Organic electronic construction element with a chemical compound of general formula i, and use of such a chemical compound as n-dopant in an organic electronic construction element

Abstract

The invention relates to an organic electronic construction element having an electrode, a counter electrode and a layer system between the electrode and the counter electrode, wherein at least one layer of the layer system has a chemical compound of general formula (I), to use of such a chemical compound as an n-dopant for doping at least one layer in a layer system of an organic electronic construction element, and to a chemical compound of general formula (II).

Description

[0001] Organic electronic component with a chemical compound of the general formula I , and use of such a chemical compound as n-dopant in an organic electronic component

[0002] The present invention relates to an organic electronic component with an electrode, a counter electrode and a layer system between the electrode and the counter electrode, wherein at least one layer of the layer system comprises a chemical compound of the general formula I, a use of 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, and a chemical compound of the general formula II.

[0003] Organic electronic components can convert electromagnetic radiation into electrical current by utilizing the photoelectric effect. For such a conversion of electromagnetic radiation, absorber materials are required that exhibit good light absorption properties. Other organic electronic components are light-emitting components, which emit light when an electrical current flows through them. Organic electronic components comprise at least two electrodes, one electrode being applied to a substrate and the other acting 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.

[0004] In organic solar cells, photoactive compounds, so-called absorbers, are typically used in a donor / acceptor system, a heterojunction, where at least the donor and / or the acceptor absorbs electromagnetic radiation. The donor / acceptor system can be a planar heterojunction or a bulk heterojunction. The absorbers absorb electromagnetic radiation of a specific wavelength, converting photons into excitons that contribute to a photocurrent. The compounds in the donor / acceptor system must have high charge carrier mobility to minimize loss of photocurrent through 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.To minimize charge carrier recombination, the layers must exhibit high conductivity. To achieve this, the transport layers are doped with dopants.

[0005] A prior art structure of an organic solar cell 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). A pin solar cell consists of a substrate with an adjoining, usually transparent, ground contact, p-layer(s), i-layer(s), n-layer(s) and a cover contact. A nip solar cell consists of a substrate with an adjoining, usually transparent, ground contact, n-layer(s), i-layer(s), p-layer(s) and a cover contact.

[0006] The use of doped organic layers or layer systems in organic components, particularly 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), boratetraazapentalenes (W02007115540A1), and organic phosphoranes (EP2724388B1). Inorganic dopants such as alkali metals (e.g.

[0007] Caesium) or Lewis acids (e.g. FeC13; SbC15) are usually disadvantageous in organic matrix materials due to their high diffusion coefficients, as the function and stability of the electronic components are impaired (D. Oeter, Ch. Ziegler, W. Göpel Synthetic Metals (1993) 61 147; Y. Yamamoto et al. (1965) 2015, J. Kido et al. Jpn J. Appl. Phys. 41 (2002) L358). In addition, the reduction potentials of these compounds are often too low to dope technically suitable hole-transport materials. In addition, the extremely aggressive reaction behavior of these dopants makes technical application difficult.

[0008] The n-doping of an electron transport layer made of the matrix material PCBM with the n-dopant trimethyltriazinane is known from the state of the art ( Li et al . , N-doping of fullerene using 1 , 3 , 5-trimethylhexahydro-l , 3 , 5-triazine as an electron transport layer for nonfullerene organic solar cells", Sustainable Energy Fuels , 2020 , 4 , 1984 ). However, the conductivity described here is moderate and decreases significantly at higher temperatures, which significantly limits the technical usability.

[0009] Although the dopants disclosed in the prior art are suitable for transport layers in electronic components, the conductivity of transport layers obtained by doping needs to be improved. Furthermore, dopants are needed that lead to increased conductivity at higher temperatures.

[0010] The present invention is therefore based on the object of providing dopants for doping organic layers of organic electronic components, wherein the aforementioned disadvantages are overcome, and wherein, in particular, the dopants have sufficiently high redox potentials, do not interfere with the matrix material, and provide an effective increase in the number of charge carriers in the matrix material to increase conductivity. To improve the efficiency of an organic photovoltaic element, the loss due to recombination of charge carriers should, in particular, be minimized.

[0011] The problem is solved by the subject matter of the independent claims. Advantageous embodiments emerge from the subclaims.

[0012] The object is achieved in particular by providing an organic electronic component having an electrode, a counterelectrode and a layer system between the electrode and the counterelectrode, wherein 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 Xe independently selected from the group consisting of H and alkyl, with Yi, Y2 and Y3 independently selected from the group consisting of unsubstituted or substituted aryl, unsubstituted or substituted heteroaryl having a heteroatom selected from O, S or N, wherein the substituent is in each case selected from the group consisting of halogen, amino, alkyl, alkenyl, alkynyl, alkoxy, thioalkoxy, aryl, heteroaryl, and an alkyl group Ia where 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 O, S or N, preferably H and alkyl, where the substituent is in each case selected from the group consisting of halogen, amino, alkyl, alkenyl, alkynyl, alkoxy, thioalkoxy, aryl, and heteroaryl having a heteroatom selected from O, S or N, with the proviso that at least one of R41, R42, and R43 is not H, where * represents the linkage to an N. The chemical compounds according to the invention serve in particular as dopants for doping, preferably for n-doping, an organic matrix material.

[0013] A substituent is understood in particular to mean the replacement of H by another group. A substituent is understood in particular to mean all atoms and atom groups other than H, preferably a halogen, an alkyl group (the alkyl group may be linear or branched), an alkenyl group, an alkynyl group, an alkoxy group, a thioalkoxy group, an aryl group, or a heteroaryl group. A halogen is understood in particular to mean F, Cl or Br, preferably F.

[0014] In a preferred embodiment of the invention, 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.

[0015] In a preferred embodiment of the invention, 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 a combination of these materials.

[0016] In a preferred embodiment of the invention, the at least one chemical compound is present in a matrix material.

[0017] The organic electronic component with the chemical compound according to the invention has advantages compared to the prior art. Advantageously, the chemical compounds are suitable for doping a matrix material, preferably for doping transport materials, in particular electron transport materials. Advantageously, the chemical compounds are suitable for doping organic transport layers in electronic components, in particular the chemical compounds have sufficiently high redox potentials for this purpose. Advantageously, the chemical compounds contribute to an increase in the number of charge carriers in a matrix material. High conductivities can be achieved, in particular in a range of ICh 2 to I Ch 6 S / cm at a doping concentration of 2 % to 25 % [w / w] , while for undoped matrix materials these are often below I CH 8S / cm or even below ICb 10S / cm. Advantageously, the conductivity of matrix material doped with a chemical compound according to the invention increases significantly at higher temperatures. Advantageously, 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. Advantageously, the chemical compounds do not have any disruptive effect on the matrix material, in particular on fullerenes. Advantageously, the dopants are easily accessible due to their relatively simple synthesis and can therefore be produced cost-effectively. Advantageously, the chemical compounds are air-stable and can be used under atmospheric conditions.Advantageously, the chemical compounds are sufficiently thermally stable and can be evaporated in a vacuum, for example, by vacuum thermal evaporation (VTE) or organic vapor phase deposition (OVPD). In particular, the chemical compounds do not decompose upon evaporation in a vacuum. Advantageously, the chemical compounds are colorless, which at least largely prevents a reduction in the efficiency of photovoltaic elements due to parasitic absorption.

[0018] According to a further development of the invention, the chemical compound has the general formula II with Xi, X2, X3, X4, X5 and Xe independently of one another selected from the group consisting of H and alkyl, with Ri, R2, R3, R4, R5 and Re independently of one another selected from the group consisting of H, unsubstituted or substituted alkyl, and unsubstituted or substituted aryl, where the substituent is in each case selected from the group consisting of halogen, amino, alkyl, alkenyl, alkynyl, alkoxy, thioalkoxy, aryl, and heteroaryl having a heteroatom selected from O, 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.

[0019] In a preferred embodiment of the invention, Ri or R2 , and R3 or R4 , and R5 or Re are each independently a non-substituted or substituted aryl or a non-substituted or substituted heteroaryl having a heteroatom selected from O , S or N, wherein the substituent is in each case selected from the group consisting of halogen, amino, alkyl, alkoxy, thioalkoxy, aryl , and heteroaryl having a heteroatom selected from O, S or N .

[0020] In a preferred embodiment of the invention, Ri and R2, R3 and R4, and / or R5 and Re each form a homocyclic or a heterocyclic aromatic or aliphatic ring.

[0021] In a preferred embodiment of the invention, R1 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 O, 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 O, S or N.

[0022] In a preferred embodiment of the invention, Ri, R3, and Rs are each a non-substituted or substituted cyclic alkyl, preferably cyclopentanyl or cyclohexanyl.

[0023] In a preferred embodiment of the invention, Ri and R2, R3 and R4, and R5 and Re are each the same, particularly preferably Ri, R2, R3, R4, Rs, and Re are the same.

[0024] In a preferred embodiment of the invention, Xi, X2, X3, X4, X5 and Xe are H. According to a further development of the invention, the chemical compound has the general formula III with Xi, X2, X3, X4, X5 and Xe independently of one another selected from the group consisting of H and alkyl, where Rn to R15, 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, preferably phenyl, and heteroaryl having a heteroatom selected from O, S or N, where H can each be further substituted, preferably with a substituent selected from the group consisting of halogen, amino, alkyl, alkoxy, aryl, and heteroaryl having a heteroatom selected from O, S or N. In a preferred embodiment of the invention, Rn to Rn, R21 to R25, and R31 to R35 are each H, or in each case at least one Rn to Rn, R21 to R25, or R31 to R35 is an amino group in each case having at least one Alkyl, aryl or heteroaryl, preferably with two alkyl, aryl or heteroaryl.

[0025] In a preferred embodiment of the invention, at least one Rn to R, R21 to R25, or R31 to R35 is an amino group with at least one alkyl or aryl, preferably with two alkyl or aryl.

[0026] In a preferred embodiment of the invention, 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, preferably phenyl, and heteroaryl having a heteroatom selected from O, S or N, where H may in each case be further substituted, with the proviso that in each case 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 having a heteroatom selected from O, S or N.

[0027] In a preferred embodiment of the invention, 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 having a heteroatom selected from O, S or N, where H can each independently be substituted with a substituent selected from the group consisting of halogen, amino, alkyl, alkoxy, aryl, and heteroaryl having a heteroatom selected from O, S or N.

[0028] In a preferred embodiment of the invention, two of Rn to R15, R21 to R25, and R31 to R35 form a homocyclic or a heterocyclic aromatic or aliphatic ring.

[0029] In a preferred embodiment of the invention, Xi, X2, X3, X4, X5 and Xg are H.

[0030] According to a further development of the invention, it is provided that Xi, X2, X3, X4, X5 and Xe are independently selected from H and CH3, and / or Xi, X2, X3, X4, X5 and Xe are the same, preferably Xi, X2, X3, X4, X5 and Xe are H, and / or Yi, Y2 and Y3 are phenyl or naphthyl, where H can each be further 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 O, S or N.

[0031] In a preferred embodiment of the invention, in the chemical compound of the general formula I, at least one R41, R42 or R43 in each of Y1, Y2 and Y3 for the alkyl group Ia is H.

[0032] According to a further development of the invention, it is provided that Y1, Y2, and Y3 are identical. According to a further development of the invention, it is provided that at least one R41, R42, or R43 is a non-substituted or substituted aryl, or a non-substituted or substituted heteroaryl having a heteroatom selected from O, S, or N.

[0033] In a preferred embodiment of the invention, 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 O, 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, preferably at least two of R41, R42 or R43 are not H.

[0034] In a preferred embodiment of the invention, one of R41, R42 and R43 is H.

[0035] In a preferred embodiment of the invention, at least one R41, R42, or R43, preferably at least two R41, R42, or R43, is a non-substituted or substituted aryl, or non-substituted or substituted heteroaryl having a heteroatom selected from O, S or N, where the substituent is selected from the group consisting of halogen, amino, alkyl, alkenyl, alkynyl, alkoxy, thioalkoxy, aryl, and heteroaryl having a heteroatom selected from O, S or N, preferably having a substituent selected from the group consisting of F and C1-C4-alkyl.

[0036] In a preferred embodiment of the invention, at least one R41, R42, or R43 is a fused unsubstituted or substituted aryl.

[0037] In a preferred embodiment of the invention, R41, R42, and R43 are selected from the group consisting of naphthalene, anthracene, phenanthrene, phenalene, tetracene, chrysene, pyrene, pentacene, perylene, benzopyrene, or pentaphene. According to a further development of the invention, the chemical compound is selected from the group consisting of:

[0038] According to a further development of the invention, 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 pn-junction layer or, alternatively, can be arranged between an electrode and a photoactive layer.

[0039] In a preferred embodiment of the invention, the at least one electron transport layer and / or the electron injection layer is in direct contact with the at least one photoactive layer.

[0040] In a preferred embodiment of the invention, the electron transport layer and / or the electron

[0041] In ection layer a layer thickness of 2 to 100 nm, preferably from 2 to 50 nm, preferably from 2 to 20 nm, preferably from 5 to 100 nm, preferably from 5 to 50 nm, preferably from 5 to 20 nm, preferably from 10 to 100 nm, preferably from 10 to 50 nm, preferably from 10 to 20 nm, or preferably from 20 to 50 nm.

[0042] According to a further development of the invention, it is provided that the chemical compound is present in a matrix material, wherein the molar doping ratio of the chemical compound to the matrix material is from 1:1 to 1:10,000, preferably from 1:2 to 1:1,000, particularly preferably from 1:5 to 1:100. This increases, in particular, the conductivity of the matrix material.

[0043] In a preferred embodiment of the invention, the proportion of the at least one chemical compound in the at least one layer is at most 35 wt.%, preferably at most 30 wt.%, preferably at most 25 wt.%, preferably at most 20 wt.%, preferably at most 15 wt.%, preferably at most 10 wt.%, preferably at most 8 wt.%, or preferably at most 6 wt.%, based on the total weight of the layer.

[0044] According to a further development of the invention, it is provided that the matrix material has a LUMO energy level of -3.5 eV to -5.0 eV, preferably of -3.0 eV to -4.5 eV, or preferably of -3.5 eV to -4.5 eV.

[0045] In a preferred embodiment of the invention, 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 the determination of the electrochemical potential by means of cyclic voltammetry.

[0046] According to a further development of the invention, 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. In a preferred embodiment of the invention, the at least one electron-transport layer and / or the electron-injection layer comprises the matrix material.

[0047] According to a further development of the invention, it is provided that 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.

[0048] In a preferred embodiment of the invention, the organic electronic component has two photoactive layers, a so-called tandem cell, with a connecting unit (pn-junction) arranged therebetween, or three photoactive layers, a so-called triple cell, each with a connecting unit (pn-junction) arranged therebetween, wherein at least one of the connecting units has a chemical compound of the general formula I.

[0049] According to a further development of the invention, it is provided that 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 an organic photovoltaic element (OPV) with at least one light-absorbing photoactive layer, or a thermal sensor.

[0050] An organic electronic component is understood in particular to be 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 by utilising the photoelectric effect. In this sense, the term "photoactive" is understood as the conversion of light energy into electrical energy. In contrast to inorganic solar cells, in organic photovoltaic elements free charge carriers are not directly generated by the light; instead, excitons, i.e. electrically neutral excited states (bound electron-hole pairs), are first 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.

[0051] Photoactive is understood in particular to mean that molecules change their charge state and / or polarization state upon exposure to light. Accordingly, a photoactive layer is understood in particular to mean 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.

[0052] In a preferred embodiment of the invention, the organic electronic component is designed 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 containing at least one i-layer.

[0053] An i-layer is specifically understood to be an intrinsic undoped layer. One or more i-layers can consist of a single material (planar heterojunctions, PHJ) or a mixture of two or more materials, so-called bulk heterojunctions (BHJ).

[0054] In a preferred embodiment of the invention, the organic electronic component is designed as a tandem, triple or multiple cell.

[0055] In a particularly preferred embodiment of the invention, the transport layer with the at least one chemical compound of the general formula I is part of a pn junction which connects a first photoactive layer to a further photoactive layer in a tandem solar cell or in a multiple solar cell, and / or connects an electrode to a photoactive layer.

[0056] In a preferred embodiment of the invention, the photoactive layer comprises a donor / acceptor system.

[0057] In a preferred embodiment of the invention, the at least one donor is an ADA oligomer and / or a BODIPY, and 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 having 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 understood to mean, in particular, a conjugated acceptor-donor-acceptor oligomer (ADA' oligomer) having an acceptor unit (A) and a further acceptor unit (A'), which are each bonded to a donor unit (D).

[0058] The organic electronic components can be produced 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 by means of CVD, PVD or OVPD. In a preferred embodiment, the chemical compound and / or a layer comprising the at least one chemical compound is deposited by means of vacuum processing, gas phase deposition or solvent processing, particularly preferably by means of vacuum processing. In a preferred embodiment of the invention, all organic layers and the electrodes are applied by evaporation in a vacuum.

[0059] The object of the present invention is also achieved by providing a use of 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, in particular according to one of the previously described 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.

[0060] 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 embodiments. In this case, the chemical compound of general formula II offers, in particular, the advantages already explained in connection with the organic electronic component and the use of the chemical compound of general formula I in an organic electronic component.In the chemical compound of the general formula II, Xi, X2, X3, X4, X5 and Xe are independently selected from the group consisting of H and alkyl, Ri, R2, R3, R4, Rs and Rg are independently selected from the group consisting of aryl, preferably phenyl, and heteroaryl having a heteroatom selected from O, S or N, where H can in each case be further substituted, where the substituent is selected from the group consisting of halogen, amino, alkyl, alkenyl, alkynyl, alkoxy, thioalkoxy, aryl, and heteroaryl having a heteroatom selected from O, S or N, with the proviso that in Ri, R2, R3, R4, Rs and Re at least one H is in each case substituted, where Ri and R2, R3 and R4, and / or R5 and Re can be bridged to one another.

[0061] According to a further development of the invention, it is provided that Xi, X2, X3, X4, X5 and Xe are independently selected from H and CH3, and / or Xi, X2, X3, X4, X5 and Xe are the same, and / or Ri, R2, R3, R4, Rs and Re, and / or Ri, R2, R3, R4, Rs and Re are phenyl or naphthyl, where H can each be further 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 O, S or N, and / or Ri, R2, R3, R4, R5 and R6 are the same.

[0062] According to a further development of the invention, it is provided that 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 having a heteroatom selected from O, S or N, with the proviso that 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, R70-R74, and R75-R79 are not H.

[0063] According to a further development of the invention, it is provided that each of R50-R54, R55-R59, Reo-R64, Res-Reg, R70-R74, and R75-R79 is an amino group with at least one alkyl or aryl, preferably with two alkyl or aryl.

[0064] According to a further development of the invention, it is provided that where X uX2, X3, X4, X5 and X6H are.

[0065] The following is a synthesis scheme for the synthesis of chemical compounds of general formula I. The synthesis is demonstrated using compound (01) as an example.

[0066] Synthesis of compound (01) : 1, 3, 5-Tris- (diphenylmethyl) -1, 3, 5- triazinanes :

[0067] Step 1

[0068] 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 refluxed under argon atmosphere for 1 hour. The excess of para-formaldehyde, water, and toluene are distilled off to a volume of 40 ml. The solid begins to precipitate, and the excess of para-formaldehyde, water, and toluene are removed. To dissolve the solid, 5 ml of toluene is added under reflux. While stirring and refluxing, 40-50 ml of n-heptane is added to the reaction mixture until the solution becomes cloudy. The solution is cooled under constant stirring for 1 hour. A white solid forms at a temperature of approximately 55°C. The reaction mixture is left to stand overnight under an argon atmosphere, during which the solid precipitates completely. The solid is collected in a 100 ml glass frit (porous).3) filtered under vacuum and washed twice with 30 ml of n-heptane. The filter cake is dried for one hour under vacuum and stored at 85 °C under a vacuum of 10~. 3 mbar for 2 hours. Product 3 is obtained as a white powder (7.42 g, 12.7 mmol, 70% yield).

[0069] The synthesis of compounds according to the invention is also known from Ma et al. (Ting Ma, Xiao Fu, Choon Wee Kee, Lili Zong, Yuanhang Pan, Kuo-Wei Huang, Choon-Hong Tan, J. Am. Chem. Soc. 2011, 133 (9), 2828-2831) and Giumanini et al. (Angelo G. Giumanini, Giancarlo Verardo, Ennio Zangrando, Lucia Lassiani, J. Prakt. Chem. 1987, 329(6), 1087-1103).

[0070] The invention is explained in more detail below with reference to the exemplary embodiments. In particular, it has been shown that at least one chemical compound in a transport layer of a layer system of an organic electronic component surprisingly leads to an increase in the conductivity of the layer system.

[0071] Examples of implementation

[0072] Example 1

[0073] Fig. 1 shows, in one embodiment, a schematic representation of a structure of an organic electronic component 1 in cross section. In this embodiment, 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, wherein the layer system 8 has 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 Xe independently selected from the group consisting of H and alkyl, with Yi, Y2 and Y3 independently selected from the group consisting of unsubstituted or substituted aryl, unsubstituted or substituted heteroaryl having a heteroatom selected from O, S or N, wherein the substituent is in each case selected from the group consisting of halogen, amino, alkyl, alkenyl, alkynyl, alkoxy, thioalkoxy, aryl, heteroaryl, and an alkyl group Ia 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 O, S or N, preferably H and alkyl, wherein the substituent is in each case selected from the group consisting of halogen, amino, alkyl, alkenyl, alkynyl, alkoxy, thioalkoxy, aryl, and heteroaryl having a heteroatom selected from O, S or N, with the proviso that at least one of R41, R42, and R43 is not H, wherein * represents the linkage to an N.

[0074] In one embodiment of the invention, the chemical compound has the general formula II with Xi, X2, X3, X4, X5 and Xg independently selected from the group consisting of H and alkyl, with Ri, R2, R3, R4, R5 and Re independently selected from the group consisting of H, unsubstituted or substituted alkyl, and unsubstituted or substituted aryl, wherein the substituent is in each case selected from the group consisting of halogen, amino, alkyl, alkenyl, alkynyl, alkoxy, thioalkoxy, aryl, and heteroaryl having a heteroatom selected from O, S or N, wherein Ri and R2, R3 and R4, and / or R5 and Rg can each form a homocyclic or a heterocyclic aromatic or aliphatic ring.

[0075] In a further embodiment of the invention, the chemical compound has the general formula III with Xi, X2, X3, X4, X5 and Xg independently of one another selected from the group consisting of H and alkyl, where Rn to R15, R21 to R25, and R31 to R35 are each independently selected from the group consisting of halogen, preferably F, amino, alkyl, alkenyl, alkynyl, alkoxy, thioalkoxy, aryl, preferably phenyl, and heteroaryl having a heteroatom selected from O, S or N, where H can in each case be further substituted, preferably Rn to Rn, R21 to R25, and R31 to R35 are each H, or in each case at least one Rn to Rn, R21 to R25, or R31 to R35 is an amino group each having at least one alkyl or aryl, preferably two alkyl or aryl.

[0076] In a further embodiment of the invention, Xi, X2, X3, X4, X5 and Xg are independently selected from H and CH3, and / or Xi, X2, X3, X4, X5 and Xe are identical, preferably Xi, X2, X3, X4, X5 and Xe are H, and / or Yi, Y2 and Y3 are phenyl or naphthyl, where H may each be further substituted by a substituent selected from the group consisting of halogen, amino, alkyl, alkenyl, alkynyl, alkoxy, thioalkoxy, aryl, and heteroaryl having a heteroatom selected from O, S or N, and / or Yi, Y2 and Y3 are identical, and / or at least one R41, R42 or R43 is a non-substituted or substituted aryl, or a non-substituted or substituted heteroaryl having a heteroatom selected from 0, S or N .

[0077] In a further embodiment of the invention, the chemical compound is selected from the group consisting of:

[0078] In a further embodiment of the invention, 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.

[0079] In a further embodiment of the invention, the chemical compound is present in a matrix material, wherein the molar doping ratio of the chemical compound to the matrix material is from 1:1 to 1:10000, preferably from 1:2 to 1:1000, particularly preferably from 1:5 to 1:100, and / or wherein 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 preferably the matrix material is selected from the group consisting of C60, C70, C76, C80, C82, C84, C86, C90 and C94.

[0080] In a further embodiment of the invention, 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.

[0081] In a further embodiment of the invention, 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 is a layer of a pn junction. The pn junction can be arranged between two photoactive layers 5 or, alternatively, between an electrode 3, 7 and a photoactive layer 5.

[0082] The chemical compounds according to the invention are suitable as n-dopants 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 in ection layer.

[0083] The chemical compounds are thermally stable and allow evaporation in high vacuum with a process window between 100°C and 400°C.

[0084] Example 2

[0085] In this exemplary embodiment, the conductivity of transport layers doped with the chemical compound (01) (Table 2A), the chemical compound (06) (Table 2B), and the chemical compound (07) (Table 2C) was investigated. The chemical compounds were investigated with regard to their effect as n-dopants in an electron transport layer 4.

[0086] The conductivity was determined in a layer of fullerene C60 doped with the n-dopant as matrix material. To dope the transport layers, in particular an electron-transport layer 4, the matrix material C60, i.e., an electron-transport material (ETM), was co-evaporated with the respective chemical compound, and the conductivity of the doped layer was investigated. The transport layer contains the chemical compound according to the invention in proportion to the main component of the matrix material C60.

[0087] Table 2A shows, in one embodiment, the electrical conductivity of an electron transport layer 4 made of C60 as matrix material with different proportions of doping with the compound (01) according to the invention.

[0088] Table 2A

[0089]

[0090] 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 at a proportion of 24.73 wt.% of the n-dopant at 40°C, and of 4.0 -10- 2 S / cm at a content of 23.38 wt.% of the n-dopant at 60°C. In contrast, the conductivity of a layer consisting only of C60 is below the measuring range of 1 -10~ 6 S / cm.

[0091] Surprisingly, the triazinanenes of the invention are good n-dopants. The data show that the conductivity of layers doped with compounds of the invention is at least largely maintained or even increased at elevated temperatures up to 60°C.

[0092] Table 2B shows, in one embodiment, the electrical conductivity of an electron transport layer 4 made of C60 as matrix material with different proportions of doping with the compound (06) according to the invention.

[0093] Table 2B

[0094] Table 2C shows, in one embodiment, the electrical conductivity of an electron transport layer 4 made of C60 as matrix material with different proportions of doping with the compound (07) according to the invention.

[0095] Table 2C

[0096] The conductivity was also determined in layers doped with the n-dopants compound (06) (Table 2B) and compound (07) (Table 2C) using C60 as the matrix material. The conductivity of the electron-transport layers 4 at 22°C with compound (06) was 2.15 -IO -5 S / cm and with the compound (07) 9, 14 -IQ- 4S / cm. It has been shown that the conductivity of the matrix material C60 can also be increased with compounds (06) and (07). The conductivity of layers doped with these chemical compounds is at least largely maintained or even increased at higher temperatures.

[0097] 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 compound according to the invention significantly increases the conductivity of these layers.

[0098] Example 3

[0099] In the present embodiment, the organic electronic component 1 is an organic photovoltaic element. Identical and functionally identical elements are provided with the same reference numerals, so reference is made to the preceding description.

[0100] The parameters fill factor FF, open circuit voltage VOC, and short circuit current Jsc of an organic photovoltaic element with the compound (01) (Device No. 1 to 4), compound (06) (Device No. 6), compound (07) (Device No. 7) and the comparison compound NDN-45 (Device No. 5) as n-dopant in the electron transport layer 4 were determined.

[0101] The organic photovoltaic element comprises a substrate 2, e.g., made of glass, on which an electrode 3, e.g., made of ITO, is arranged. However, the electrode 3 can also be formed of a metal, a conductive oxide, such as ZnO:Al or another transparent conductive oxide, or a polymer, such as PEDOT:PSS or PANI.

[0102] Arranged thereon is a layer system 8 with an electron transport layer 4 (ETL) with C60 as the matrix material and an n-dopant. On top of this is a photoactive layer 5 with a donor material and an acceptor material, e.g. bullerene C60, which together form a donor / acceptor system, either as a shallow heterojunction (PHJ) or as a bulk heterojunction (BHJ). On top of this is a p-doped hole transport layer 6 (HTL) and a counter electrode 7 made of gold. In this exemplary embodiment, the photoactive layer 5 is designed as a bulk heterojunction (BHJ), with a donor and bullerene C60 as the acceptor. In this exemplary embodiment, the electron transport layer 4 comprises at least one chemical compound of the general formula I.

[0103] The organic photovoltaic element is designed in a nip-device architecture as a BHJ cell with the following layer system structure:

[0104] Glass / ITO (10nm) / C60:n dopant (10nm) / C60 (lOnm) / Donor :C60 (30nm, 2:3 wt.%, 90°C) / HTM (lOnm) / HTM:NDP9 (45nm, 4 wt.%) / NDP9 (Inm) / Au (50nm)

[0105] The compounds (01), (06) or (07) or the reference material NDN-45 were used as n-dopants.

[0106] The parameters measured in the organic photovoltaic elements, fill factor FF, open circuit voltage Voc, and short circuit current Jsc from the obtained current-voltage characteristic curve are summarized in Table 3 .

[0107] Table 3

[0108] NDN-45 : commercial n-dopant of Novaled AG NDP9: commercial p-dopant of Novaled AG

[0109] HTM-81: commercial hole-transport material from Merck AG

[0110] BDP-1 : published in Tian-yi Li et al. , J. Mater. Chem. A, 2018, 6, 18583

[0111] Example 4

[0112] In the present embodiment, the organic electronic component 1 is an organic photovoltaic element. Identical and functionally identical elements are provided with the same reference numerals, so reference is made to the preceding description.

[0113] The parameters fill factor FF, open circuit voltage VOC, and short circuit current Jsc of an organic photovoltaic element with compound (01) (Device No. 8 to 11), compound (06) (Device No. 13), compound (07) (Device No. 14) and the reference compound NDN-45 (Device No. 12) as n-dopant in the electron transport layer were determined.

[0114] The organic photovoltaic element is designed in a pnip device architecture as a BHJ cell with the following layer system structure:

[0115] Glass / ITO (10nm) / HTM:NDP9 (1Onm, 10 wt%) / C60:n-dopant (10nm) / C60 (10nm) / Donor:C60 (30nm, 2:3 wt%, 90°C) / HTM (10nm) / HTM:NDP9 (45nm, 4 wt%) / NDP9 (Inm) / Au (50nm)

[0116] The compounds (01), (06) or (07) or the reference material NDN-45 were used as n-dopants.

[0117] The parameters measured in the organic photovoltaic elements are fill factor FF, open circuit voltage V oc , and short-circuit current Jsc from the obtained current-voltage characteristic are summarized in Table 4 .

[0118] Table 4

[0119] The designations of the materials correspond to those in Example 3.

[0120] Example 5

[0121] In this exemplary embodiment, the conductivity of transport layers doped with the chemical compound (01) was investigated at different temperatures. Identical and functionally equivalent elements are provided with the same reference numerals, so reference is made to the previous description.

[0122] The conductivity of a layer of fullerene C60 doped with the n-dopant as a matrix material was determined. The transport layer contains the chemical compound (01) according to the invention at a doping concentration of 20 wt.% in proportion to the matrix material C60. The electrical conductivity of such a transport layer at different temperatures is shown in Fig. 2.

[0123] The conductivity of the electron transport layer 4 decreases depending on the temperature of 1,2 -IO -7 S / cm at 30°C and reaches a value of 1.5 S / cm at 100°C.

[0124] The conductivity of a C60 layer doped with 20 wt.% of the compound (01) according to the invention thus increases with increasing substrate temperature to 1.5 S / cm 100°C. Upon cooling a substrate previously heated to 100°C with such a transport layer to a temperature of 35°C, the increased conductivity remains at least largely at a value of 7.0 -10- 1 S / cm. The increase in conductivity is therefore largely irreversible.

[0125] Surprisingly, the increased electrical conductivity by using the chemical compound (01) according to the invention as n-dopant is at least partially irreversible, so that even at a reduced temperature an increase in the conductivity of once heated layers is largely maintained.

Claims

Patent claims 1. Organic electronic component (1) with an electrode (3), a counter electrode (7) and a layer system (8) between the electrode (3) and the counter electrode (7), wherein the layer system (8) has at least one photoactive layer (5), characterized in that 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 Xg independently selected from the group consisting of H and alkyl, with Yi, Y2 and Y3 independently selected from the group consisting of unsubstituted or substituted aryl, unsubstituted or substituted heteroaryl having a heteroatom selected from O, S or N, wherein the substituent is in each case selected from the group consisting of halogen, amino, alkyl, alkenyl, alkynyl, alkoxy, thioalkoxy, aryl, heteroaryl, and an alkyl group Ia 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 O, S or N, preferably H and alkyl, wherein the substituent is in each case selected from the group consisting of halogen, amino, alkyl, alkenyl, alkynyl, alkoxy, thioalkoxy, aryl, and heteroaryl having one heteroatom selected from O, S or N, with the proviso that at least one of R41, R42, and R43 is not H, where * represents the linkage to an N.

2. Organic electronic component (1) according to claim 1, wherein the chemical compound has the general formula II with Xi, X2, X3, X4, X5 and Xe independently selected from the group consisting of H and alkyl, with Ri, R2, R3, R4, Rs and Re independently selected from the group consisting of H, unsubstituted or substituted alkyl, and unsubstituted or substituted aryl, wherein the substituent is selected from the group consisting of halogen, amino, alkyl, alkenyl, alkynyl, alkoxy, thioalkoxy, aryl, and heteroaryl having a heteroatom selected from O, S or N, wherein Ri and R2, R3 and R4, and / or R5 and Re can each form a homocyclic or a heterocyclic aromatic or aliphatic ring.

3. Organic electronic component (1) according to claim 1, wherein the chemical compound has the general formula III with Xi, X2, X3, X4, X5 and Xg independently of one another selected from the group consisting of H and alkyl, where Rn to R15, 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, preferably phenyl, and heteroaryl having a heteroatom selected from O, S or N, where H may in each case be further substituted, preferably Rn to R15, R21 to R25, and R31 to R35 are each H, or in each case at least one Rn to Rn, R21 to R25, or R31 to R35 is an amino group each having at least one alkyl, aryl or heteroaryl, preferably two alkyl, aryl or heteroaryl.

4. Organic electronic component (1) according to one of the preceding claims, wherein Xi, X2, X3, X4, X5 and Xe are independently selected from H and CH3, and / or Xi, X2, X3, X4, X5 and Xg are the same, preferably Xi, X2, X3, X4, X5 and Xe are H, and / or Yi, Y2 and Y3 are phenyl or naphthyl, where H may each be further substituted with a substituent selected from the group consisting of halogen, amino, alkyl, alkenyl, alkynyl, alkoxy, thioalkoxy, aryl, and heteroaryl having a heteroatom selected from O, S or N, and / or Yi, Y2 and Y3 are the same, and / or at least one R41, R42, or R43 is a non-substituted or substituted aryl, or a non-substituted or substituted heteroaryl having a heteroatom selected from O, S or N.

5. Organic electronic component (1) according to one of the preceding claims, wherein the chemical compound is selected from the group consisting of:

6. Organic electronic component (1) according to one of the preceding claims, wherein the chemical compound is an n-dopant in an electron transport layer (4) or an electron injection layer of the layer system (8).

7. Organic electronic component (1) according to one of the preceding claims, wherein the chemical compound is present in a matrix material, wherein the molar doping ratio of the chemical compound to the matrix material is from 1:1 to 1:10000, preferably from 1:2 to 1:1000, particularly preferably from 1:5 to 1:100, and / or wherein the matrix material has a LUMO energy level of -3.0 eV to -5.0 eV, preferably the matrix material is a bullerene 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.

8. Organic electronic component (1) according to one of the preceding claims, wherein the at least one layer with the at least one chemical compound is in direct contact with an electrode (3, 7), is an electron transport layer (4) and / or electron injection layer or is in direct contact with such a layer, or is a layer of a pn junction.

9. Organic electronic component (1) according to one of the preceding claims, wherein 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.

10. Use of a chemical compound according to one of claims 1 to 5 as an n-dopant for doping at least one layer in a layer system (8) of an organic electronic component (1), in particular at least one electron transport layer (4) and / or electron injection layer.

11. Chemical compound of general formula II with Xi, X2, X3, X4, X5 and Xe independently of one another selected from the group consisting of H and alkyl, with Ri, R2, R3, R4, Rs and Re independently of one another selected from the group consisting of aryl, preferably phenyl, and heteroaryl having a heteroatom selected from O, S or N, where H can in each case be further substituted, where the substituent is selected from the group consisting of halogen, amino, alkyl, alkenyl, alkynyl, alkoxy, thioalkoxy, aryl, and heteroaryl having a heteroatom selected from O, S or N, with the proviso that in Ri, R2, R3, R4, Rs and Rg at least one H is in each case substituted, where Ri and R2, R3 and R4, and / or R5 and Re can be bridged to one another.

12. Chemical compound according to claim 11, wherein Xi, X2, X3, X4, X5 and Xe are independently selected from H and CH3, and / or Xi, X2, X3, X4, X5 and Xe are the same, and / or Ri, R2, R3, R4, Rs and Re, and / or Ri, R2, R3, R4, Rs and Re are phenyl or naphthyl, wherein H is each further substituted with a substituent selected from the group consisting of from halogen, amino, alkyl, alkenyl, alkynyl, alkoxy, thioalkoxy, aryl, and heteroaryl with a heteroatom selected from O, S or N, and / or Ri, R2, R3, R4, Rs and Rg are the same.

13. Chemical compound according to claim 11 or 12, wherein the chemical compound has the general formula X with Xi, X2, X3, X4, X5 and Xe independently selected from the group consisting of H and alkyl, with R50- R54, R55- R59, Reo-Re4, Re5-Re9, R?o _R74, and R75-R79 are each independently selected from the group consisting of H, halogen, preferably F, amino, alkyl, alkenyl, alkynyl, alkoxy, thioalkoxy, aryl, preferably phenyl, and heteroaryl having a heteroatom selected from O, S or N, with the proviso that at least one of Rso-Rs4, Rss-Rsg, Reo-R64, Res-Reg, R7o-R74, and R75-R79 is not H, preferably at least two of Rso-Rs4, Rss-Rsg, Reo-R64, Res-Reg, R70-R74, and Rgs-Rgg are not H.

14. Chemical compound according to claim 13, wherein each of Rso-Rs4, R55-R59, Reo-Re4, Res-Reg, R7o-R74, and Rgs-Rgg is an amino group having at least one alkyl or aryl, preferably having two alkyl or aryl.

15. Chemical compound according to any one of claims 11 to 14, wherein X u X2, X3, X4, X5 and X6H are.

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