 and Y3 are the same. According to a development of the invention, it is provided that at least one R41, R42, or R43 is an unsubstituted or substituted aryl, or an unsubstituted or substituted heteroaryl with a heteroatom selected from 0, S or N.
  • R41, R42, and R43 are each independently selected from the group consisting of H, unsubstituted or substituted alkyl, unsubstituted or substituted aryl, and unsubstituted or substituted heteroaryl with a heteroatom selected from 0 , S or N, where the substituent is in each case selected from the group consisting of halogen, amino, alkyl, alkoxy, aryl, with the proviso that at least one of R41, R42 and R43 is not H, are preferred at least two of R41, R42 , or R43 no H .
  • one of R41, R42, and R43 is H.
  • At least one R41, R42, or R43 is an unsubstituted or substituted aryl, or unsubstituted or substituted heteroaryl with a heteroatom selected from 0, S or N, where the substituent is selected from the group consisting of halogen, amino, alkyl, alkenyl, alkynyl, alkoxy, thioalkoxy, aryl, and heteroaryl with a heteroatom selected from 0, S or N, preferably with a substituent selected from the group consist of F and Cl-C4-alkyl.
  • At least one R41, R42, or R43 is a fused unsubstituted or substituted aryl.
  • R41, R42, and R43 are selected from the group consisting of naphthalene, anthracene, phenanthrene, phenalene, tetracene, chrysene, pyrene, pentacene, perylene, benzopyrene, or pentaphene.
  • the chemical compound is selected from the group consisting of:
  • the chemical compound is an n-dopant in an electron transport layer or an electron injection layer of the layer system, in particular in an electron transport layer.
  • the electron transport layer can be a layer of a pn junction or alternatively can be arranged between an electrode and a photoactive layer.
  • the at least one electron transport layer and/or the electron injection layer is in direct contact with the at least one photoactive layer.
  • the chemical compound is present in a matrix material, the molar doping ratio of the chemical compound to the matrix material being from 1:1 to 1:10,000, preferably from 1:2 to 1:1000, particularly preferably from 1:5 to 1:100. This increases the conductivity of the matrix material in particular.
  • the matrix material has a LUMO energy level of -3.5 eV to -5.0 eV, preferably from -3.0 eV to -4.5 eV, or preferably from -3.5 eV to -4.5 eV.
  • the matrix material has a reduction potential of less than -0.3 V vs. Fc/Fc+, preferably less than -0.5 V vs . Fc/Fc+, or preferably less than -0.8 V vs . Fc/Fc+, where Fc/Fc+ refers to the redox couple ferrocene/ferrocenium, which is used as a reference in determining the electrochemical potential using cyclic voltammetry.
  • the matrix material is a fullerene or fullerene derivative, particularly preferably the matrix material is selected from the group consisting of C60, C70, C76, C80, C82, C84, C86, C90 and C94.
  • the at least one electron transport layer and/or the electron injection layer has the matrix material.
  • the at least one layer with the at least one chemical compound is in direct contact with an electrode, is an electron transport layer and / or electron injection layer or is in direct contact with such a layer, or is a layer of a pn junction.
  • the organic electronic component has two photoactive layers, a so-called tandem cell, with a connection unit (pn-unction) arranged between them, or three photoactive layers, a so-called triple cell, each with a connection unit arranged between them (pn-unction). pn-j union), on, where at least one of the connecting units has a chemical compound of the general formula I.
  • the organic electronic component is an organic optoelectronic component, preferably an organic light-emitting diode (OLED), an organic photovoltaic element (OPV), an organic field effect transistor (OFET), or an organic photodetector, particularly preferably a organic photovoltaic element (OPV) with at least one light-absorbing photoactive layer, or a thermal sensor.
  • OLED organic light-emitting diode
  • OFET organic field effect transistor
  • OFET organic field effect transistor
  • an organic photodetector particularly preferably a organic photovoltaic element (OPV) with at least one light-absorbing photoactive layer, or a thermal sensor.
  • An organic electronic component is understood to mean, in particular, an organic photovoltaic element with at least one organic photoactive layer.
  • An organic photovoltaic element makes it possible to convert electromagnetic radiation into electrical current using the photoelectric effect.
  • photoactive is understood as the conversion of light energy into electrical energy.
  • free charge carriers are not directly generated by the light, but rather excitons, i.e. electrically neutral excitation states (bound electron-hole pairs), are initially formed. Only in a second step are these excitons separated into free charge carriers in a photoactive donor-acceptor transition, which then contribute to the flow of electrical current.
  • Photoactive is understood in particular to mean that molecules change their charge state and/or their polarization state when light is applied. Accordingly, a photoactive layer is understood to mean, in particular, a layer of an electronic component that has at least one photoactive molecule that contributes to the absorption of radiation and/or the emission of radiation.
  • the organic electronic component is as a nip, ni, ip, pnip, pni, pip, nipn, nin, ipn, pnipn, or pipn cell or a combination of nip, ni, ip, pnip, pni , pip, nipn, nin, ipn, pnipn, or pipn- Cells that contain at least one i-layer are formed.
  • An i-layer is understood to mean, in particular, an intrinsic, undoped layer.
  • One or more i-layers can consist of one material (planar heterojunctions, PHJ) or of a mixture of two or more materials, so-called bulk heterojunctions (BHJ).
  • the organic electronic component is designed as a tandem, triple or multiple cells.
  • the transport layer with the at least one chemical compound of the general formula I is part of a pn junction (pn-junction), which has a first photoactive layer with a further photoactive layer in a tandem solar cell or in a Multiple solar cell connects, and/or connects an electrode with a photoactive layer.
  • pn-junction pn-junction
  • the photoactive layer has a donor/acceptor system.
  • the at least one donor is an ADA oligomer and/or a BODIPY
  • the at least one acceptor is an ADA oligomer and/or a fullerene and/or fullerene derivative.
  • a BODIPY compound is understood to mean, in particular, a compound of the general formula C9H7BN2 F2 as the basic structure, i.e. a compound with a boron difluoride group with a dipyrromethene group, in particular a compound 4, 4 -Dif luoro-4-bora-3a, 4a-diaza-s-indacene.
  • An ADA oligomer is in particular a conjugated acceptor-donor-acceptor oligomer (A-D-A' oligomer) with an acceptor unit (A) and a further acceptor unit (A'), each of which is connected to a donor unit (D) bound are understood.
  • the organic electronic components can be manufactured in various ways.
  • the layers of the layer system can be applied in liquid form as a solution or dispersion by printing or coating, or by vapor deposition in a vacuum, for example using CVD, PVD or OVPD.
  • the chemical compound and/or a layer with the at least one chemical compound is deposited by means of vacuum processing, vapor deposition or solvent processing, particularly preferably by means of vacuum processing.
  • all organic layers and the electrodes are applied by evaporation in a vacuum.
  • the object of the present invention is also achieved by using a chemical compound of the general formula I as an n-dopant for doping at least one layer in a layer system of an organic electronic component, in particular at least one electron transport layer and/or electron injection layer , is provided, in particular according to one of the previously described exemplary embodiments.
  • a chemical compound of the general formula I for doping at least one layer in a layer system of an organic electronic component, in particular at least one electron transport layer and/or electron injection layer , is provided, in particular according to one of the previously described exemplary embodiments.
  • the use of the chemical compound of the general formula I in an organic electronic component results in particular in the advantages that have already been explained in connection with the organic electronic component.
  • the at least one chemical compound is used as an n-dopant.
  • the object of the present invention is also achieved by providing a chemical compound of the general formula II in particular according to one of the previously described exemplary embodiments.
  • the chemical compound of the general formula II in particular has the advantages that have already been explained in connection with the organic electronic component and the use of the chemical compound of the general formula I in an organic electronic component.
  • Xi, X2, X3, X4, X5 and Xe are independent of each other selected from the group consisting of H and alkyl, Ri, R2, R3, R4, Rs and Rg independently selected from the group consisting of aryl, preferably phenyl, and heteroaryl with a heteroatom selected from 0, S or N, where H respectively may be further substituted, wherein the substituent is selected from the group consisting of halogen, amino, alkyl, alkenyl, alkynyl, alkoxy, thioalkoxy, aryl, and heteroaryl with a heteroatom selected from 0, S or N, with the proviso that in Ri, R2, R3, R4, Rs and Re each have at least one H substituted, where Ri and R2, R3 and R4, and/or R5 and Re can be bridged together.
  • Xi, X2, X3, X4, X5 and Xe are independently selected from H and CH3, and/or Xi, X2, X3, X4, X5 and Ri, R2, R3, R4, Rs and Re, and/or Ri, R2, R3, R4, Rs and Re are phenyl or naphthyl, where H is each further replaced with a substituent selected from the group consisting of halogen, amino, alkyl, Alkenyl, alkynyl, alkoxy, thioalkoxy, aryl, and heteroaryl may be substituted with a heteroatom selected from 0, S or N, and / or RI, R2, R3, R4, R5 and R6 are the same.
  • the chemical compound is a chemical compound of the general formula X with Xi, X2, X3, X4, X5 and Xe independently selected from the group consisting of H and alkyl, with R-50-R54, R55-R59, Reo-Rg4, Rgs-Rgg, R70-R74, and R75-R79 each independently selected from the group consisting of H, halogen, preferably F, amino, alkyl, alkenyl, alkynyl , alkoxy, thioalkoxy, aryl, preferably phenyl, and heteroaryl with a heteroatom selected from 0, S or N, with the proviso that in each case at least one of R50-R54, R55-R59, Reo-R64, Res-Reg, R7o- R74, and R75-R79 is not H, preferably at least two of R50-R54, R55-R59, Reo-R64, Res-Reg
  • one R50-R54, R55-R59, Reo-R64, Res-Reg, R70-R74, and R75-R79 is an amino group each with at least one alkyl or aryl, preferably with two alkyl or aryl.
  • 1, 1 '-Diphenylmethanamine (1) (10.0 g, 52.9 mmol) and para-formaldehyde (2) (1.84 g, 58.2 mmol) are dissolved in 253 ml of toluene in a 500 ml three-necked flask and placed under Reflux dissolved under an argon atmosphere for 1 hour.
  • the excess of para-formaldehyde, water and toluene is distilled off to a volume of 40 ml.
  • the solid begins to precipitate and the excess para- Formaldehydes, water and toluene are removed.
  • 5 ml of toluene are added under reflux.
  • FIG. 1 shows a schematic representation of a structure of an organic electronic component 1 in cross section.
  • the organic electronic component 1 is an organic photovoltaic element.
  • the organic electronic component 1 has an electrode 3 , a counterelectrode 7 and a layer system 8 between the electrode 3 and the counterelectrode 7 , the layer system 8 having at least one photoactive layer 5 .
  • At least one layer of the layer system 8 has at least one chemical compound of the general formula I, with Xi, X2, X3, X4, X5 and Heteroatom selected from 0, S or N, the substituent being selected in each case from the group consisting of halogen, amino, alkyl, alkenyl, alkynyl, alkoxy, thioalkoxy, aryl, heteroaryl, and an alkyl group la wherein R41, R42, and R43 are each independently selected from the group consisting of H, unsubstituted or substituted alkyl, unsubstituted or substituted aryl, and unsubstituted or substituted heteroaryl having a heteroatom selected from 0, S or N, preferably H and alkyl, where the substituent is each selected from the group consisting of halogen, amino, alkyl, alkenyl, alkynyl, alkoxy, thioalkoxy, aryl, and heteroaryl with a heteroatom selected from 0,
  • the chemical compound has the general formula II with Xi, X2, X3, X4, X5 and alkyl, and unsubstituted or substituted aryl, wherein the substituent in each case is selected from the group consisting of halogen, amino, alkyl, alkenyl, alkynyl, alkoxy, thioalkoxy, aryl, and heteroaryl with a heteroatom selected from 0, S or N, where Ri and R2, R3 and R4, and/or R5 and Rg can each form a homocyclic or a heterocyclic aromatic or aliphatic ring.
  • the chemical compound has the general formula III with Xi, X2, X3, X4, X5 and , amino, alkyl, alkenyl, alkynyl, alkoxy, thioalkoxy, aryl, preferably phenyl, and heteroaryl with a heteroatom selected from 0, S or N, where H can each be further substituted, preference is given to Rn to Rn, R21 to R25, and R31 to R35 each being H, or at least one Rn to Rn, R21 to R25 each , or R31 to R35 is an amino group each with at least one alkyl or aryl, preferably with two alkyl or aryl.
  • Xi, X2, X3, X4, X5 and Xg are independently selected from H and CH3, and/or Xi, X2, and Heteroatom selected from 0, S or N can be substituted, and/or Yi, Y2 and Y3 are the same, and/or at least one R41, R42, or R43 is an unsubstituted or substituted aryl, or an unsubstituted or substituted heteroaryl a heteroatom selected from 0, S or N.
  • the chemical compound is selected from the group consisting of:
  • the chemical compound is an n-dopant in an electron transport layer 4 or an electron injection layer of the layer system 8, in particular in an electron transport layer 4.
  • the chemical compound is present in a matrix material, the molar doping ratio of the chemical compound to the matrix material being from 1:1 to 1:10,000, preferably from 1:2 to 1:1,000, especially preferably from 1:5 to 1:100, and/or where the matrix material has a LUMO energy level of -3.0 eV to -5.0 eV, preferably the matrix material is a fullerene or fullerene derivative, particularly preferred is the matrix material selected from the group consisting of C60, C70, C76, C80, C82, C84, C86, C90 and C94.
  • the organic electronic component 1 is an organic optoelectronic component, preferably an organic light-emitting diode (OLED), an organic photovoltaic element (OPV), an organic field effect transistor (OFET), or an organic photodetector, particularly preferably an organic photovoltaic Element (OPV) with at least one light-absorbing photoactive layer, or a thermal sensor.
  • OLED organic light-emitting diode
  • OFET organic field effect transistor
  • OFET organic field effect transistor
  • the at least one layer with the at least one chemical compound is in direct contact with an electrode 3, 7, an electron transport layer 4 and / or electron injection layer or is in direct contact with such a layer, or a layer of a pn junction.
  • the pn junction can be arranged between two photoactive layers 5 or alternatively can be arranged between an electrode 3,7 and a photoactive 5 layer.
  • the chemical compounds according to the invention are suitable as n-dopant for doping at least one layer in a layer system 8 of the organic electronic component 1, in particular at least one electron transport layer 4 and/or electron induction layer.
  • the chemical compounds are thermally stable and enable evaporation in a high vacuum with a process window between 100°C and 400°C.
  • the conductivity of was determined with the chemical compound (01) (Table 2A), the chemical compound (06) (Table 2B), and the chemical compound (07) (Table 2C). doped transport layers investigated. The chemical compounds were examined with regard to their effect as n-dopant in an electron transport layer 4.
  • the conductivity was determined in a layer doped with the n-dopant made of fullerene C60 as a matrix material.
  • the matrix material C60 i.e. an electron transport material (ETM)
  • ETM electron transport material
  • Table 2A shows the electrical conductivity of an electron transport layer 4 made of C60 as a matrix material with different proportions of doping with the compound (01) according to the invention.
  • the conductivity of the electron transport layer 4 increases depending on the proportion of doping with the compound (01) according to the invention and reaches a value of 2.82 -IO -4 S/cm with a proportion of 24.73% by weight of the n -Dopants at 40°C, and of 4.0 -10- 2 S/cm with a proportion of 23.38% by weight of the n-dopant at 60°C.
  • the conductivity of a layer consisting only of C60 is below the measurement range of 1 -10 ⁇ 6 S/cm.
  • the triazinanes according to the invention are good n-dopants.
  • the data show that the conductivity of layers doped with compounds according to the invention is higher Temperatures up to 60°C are at least largely maintained or even increase.
  • Table 2B shows the electrical conductivity of an electron transport layer 4 made of C60 as a matrix material with different proportions of doping with the compound (06) according to the invention.
  • Table 2C shows the electrical conductivity of an electron transport layer 4 made of C60 as a matrix material with different proportions of doping with the compound (07) according to the invention.
  • the conductivity was also determined in each case with the n-dopant compound (06) (Table 2B) and compound (07) (Table 2C) doped layer with C60 as matrix material.
  • the conductivity of the electron transport layers 4 at 22° C. was 2.15 -IO -5 S/cm with the compound (06) and 9.14 -IQ- 4 S/cm with the compound (07). It was shown that the conductivity of the matrix material C60 can also be increased with the compounds (06) and (07).
  • the conductivity of layers doped with the chemical compounds is at least largely maintained or even increased at higher temperatures.
  • the chemical compounds of the general formula I increase the conductivity of an electron transport layer 4 of a layer system of an organic electronic component 1. It is shown in particular that the doping of a matrix material of a transport layer, in particular the matrix material C60 of an electron transport layer 4, with a chemical according to the invention Connection significantly increases the conductivity of these layers.
  • the organic electronic component 1 is an organic photovoltaic element. Identical and functionally identical elements are provided with the same reference numbers, so that reference is made to the previous description.
  • the parameters fill factor FF, open-circuit voltage VOC, and short-circuit current Jsc of an organic photovoltaic element with connection (01) (Device No. 1 to 4), connection (06) (Device No. 6), connection (07) (Device No. 7) were determined ) and the comparison compound NDN-45 (Device No. 5) as n-dopant in the electron transport layer 4.
  • the organic photovoltaic element has a substrate 2, e.g. B. made of glass, on which an electrode 3 is arranged, e.g. made of ITO.
  • the electrode 3 can also be made of a metal, a conductive oxide, such as ZnO:Al or other transparent, conductive oxide or a polymer, such as PEDOT:PSS or PANI.
  • a layer system 8 Arranged thereon is a layer system 8 with an electron transport layer 4 (ETL) with C60 as matrix material and an n- Dopants.
  • ETL electron transport layer 4
  • a photoactive layer 5 with a donor material and an acceptor material, e.g. B. Bullerene C60, which together form a donor/acceptor system, either as a flat heterojunction (PHJ) or as a bulk heterojunction (BHJ).
  • PHJ flat heterojunction
  • BHJ bulk heterojunction
  • HTL p-doped hole transport layer 6
  • the photoactive layer 5 is designed as a bulk heterojunction (BHJ), with a donor and bullerene C60 as an acceptor.
  • the electron transport layer 4 has at least one chemical compound of the general formula I.
  • the organic photovoltaic element is designed in a nip device architecture as a BHJ cell with the following structure of the layer system:
  • the compounds (01), (06) or (07) or the comparison material NDN-45 were used as n-dopant.
  • NDN-45 commercial n-dopant from Novaled AG
  • NDP9 commercial p-dopant from Novaled AG
  • HTM-81 commercial hole transport material from Merck AG
  • the organic electronic component 1 is an organic photovoltaic element. Identical and functionally identical elements are provided with the same reference numbers, so that reference is made to the previous description.
  • the parameters fill factor FF, open-circuit voltage VOC, and short-circuit current Jsc of an organic photovoltaic element with connection (01) (Device No. 8 to 11), connection (06) (Device No. 13), connection (07) (Device No. 14) were determined ) and the comparison compound NDN-45 (Device No. 12) as an n-dopant in the electron Transport layer determined.
  • the organic photovoltaic element is designed in a pnip device architecture as a BHJ cell with the following structure of the layer system:
  • the compounds (01), (06) or (07) or the comparison material NDN-45 were used as n-dopant.
  • the conductivity of a layer doped with the n-dopant from the Fullerene C60 was determined as a matrix material.
  • the transport layer contains the chemical compound (01) according to the invention in a doping concentration of 20% by weight in proportion to the matrix material C60.
  • the electrical conductivity of such a transport layer at different temperatures is shown in Fig. 2.
  • the conductivity of the electron transport layer 4 increases depending on the temperature from 1.2 -IO -7 S/cm at 30 ° C and reaches a value of 1.5 S / cm at 100 ° C.
  • the conductivity of a C60 layer that is doped with 20% by weight of the compound (01) according to the invention increases to 1.5 S/cm 100° C. as the temperature of the substrate increases.
  • the increased conductivity is at least largely retained at a value of 7.0 -10 - 1 S / cm.
  • the increase in conductivity is therefore at least largely irreversible.
  • the increased electrical conductivity due to the use of the chemical compound (01) according to the invention as an n-dopant is at least partially irreversible, so that an increase in the conductivity of layers once heated is largely retained even at a reduced temperature.

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Abstract

L'invention concerne un élément de construction électronique organique ayant une électrode, une contre-électrode et un système de couches entre l'électrode et la contre-électrode, au moins une couche du système de couches ayant un composé chimique de formule générale (I), l'utilisation d'un tel composé chimique en tant que dopant n pour doper au moins une couche dans un système de couches d'un élément de construction électronique organique, et un composé chimique de formule générale (II).
PCT/DE2023/100489 2022-06-29 2023-06-29 Élément de construction électronique organique avec un composé chimique de formule générale i, et utilisation d'un tel composé chimique en tant que dopant n dans un élément de construction électronique organique WO2024002424A1 (fr)

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DE102022116253.2A DE102022116253A1 (de) 2022-06-29 2022-06-29 Organisches elektronisches Bauelement mit einer chemischen Verbindung der allgemeinen Formel I, sowie Verwendung einer solchen chemischen Verbindung als n-Dotand in einem organischen elektronischen Bauelement

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