WO2023274452A1 - Procédé de fabrication d'au moins une couche de transport de charge dopée d'un système de couches d'un composant électronique organique - Google Patents

Procédé de fabrication d'au moins une couche de transport de charge dopée d'un système de couches d'un composant électronique organique Download PDF

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WO2023274452A1
WO2023274452A1 PCT/DE2022/100472 DE2022100472W WO2023274452A1 WO 2023274452 A1 WO2023274452 A1 WO 2023274452A1 DE 2022100472 W DE2022100472 W DE 2022100472W WO 2023274452 A1 WO2023274452 A1 WO 2023274452A1
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dopant
charge transport
transport layer
matrix material
layer
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PCT/DE2022/100472
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German (de)
English (en)
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Andre Weiss
Gunter Mattersteig
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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
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/16—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering
    • H10K71/164—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering using vacuum deposition
    • 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
    • H10K30/20—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising organic-organic junctions, e.g. donor-acceptor junctions
    • 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
    • H10K50/15—Hole transporting layers
    • H10K50/155—Hole transporting layers comprising dopants
    • 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
    • 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

Definitions

  • WCA general formula NO
  • Organic electronic components with a photoactive layer make it possible to convert electromagnetic radiation into electric current using the photoelectric effect, or make it possible to emit light when electric current flows through them.
  • Organic electronic components include at least two electrodes, one electrode being applied to a substrate and another functioning as a counter-electrode.
  • At least one photoactive layer between the electrodes there is at least one photoactive layer between the electrodes, with further layers, in particular charge transport layers, often being additionally arranged between the electrodes.
  • 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 heterojunction or as a bulk heterojunction.
  • the absorbers absorb electromagnetic radiation of a specific wavelength, where Photons are converted into excitons, which contribute to a photocurrent.
  • the compounds in the donor-acceptor system must have a high exciton diffusion length and high mobility of the charge carriers in order to minimize loss of photocurrent by recombination of the exciton within the donor-acceptor system.
  • the excitons are separated into charge carriers at an interface and the charge carriers leave the photoactive layer before recombination.
  • the conductivity of the layers in particular the charge transport layers, must be high.
  • the charge transport layers used for this purpose in particular electron transport layers and/or hole transport layers, are doped to increase conductivity.
  • 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 WO2011/ 161108A1).
  • a pin solar cell consists of a substrate with an adjoining mostly transparent base contact, p-layer(s), i-layer(s), n-layer(s) and a top contact Substrate with subsequent mostly transparent base contact, n-layer(s), i-layer(s), p-layer(s) and a top contact.
  • Organic electronic components can be greatly improved in terms of their electrical conductivity by doping.
  • To increase the conductivity of charge transport layers a significantly higher conductivity of these layers for electrons or holes is generated by means of a charge transfer between a matrix material and a strong donor or a strong acceptor as doping material for doping.
  • Matrix materials can be built up either from compounds with good electron donor properties or from compounds with good electron acceptor properties. Strong electron acceptors such as tetracyanoquinonedimethane (TCNQ) or 2,3,5,6-tetrafluoro-tetracyano-1,4-benzoquinonedimethane (F4TCNQ) are known for doping hole transport materials (HT) (M. Pfeiffer, A. Beyer, T. Fritz, K. Leo, Appl. physics Lett., 73 (22), 3202-3204 (1998). and J. Blochwitz, M. Pfeiffer, T. Fritz, K. Leo, Appl. physics Lett., 73 (6), 729-731 (1998)).
  • TCNQ tetracyanoquinonedimethane
  • F4TCNQ 2,3,5,6-tetrafluoro-tetracyano-1,4-benzoquinonedimethane
  • HT doping hole transport materials
  • N,N′-perarylated benzidines TPD or N,N′,N′′-perarylated starburst compounds, such as the substance TDATA, or certain metal phthalocyanines, such as in particular zinc phthalocyanine ZnPc, are known as matrix materials with hole transport properties.
  • Suitable dopants for hole transport materials simultaneously have a high electron affinity (oxidation potential) and increase the conductivity of the matrix.
  • the energy level of the HOMO (highest occupied molecular orbital) of the matrix material and the energy level of the LUMO (lowest unoccupied molecular orbital) of the dopant are particularly important.
  • Charge transport layers in optoelectronic components should be as transparent as possible, particularly in the wavelength range in which absorption takes place, and have good conductivity.
  • doped organic layers or layer systems in organic electronic components is known, with various materials or material classes being proposed as dopants, as described in DE102007018456, WO2005086251, WO2006081780, WO2007115540, WO2008058525, WO2009000237 and DE102008051737.
  • US4711742A discloses new electrically conductive forms of poly-substituted heterocycles, solutions comprising such polymers in either conductive or non-conductive form and a method of using the solution to form conductive polymers.
  • US10333070B2 discloses organometallic and organic dopants suitable for use in organic carrier transport materials and organic light emitting devices containing doped organic carrier transport materials.
  • the dopants disclosed in the prior art are suitable for charge transport layers in organic electronic components, there is a need for improved dopants for doping a matrix material during processing by vacuum deposition, in particular with regard to evaporability, with the charge transport layers doped in this way having to show good conductivity .
  • the present invention is therefore based on the object of providing a method for producing at least one doped charge transport layer of an organic electronic component, and a dopant for doping a charge transport layer of a layer system of an organic electronic component, which in particular provide an effective increase in the number of charge carriers in a matrix material and in vacuum are processable.
  • the dopants must have a sufficiently high redox potential and must not have any disruptive effects on the matrix material. It is also an object of the invention to provide a use of a dopant for doping at least one charge transport layer of an organic electronic component, and an electronic component produced by such a method.
  • dopants are provided which meet the technical requirements for vacuum processing in the production of organic electronic components, in particular with regard to the donor strength and the processability of such dopants.
  • the organic layer in particular a photoactive organic layer, can be designed as a planar heterojunction with donor and acceptor in different adjacent layers or as a bulk heterojunction with a mixed layer of donor and acceptor.
  • the organic layer is in particular a photoactive layer containing compounds with a high
  • the donor and the acceptor form a donor/acceptor system, with the donor and/or the acceptor being the light-absorbing compound.
  • the excitons formed are separated into charge carriers at the interface of the donor/acceptor system.
  • the loss due to undesired recombination of the generated charge carriers must be minimized in order to increase the efficiency of solar cells.
  • the compounds in the heterojunction have in particular a high mobility of the charge carriers and a large diffusion length of the excitons, so that the excitons are separated into charge carriers at the interface and leave the photoactive layer before recombination takes place.
  • a weakly coordinating anion is understood to mean, in particular, an anion which only interacts weakly with other molecules or ions, preferably by means of coordinate bonds.
  • the charge on the anion is preferably at least partially delocalized over the surface of the anion.
  • a substrate is understood to mean, in particular, a layer onto which a charge transport layer is applied.
  • the substrate is preferably a foil, an electrode, or even a layer of a layer system of an organic electronic component. According to the invention, layers of the layer system can therefore be present before and on which the at least one charge transport layer is applied.
  • the substrate itself can consist of several layers.
  • the substrate can be flexible or rigid.
  • the at least one matrix material and/or the at least one dopant are vaporized at a temperature of 100 to 400° C., preferably 150 to 350° C., particularly preferably 180 to 300° C., in step b). .
  • the substrate is heated to a specific temperature, preferably to a temperature of 30 to 50° C., when the at least one charge transport layer, in particular the at least one matrix material and/or the at least one dopant, is applied.
  • the doped charge transport layer forms completely directly during application by means of vaporization.
  • the doped charge transport layer forms after activation.
  • the charge transport layer after the charge transport layer has been applied, in particular the at least one matrix material and/or the at least one
  • the charge transport layer for activation by an energy input, in particular temperature and/or radiation, finalized during and/or after step c).
  • the at least one matrix material and the at least one dopant are deposited homogeneously on the substrate; the deposited mixture is preferably homogeneous.
  • the at least one charge transport layer is at least one electron transport layer (ETL) and/or at least one hole transport layer (HTL), preferably at least one hole transport layer.
  • ETL electron transport layer
  • HTL hole transport layer
  • evaporation is understood to mean both a transition of a compound from a liquid phase into a gaseous phase and a transition from a solid phase into a gaseous phase, ie sublimation.
  • the at least one matrix material and/or the at least one dopant are vaporized from the solid phase.
  • the evaporation in step b) and/or the deposition in step c) is carried out by thermal evaporation in vacuo (vacuum thermal evaporation, VTE) or by organic vapor phase deposition (OVPD).
  • VTE vacuum thermal evaporation
  • OVPD organic vapor phase deposition
  • the at least one matrix material is vaporized from a first vaporization source and the at least one dopant is vaporized from a second vaporization source.
  • the at least one matrix material and the at least one dopant are co-evaporated from the same evaporation source.
  • the at least one matrix material and the at least one dopant are co-evaporated, that is to say evaporated at the same time, in particular from a first evaporation source for the matrix material and from one second vaporization source for the dopant, or vaporized from one vaporization source, wherein the matrix material is mixed with the dopant prior to vaporization.
  • An organic electronic, in particular optoelectronic, component is understood as meaning a component which has at least one organic layer in the layer system, preferably an organic photoactive layer.
  • a photoactive layer is understood to mean, in particular, a layer which emits electromagnetic radiation when it is excited to do so by an applied voltage, or which absorbs electromagnetic radiation.
  • the photoactive layer can be made up of one layer and have one or more absorbers, or the photoactive layer can be made up of several layers, each of these layers having one or more absorbers.
  • Photoactive means, in particular, that molecules change their charge state and/or their polarization state when exposed to light. In particular, the molecules show an absorption of electromagnetic radiation in a specific wavelength range, with absorbed electromagnetic radiation, ie photons, being converted into excitons.
  • the organic 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
  • the at least one dopant is applied directly to a layer of the at least one matrix material, preferably for surface doping.
  • the at least one charge transport layer preferably the hole transport layer
  • the hole transport layer is in direct contact with an electrode, preferably the anode.
  • Direct contact is understood to mean in particular that there is no further layer between the layers that are in direct contact.
  • the doping of the matrix material for producing the doped charge transport layer is obtained by evaporating a mixture of the matrix material and the dopant or by simultaneously evaporating the matrix material with the dopant in a vacuum and subsequent deposition.
  • layers of the at least one matrix material and layers of the at least one dopant are applied sequentially to the substrate in alternation. Preference is given to the sequential vapor deposition of layers with a small layer thickness, preferably layers of less than 10 nm, preferably less than 5 nm, preferably less than 3 nm, or preferably less than 2 nm.
  • the dopant is vapor-deposited on the surface of the matrix material.
  • the method according to the invention and the dopants according to the invention have advantages compared to the prior art.
  • a method of doping a charge transport layer with a dopant by vacuum evaporation is provided.
  • the dopants provide an effective increase in carrier count in the matrix material.
  • the conductivity of charge transport layers is advantageously increased by the doping.
  • the dopants advantageously lead to an improved transfer of charge carriers between electrode layers and a layer of the layer system and/or between layers of the layer system, in particular between two photoactive layers of the layer system.
  • processing and stability properties of the dopant can be varied through the choice of the anion.
  • the introduction of dopants into a matrix material is advantageously improved.
  • the dopants do not have a disruptive effect on the matrix material.
  • the stability of charge transport layers produced by the method and thus also the stability of such organic electronic components is increased.
  • the dopants examined are colorless, so that they do not contribute to any parasitic absorption in solar cells and/or to a change in the light emitted by light-emitting diodes.
  • the joint and/or sequential deposition of the at least one matrix material and the at least one dopant onto the substrate is carried out by evaporating the at least one dopant in a vacuum.
  • the evaporation is regulated by means of the evaporation sources via a quartz oscillator.
  • the at least one matrix material and the at least one dopant are jointly deposited onto the substrate by co-evaporation in a vacuum.
  • non-coordinating or at least weakly coordinating anion is selected from the group consisting of:
  • [MR 1 R 2 R 3 R 4 ]- with M B, Al, Ga, In, Nb, Ta, Y, La, and R 1 to R 4 independently selected from halogen, alkyl, partially or perfluorinated alkyl, CN, SCN, OCN, NC, alkoxy, partially or perfluorinated alkoxy or dialkoxy, oxalate, substituted or unsubstituted aryl or heteroaryl, teflate, substituted or unsubstituted phenolate, substituted or unsubstituted catecholate, preferably [BF4]-, [AlCl 4 ]-, [GaCl 4 ]-, [B(CF 3 ) 4 ]-,
  • R 11 alkyl, partially or perfluorinated alkyl, substituted or unsubstituted aryl or heteroaryl.
  • a particular advantage of the dopants is that they are largely thermally very stable and enable evaporation in a vacuum, particularly in a temperature range between 100°C and 400°C.
  • a substituent is understood to mean, in particular, an atom or a group for replacing an H atom.
  • a substituent includes in particular all atoms and groups except H understood, preferably a halogen, an alkyl group, the alkyl group can be linear or branched, an alkenyl group, an alkynyl group, an alkoxy group, a thioalkoxy group, an aryl group, or a heteroaryl group.
  • the matrix material has an oligothiophene compound, an oligophenylene compound, a pentacene compound, a phthalocyanine complex, a compound with at least one arylamine unit, at least one spirobifluorene unit, at least one fluorene unit, and/or at least one carbazole unit, and particularly preferably consists of them .
  • the matrix material is a compound having at least two arylamine units, at least two spirobifluorene units, at least two fluorene units, and/or at least two carbazole units.
  • the matrix material has small molecules with a molecular weight of ⁇ 2000 g/mol, preferably ⁇ 1500 g/mol.
  • the matrix material consists of small molecules.
  • Small molecules are understood to mean, in particular, non-polymeric organic molecules with monodisperse molar masses between 100 and 2000 g/mol, preferably between 100 and 1500 g/mol, which are in the solid phase under normal pressure (air pressure of the atmosphere surrounding us) and at room temperature .
  • the matrix material does not have or is not a polymer.
  • the dopant is a p-dopant, and/or the
  • Charge transport layer is a p-doped hole transport layer.
  • the dopant is a p-dopant or forms a p-dopant, in particular, the p-dopant in the matrix material is released from the dopant.
  • the at least one dopant is selected from the group consisting of NOAsF 6 , NOSbF 6 , NOBF 4 , NOPF 6 , NOCH 3 SO 3 ,
  • a certain proportion of the nitrosyl cations remains in the at least one matrix material; the nitrosyl cations are preferably free in the matrix material or are at least partially bound to the matrix material.
  • the at least one doped charge transport layer has a ratio of the nitrosyl cations to the non-coordinating or at least weakly coordinating anions of less than 1:1, preferably less than 1 :2, preferably less than 1:5, preferably less than 1:10, preferably less than 1:100, or preferably from 1:1 to 1:100, preferably from 1:1 to 1:10, preferably from 1:1 to 1:5, 1:2 to 1:100, preferably from 1:2 to 1:10, preferably from 1:2 to 1:5, preferably from 1:5 to 1:100, preferably from 1:5 to 1:10, or preferably from 1:10 to 1:100 (in each case based on the total weight of the nitrosyl cations and the anions in the matrix material).
  • the proportion of at least one dopant in the matrix material is in the range from 0.1% by weight to 30.0% by weight, preferably in the range from 0.1% by weight to 20.0% by weight (in each case based on the total weight of the charge transport layer).
  • the molar ratio of the dopant to the matrix material is less than 1:2, preferably less than 1:4, preferably less than 1:10, or preferably less than 1:100, or is in a range of 1: 2 to 1:100000, preferably from 1:2 to 1:10000, preferably from 1:2 to 1:1000, preferably 1:2 to 1:100, preferably from 1:2 to 1:10, preferably from 1:10 to 1:100,000, preferably from 1:10 to 1:10,000, preferably from 1:10 to 1:1000, or preferably from 1:10 to 1:100 (in each case based on the proportion by weight).
  • the layer thickness of the at least one charge transport layer is less than 150 nm, preferably less than 100 nm, particularly preferably less than 50 nm.
  • the charge transport layer preferably the hole transport layer, has a layer thickness of 5 to 100 nm, preferably 5 to 50 nm, preferably 5 to 20 nm, preferably 5 to 10 nm, preferably 10 to 100 nm on, preferably from 10 to 50 nm, preferably from 10 to 20 nm, or preferably from 20 to 50 nm.
  • the matrix material has at least one triarylamine, and the matrix material preferably consists of at least one triarylamine.
  • a triarylamine is understood to mean, in particular, a compound having a triarylamine unit.
  • the triarylamine is selected from the group consisting of
  • Ar 2 -Ar 33 are independently selected from the group consisting of: a substituted or unsubstituted mono-, oligo-, aryl or heteroaryl ring, a substituted or unsubstituted aromatic homo- or hetero-oligocycle, a substituted or unsubstituted dihydro-acridines , where in each case two of Ar 2 -Ar 33 can be bridged to one another via a single bond, Ar 2 -Ar 33 are preferably selected independently of one another from the group consisting of: a substituted or unsubstituted dihydroacridine, phenyl, biphenyl, terphenyl, quarterphenyl, Dibenzofuran, dibenzothiophene, carbazole, fluorene, 9,9-diarylfluorene, spirobiphenyl, spiro[fluorene-9,9′-xanthene], naphthalene, anthracene, and
  • the matrix material is a triarylamine-based charge transport layer doped with a dopant according to the invention.
  • the dopants according to the invention can be vaporized largely without decomposition in a high vacuum, in particular at 10 -4 Pa to 10 -6 Pa, under typical process conditions, which enables the vacuum co-deposition of these dopants with arylamine-based hole-transport materials.
  • the object of the present invention is also achieved by providing a dopant for doping a charge transport layer of an organic electronic component, preferably using a method according to the invention, in particular using one of the previously described embodiments.
  • Aryl or heteroaryl, and Rll alkyl, partially or perfluorinated alkyl, substituted or unsubstituted aryl or heteroaryl.
  • the dopant for doping a charge transport layer of an organic electronic component has in particular the advantages that have already been explained in connection with the method according to the invention for producing at least one doped charge transport layer in a layer system of an organic electronic component.
  • the dopant is a precursor, the dopant being released or formed in the charge transport layer during and/or after the application of the dopant and the matrix material to the substrate.
  • the dopant is preferably a p-dopant.
  • the use of the dopant results in particular in the advantages that have already been explained in connection with the method and the dopant.
  • the chemical compound is preferably used as a dopant for doping at least one charge transport layer and/or for introducing a dopant into at least one charge transport layer.
  • the chemical compound is used as a dopant, preferably as a p-dopant, for doping a matrix material.
  • the chemical compound of the general formula NO(WCA) is used as a p-dopant for p-doping at least one charge transport layer, preferably a hole transport layer, and/or for introducing a p-dopant into at least one charge transport layer, preferably a hole transport layer , used.
  • the matrix material of the at least one charge transport layer has an oligothiophene compound, an oligophenylene compound, a pentacene compound, a phthalocyanine complex, a compound having at least one arylamine unit, at least one spirobifluorene unit, at least one fluorene unit, and/or at least one carbazole unit.
  • the object of the present invention is also achieved by providing an organic electronic component produced by a method according to the invention, the organic electronic component having an electrode, a counter-electrode and a layer system between the electrode and the Having a counter electrode, wherein the layer system has at least one organic layer, preferably at least one photoactive organic layer, and at least one doped charge transport layer, in particular according to one of the exemplary embodiments described above.
  • the organic electronic component has in particular the advantages which have already been explained in connection with the method, the doping agent and the use of the doping agent.
  • the organic electronic component is an organic optoelectronic component.
  • the organic electronic component is an OLED, an organic solar cell, an organic field effect transistor (OFET), or an organic photodetector.
  • the matrix material of the at least one charge transport layer of the organic electronic component corresponds to the matrix material in the method for producing at least one doped charge transport layer of an organic electronic component.
  • the at least one dopant is integrated in the at least one matrix material, preferably distributed homogeneously in the at least one matrix material.
  • the organic electronic component is 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 are formed.
  • the doped charge transport layer is part of a pn junction connecting a photoactive layer to another photoactive layer in a tandem solar cell or in a multi-junction solar cell and/or connects an electrode to a photoactive layer.
  • the matrix material of the n-layer of a pn junction has at least one fullerene, preferably C60 or C70.
  • the organic electronic component is preferably in the form of tandem, triple or multiple cells.
  • the photoactive layers of a cell can be designed as a single layer with multiple absorber materials or as a layered system with multiple layers.
  • An i-layer is understood to mean, in particular, an intrinsic undoped layer.
  • One or more i-layers can consist of one material (planar heterojunction, PHJ) or a mixture of two or more materials (bulk heterojunction,
  • 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, in particular from a combination of one of the metals with one or more oxides.
  • 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)
  • FIG. 1 shows a schematic illustration of an exemplary embodiment of an organic electronic component 1 in cross section
  • FIG. 3 shows the conductivity of a doped charge transport layer produced with NOSbF 6 as a dopant, with BPAPF as the matrix material;
  • Fig. 5 shows a film spectrum of the dopant NOSbF 6 and the dopant NDP-9.
  • a method for producing a doped charge transport layer of a layer system of an organic electronic component and such a doped charge transport layer are presented.
  • NO nitrosyl cation
  • WCA non-coordinating or at least weakly coordinating anion
  • the substrate is a layer of a layer system of a solar cell.
  • the layers of the layer system can be applied by vapor deposition in a vacuum, for example by means of CVD, PVD or OVPD.
  • the joint and/or sequential deposition of the at least one matrix material and the at least one dopant is carried out on the substrate by evaporation in vacuo.
  • Doped layers can be produced by means of mixed evaporation, with matrix material and dopant being placed in one or two evaporation sources and being sublimed under vacuum simultaneously or one after the other.
  • the compounds are deposited from the gas phase obtained on the substrate in a specific mixing ratio.
  • the dopant and the matrix material were evaporated using different evaporation sources.
  • the dopant and matrix material may be mixed prior to evaporation and evaporated from an evaporation source.
  • the non-coordinating or at least weakly coordinating anion is selected from the group consisting of:
  • [MR 1 R 2 R 3 R 4 ]- with M B, Al, Ga, In, Nb, Ta, Y, La, and R 1 to R 4 independently selected from halogen, alkyl, partially or perfluorinated alkyl, CN, SCN, OCN, NC, alkoxy, partially or perfluorinated alkoxy or dialkoxy, oxalate, substituted or unsubstituted aryl or heteroaryl, teflate, substituted or unsubstituted phenolate, substituted or unsubstituted catecholate, preferably [BF 4 ]-, [AlCl 4 ] -, [GaCl 4 ]-, [B(CF3) 4 ]-,
  • R 11 alkyl, partially or perfluorinated alkyl, substituted or unsubstituted aryl or heteroaryl.
  • the matrix material has an oligothiophene compound, an oligophenylene compound, a pentacene compound, a phthalocyanine complex, a compound with at least one arylamine unit, at least one spirobifluorene unit, at least one fluorene unit, and/or at least one carbazole unit.
  • the at least one matrix material has small molecules with a molecular weight of ⁇ 2000 g/mol, preferably ⁇ 1500 g/mol, and/or the matrix material preferably has no polymer or is not a polymer and/or is the dopant is a p-dopant, and/or the charge transport layer is a p-doped hole transport layer.
  • the triarylamine is selected from the group consisting of
  • Ar 2 -Ar 33 are independently selected from the group consisting of: a substituted or unsubstituted mono-, oligo-, aryl or heteroaryl ring, a substituted or unsubstituted aromatic homo- or hetero-oligocycle, a substituted or unsubstituted dihydro-acridines , where in each case two of Ar 2 -Ar 33 can be bridged to one another via a single bond, Ar 2 -Ar 33 are preferably selected independently of one another from the group consisting of: a substituted or unsubstituted dihydroacridine, phenyl, biphenyl, terphenyl, quarterphenyl, Dibenzofuran, dibenzothiophene, carbazole, fluorene, 9,9-diarylfluorene, spirobiphenyl, spiro[fluorene-9,9′-xanthene], naphthalene, anthracene, and
  • the at least one dopant is selected from the group consisting of NOAsF 6 , NOSbF 6 , NOBF 4 , NOPF 6 , NOCH 3 SO 3 , NO[Al(OCH 2 CF 3 ) 4 ], NO[Al( OC(CF 3 ) 3 ) 4 ], and NOCIO 4 .
  • the proportion of the at least one dopant in the matrix material is in the range from 0.1% by weight to 30.0% by weight, preferably in the range from 0.1% by weight to 20.0% by weight (in each case based on the total weight of the charge transport layer).
  • the layer thickness of the at least one charge transport layer is less than 150 nm, preferably less than 100 nm, particularly preferably less than 50 nm. 1 shows a schematic representation of an organic electronic component 1 in cross section.
  • the organic electronic component 1 has a layer system 8 with a doped charge transport layer 6, produced using a method according to the invention.
  • the organic electronic component 1 has an electrode 3 , a counter-electrode 7 and the layer system 8 , with the layer system 8 being arranged between the electrode 3 and the counter-electrode 7 .
  • the electrode 3 is arranged on a substrate 2 .
  • the layer system 8 has a charge transport layer 4, at least one photoactive layer 5, preferably at least one photoactive organic layer 5, and the at least one doped charge transport layer 6.
  • the at least one charge transport layer 6 has at least one dopant and/or is doped by means of at least one dopant using such a method.
  • the organic electronic component 1 is an OLED, an organic solar cell, an organic field effect transistor (OFET), or an organic photodetector.
  • the electronic component 1 is a solar cell, in particular an organic solar cell.
  • the dopant is used for doping layers of an organic electronic component 1, in particular at least one charge transport layer 6 of a layer system 8 of an organic electronic component 1, particularly preferably for p-doping.
  • the organic electronic component 1 has the following structure:
  • An electrode 3 made of ITO (indium tin oxide) with a layer thickness of 15 nm is arranged on the glass substrate 2 .
  • a layer system 8 is arranged with a charge transport layer 4, formed as
  • Electron transport layer 4 made of C60 in a layer thickness of 20 nm.
  • the photoactive layer 5 is arranged in a layer thickness of 30 nm, which comprises at least one donor and one acceptor, the donor being the ADA oligomer absorber 1, for example and the acceptor is C60, which together form a donor-acceptor system, either as a planar heterojunction or as a bulk heterojunction.
  • the photoactive layer 5 can also consist of more than one layer, in particular of a donor and acceptor layer, so that a planar, photoactive donor-acceptor transition is formed.
  • a charge transport layer 6 and the counter electrode 7 made of aluminum (100 nm).
  • Charge transport layer 6 is designed as a p-doped hole transport layer (HTL), with the matrix material BPAPF and p-doped with the dopant NOSbF 6 in a proportion of 10% by weight, and has a layer thickness of 20 nm.
  • HTL hole transport layer
  • a BODIPY compound can also be used as a donor instead of an ADA oligomer.
  • the dopant is used as a dopant, preferably as a p-dopant, for doping at least one charge transport layer 6 and/or for introducing a dopant, preferably a p-dopant, into at least one charge transport layer 6 .
  • the charge transport layer is a hole transport layer p-doped by means of the dopant NOSbF 6 or a hole transport layer p-doped by means of the comparison material NDP-9.
  • the conductivity of the charge transport layer was determined after the matrix material and the
  • the matrix material was co-evaporated with the dopant NOSbF 6 or the reference material NDP-9, deposited on a substrate and the conductivity of the obtained doped charge transport layer examined.
  • the matrix material and the dopant were each placed in an evaporation source of a vacuum chamber and thermally co-evaporated from the two separate evaporation sources.
  • a doped charge transport layer was deposited on a quartz substrate in a layer thickness of 20 nm in the respective doping concentration by thermal evaporation at about 150 to 350° C. and at a pressure of about 10 -6 Pa. The evaporation rate was controlled by a quartz crystal monitor.
  • Evaporation temperature was 160-210°C for the dopant NOSbF 6 and 330°C for the matrix material BPAPF.
  • the conductivity of the layer was determined from the increase in the measured current when an external voltage was applied as a function of the layer thickness.
  • Fig. 2 shows the conductivity of charge transport layers doped with NOSbF 6 as dopant and with the comparison material NDP-9 with TaTm as matrix material.
  • the matrix material TaTm was doped in different proportions using the dopant NOSbF 6 and the dopant NDP-9 as a comparison material (see Table 1).
  • NDP-9 is a commercial p-dopant from Novaled GmbH. Table 1
  • the measured conductivity is plotted against the proportion of dopant in FIG.
  • the conductivity of the charge transport layer increases as a function of the proportion with the dopant NOSbF 6 and is at a value of 1.08 ⁇ 10 -3 Scm -1 at a proportion of approximately 10% by weight.
  • the conductivity of the inventive dopant NOSbF 6 in TaTm is higher than that of NDP-9.
  • Fig. 3 shows the conductivity of charge transport layers doped with NOSbF 6 as dopant and with the comparison material NDP-9 with BPAPF as matrix material.
  • the matrix material BPAPF was doped in different proportions using the dopant NOSbF 6 and the dopant NDP-9 as a comparison material (see Table 2).
  • NDP-9 is a commercial p-dopant from Novaled GmbH.
  • the measured conductivity is plotted against the proportion of dopant in FIG.
  • the conductivity of the charge transport layer increases depending on the proportion with the dopant NOSbF 6 and is at a proportion of about 5% by weight at a value of 1 ⁇ 10 -6 Scm -1 and at a proportion of about 25% by weight at a value of about 0.96 ⁇ 10 -3 Scm -1 .
  • the conductivity of NOSbF 6 in BPAPF is comparable to that of NDP-9.
  • Fig. 4 shows the conductivity of charge transport layers doped with NOSbF 6 as dopant and with the comparison material NDP-9 with NHT169 as matrix material.
  • the matrix material NHT169 was doped in different proportions using the dopant NOSbF 6 and the dopant NDP-9 as a comparison material (see Table 3).
  • NDP-9 is a commercial p-dopant from Novaled GmbH.
  • NHT169 is a commercial hole conductor from Novaled GmbH. Table 3
  • the measured conductivity is plotted against the proportion of dopant in FIG.
  • the conductivity of the charge transport layer increases depending on the proportion with the dopant NOSbF 6 and is at a proportion of about 5% by weight at a value of about 1.1 ⁇ 10 -5 Scm -1 and at a proportion of about 20% by weight % at a value of 1.6 ⁇ 10 -4 Scm -1 .
  • the conductivity of NOSbF 6 in NHT169 is slightly worse than that of NDP-9.
  • the dopant NOSbF 6 according to the invention leads to a comparatively good conductivity in comparison to the dopant NDP-9 in a doped charge transport layer obtained therewith of a layer system of an organic electronic component.
  • the evaporability of NOSbF 6 was investigated.
  • the compound NOSbF 6 according to the invention and the comparison material NDP-9 were each evaporated under high vacuum conditions, in this Example at 10 -5 Pa.
  • the temperature was determined at which a constant deposition rate of 0.02 nm/s is generated on a substrate (see Table 4).
  • the evaporability of the dopant NOSbF 6 according to the invention is comparable to that of the comparison material NDP-9. At these evaporation temperatures, it is possible to maintain a constant deposition rate when evaporating in a vacuum on an uncooled substrate. As a result, a uniform deposition rate that can be controlled without increased technical effort can be set on the substrate.
  • a film spectrum of the dopant NOSbF 6 and the reference material NDP-9 was recorded.
  • a 30 nm thick layer was evaporated onto a glass substrate in a high vacuum at 10 -5 to 10 -7 mbar, the evaporation rate can be in a range from 0.001 to 0.5 nm/s. In the present exemplary embodiment, the evaporation rate was approximately 0.02 nm/s.
  • the layer thickness is checked using an oscillating quartz monitor. A film spectrum was recorded of the layer obtained.
  • the film spectrum of the dopant NOSbF 6 and the comparison material NDP-9 is shown in FIG. In the film spectrum, the optical density (absorbance) of the dopant NOSbF 6 and the comparison material NDP-9 is shown in FIG. In the film spectrum, the optical density (absorbance) of the dopant NOSbF 6 and the comparison material NDP-9 is shown in FIG. In the film spectrum, the optical density (absorbance) of the
  • the comparison material NDP-9 shows a high parasitic extinction in a wavelength range from approx. 200 to 600 nm, in particular from approx. 450 to 550 nm Dopant NOSbF 6 no significant parasitic absorption, allowing higher efficiency of solar cells.

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  • Optics & Photonics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Electromagnetism (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

L'invention concerne un procédé de fabrication d'au moins une couche de transport de charge dopée d'un système de couches d'un composant électronique organique, à un dopant pour doper une couche de transport de charge d'un composant électronique organique, à un composant électronique organique produisant au moyen d'un procédé de ce type, et à une utilisation d'un composé chimique de formule générale : NO (WCA) (NO = nitrosyle cationique, WCA = non coordinateur ou au moins un anion de coordination faible) en tant que dopant pour doper au moins une couche de transport de charge d'un composant électronique organique de ce type.
PCT/DE2022/100472 2021-06-30 2022-06-29 Procédé de fabrication d'au moins une couche de transport de charge dopée d'un système de couches d'un composant électronique organique WO2023274452A1 (fr)

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Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4711742A (en) 1985-05-31 1987-12-08 Allied Corporation Solution processible forms of neutral and electrically conductive poly(substituted heterocycles)
EP1209708A1 (fr) * 2000-11-24 2002-05-29 Sony International (Europe) GmbH Cellule solaire hybride avec une couche d'oxyde de semiconducteur deposée thermiquement
WO2005086251A2 (fr) 2004-03-03 2005-09-15 Novaled Gmbh Utilisation d'un complexe metallique comme dopant n d'un materiau matrice semi-conducteur organique et composant electronique, ainsi que dopant et ligand, et son procede de production
WO2006081780A1 (fr) 2005-02-04 2006-08-10 Novaled Ag Dopants pour semi-conducteurs organiques
WO2007115540A1 (fr) 2006-03-30 2007-10-18 Novaled Ag Utilisation de bora-tétraazapentalènes
WO2008058525A2 (fr) 2006-11-13 2008-05-22 Novaled Ag Utilisation d'une liaison de coordination pour doper des semiconducteurs organiques
DE102007018456A1 (de) 2007-04-19 2008-10-23 Novaled Ag Aryl- und/oder Heteroaryl-substituierte Hauptgruppenelementhalogenide und/oder -pseudohalogenide, Verwendung von Hauptgruppenelementhalogeniden und/oder -pseudohalogeniden, organisches halbleitendes Matrixmaterial, elektronische und optoelektronische Bauelemente
WO2009000237A1 (fr) 2007-06-22 2008-12-31 Novaled Ag Utilisation du précurseur d'un dopant n pour le dopage d'un matériau semi-conducteur, précurseur et composant électronique ou optoélectronique
DE102008051737A1 (de) 2007-10-24 2009-05-07 Novaled Ag Quadratisch planare Übergangsmetallkomplexe und diese verwendende organische halbleitende Materialien sowie elektronische oder optoelektronische Bauelemente
WO2011161108A1 (fr) 2010-06-21 2011-12-29 Heliatek Gmbh Composant photoactif comportant plusieurs systèmes de couches de transport
US20170084853A1 (en) * 2015-09-17 2017-03-23 International Business Machines Corporation Hybrid heterojunction photovoltaic device
US10333070B2 (en) 2002-04-08 2019-06-25 The University Of Southern California Doped organic carrier transport materials

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4711742A (en) 1985-05-31 1987-12-08 Allied Corporation Solution processible forms of neutral and electrically conductive poly(substituted heterocycles)
EP1209708A1 (fr) * 2000-11-24 2002-05-29 Sony International (Europe) GmbH Cellule solaire hybride avec une couche d'oxyde de semiconducteur deposée thermiquement
US10333070B2 (en) 2002-04-08 2019-06-25 The University Of Southern California Doped organic carrier transport materials
WO2005086251A2 (fr) 2004-03-03 2005-09-15 Novaled Gmbh Utilisation d'un complexe metallique comme dopant n d'un materiau matrice semi-conducteur organique et composant electronique, ainsi que dopant et ligand, et son procede de production
WO2006081780A1 (fr) 2005-02-04 2006-08-10 Novaled Ag Dopants pour semi-conducteurs organiques
WO2007115540A1 (fr) 2006-03-30 2007-10-18 Novaled Ag Utilisation de bora-tétraazapentalènes
WO2008058525A2 (fr) 2006-11-13 2008-05-22 Novaled Ag Utilisation d'une liaison de coordination pour doper des semiconducteurs organiques
DE102007018456A1 (de) 2007-04-19 2008-10-23 Novaled Ag Aryl- und/oder Heteroaryl-substituierte Hauptgruppenelementhalogenide und/oder -pseudohalogenide, Verwendung von Hauptgruppenelementhalogeniden und/oder -pseudohalogeniden, organisches halbleitendes Matrixmaterial, elektronische und optoelektronische Bauelemente
WO2009000237A1 (fr) 2007-06-22 2008-12-31 Novaled Ag Utilisation du précurseur d'un dopant n pour le dopage d'un matériau semi-conducteur, précurseur et composant électronique ou optoélectronique
DE102008051737A1 (de) 2007-10-24 2009-05-07 Novaled Ag Quadratisch planare Übergangsmetallkomplexe und diese verwendende organische halbleitende Materialien sowie elektronische oder optoelektronische Bauelemente
WO2011161108A1 (fr) 2010-06-21 2011-12-29 Heliatek Gmbh Composant photoactif comportant plusieurs systèmes de couches de transport
US20170084853A1 (en) * 2015-09-17 2017-03-23 International Business Machines Corporation Hybrid heterojunction photovoltaic device

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
J. BLOCHWITZM. PFEIFFERT. FRITZK. LEO, APPL. PHYS. LETT., vol. 73, no. 22, 1998, pages 3202 - 3204
MARTIN PFEIFFER: "PhD thesis TU-Dresden", 1999, article "Controlled doping of organic vacuum deposited dye layers: basics and applications"
YING SUN ET AL: "Chemically Doped and Cross-linked Hole-Transporting Materials as an Efficient Anode Buffer Layer for Polymer Solar Cells", CHEMISTRY OF MATERIALS, vol. 23, no. 22, 22 November 2011 (2011-11-22), pages 5006 - 5015, XP055121934, ISSN: 0897-4756, DOI: 10.1021/cm2024235 *

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