Electronic semiconductor device and method for manufacturing the electronic semiconductor device

Abstract

Electronic device comprising at least one first hole transport layer between a first electrode and a second electrode, wherein the first hole transport layer comprises: (i) at least one first hole transport matrix compound consisting of covalently bonded atoms, and (ii) at least one electrical p-dotande selected from metal salts and electrically neutral metal complexes comprising a metal cation and at least one anion and / or at least one anionic ligand consisting of at least four covalently bonded atoms, wherein the metal cation of the electrical p-dotande is selected from Li(I), Na(I), K(I), Rb(I), Cs(I); Mg(II), Ca(II), Sr(II), Ba(II), Sn(II), Pb(II), Mn(II), Fe(II), Co(II), Ni(II), Zn(II), Cd(II), Al(III); Rare earth metal in the oxidized state (III), V(III), Nb(III), Ta(III), Cr(III), Mo(III), W(III) Ga(III), In(III) and from Ti(IV), Zr(IV), Hf(IV), Sn(IV);where a) electrical p-dopeds having an anion or an anionic ligand having generic formula (Ia) or (Ib) where A1, A2, A3 and A4 are independently selected from CO, SO2 or POR1; R1 = electron-withdrawing group selected from the group comprising halide, nitrile, halogenated or perhalogenated C1- to C20-alkyl, halogenated or perhalogenated C6- to C20-aryl, or halogenated or perhalogenated heteroaryl with 5 to 20 ring-forming atoms; B1, B2, B3, B4 are equally or independently selected from substituted or unsubstituted C1- to C20-alkyl, substituted or unsubstituted C1- to C20-heteroalkyl, substituted or unsubstituted C6- to C20-aryl, substituted or unsubstituted C5- to C20 heteroaryl, or B1 and B2 form a ring;and b) electrical p-doping consisting of a Li cation and an anion selected from perchlorate and tetrafluoroborate are excluded, and the first hole transport layer comprises a sublayer wherein the electrical p-doping is contained in an amount, by weight and / or by volume, which exceeds the total amount of other components that may also be contained in the sublayer.

Description

[0001] The disclosure relates to an electronic semiconductor device comprising a non-oxidizing p-doped in a hole injection and / or hole transport layer, and to a method for preparing the electronic semiconductor device. General state of the art

[0002] A wide range of prior art electronic devices that already utilize organic semiconductor materials often have very different requirements for a specific class of materials that must perform an analogous function, such as hole injection and / or hole transport, even in seemingly similar devices. As a more specific example, the definition of materials suitable for a hole transport layer can differ significantly depending on whether the OLED is intended to serve as a single unstructured OLED for illumination or as a pixel in a complex display device comprising multiple OLED pixels. From a chemical perspective, it can be quite difficult to meet such diverse requirements for materials within the same structural class.This fact necessitates the parallel research and development of many structurally diverse material classes; under such circumstances, a commercial invention is not only economically, but also technically and scientifically challenging. Accordingly, any material class exhibiting high versatility across a wide range of applications can be invaluable.

[0003] In some cases, conflicting requirements for a material with a specific function can arise even for a material used in the same device. A typical example is an active-matrix OLED (AMOLED) display. Active OLED displays, which comprise multiple OLED pixels sharing a common hole transport layer, place challenging demands on semiconductor materials used in the layers located between the anode and the emitting layer, which divide the multiple pixels. On the one hand, the materials must enable individual pixels to be driven with operating voltages that are as low as possible. On the other hand, electrical crosstalk between neighboring pixels must be avoided.Application WO2016 / 050834, which is incorporated herein by reference, teaches that these conflicting requirements can be met by p-doped layers having an electrical conductivity in the range of 1×10. -3 S·m -1 and 1x10 -8 S·m -1 , ideally between 1x10 -5 S·m -1 and 1x10 -6 S·m -1 Such p-doped hole transport layers with low conductivity can be achieved using conventional redox dopants in the state of the art, such as highly electron-accepting radial compounds, in matrices that are poorly doped with respect to their deep HOMO plane. However, there is a continuing need for p-dopants that meet these criteria and are improved in other parameters, e.g., processability and fixture stability. Summary

[0004] The goal is to provide a wide variety of state-of-the-art electronic devices comprising electrically p-doped hole injection and / or hole transport layers based on a broad class of p-dopeds.

[0005] Another objective is to provide specific compounds within the broad class of p-dots that exhibit high versatility in their use in devices. This versatility encompasses simple devices as well as enhanced active OLED displays. In one aspect, the performance of simple devices incorporating the new p-dots is fully comparable to, or superior to, analogous simple devices incorporating prior art p-dots. In another aspect, the new p-dots overcome some disadvantages of prior art dots in complex devices such as AMOLED displays. Specifically, they reduce electrical crosstalk between neighboring pixels in the active OLED display. Furthermore, they enable high performance in simple devices as well as in individual OLED pixels within a complex display device.In another aspect, the improved materials should enable robust device manufacturing, e.g., with regard to improved device stability during a processing step that allows treatment of the device or its specific layer at an elevated temperature. This objective is achieved by an electronic device comprising at least one first hole transport layer between a first electrode and a second electrode, wherein the first hole transport layer comprises: . (i) at least one first hole transport matrix compound consisting of covalently bonded atoms, and (ii) at least one electrical p-dotande selected from metal salts and from electrically neutral metal complexes comprising a metal cation and at least one anion and / or at least one anionic ligand consisting of at least 4 covalently bonded atoms, wherein the metal cation of the electrical p-dotande is selected from: Alkali metals; Alkali earth metals, Pb, Mn, Fe, Co, Ni, Zn, Cd; Rare earth metals in oxidation state (II) or (III); Al, Ga, In; and from Sn, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo and W in oxidation state (IV) or less; wherein a) p-dotandes having an anion or an anionic ligand having generic formula (Ia) or (Ib) wherein A 1 , A 2 , A 3 and A 4 independent of CO, SO2 or POR 1 are chosen; R 1= electron-withdrawing group, chosen from the group comprising halide, nitrile, halogenated or perhalogenated C1- to C 20 -Alkyl, halogenated or perhalogenated C6- to C 20 -Aryl, or halogenated or perhalogenated heteroaryl with 5 to 20 ring-forming atoms; B 1 , B 2 , B 3 are B 4 are chosen equally or independently from substituted or unsubstituted C1- to C 20 -Alkyl, substituted or unsubstituted C1- to C 20 -Heteroalkyl, substituted or unsubstituted C6- to C 20 -Aryl, substituted or unsubstituted C5- to C 20 -Heteroaryl, or B 1 and B 2 form a ring; and b) p-dotandes consisting of a Li cation and an anion selected from perchlorate and tetrafluoroborate are excluded, and The first hole transport layer comprises a sublayer, wherein the electrical dopant is contained in an amount, by weight and / or by volume, that exceeds the total amount of other components that may also be contained in the sublayer.

[0006] In one embodiment, p-dotandes consisting of a metal cation and a carboxylate anion can be excluded. In another embodiment, p-dotandes consisting of a divalent or trivalent metal cation and an alcohol ligand can be excluded. In yet another embodiment, p-dotandes consisting of a metal cation and an alcohol ligand can be excluded. In still another embodiment, lithium salt of trifluoromethanesulfonic acid can also be excluded as the p-dotande.

[0007] In one embodiment, the sublayer comprises the p-dotande in an amount of at least 60 wt.%, alternatively at least 75 wt.%, alternatively at least 90 wt.%, alternatively at least 95 wt.%, alternatively at least 98 wt.%, alternatively at least 99 wt.%, alternatively at least 99.5 wt.%, alternatively at least 99.9 wt.%, with respect to the total weight of the sublayer.

[0008] In one embodiment, the anion and / or the anionic ligand is bound to the metal cation of the p-doped by an oxygen atom, preferably by two oxygen atoms.

[0009] It is understood that the term "bound" includes structures of the p-doping agent, where the distance between the metal cation and the oxygen atom(s) is shorter than the distance between the metal cation and another atom of the anion and / or the anionic ligand.

[0010] For example, solid-state structural studies of some bis(sulfonyl)imide complexes of divalent and / or trivalent metals have shown that the bis(sulfonyl)imide ligand may be attached to the central metal atom by oxygen atoms of the sulfonyl groups, rather than by the imide nitrogen atom, which may in fact be located further away from the central metal atom than the oxygen atoms.

[0011] In one embodiment, the oxygen atom of the anion and / or the anionic ligand, which is bound to the metal cation in the metal salt and / or in the metal complex, has a lower basicity in dichloroethane than at least one non-oxygen atom of the anion and / or the anionic ligand.

[0012] Similarly, in one embodiment, the oxygen atoms of the anion and / or the anionic ligand bound to the metal cation in the metal salt and / or in the metal complex exhibit a lower basicity in dichloroethane than at least one non-oxygen atom of the anion and / or the anionic ligand.

[0013] It is understood that the basicity of an atom in the anion and / or in the anionic ligand in an environment, e.g., in 1,2-dichloroethane, is inversely proportional to the basicity of a corresponding tautomeric form of the electrically neutral conjugated acid formed by the addition of one or more protons in the same environment. The measurement of acidity in 1,2-dichloroethane as a versatile tool for comparing different acids is described in the Journal of Organic Chemistry (2011), 76(2), 391-395. It is understood that when the basicity of a particular atom in an anion and / or anionic ligand needs to be evaluated, the “corresponding tautomeric form” of the electrically neutral conjugated acid is the acid formed by proton addition to that particular atom.

[0014] In one embodiment, the anion and / or the anionic ligand consists of at least 5, preferably at least 6, even better at least 7, even better at least 8, preferably at least 9 covalently bonded atoms.

[0015] In one embodiment, the anion and / or the anionic ligand comprises at least one atom selected from B, C, N.

[0016] In one embodiment, the anion and / or the anionic ligand comprises at least two atoms selected from B, C and N, which are bonded to each other by a covalent bond.

[0017] In one embodiment, the anion and / or the anionic ligand comprises at least one peripheral atom selected from H, N, O, F, Cl, Br, and I. A "peripheral atom" is defined as an atom covalently bonded to only one atom of the anion and / or the anionic ligand. In contrast, atoms covalently bonded to at least two other atoms of the anion and / or the anionic ligand are designated as inner atoms.

[0018] A covalent bond is defined as a bond interaction involving electron density sharing between the two atoms involved, where the bond is stronger than van der Waals dispersive interactions. For simplicity, a bond energy of 10 kJ / mol can be used as an arbitrary lower limit. In this sense, the term includes coordination compounds or hydrogen compounds. However, anions and / or anionic ligands containing hydrogen compounds are not particularly favored.

[0019] In one embodiment, the anion and / or the anionic ligand comprises at least one electron-withdrawing group selected from halogenated alkyl, halogenated (hetero)aryl, halogenated (hetero)arylalkyl, halogenated alkylsulfonyl, halogenated (hetero)arylsulfonyl, halogenated (hetero)arylalkylsulfonyl, or cyano. For the sake of brevity, halogenated (hetero)aryl means "halogenated aryl or halogenated heteroaryl," halogenated (hetero)arylalkyl means "halogenated heteroarylalkyl or halogenated arylalkyl," halogenated (hetero)arylsulfonyl means "halogenated heteroarylsulfonyl or halogenated arylsulfonyl," and halogenated (hetero)arylalkylsulfonyl means "halogenated heteroarylalkylsulfonyl or halogenated arylalkylsulfonyl."

[0020] In one embodiment, the electron-withdrawing group is a perhalogenated group. The term "halogenated" is understood to mean that at least one hydrogen atom of a group comprising peripheral or internal hydrogen atoms is replaced by an atom selected from F, Cl, Br, and I. It is further understood that in a perhalogenated group, all hydrogen atoms contained in the unsubstituted group are replaced by atoms independently selected from F, Cl, Br, and I. Accordingly, a perfluorinated group is understood to be a perhalogenated group wherein all halogen atoms replacing hydrogen atoms are fluorine atoms.

[0021] In one embodiment, the metal cation of the p-doping agent is selected from Li(I), Na(I), K(I), Rb(I), Cs(I); Mg(II), Ca(II), Sr(II), Ba(II), Sn(II), Pb(II), Mn(II), Fe(II), Co(II), Ni(II), Zn(II), Cd(II), Al(III); rare earth metal in the oxidized state (III), V(III), Nb(III), Ta(III), Cr(III), Mo(III), W(III) Ga(III), In(III) and from Ti(IV), Zr(IV), Hf(IV), Sn(IV).

[0022] In one embodiment, the atom of the anion and / or the anionic ligand that is closest to the metal cation in the p-dotande molecule is a C or an N atom.

[0023] In one embodiment, the acidity of the electrically neutral conjugated acid formed from the anion and / or the anionic ligand by adding one or more protons to 1,2-dichloroethane is higher than that of HCl, preferably higher than that of HBr, better higher than that of HI, even better higher than that of fluorosulfuric acid, and best of all higher than that of perchloric acid.

[0024] In one embodiment, the electric p-doped has an energy level of its lowest unoccupied molecular orbital, calculated by standard quantum chemical methods and expressed on an absolute vacuum scale, at least 0.5 eV, preferably at least 0.6 eV, better at least 0.8 eV, even better at least 1.0 eV, best at least 1.2 eV above the energy level of the highest occupied orbital of the covalent hole transport compound calculated by the standard quantum chemical method.

[0025] The standard quantum chemical method can be the software package TURBOMOLE using DFT function B3LYP with the basis set def2-TZVP.

[0026] In one embodiment, the first hole transport matrix compound is an organic compound, preferably an organic compound comprising a conjugated system of at least 6, preferably at least 10 delocalized electrons; furthermore, the first hole transport matrix compound preferably comprises at least one triarylamine structural part, and better, the first hole transport matrix compound comprises at least two triarylamine structural parts.

[0027] In one embodiment, all layers between the first and second electrodes, as well as the electrode deposited on the last organic layer, are deposited by vacuum deposition at a pressure below 1×10 -3 Pa, preferably at a pressure below 5×10 -4 Pa, better at a pressure below 1×10 -4 Pa can be prepared.

[0028] In one embodiment, the electronic device is an organic electroluminescent device, an organic transistor, or an organic photovoltaic device.

[0029] In one embodiment, the electronic device comprises a display device. - several OLED pixels, comprising at least two OLED pixels, the OLED pixels comprising an anode, a cathode and a stack of organic layers, wherein the stack of organic layers - is positioned between and in contact with the cathode and the anode, and - comprises a first electron transport layer, a first hole transport layer and a first light-emitting layer provided between the first hole transport layer and the first electron transport layer, and - a driver circuit configured to drive the pixels of the multiple OLED pixels separately, wherein for the multiple OLED pixels, the first hole transport layer in the stack of organic layers is provided as a common hole transport layer shared by the multiple OLED pixels.

[0030] The objective is further achieved by a method for manufacturing the electronic device according to one of the preceding embodiments, the method comprising at least one step in which the first hole transport matrix connection and the electrical p-dot are in mutual contact and are exposed to a temperature above 50 °C.

[0031] It is understood that “in mutual contact” means the presence of both components in one condensed phase or their presence in two condensed phases that share a common phase interface.

[0032] The process can further comprise at least one step in which the p-doping agent is evaporated at reduced pressure, preferably at a pressure below 1×10 -2 Pa and at a temperature above 50 °C, preferably at a pressure below 5×10 -2 Pa and at a temperature above 80 °C, even better at a pressure below 1×10 -3 Pa and at a temperature above 120 °C, ideally at a pressure below 5×10 -4 Pa and at a temperature above 150 °C.

[0033] In another embodiment, the method may include the steps wherein (i) the p-doped molecule and the first hole transport matrix compound are dispersed in a solvent, (ii) the dispersion is deposited on a solid support and (iii) the solvent evaporates at an elevated temperature.

[0034] In one embodiment, the p-doping agent can be used in the form of a solid hydrate.

[0035] In another embodiment, the p-dot can be used as an anhydrous solid comprising less than 0.10 wt.% water, and preferably less than 0.05 wt.% water.

[0036] The objective is further achieved by a compound with formula (I) where M is a metal ion; each from A 1 - A 4 independently chosen is from (i) H, (ii) F, (iii) CN, (iv) C6-C 60 -Aryl, (v) C7-C 60 -Arylalkyl, (vi) C1-C 60 -Alkyl, (vii) C2-C 60 -Alkenyl, (viii) C2-C 60 -Alkynyl, (ix) C3-C 60 -Cycloalkyl and (x) C2-C 60-Heteroaryl; wherein, provided that the total number of carbon atoms in a carbon-containing group does not exceed 60, each hydrogen atom in a carbon-containing group selected from (iv), (v), (vi), (vii), (viii), (ix) and (x) may be replaced by a substitute independently selected from F, Cl, Br, I, CN, unsubstituted or halogenated alkyl, unsubstituted or halogenated (hetero)aryl, unsubstituted or halogenated (hetero)arylalkyl, unsubstituted or halogenated alkylsulfonyl, unsubstituted or halogenated (hetero)arylsulfonyl, unsubstituted or halogenated (hetero)arylalkylsulfonyl, unsubstituted or halogenated boron-containing hydrocarbyl, unsubstituted or halogenated silicon-containing hydrocarbyl; n is the valence of the metal ion; and at least one from A 1 -A 4is F, CN, or an electron-withdrawing carbon group, wherein the electron-withdrawing carbon group is a carbon group selected from hydrocarbyl, boron-containing hydrocarbyl, silicon-containing hydrocarbyl and heteroaryl, and at least half of its hydrogen atoms are replaced by substitutes independently selected from F, Cl, Br, I, CN.

[0037] In one embodiment, heteroaryl is chosen to refer to heteroaryls comprising an aromatic ring with five or six elements, including up to three heteroatoms selected from N, O and S. Effect of the invention

[0038] An important property of the materials present in organic semiconductor devices is their conductivity. In a display device having a structured anode and at least two pixels sharing at least one hole transport and / or hole injection layer, as described in WO2016 / 050834, limited conductivity of the shared layer may be preferable to achieve a low level of unwanted electrical crosstalk in the display. On the other hand, very low conductivity of the shared layer may increase the operating voltage of the display. WO2016 / 050834 teaches a conductivity range that represents a compromise between these opposing requirements.

[0039] However, the authors of this application surprisingly found that, under certain circumstances, electrical p-dopeds based on certain metal salts and metal complexes enable the fabrication of p-doped materials and / or p-doped layers, providing stable hole injection of prior art anodes into prior art hole transport matrices without increasing the concentration of free charge carriers beyond the level corresponding to the conductivities observed in a pure matrix.

[0040] This surprising finding provided an opportunity to develop the WO2016 / 050834 displays, which function at completely comparable voltages, even when the hole transport and / or hole injection layers, divided by the multitude of pixels, have conductivities below the optimal range of 1×10 -5 S·m -1 and 1x10 -6 S·m -1exhibiting characteristics as disclosed in WO2016 / 050834. The dopants of this application enable the efficient operation of the display devices of WO2016 / 050834 at the level of electrical conductivity in p-doped layers, divided by the multitude of pixels, which is near or below the detection limit of the available measurement method. Thus, the dopants of this application enable further suppression of electrical crosstalk in OLED displays and offer new opportunities for the design of efficient OLED displays that exhibit a very low level of electrical crosstalk. These observations of the authors are described in more detail below.

[0041] In a previous application EP15181385 of the applicant, now published as EP 3 133 663, some of the authors described the successful use of some metal imides as hole injection materials in organic electronic devices.

[0042] In parallel with further investigation of analogous metalimide compounds, the authors surprisingly found that some structurally very different compounds, namely metal alborate complexes, can also be used in an analogous manner.

[0043] Some of the authors disclosed in another application, namely EP17209023, a compound E3 which is created by sublimation of a zinc sulfonamide complex having the composition C 42 F 48 N6O 13 exhibits S6Zn4 and crystallizes in a monoclinic crystal lattice belonging to the space group P 1 21 1 with unit cell dimensions a = 14.1358 (5) Å, α = 90°; b = 16.0291 (6) Å, β = 113.2920 (10); c = 15.9888 (6) Å; γ = 90° and unit cell volume 3327.6 (2) Å 3 belongs. Surprisingly, this connection exhibits an inverted coordination complex structure, as in Fig.5 can be seen. Specifically, one molecule of the complex comprises a central oxygen dianion surrounded by a first coordination sphere consisting of four tetrahedral zinc dications and a second coordination sphere consisting of six sulfonylamide monoanionic ligands bridging all six edges of the Zn4 cluster with triatomic -NSO- bridges.

[0044] Most surprisingly, the authors found that these structurally different compounds all exhibit two analogous modes in their p-doping activity, depending on the process conditions during the creation of the doped material and / or layer.

[0045] In the first mode, semiconductor materials and / or layers doped with these compounds (which can be generalized as metal salts and / or electrically neutral metal complexes with an anionic ligand) exhibit readily measurable electrical conductivities that are only slightly lower than those of materials and / or layers doped with typical redox p-dopeds. It appears that this mode occurs when the doped material and / or layer is exposed to oxygen, even in trace amounts.

[0046] In the second mode, the semiconductor materials and / or layers doped with the disclosed metal salts and / or electrically neutral metal complexes comprising an anionic ligand exhibit barely measurable electrical conductivities. This mode occurs when oxygen access to the doped material and / or layer is strictly avoided throughout the entire processing. The authors found that despite the extremely low conductivity of the materials and / or layers doped in the second mode, devices incorporating such materials and / or layers, particularly as hole transport or hole injection layers, nevertheless exhibit behavior corresponding to excellent hole injection.

[0047] The existence of the two modes of p-doping activity described above provides the disclosed p-dopeds with a unique versatility in their use in organic electronic devices, and in particular displays comprising an anode structured in a plurality of pixels sharing a common hole transport layer. The conductivity of the common p-doped layer can either be set within the limits taught in WO2016 / 050834 by using the first doping mode, or below these limits by using the second doping mode.

[0048] Furthermore, recent investigations by the authors have provided evidence that materials and / or layers doped with the specified metal salts and / or metal complexes can offer favorable thermal stability, especially for materials prepared using the second mode of p-doping described above. These properties may again be particularly suitable for the use of the disclosed p-doped compound in AMOLED displays, because the necessary structuring of such displays into separate pixels often requires heat treatment of the p-doped layers or the use of another treatment that can lead to unavoidable heating of a previously deposited p-doped layer.

[0049] In a specific embodiment of the invention, the authors reported new borate compounds comprising specific heterocyclic ligands, wherein at least half of the hydrogen atoms are replaced by electron-withdrawing groups such as halogen atoms or nitrile groups. In addition to p-doping activity that is fully comparable to that of metal salts and / or anionic metal complexes of EP15181385, the borate complexes are essentially non-hygroscopic and remain solid even at high humidity, whereas LiTFSI and analogous TFSI salts tend to liquefy. Detailed description

[0050] The electrical conductivity of a thin film sample can be measured, for example, using the so-called two-point method. In this method, a voltage is applied to the thin film, and the current flowing through the film is measured. The resistance, or electrical conductivity, is determined by considering the geometry of the contacts and the thickness of the sample film. The experimental setup for conductivity measurement used by the authors of this application enables the deposition of p-doped films and the measurement of conductivity under controlled conditions, particularly with regard to the contact of the deposited films with an atmosphere containing oxygen.In this regard, the entire deposition measurement sequence can be performed either in a glove box or in a chamber comprising a controlled atmosphere, using solution processing techniques, or entirely in a vacuum chamber, using vacuum thermal evaporation (VTE) as the method of choice, which is particularly suitable when materials and / or layers doped in the second mode are required.

[0051] In one embodiment, the electronic device can be an AMOLED display comprising multiple pixels, each comprising at least two pixels, wherein the first hole transport layer, comprising the p-dot, is positioned between a structured anode and a structured light-emitting layer. In this embodiment, the first hole transport layer is shared by the multiple pixels, and in this case, it can be advantageous for limiting electrical crosstalk between individual pixels operating at different voltages that the electrical conductivity of the shared layer is as low as possible.

[0052] In this case, the conductivity of the first hole transport layer can be less than 1×10 -6 S·m -1 be, preferably less than 1×10 -7 S·m -1 , better less than 1×10 -8 S·m -1Alternatively, if the detection limit of the conductivity measurement method used is less than 1×10 -6 S·m -1 It is preferred that in this embodiment of the electronic device the conductivity of the first hole transport layer is lower than the detection limit.

[0053] In an AMOLED display, the cathode can be configured as a common cathode for multiple pixels. This common cathode can extend across all pixels in an OLED display. Alternatively, each individual pixel can have its own anode, which does not necessarily touch the anodes of other individual pixels.

[0054] Optionally, the following organic layers can be provided for one or more of the multiple OLED pixels: a hole-blocking layer, an electron injection layer, and / or an electron-blocking layer.

[0055] Furthermore, the AMOLED display features a drive circuit configured to individually drive each of the multiple pixels provided in the OLED display. In one embodiment, an individual drive step may include the individual control of the drive current applied to each pixel.

[0056] The first HTL consists of a hole transport matrix (HTM) material electrically doped with the p-doped element. The hole transport matrix material may be electrically doped with more than one p-doped element. It is understood that the HTM material consists of one or more HTM compounds, the term "hole transport material" being a broader term used in this application for all semiconductor materials comprising at least one hole transport matrix compound. The hole transport matrix material is not specifically restricted. In general, it is any material consisting of covalently bonded atoms that permits the embedding of the p-doped element. In this sense, infinite inorganic crystals exhibiting predominantly covalent bonds, such as silicon or germanium, or extremely cross-linked inorganic glasses such as silicate glass, do not fall within the scope of the definition of the hole transport matrix material.Preferably, the hole transport matrix material can consist of one or more organic compounds.

[0057] In the electronic device, the first hole transport layer can have a thickness of less than 150 nm, less than 100 nm, less than 50 nm, less than 40 nm, less than 30 nm, less than 20 nm, or less than 15 nm.

[0058] The first hole transport layer can have a thickness of more than 3 nm, more than 5 nm, more than 8 nm, or more than 10 nm.

[0059] In one embodiment of the first hole transport layer, the p-doping agent can be homogeneously and isotropically distributed. In another embodiment, the p-doping agent can be homogeneously mixed with the matrix, but the concentration of the p-doping agent can exhibit a gradient across the layer. This invention encompasses each embodiment, wherein the first hole transport layer can comprise a sublayer, wherein the amount of the p-doping agent, by weight and / or by volume, can exceed the total amount of other components that may also be present in the layer.

[0060] In one embodiment, the weight concentration of the p-dotan, based on the total weight of the sublayer, can exceed 50%; alternatively, the p-dotan can constitute at least 75 wt.%, alternatively at least 90 wt.%, alternatively at least 95 wt.%, alternatively at least 98 wt.%, alternatively at least 99 wt.%, alternatively at least 99.5 wt.%, or alternatively at least 99.9 wt.%, with respect to the total weight of the sublayer. For simplicity, any sublayer of the first transport layer produced by deposition of only the p-dotan may be referred to as an ordinary p-dotan sublayer, for example, an ordinary hole injection sublayer.

[0061] The same can apply to any upper layer in the display device, which may comprise a combination of a hole transport matrix with a metal salt and / or metal complex that are brought into mutual contact, analogous to the first hole transport layer.

[0062] For example, pixels contained in the display device can have a hole-generating layer, which in one embodiment can consist of a hole transport matrix homogeneously doped with the p-doped matrix. In another embodiment, the hole-generating layer can comprise a sublayer in which the amount of the p-doped matrix, by weight and / or by volume, exceeds the total amount of other components.

[0063] The anode can consist of a transparent conductive oxide (TCO), such as indium tin oxide (ITO) or aluminum zinc oxide (AZO). Alternatively, the anode can consist of one or more thin metallic layers, resulting in a semi-transparent anode. In another embodiment, the anode can consist of a thick metallic layer that is not transparent to visible light.

[0064] The electronic device may include an electron-blocking layer (EBL) positioned between the first hole transport layer and the light-emitting layer. The EBL may be in direct contact with the first HTL and the EML. The electron-blocking layer may be an electrically undoped layer (in other words, free of an electrical dopant) composed of an organic hole transport matrix material. The composition of the organic hole transport matrix material of the first hole transport layer may be the same as the composition of the organic hole transport matrix material of the electron-blocking layer. In another embodiment of the invention, the composition of the two hole transport matrix materials may be different.

[0065] The EBL can have a layer thickness of more than 30 nm, more than 50 nm, more than 70 nm, more than 100 nm, or more than 110 nm.

[0066] The thickness of the EBL can be less than 200 nm, less than 170 nm, less than 140 nm, or less than 130 nm. Compared to the EBL, the common HTL can be about an order of magnitude thinner.

[0067] Each compound forming the electron-blocking layer can have a highest occupied molecular orbital (HOMO) energy level, expressed on an absolute scale with reference to the vacuum energy level of zero, that is higher than a HOMO level of a compound forming the hole transport matrix material of the common hole transport layer.

[0068] The organic matrix material of the electron-blocking layer can have a hole mobility that is equal to or higher than the hole mobility of the matrix material of the hole transport layer.

[0069] The hole transport matrix (HTM) material of the common HTL and / or the EBL can be selected from compounds comprising a conjugated system of delocalized electrons, wherein the conjugated system comprises single electron pairs of at least two tertiary amine nitrogen atoms.

[0070] Suitable compounds for the hole transport matrix material of the doped hole transport layer and / or the common hole transport layer can be selected from known hole transport matrices (HTMs), e.g., from triarylamine compounds. HTMs for the doped hole transport material can be compounds comprising a conjugated system of delocalized electrons, wherein the conjugated system includes single electron pairs from at least two tertiary amine nitrogen atoms. Examples are N4,N4'-di(naphthalen-1-yl)-N4,N4'-diphenyl-[1,1'-biphenyl]-4,4'-diamine (HT1) and N4,N4,N4",N4"-tetra([1,1'-biphenyl]-4-yl)-[1,1':4',1"-terphenyl]-4,4"-diamine (HT4). The synthesis of terphenyldiamine HTMs is, for example, 1,3-Phenylenediamine matrices are described, for example, in WO 2011 / 134458 A1, US 2012 / 223296 A1, or WO 2013 / 135237 A1; 1,3-phenylenediamine matrices are described, for example, in WO 2014 / 060526 A1. These documents are included herein by reference. Many triarylamine HTMs are commercially available.

[0071] The electronic device can further comprise a light-absorbing layer arranged between the first and second electrodes, e.g., in a solar cell. In another embodiment, the electronic device can be an electroluminescent device comprising at least one light-emitting layer between the first and second electrodes.

[0072] The light-emitting layer of the electroluminescent device can be continuous or structured. An example of an electroluminescent device having a structured light-emitting layer is the AMOLED display, which may comprise several subregions, each subregion being assigned to one of the pixels of the multiple pixels. The light-emitting layer of a single pixel, corresponding to a subregion of the display's emitting layer, preferably does not touch the light-emitting layers of neighboring pixels. In the display manufacturing process, the organic layer comprising the EMLs of individual pixels can be structured by known methods, such as fine metal masking (FMM), laser-induced thermal imaging (LITI), and / or inkjet printing (IJP) in top-out, bottom-out, or bottom-out with microcavities (see, for example, Chung et al. (2006), 70).1: Invited Paper: Large-Sized Full Color AMOLED TV: Advancements and Issues. SID Symposium Digest of Technical Papers, 37: 1958-1963. doi: 10.1889 / 1.2451418; Lee et al. (2009), 53.4: Development of 31-Inch Full-HD AMOLED TV Using LTPS-TFT and RGB FMM. SID Symposium Digest of Technical Papers, 40: 802-804. doi: 10.1889 / 1.3256911). An RGB layout can be provided.

[0073] For multiple OLED pixels, a common electron transport layer can be formed by the electron transport layers provided in the organic layers of the multiple OLED pixels.

[0074] The electron transport layer of the electronic device can comprise an organic electron transport matrix (ETM) material. Furthermore, the electron transport layer can comprise one or more n-doped atoms. Suitable compounds for the ETM are not specifically restricted. In one embodiment, the electron transport matrix compounds consist of covalently bonded atoms. Preferably, the electron transport matrix compound comprises a conjugated system of at least 6, preferably at least 10, delocalized electrons. In one embodiment, the conjugated system of delocalized electrons can consist of aromatic or heteroaromatic structural elements, as disclosed, for example, in documents EP 1970 371 A1 or WO 2013 / 079217 A1.

[0075] The cathode can be made of a metal or a metal alloy with a low work function. Transparent cathodes made of a TCO are also well-known in engineering.

[0076] The stack of organic layers can consist of organic compounds having a molecular weight of less than 2000 g / mol. In an alternative embodiment, the organic compounds can have a molecular weight of less than 1000 g / mol. List of characters

[0077] Further embodiments with additional details are described below by way of example, with reference to the figures. The figures illustrate: Fig. 1 a schematic representation of an active OLED display, wherein the display has multiple OLED pixels, Fig. Figure 2 is a schematic sectional view of an organic light-emitting diode (OLED) according to an exemplary embodiment of this invention; Fig. Figure 3 is a schematic sectional view of an OLED according to an exemplary embodiment of this invention. Fig.Figure 4 is a schematic sectional view of a tandem OLED comprising a charge generation layer, according to an exemplary embodiment of this invention. Fig. Figure 5 shows the crystal structure of the inverted coordination complex E3, with the molecular formula C 42 F 48 N6O 13 S6Zn4. Description of the embodiments

[0078] Fig. Figure 1 shows a schematic representation of an active OLED display 1, which has several OLED pixels 2, 3, 4 provided in an OLED display 1.

[0079] In the OLED display 1, each pixel 2 , 3 , 4 with an anode 2a , 3a , 4aequipped with a driver circuit (not shown). Various components capable of serving as a drive circuit for an active matrix display are known in the art. In one embodiment, the anodes consist of 2a , 3a , 4a from a TCO, for example ITO.

[0080] A cathode 6 is provided at the top of an organic stack that includes an electrically doped hole transport layer (HTL) 7 , an electron-blocking layer (EBL) 5 , a light-emitting layer (EML) with subregions 2b , 3b , 4b , which the pixels 2 , 3 , 4 are assigned and are located separately in an electron transport layer (ETL) 9 are provided, including, for example, the subregions. 2b , 3b , 4bProvide an RGB combination for a color display (R - red, G - green, B - blue). In another embodiment, pixels for individual colors can comprise analog white OLEDs equipped with a suitable combination of color filters. By applying individual drive currents to the pixels 2 , 3 , 4 via the anodes 2a , 3a , 4a and the cathode 6 will the display pixels 2 , 3 , 4 operated independently.

[0081] Fig. Figure 2 is a schematic sectional view of an organic light-emitting diode ( OLED ) 100 , according to an exemplary embodiment of this invention. The OLED 100 includes a substrate 110 , an anode 120 , a hole injection layer ( HIL ) 130 , a hole transport layer ( HTL ) 140 , an emission layer ( EML ) 150, an electron transport layer ( ETL ) 160 The electron transport layer ( ETL ) 160 directly on the EML 150 formed. On the electron transport layer ( ETL ) 160 An electron injection layer ( Urgent ) 180 isolated. The cathode 190 is directly on the electron injection layer ( Urgent ) 180 arranged.

[0082] Instead of a single electron transport layer 160 can optionally include an electron transport layer stack ( ETL ) be used.

[0083] Fig. 3 is a schematic cross-sectional view of an OLED 100 , according to another exemplary embodiment of this invention. Fig. 3 differs from Fig. 2 in that the OLED 100 out of Fig. 3 an electron-blocking layer (EBL) 145 and a hole-blocking layer ( HBL )155 includes.

[0084] With reference to Fig. 3 includes the OLED 100 a substrate 110 , an anode 120 , a hole injection layer ( HIL ) 130 , a hole transport layer ( HTL ) 140 , an electron-blocking layer (EBL) 145 , an emission layer ( EML ) 150 , a hole-blocking layer ( HBL ) 155 , an electron transport layer ( ETL ) 160, an electron injection layer ( Urgent ) 180 and a cathode electrode 190 .

[0085] Fig. Figure 4 is a schematic sectional view of a tandem OLED. 200 according to another exemplary embodiment of this invention. Fig. 4 differs from Fig. 3 in that the OLED 100 out of Fig. 3 further comprises a charge generation layer and a second emission layer.

[0086] With reference to Fig. 4 includes the OLED 200 a substrate 110 , an anode 120 , a first hole injection layer ( HIL ) 130 , a first hole transport layer ( HTL ) 140 , a first electron-blocking layer ( EBL ) 145 , a first emission layer ( EML ) 150 , a first hole-blocking layer ( HBL ) 155 , a first electron transport layer ( ETL ) 160 , an n-type charge generation layer (n-type CGL) 185 , a hole-generating layer (p-type charge-generating layer; p-type GCL) 135 , a second hole transport layer ( HTL ) 141 , a second electron-blocking layer ( EBL ) 146 , a second emission layer ( EML ) 151 , a second hole-blocking layer ( EBL ) 156 , a second electron transport layer ( ETL ) 161, a second electron injection layer ( Urgent ) 181 and a cathode 190 .

[0087] Even if in Fig. 2, Fig. 3 and Fig. 4 not shown, a sealing layer can also be applied to the cathode electrodes. 190 be educated to understand the OLEDs 100 and 200 to seal it. Furthermore, various other modifications can be applied to it. Synthesis ExamplesLithium tris(4,5,6,7-tetrafluoro-3-(tri.fluoromethyl)-1H-indazole-1-y1)hydroborate (PB-1)

[0088] Step 1: 11.09 g (45.1 mmol) of 4,5,6,7-tetrafluoro-3-(trifluoromethyl)-1H-indazole perfluoroacetophenone are dissolved in 100 mL of toluene. The solution is cooled with an ice bath, and 2.3 mL (2.37 g, 47.3 mmol, 1.05 eq) of hydrazine monohydrate is added dropwise. The mixture is heated to reflux for 3 days. After cooling to room temperature, the mixture is washed twice with 100 mL of saturated aqueous sodium bicarbonate solution and twice with 100 mL of water, dried over magnesium sulfate, and the solvent is removed under reduced pressure. The yellow, oily residue is distilled from flask to flask at a temperature of about 140 °C and a pressure of about 12 Pa. The crude product is dissolved in hot hexane, and the solution is stored at -18 °C. The precipitated solid is filtered off, and the suspension is washed twice with 10 mL of hexane. 5.0 g (43%) of the product is obtained as a light yellow solid. GCMS: confirms the expected M / z (mass / charge) ratio 258

[0089] Step 2: Lithium tris(4,5,6,7-tetrafluoro-3-(trifluoromethyl)-1H-indazol-1-yl)hydroborate 5.1 g (19.8 mmol) of 4,5,6,7-tetrafluoro-3-(trifluoromethyl)-1H-indazole is added to a heated Schlenk flask under argon counterflow and treated with 3 mL of toluene. Freshly powdered lithium borohydride is added to the starting material. The mixture is heated to 100 °C until hydrogen evolution ceases (approx. 4 h). After slight cooling, 15 mL of hexane are added, the mixture is heated under reflux for 10 minutes, and then cooled to room temperature. The precipitated solid is filtered, washed with 10 mL of hot hexane, and dried under high vacuum. 2.55 g (49%) of product is obtained as a whitish solid. Lithium tris(3,5-bis(trifluoromethyl)-1H-pyrazole-1-κ1)hydroborate (PB-2) 2.0 g (9.8 mmol, 5 eq) of 3,5-bis(trifluoromethyl)pyrazole are dissolved in 5 mL of dry toluene in a heated Schlenk flask. 43 mg (1.96 mmol, 1 eq) of freshly powdered lithium borohydride are added under argon counterflow, and the mixture is heated for 3 days under reflux. The solvent and excess starting material are removed by distillation under reduced pressure, and the residue is crystallized from n-chlorohexane. 0.25 g (20%) of product is obtained as a white solid. Lithium tris(4,5,6,7-tetrafluoro-3-(perfluorophenyl)-1H-indazol-1-yl)hydroborate (PB-3)

[0090] Step 1: 20.0 g (54.8 mmol) of 4,5,6,7-tetrafluoro-3-(perfluorophenyl)-1H-indazole perfluorobenzophenone is dissolved in 200 mL of toluene. 4.0 mL (4.11 g, 82.1 mmol, approx. 1.5 eq) of hydrazine monohydrate is added dropwise to the ice-cold solution. 40 g of sodium sulfate is added, and the mixture is heated for reflux for 2 days. After cooling, 10 mL of acetone is added to the reaction mixture, and the resulting sludge is stirred for 1 h at room temperature. The solid is filtered off, washed thoroughly with 4 × 50 mL of toluene, the organic fractions are combined, and washed twice with saturated aqueous sodium bicarbonate. The solvent is removed under reduced pressure, and the residue is purified by column chromatography. 7.92 g (41%) of product are obtained as a light yellow solid. GC-MS: confirms the expected M / z (mass / charge) ratio 356

[0091] Step 2: Lithium tris(4,5,6,7-tetrafluoro-3-(perfluorophenyl)-1H-indazol-1-yl)hydroborate 1.02 g (2.86 mmol, 3.0 eq) of 4,5,6,7-tetrafluoro-3-(perfluorophenyl)-1H-indazole are dissolved in 5 mL of chlorobenzene in a heated Schlenk flask. Freshly powdered lithium borohydride (21 mg, 0.95 mmol, 1.0 eq) is added under argon counterflow. The mixture is heated to 150 °C for 2 days and cooled to room temperature. The solvent is removed under reduced pressure, and the residue is dried under high vacuum. The crude material is further purified by drying in a flask-to-flask apparatus at a temperature of approximately 150 °C and a pressure of approximately 12 Pa. 0.57 g (70%) of product are obtained as a whitish solid. Lithium tris(3-cyano-5,6-difluoro-1H-indazol-1-yl)hydroborate (PB-4): Freshly powdered lithium borohydride (15 mg, 0.7 mmol, 1.0 eq) is placed in a heated pressure tube. 0.5 g (2.79 mmol, 4.0 eq) of 5,6-difluoro-1H-indazol-3-carbonitrile is added under counterflow with argon and washed with 1 mL of toluene. The pressure tube is closed and heated to approximately 160 °C for about 21 h. After cooling to room temperature, the mixture is treated with 5 mL of hexane in an ultrasonic bath for about 30 minutes. The precipitated solid is filtered off and washed with hexane (20 mL total). After drying, 0.48 g of yellowish solid is obtained. Zinc(II) tris(3,5-bis(trifluoromethyl)-1H-pyrazol-1-yl)hydroborate (PB-5) 0.57 g (0.91 mmol) of lithium tris(3,5-bis(trifluoromethyl)-1H-pyrazol-1-yl)hydroborate are dissolved in 6 mL of N,N-dimethylformamide. An aqueous solution of 62 mg zinc dichloride in 1 mL of water is added dropwise. A further 20 mL of water is added, and the mixture is treated in an ultrasonic bath for 2 h. The deposited material is filtered and dried under high vacuum. 0.485 g (82%) of the product are obtained as a further solid. Example connection E3

[0092] A precursor connection E2 was obtained according to scheme 1.

[0093] Step 1: Synthesis of 1,1,1-Trifluoro-N-(perfluorophenyl)methanesulfonamide

[0094] A 250 mL Schlenk flask is heated under vacuum and, after cooling, purified with nitrogen. Perfluoroaniline is dissolved in 100 mL of toluene, and the solution is cooled to -80 °C. A 1.7 M t-butyllithium solution in hexane is added dropwise via syringe over 10 minutes. The reaction solution changes from clear to cloudy and is stirred for 1 hour at -80 °C. The solution is then allowed to warm to -60 °C, and 1.1 eq of trifluoromethanesulfonic anhydride is added dropwise. The cooling bath is then removed, and the reaction mixture is allowed to warm slowly to ambient temperature and is stirred overnight, during which time the color changes to a light orange. A white solid also forms. The precipitated by-product lithium trifluoromethanesulfonate is filtered off by suction filtration through a winterized glass filter and washed with 2 × 30 mL toluene and 30 mL n-hexane.The orange filtrate is evaporated and dried under high vacuum until crystals form. The crude product is then distilled by flask-to-flask distillation (135 °C @ 1.2 × 10⁻⁶). -1 mbar) purified, resulting in a crystalline colourless solid (main fraction). 1 H NMR [d 6 -DMSO, ppm] δ: 13.09 (s, 1H, NH). 13 C{ 1 H} NMR [d 6 -DMSO, ppm] δ: 116.75 (m, Ci-C6F5), 120.74 (q, 1 J CF = 325 Hz, CF3), 136.39, 138.35 (2m, 2 J CF = 247 Hz, m-C6F5), 137.08, 139.06 (2m, 2 J CF = 247 Hz, p-C6F5), 142.98, 144.93 (2m, 2 J CF = 247, Hz o-C6F5). 19 F NMR [d 6 -DMSO, ppm] δ: -77.45 (m, CF3), -148.12 (m, C6F5), -160.79 (m, p-C6F5), -164.51 (m, C6F5). ESI-MS: m / z-neg = 314 (MH). EI-MS: m / z = 315 (M), 182 (M-SO2CF3), 69 (CF3). Step 2: Synthesis of Bis((1,1,1-trifluoro-N-(perfluorophenyl)methyl)-sulfonamido)zinc

[0095] A 100 mL Schlenk flask is heated under vacuum and, after cooling, purified with nitrogen. 1,1,1-Trifluoro-N-(perfluorophenyl)methanesulfonamide is dissolved in 10 mL of toluene, and 0.5 eq of diethylzinc in hexane is added dropwise to the solution via a syringe at ambient temperature. During the addition, a mist forms in the flask, and the reaction solution gels and becomes cloudy. The solution is stirred continuously at this temperature for 30 minutes. Then, 30 mL of n-hexane is added, and a white precipitate forms, which is subsequently filtered through a sintered glass filter (pore size 4) under an inert atmosphere. The filter cake is washed twice with 15 mL of n-hexane and dried under high vacuum at 100 °C for 2 hours. Yield: 660 mg (0.95 mmol, 60% based on 1,1,1-trifluoro-N-perfluorophenyl)methanesulfonamide) as a white solid. 13 C{ 1 H} NMR [d 6 -DMSO, ppm] δ: 121.68 (q, 1 J CF = 328 Hz, CF3), 123.56 (m, Ci-C6F5), 133.98, 135.91 (2m, 2 J CF = 243 Hz, p-C6F5), 136.15, 138.13 (2m, 2 J CF = 249 Hz, m-C6F5), 142.33, 144.24 (2m, 2 J CF = 240, Hz o-C6F5). 19F NMR [d 6 -DMSO, ppm] δ: -77.52 (m, CF3), -150.43 (m, C6F5), -166.77 (m, C6F5), - 168.23 (m, p-C6F5). ESI-MS: m / z-neg = 314 (M-Zn-L). EI-MS: m / z = 692 (M), 559 (M-SO2CF3) 315 (C6F5NHSO2CF3), 182 (C6F5NH), 69 (CF3). Example connection E3

[0096] 9.1 g E2 is produced at a temperature of 240 °C and a pressure of 10 -3 Pa sublimates. Yield 5.9 g (65%).

[0097] The sublimated material forms colorless crystals. A crystal of a suitable shape and size (0.094 × 0.052 × 0.043 mm) 3 The sample was enclosed in a glass capillary under an argon atmosphere and analyzed on the Kappa Apex II diffractometer (Bruker-AXS, Karlsruhe, Germany) using monochromatic X-rays from a source equipped with a molybdenum cathode (λ = 71.073 pm). A total of 37,362 reflections were recorded in the theta range from 1.881° to 28.306°.

[0098] The structure was solved using a direct method (SHELXS-97, Sheldrick, 2008) and refined using a “Full-Matrix Least-Squares” method (SHELXL-2014 / 7, Olex2 (Dolomanov, 2017)). Table 1 Auxiliary materials for device examples Connection structure F1 (CAS 1242056-42-3) F2 (CAS 1440545-225-1) F3 (CAS 597578-38-6) F4 (CAS 1207671-22-4) F5 CAS 1638271-85-8 F6 CAS 721969-94-4 PD2 2,2',2" -(Cyclopropane-1,2,3-triylidene)-tris[2-(4-cyanoperfluorophenyl)acetonitrile] (CAS1224447-88-4) LiQ 8-Hydroxyquinolatolithium (CAS 850918-68-2) CN-HAT (CAS 105598-27-4)

[0099] ABH-113 is an emitter host and NUBD-370 and DB-200 are blue fluorescent emitter dots, all commercially available from SFC, Korea.

[0100] Prior to use in vacuum deposition processes, the auxiliary materials and the tested compounds were purified by preparatory vacuum sublimation. Examples of devices

[0101] Example 1 (floor-emitting white OLED pixel comprising a metal complex or metal salt as a p-dotant concentrated in an orderly hole-generating sublayer)

[0102] On a glass substrate equipped with a 90 nm thick ITO anode, a 10 nm hole injection layer was subsequently deposited, consisting of F1 doped with 8 wt% PD-2; a 140 nm thick undoped hole transport layer of ordinary F1; a 20 nm thick first emitting layer consisting of ABH113 doped with 3 wt% BD200 (both supplied by SFC, Korea); a 25 nm thick first electron transport layer of ordinary F2; and a 10 nm thick electron generating portion of the charge-generating layer (n-CGL) of F3 doped with 5 wt% PD-2.% Yb; a 2 nm thick intermediate layer of F4; a 30 nm thick hole-generating part of the charge-generating layer (p-CGL) of PB-1; a 10 nm thick second hole transport layer of ordinary F1; a 20 nm second emitting layer of the same thickness and composition as the first emitting layer; a 25 nm thick first electron transport layer of ordinary F2; a 10 nm thick electron injection layer (EIL) of F3 doped with 5 wt.% Yb; a 100 nm Al cathode.

[0103] All layers were deposited by vacuum thermal evaporation (VTE).

[0104] At a current density of 10 mA / cm² 2The operating voltage of the device (8 V) and the observed luminosity were comparable to the same device using a commercial p-dot of the state of the art instead of PB-1. A precise calibration, necessary for efficiency evaluation, was omitted from this preliminary experiment.

[0105] Example 2 (ground-emitting blue OLED pixel comprising a metal complex or metal salt as a p-dotande concentrated in a neat hole-injection sublayer)

[0106] On the same glass substrate equipped with an ITO anode as in Example 1, the following layers were subsequently deposited by VTE: a 10 nm hole injection layer of compound PB-1; a 120 nm thick HTL of ordinary F1; a 20 nm EML of ABH113 doped with 3 wt.% NUBD370 (both supplied by SFC, Korea); a 36 nm EIL / ETL of F2 doped with 50 wt.% LiQ; and a 100 nm Al cathode.

[0107] The comparison device included the HIL from the compound CN-HAT (CAS 105598-27-4) instead of PB-1.

[0108] The device according to the invention achieved a current density of 15 mA / cm². 2 and EQE 5.4% at a voltage of 5.2 V, while the comparator ran at 5.4 V with EQE 4.9%.

[0109] Example 3 (blue display pixel comprising a metal complex or metal salt as a p-dotant concentrated in a neat hole injection sublayer)

[0110] Table 2a schematically describes the model device Table 2a material c d [Weight %] [nm] ITO 100 90 p-dot 100 3* F1 100 120 ABH113: NUBD370 97:3 20 F2: LiQ 50:50 36 A1 100 100 * E3 was also tested as a layer that is only 1nm thin.

[0111] The results for LiTFSI as a reference and an example p-donor are given in Table 2b. Table 2b *j = 15 mA / cm 2 U* EQE* CIE-y* U(50 h)-U(1 h) ** **j = 30 mA / cm 2 [V] [%] [V] 3 nm LiTFSI 5,28 6,6 0,090 0,275 3 nm E3 5,38 5,7 0,094 0,246 1 nm E3 5,11 5,4 0,096 0,040

[0112] Example 4 (blue display pixel comprising a metal complex or metal salt as a p-dotande concentrated in a tidy hole-generating sublayer) Table 3a schematically describes the model device. Table 3a material c d [Weight %] [nm] ITO 100 90 F1: PD-2 92:8 10 F1 100 145 ABH113: BD200 97:3 20 F5 100 25 F6: Li 99:1 10 ZnPc 100 2 p-dot 100 1 F1 100 30 ABH113: BD200 97:3 20 F5 100 26 F6: Li 99:1 10 Al 100 100

[0113] The results for LiTFSI as a reference and an example p-donor are given in Table 3b. Table 3b *j = 10 mA / cm 2 U* EQE* CIE-y* **j = 30 mA / cm 2 [V] [%] 1 nm LiTFSI 10,65 6,3 0,066 1 nm E3 7,52 13,5 0,083

[0114] The features disclosed in the above description and in the dependent claims can, separately and in any combination, be material for implementing aspects of the disclosure made in the independent claims in various forms thereof.

[0115] Key symbols and abbreviations used in this application: CV Cyclovoltametry DSC Dynamic Differential Calorimetry EBL electron-blocking layer EIL electron injection layer EML emitter layer eq. equivalent ETL electron transport layer ETM Electron Transport Matrix FC Ferrocen FC + Ferrocenium HBL hole-blocking layer HIL Lock Injection Layer HOMO Highest occupied molecular orbital HPLC High-performance liquid chromatography HTL perforated transport layer p-HTL p-doped hole transport layer HTM Hole Transport Matrix ITO (Indium Tin Oxide) LUMO Lowest unoccupied molecular orbital mol% mol% NMR Nuclear Magnetic Resonance OLED Organic Light Emitting Diode OPV Organic Photovoltaics QE Quantum efficiency R f Retention factor in DC RGB Red-Green-Blue TCO Transparent Conductive Oxide TFT thin-film transistor T g Glass transition temperature TLC thin-layer chromatography wt.% weight percent QUOTES INCLUDED IN THE DESCRIPTION

[0000] This list of documents cited by the applicant was automatically generated and is included solely for the reader's convenience. The list is not part of the German patent or utility model application. The DPMA accepts no liability for any errors or omissions. Cited patent literature

[0000] WO 2016 / 050834 [0003, 0038, 0040, 0047] EP 15181385 [0041, 0049] EP 3133663

[0041] EP 17209023

[0043] WO 2011 / 134458 A1

[0070] US 2012223296 A1

[0070] WO 2013 / 135237 A1

[0070] WO 2014 / 060526 A1

[0070] EP 1970371 A1

[0074] WO 2013 / 079217 A1

[0074] Zitierte Nicht-Patentliteratur

[0000] Journal of Organic Chemistry (2011), 76(2), 391-395

[0013] Chung et al. (2006), 70.1: Invited Paper: Large-Sized Full Color AMOLED TV: Advancements and Issues. SID Symposium Digest of Technical Papers, 37: 1958-1963. doi: 10.1889 / 1.2451418

[0072] Lee et al. (2009), 53.4: Development of 31-Inch Full-HD AMOLED TV Using LTPS-TFT and RGB FMM. SID Symposium Digest of Technical Papers, 40: 802-804. doi: 10.1889 / 1.3256911

[0072]

Claims

[1] Electronic device comprising at least one first hole transport layer between a first electrode and a second electrode, wherein the first hole transport layer comprises: (i) at least one first hole transport matrix compound consisting of covalently bonded atoms, and (ii) at least one electrical p-dotande selected from metal salts and from electrically neutral metal complexes comprising a metal cation and at least one anion and / or at least one anionic ligand consisting of at least 4 covalently bonded atoms, wherein the metal cation of the electrical p-dotande is selected from: Alkali metals; Alkali earth metals, Pb, Mn, Fe, Co, Ni, Zn, Cd; Rare earth metals in oxidation state (II) or (III); Al, Ga, In; and from Sn, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo and W in oxidation state (IV) or less; wherein a) p-dotandes having an anion or an anionic ligand having generic formula (Ia) or (Ib) wherein A 1 , A 2 , A 3 and A 4 independent of CO, SO2 or POR 1 are chosen; R 1 = electron-withdrawing group, chosen from the group comprising halide, nitrile, halogenated or perhalogenated C1- to C 20 -Alkyl, halogenated or perhalogenated C6- to C 20 -Aryl, or halogenated or perhalogenated heteroaryl with 5 to 20 ring-forming atoms;B 1 , B 2 , B 3 are B 4 are chosen equally or independently from substituted or unsubstituted C1- to C 20 -Alkyl, substituted or unsubstituted C1- to C 20 -Heteroalkyl, substituted or unsubstituted C6- to C 20 -Aryl, substituted or unsubstituted C5- to C 20 -Heteroaryl, or B 1 and B2 form a ring; and b) p-doping consisting of a Li cation and an anion selected from perchlorate and tetrafluoroborate are excluded, and The first hole transport layer comprises a sublayer, wherein the electrical dopant is contained in an amount, by weight and / or by volume, that exceeds the total amount of other components that may also be contained in the sublayer. [2] Electronic device according to claim 1, wherein the sublayer comprises the p-dot in an amount of at least 60 wt. 96, alternatively at least 75 wt.%, alternatively at least 90 wt.%, alternatively at least 95 wt.%, alternatively at least 98 wt.%, alternatively at least 99 wt.%, alternatively at least 99.5 wt.%, alternatively at least 99.9 wt.96, with respect to the total weight of the sublayer. [3] Electronic device according to one of the preceding claims, wherein the anion and / or the anionic ligand consists of at least 5, preferably at least 6, better at least 7, better at least 8, preferably at least 9 covalently bonded atoms. [4] Electronic device according to any of the preceding claims, wherein the anion and / or the anionic ligand comprises at least one atom selected from B, C, N. [5] Electronic device according to any of the preceding claims, wherein the anion and / or the anionic ligand comprises at least two atoms selected from B, C and N, which are bonded to each other by a covalent bond. [6] Electronic device according to any of the preceding claims, wherein the anion and / or the anionic ligand comprises at least one peripheral atom selected from H, N, O, F, Cl, Br and I. [7] Electronic device according to any of the preceding claims, wherein the anion and / or the anionic ligand comprises at least one electron-withdrawing group selected from halogenated alkyl, halogenated (hetero)aryl, halogenated (hetero)arylalkyl, halogenated alkylsulfonyl, halogenated (hetero)arylsulfonyl, halogenated (hetero)arylalkylsulfonyl, cyano. [8] Electronic device according to claim 7, wherein the electron-withdrawing group is a perhalogenated group. [9] Electronic device according to claim 8, wherein the perhalogenated electron-withdrawing group is a perfluorinated group. [10] Electronic device according to any of the preceding claims, wherein the metal cation of the p-doping is selected from Li(I), Na(I), K(I), Rb(I), Cs(I); Mg(II), Ca(II), Sr(II), Ba(II), Sn(II), Pb(II), Mn(II), Fe(II), Co(II), Ni(II), Zn(II), Cd(II), Al(III); rare earth metal in the oxidized state (III), V(III), Nb(III), Ta(III), Cr(III), Mo(III), W(III) Ga(III), In(III) and from Ti(IV), Zr(IV), Hf(IV), Sn(IV). [11] Electronic device according to any one of claims 4 to 10, wherein in the p-doped molecule the atom of the anion and / or the anionic ligand that is closest to the metal cation is a C or an N atom. [12] Electronic device according to any of the preceding claims, wherein the acidity of the electrically neutral conjugated acid formed from the anion and / or the anionic ligand by the addition of one or more protons in 1,2-dichloroethane is higher than that of HCl, preferably higher than that of HBr, better higher than that of HI, even better higher than that of fluorosulfuric acid, and best of all higher than that of perchloric acid, wherein the measurement of the acidity in 1,2-dichloroethane is carried out according to the disclosure in the Journal of Organic Chemistry (2011), 76(2), 391-395. [13] Electronic device according to one of the preceding claims, wherein the electrical p-doped has an energy level of its lowest unoccupied molecular orbital which, expressed by standard quantum chemical methods and on an absolute vacuum scale, is at least 0.5 eV, preferably at least 0.6 eV, better at least 0.8 eV, even better at least 1.0 eV, best at least 1.2 eV above the energy level of the highest occupied orbital of the covalent hole transport compound calculated by the standard quantum chemical method, wherein the standard quantum chemical method uses the TURBOMOLE software package using the DFT functional B3LYP with the basis set def2-TZVP. [14] Electronic device according to one of the preceding claims, wherein the first hole transport matrix compound is an organic compound, preferably an organic compound comprising a conjugated system of at least 6, preferably at least 10 delocalized electrons; furthermore, the first hole transport matrix compound preferably comprises at least one triarylamine structural part, and better, the first hole transport matrix compound comprises at least two triarylamine structural parts. [15] Electronic device according to any of the preceding claims, wherein the electronic device is an organic electroluminescent device, an organic transistor, or an organic photovoltaic device. [16] Electronic device according to one of the preceding claims, wherein all layers between the first and second electrodes and the electrode deposited on the last organic layer are deposited by vacuum deposition at a pressure below 1×10 -3 Pa, preferably at a pressure below 5×10 -4 Pa, better at a pressure below 1×10 -4 Pa can be prepared. [17] Method for manufacturing the electronic device according to one of the preceding claims, wherein the method comprises at least one step in which the covalent hole transport matrix compound and the electrical p-doping agent are in mutual contact and are exposed to a temperature above 50 °C. [18] Method according to claim 18, further comprising a step in which the p-doping agent is evaporated at reduced pressure, preferably at a pressure below 1×10 -2Pa and at a temperature above 50 °C, preferably at a pressure below 5×10 -2 Pa and at a temperature above 80 °C, even better at a pressure below 1×10 -3 Pa and at a temperature above 120 °C, ideally at a pressure below 5×10 -4 Pa and at a temperature above 150 °C.

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