An organic electronic device and a metal complex for use in the organic electronic device or layer of the organic electronic device

Abstract

The present invention relates to an organic electronic device comprising a substrate, an anode layer, a cathode layer, at least one emitter layer, and at least one or more hole injection layers, wherein the hole injection layers are disposed between the anode layer and the at least one emitter layer, and wherein the hole injection layers comprise metal complexes.

Description

[Technical Field]

[0001] The present invention relates to an organic electronic device comprising a substrate, an anode layer, a cathode layer, at least one first emission layer and at least one hole injection layer comprising a metal complex. [Previous Technology]

[0002] Organic electronic devices that are self-emissive (e.g., organic light-emitting diodes, OLEDs) possess wide viewing angles, excellent contrast ratios, fast response times, high brightness, excellent operating voltage characteristics, and color reproduction. A typical OLED comprises, in sequence, an anode layer, a hole injection layer (HIL), a hole transport layer (HTL), an emitter layer (EML), an electron transport layer (ETL), and a cathode layer stacked on a substrate. In this respect, HIL, HTL, EML, and ETL are thin films formed from organic compounds.

[0003] When a voltage is applied to the anode and cathode, holes injected from the anode move to the EML via the HIL and HTL, and electrons injected from the cathode move to the EML via the ETL. The holes and electrons recombine in the EML to generate excitons. When the excitons descend from the excited state to the ground state, they emit light. The injection and flow of holes and electrons should be balanced to ensure that the OLED with the above structure has a low operating voltage, excellent efficiency, and / or a long lifetime.

[0004] The performance of organic light-emitting diodes may be affected by the characteristics of the hole injection layer, which may be affected by the characteristics of the hole transport compounds and metal complexes contained in the hole injection layer.

[0005] WO2017029370 relates to metal amides of general formula Ia and their use as hole injection layers (HILs) in organic light-emitting diodes (OLEDs), and a method for manufacturing an OLED including a hole injection layer comprising a metal amide as defined.

[0006] WO2017029366 relates to a hole injection layer for OLEDs, comprising a triarylamine compound doped with a charge-neutralized metal amide compound, characterized in that the hole injection layer has a thickness of at least about ≥20 nm to about ≤1000 nm and the defined charge-neutralized metal amide compound.

[0007] WO2017102861 relates to an organic electronic element comprising at least one organic layer having a fluorinated sulfonamide metal salt of the following formula 1: (1) wherein M is a divalent or higher metal having an atomic mass greater than 26 g / mol or a monovalent metal having an atomic mass greater than or equal to 39 g / mol, wherein 1 ≤ n ≤ 7, and wherein R1 and R2 are independently selected from the group consisting of fluorinated aryl radicals, fluorinated alkyl radicals and fluorinated aryl-alkyl radicals.

[0008] It is still necessary to improve the performance of organic electronic devices by providing a hole injection layer with improved performance, especially by improving the characteristics of the hole injection layer and the organic electronic device to achieve improved operating voltage.

[0009] In addition, it is still necessary to provide a hole injection layer that can be injected into an adjacent layer, which includes compounds whose HOMO energy level is far from the vacuum energy level.

[0010] A further objective is to provide a hole-injection layer comprising a compound that can be deposited via vacuum thermal evaporation under conditions suitable for mass production. [Summary of the Invention]

[0011] One aspect of the present invention provides an organic electronic device comprising a substrate, an anode layer, a cathode layer, at least one emitter layer, and at least one or more hole injection layers, wherein the hole injection layers are disposed between the anode layer and the at least one emitter layer, and wherein the hole injection layers comprise: - a metal complex having formula (I): (I) where M is a metal ion; n is the valence of M; m is n; L is a ligand (II) of formula (II), where A1 and A2 are SO2; X is N; B1 and B2 are independently selected from substituted C6 to C19 aryl or substituted or unsubstituted C2 to C20 heteroaryl, wherein at least one substituent of the substituted C6 to C19 aryl or substituted C2 to C20 heteroaryl is independently selected from halogens, Cl, F, CN, partially or perfluoro C1 to C8 alkyl, partially or perfluoro C1 to C8 alkoxy; and - a compound of formula (III) or (IV): (III) Or (IV), wherein T1, T2, T3, T4 and T5 are independently selected from single bonds, phenyl, biphenyl, triphenyl or naphthenylene, preferably single bonds or phenyl; T6 is selected from substituted or unsubstituted phenyl, biphenyl, triphenyl or naphthenylene, wherein the substituent on the phenyl group is selected from C6 to C18 aryl, C3 to C18 heteroaryl, phenyl, biphenyl, carbazole, phenylcarbazole, preferably biphenyl or 9-phenylcarbazole;Ar1, Ar2, Ar3, Ar4, and Ar5 are independently selected from: substituted or unsubstituted C6 to C20 aryl groups, or substituted or unsubstituted C3 to C20 heteroaryl groups, substituted or unsubstituted biphenyls, substituted or unsubstituted phenanthrene, substituted or unsubstituted 9-phenanthrene, substituted 9,9-phenanthrene, substituted or unsubstituted naphthalene, substituted or unsubstituted anthracene, substituted or unsubstituted phenanthrene, substituted or unsubstituted pyrene, substituted or unsubstituted perylene, substituted or unsubstituted triphenylene, substituted or unsubstituted tetraphenylene, substituted or unsubstituted tetraphenylene, substituted or unsubstituted tetraphenylene, substituted... Substituted or unsubstituted dibenzofuran, substituted or unsubstituted dibenzothiophene, substituted or unsubstituted dibenzopiperan, substituted or unsubstituted carbazole, substituted 9-phenylcarbazole, substituted or unsubstituted aziridine, substituted or unsubstituted dibenzo[b,f]aziridine, substituted or unsubstituted 9,9'-spirodi[fu], substituted or unsubstituted 9,9'-spirodi[fu] having at least one fused aromatic ring, substituted or unsubstituted spiro[fu]-9,9'-dibenzopiperan, comprising two aromatic 6-membered rings and two aromatic 5-membered rings, wherein at least one of the 5-membered rings is a 5-membered ring. The fused rings include substituted or unsubstituted aromatic fused ring systems with heteroatoms, substituted or unsubstituted aromatic fused ring systems with two aromatic 6-membered rings and two aromatic 5-membered rings, wherein at least one 5-membered ring includes an O atom, or substituted or unsubstituted aromatic fused ring systems with at least three substituted or unsubstituted aromatic rings selected from the group consisting of: substituted or unsubstituted non-hetero-5-membered rings, substituted or unsubstituted hetero-5-membered rings, substituted or unsubstituted 6-membered rings and / or substituted or unsubstituted 7-membered rings. Substituted or unsubstituted cyclohexane, substituted or unsubstituted heterocyclic or non-heterocyclic system comprising 2 to 6 substituted or unsubstituted 5, 6 or 7-membered rings, or fused ring system comprising 2 to 6 substituted or unsubstituted 5 to 7-membered rings, wherein the substituted or unsubstituted 5 to 7-membered rings are selected from the group consisting of: (i) unsaturated 5 to 7-membered heterocyclic rings, (ii) 5 to 6-membered aromatic heterocyclic rings, (iii) unsaturated 5 to 7-membered non-heterocyclic rings, and (iv) 6-membered aromatic non-heterocyclic rings.The substituents of Ar1, Ar2, Ar3, Ar4, and Ar5 are selected from the group consisting of the same or different groups including: H, D, F, C(=O)R2, CN, Si(R2)3, P(=O)(R2)2, OR2, S(=O)R2, S(=O)2R2, substituted or unsubstituted linear alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted branched alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 20 carbon atoms, and substituted or unsubstituted alkenyl or ynyl groups having 2 to 20 carbon atoms. The following are included: substituted or unsubstituted alkoxy groups having 1 to 20 carbon atoms; substituted or unsubstituted aromatic ring systems having 6 to 40 aromatic ring atoms; substituted or unsubstituted heteroaromatic ring systems having 5 to 40 aromatic ring atoms; unsubstituted C6 to C18 aryl groups; unsubstituted C3 to C18 heteroaromatic groups; and fused ring systems comprising 2 to 6 unsubstituted 5 to 7-membered rings, wherein the 5 to 7-membered rings are selected from the group consisting of unsaturated 5 to 7-membered heterocycles, 5 to 6-membered aromatic heterocycles, unsaturated 5 to 7-membered non-heterocycles, and 6-membered aromatic non-heterocycles. R2 is selected from H, D, straight-chain alkyl groups having 1 to 6 carbon atoms, branched alkyl groups having 1 to 6 carbon atoms, cycloalkyl groups having 3 to 6 carbon atoms, alkenyl or ynyl groups having 2 to 6 carbon atoms, C6 to C18 aryl or C3 to C18 heteroaryl groups; When the HOMO is calculated using TURBOMOLE V6.5 (TURBOMOLE GmbH, Litzenhardtstrasse 19, 76135 Karlsruhe, Germany) by applying the mixing function B3LYP with a 6-31G* basis set in the gas phase, the compounds of formula (III) or (IV) have calculated HOMO values ​​in the range of <-4.79 eV and >6.5 eV.

[0012] Note that the ligand L has a negative charge.

[0013] According to one embodiment, the negative charge of the ligand L may correspond to the valence of the metal ion M.

[0014] According to one embodiment of the organic electronic device, the following compounds E1 to E5 are excluded from the hole injection layer of the organic electronic device:

[0015] According to one embodiment of the organic electronic device, the following compounds named with CAS numbers are excluded from the hole injection layer of the organic electronic device: 1835250-94-6, 139255-16-6, 174141-92-5, 948552-24-7, 139092-78-7, 1458062-55-9, 2417957-16-3, 2417957-19-6, 58328-31-7, and / or 1643480-23-2.

[0016] According to one embodiment of the organic electronic device, the hole injection layer of the organic electronic device may be free of metal phthalocyanine or CuPc, or the layer of the organic electronic device may be free of metal phthalocyanine or CuPc. Preferably, the hole injection layer may be free of ionic liquids, metal phthalocyanine, CuPc, HAT-CN, pyrazino[2,3-f][1,10]phenanthroline-2,3-dinitrile, F4TCNQ, metal fluorides and / or metal oxides, wherein the metal in the metal oxide is selected from Re and / or Mo. Definition

[0017] It should be noted that, throughout this application and the scope of the patent application, any of An, Arn, Rn, Tn, etc., always refers to the same part, unless otherwise stated.

[0018] In this specification, unless otherwise defined, "substituted" means a substituent substituted with deuterium, C1 to C12 alkyl and C1 to C12 alkoxy groups.

[0019] In this specification, unless otherwise defined, a substituted aryl group having at least 6 C-ring atoms may be substituted with 1, 2, 3, 4 or 5 substituents. For example, a substituted C6 aryl group may have 1, 2, 3, 4 or 5 phenyl substituents.

[0020] However, in this specification, "aryl-substituted" means substitution of one or more aryl groups, which are themselves replaced by one or more aryl and / or heteroaryl groups.

[0021] Correspondingly, in this specification, "heteroaryl substituted" means that there is one or more heteroaryl substitutions, which are themselves replaced by one or more aryl and / or heteroaryl groups.

[0022] In this specification, unless otherwise defined, a substituted heteroaryl group having at least two C ring atoms may be substituted with one or more substituents. For example, a substituted C2 heteroaryl group may have one or two substituents.

[0023] In this specification, unless otherwise defined, "alkyl group" refers to a saturated aliphatic hydrocarbon group. The alkyl group may be a C1 to C12 alkyl group. More specifically, the alkyl group may be a C1 to C10 alkyl group or a C1 to C6 alkyl group. For example, C1 to C4 alkyl groups include 1 to 4 carbons in the alkyl chain and may be selected from methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, secondary butyl, and tertiary butyl.

[0024] Specific examples of alkyl groups may be methyl groups, ethyl groups, propyl groups, isopropyl groups, butyl groups, isobutyl groups, secondary butyl groups, tertiary butyl groups, pentyl groups, branched pentyl groups, and hexyl groups.

[0025] The term "cycloalkyl" refers to a saturated hydrocarbon group derived from a cycloalkane by removing a hydrogen atom from the ring atom form included in the corresponding cycloalkane. Examples of cycloalkyl groups may be cyclopropyl groups, cyclobutyl groups, cyclopentyl groups, cyclohexyl groups, methylcyclohexyl groups, adamantyl groups, and the like.

[0026] The term "heteroatom" is understood to mean that at least one carbon atom in a structure formed by covalently bonded carbon atoms is replaced by another polyvalent atom. Preferably, the heteroatom is selected from B, Si, N, P, O, and S; more preferably, it is selected from N, P, O, and S.

[0027] Preferred examples of hole-transporting compounds that can be covalent hole-transporting compounds are organic compounds composed of or substantially composed of covalently bonded C, H, O, N, and S, and may also optionally include covalently bonded B, P, or Si. In one embodiment, the hole-transporting compound that can be a covalent compound has no metal atoms, and most of its framework atoms are selected from C, O, S, and N. Alternatively, the covalent compound has no metal atoms, and most of its framework atoms are selected from C and N.

[0028] In this specification, "aryl group" and "aromatic ring" refer to hydrocarbon groups that can be formally abstracted from a hydrogen atom of an aromatic ring in the corresponding aromatic hydrocarbon. An aromatic hydrocarbon refers to a hydrocarbon containing at least one aromatic ring or aromatic ring system. An aromatic ring or aromatic ring system refers to a planar ring or ring system of covalently bonded carbon atoms, wherein the planar ring or ring system includes a conjugated system of nonlocalized electrons satisfying Hückel's rule. Examples of aryl groups include: monocyclic groups, such as phenyl or tolyl; polycyclic groups comprising more aromatic rings linked by single bonds, such as biphenyl; and polycyclic groups comprising fused rings, such as naphthyl or fumonisinyl.

[0029] Similarly, under “heteroaryl” and “heteroaromatic”, it is particularly suitable to understand that a group derived from a cyclic hydrogen of a heterocyclic aromatic ring in a compound comprising at least one heterocyclic aromatic ring is used.

[0030] The term "non-heterocyclic" is understood to mean a ring or ring system that does not include heteroatoms as ring members.

[0031] The term "heterocycle" is understood to mean that a heterocycle includes at least one ring, which includes one or more heteroatoms. A heterocycle including more than one ring means all rings that include heteroatoms, or at least one ring that includes heteroatoms, and at least one ring that includes only C atoms and does not include heteroatoms.

[0032] In the case of heterocyclic alkyl groups, it is particularly suitable to understand the derivation of a group derived from a cyclic hydrogen of a saturated cycloalkyl ring in a compound comprising at least one saturated cycloalkyl ring.

[0033] The terms "fused aryl ring" or "condensed aryl ring" are understood to mean that when two aryl rings share at least two common sp2- atoms to form carbon atoms, the two aryl rings are considered to be fused or condensed.

[0034] The term "fused ring system" is understood to mean a ring system in which two or more rings share at least two atoms.

[0035] The term "5, 6 or 7-membered ring" is understood to mean a ring consisting of 5, 6 or 7 atoms. The atoms may be selected from C and one or more heteroatoms.

[0036] In this specification, a single key refers to a direct key.

[0037] In this specification, unless otherwise defined, “substituted” means a substituent substituted with H, deuterium, C1 to C12 alkyl, unsubstituted C6 to C18 aryl, and unsubstituted C2 to C18 heteroaryl.

[0038] In this specification, when the substituent is not named, the substituent may be H.

[0039] In the context of this invention, "different" means that the compounds do not have the same chemical structure.

[0040] The terms "without", "does not contain", and "does not include" do not exclude impurities that may be present in the compound prior to deposition. Impurities have no technical impact on the objective of this invention.

[0041] The term "contacting sandwiched" refers to a three-layer configuration in which the middle layer is in direct contact with the two adjacent layers.

[0042] The terms “light-absorbing layer” and “light absorption layer” are used synonymously.

[0043] The terms "light-emitting layer", "light emission layer" and "emission layer" are used synonymously.

[0044] The terms "OLED", "organic light-emitting diode" and "organic light-emitting device" are used synonymously.

[0045] The terms anode, anode layer and anode electrode are used synonymously.

[0046] The term "at least two anode sublayers" is understood to mean two or more anode sublayers, for example, two or three anode sublayers. The terms cathode, cathode layer and cathode electrode are used synonymously.

[0047] The term "hole injection layer" is understood to mean a layer that improves the injection of charge from the anode layer into other layers of an organic electronic device or from other layers of an organic electronic device into the anode.

[0048] The term "hole transport layer" is understood to mean the layer that transports holes between the hole injection layer and other layers disposed between the hole injection layer and the cathode layer.

[0049] The operating voltage U is measured in volts.

[0050] In the context of this specification, the terms "substantially non-emissive" or "non-emissive" mean that the matrix compound of formula (III) or (IV), the metal complex (I), and / or a layer such as a hole injection layer contributes less than 10%, preferably less than 5%, to the visible emission spectrum of an organic electronic device (e.g., an OLED or a display device). The visible emission spectrum is an emission spectrum with a wavelength of about ≥380 nm to about ≤780 nm.

[0051] In the specification, the hole characteristic refers to the ability to form a hole by giving electrons when an electric field is applied, and the ability of the hole formed in the anode to be easily injected into the emitter layer and transported in the emitter layer due to its conductivity, based on the highest occupied molecular orbital (HOMO) energy level.

[0052] Furthermore, electronic properties refer to the following capabilities: when an electric field is applied, it accepts electrons, and based on the lowest unoccupied molecular orbital (LUMO) energy level, due to its conductivity, electrons formed in the cathode can be easily injected into the emitter layer and transported in the emitter layer.

[0053] The term "HOMO level" is understood to refer to the highest occupied molecular orbital, and it is measured in eV (electron volts).

[0054] The phrase “HOMO level that deviates further from the vacuum level” is understood to mean that the absolute value of the HOMO level is higher than that of the reference compound. For example, the phrase “more deviating from the vacuum level than the HOMO level of N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-N-(4-(9-phenyl-9H-carbazole-3-yl)phenyl)-9H-furon-2-amine” is understood to mean that the absolute value of the HOMO level of the hole-injected layer is higher than that of the HOMO level of N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-N-(4-(9-phenyl-9H-carbazole-3-yl)phenyl)-9H-furon-2-amine”.

[0055] The term "absolute value" is understood to mean a value without a "-" sign. According to one embodiment of the present invention, the HOMO energy level of the hole injection layer can be calculated by quantum mechanical methods.

[0056] The work function of the first metal is measured in eV (electron volts). For example, a list of work function values ​​can be found on pages 12-114 of the CRC Handbook of Chemistry and Physics, version 2008. Furthermore, a list of work function values ​​can be found, for example, at https: / / en.wikipedia.org / wiki / Work_function#cite_note-12. Beneficial effects

[0057] Surprisingly, it has been found that by implementing organic electronic devices (e.g., organic light-emitting diodes), which are superior to known organic electronic devices in the art in all respects, particularly regarding operating voltage, efficiency, and / or voltage stability over time, the organic electronic devices according to the invention solve the problems of the invention. Further embodiments

[0058] It has also been found that, under conditions suitable for mass production, the problems in this invention can be solved by providing compounds suitable for deposition via vacuum thermal evaporation. In particular, the rate-starting temperature of the metal complexes of this invention is within a range suitable for mass production.

[0059] According to another embodiment, an organic electronic device includes a substrate, an anode layer including at least three anode sublayers, a cathode layer, at least one first emission layer, and a hole injection layer, wherein the hole injection layer includes: - a metal complex having formula (I): (I), wherein M is a metal ion, n is the valence of M and is an integer from 1 to 4, m is n, L is a ligand (II) of formula (II), wherein A1 and A2 are SO2; X is N; B1 and B2 are independently selected from substituted C6 to C19 aryl or substituted or unsubstituted C2 to C20 heteroaryl, wherein at least one of the substituents of the substituted C6 to C19 aryl or substituted C2 to C20 heteroaryl is independently selected from halogen, Cl, F, CN, partially or perfluoro C1 to C8 alkyl, partially or perfluoro C1 to C8 alkoxy; and wherein the charge-neutral form of M has an optional electronegativity of less than 2.4 according to Allen; And compounds of formula (III) or (IV): (III) or (IV), wherein T1, T2, T3, T4 and T5 are independently selected from single bonds, phenyl, biphenyl, triphenyl or naphthylmethylene, preferably single bonds or phenyl; T6 is selected from substituted or unsubstituted phenyl, biphenyl, triphenyl or naphthylmethylene, wherein the substituent on the phenyl group is selected from C6 to C18 aryl, C3 to C18 heteroaryl, phenyl, biphenyl, carbazole, phenylcarbazole, preferably biphenyl or 9-phenylcarbazole;Ar1, Ar2, Ar3, Ar4, and Ar5 are independently selected from: substituted or unsubstituted C6 to C20 aryl groups, or substituted or unsubstituted C3 to C20 heteroaryl groups, substituted or unsubstituted biphenyls, substituted or unsubstituted phenanthrene, substituted or unsubstituted 9-phenanthrene, substituted 9,9-phenanthrene, substituted or unsubstituted naphthalene, substituted or unsubstituted anthracene, substituted or unsubstituted phenanthrene, substituted or unsubstituted pyrene, substituted or unsubstituted perylene, substituted or unsubstituted triphenylene, substituted or unsubstituted tetraphenylene, substituted or unsubstituted tetraphenylene, substituted or unsubstituted tetraphenylene, substituted... Substituted or unsubstituted dibenzofuran, substituted or unsubstituted dibenzothiophene, substituted or unsubstituted dibenzopiperan, substituted or unsubstituted carbazole, substituted 9-phenylcarbazole, substituted or unsubstituted aziridine, substituted or unsubstituted dibenzo[b,f]aziridine, substituted or unsubstituted 9,9'-spirodi[fu], substituted or unsubstituted 9,9'-spirodi[fu] having at least one fused aromatic ring, substituted or unsubstituted spiro[fu]-9,9'-dibenzopiperan, comprising two aromatic 6-membered rings and two aromatic 5-membered rings, wherein at least one of the 5-membered rings is a 5-membered ring. The fused rings include substituted or unsubstituted aromatic fused ring systems with heteroatoms, substituted or unsubstituted aromatic fused ring systems with two aromatic 6-membered rings and two aromatic 5-membered rings, wherein at least one 5-membered ring includes an O atom, or substituted or unsubstituted aromatic fused ring systems with at least three substituted or unsubstituted aromatic rings selected from the group consisting of: substituted or unsubstituted non-hetero-5-membered rings, substituted or unsubstituted hetero-5-membered rings, substituted or unsubstituted 6-membered rings and / or substituted or unsubstituted 7-membered rings. Substituted or unsubstituted cyclohexane, substituted or unsubstituted heterocyclic or non-heterocyclic system comprising 2 to 6 substituted or unsubstituted 5, 6 or 7-membered rings, or fused ring system comprising 2 to 6 substituted or unsubstituted 5 to 7-membered rings, wherein the substituted or unsubstituted 5 to 7-membered rings are selected from the group consisting of: (i) unsaturated 5 to 7-membered heterocyclic rings, (ii) 5 to 6-membered aromatic heterocyclic rings, (iii) unsaturated 5 to 7-membered non-heterocyclic rings, and (iv) 6-membered aromatic non-heterocyclic rings.The substituents of Ar1, Ar2, Ar3, Ar4, and Ar5 are selected from the group consisting of the same or different groups including: H, D, F, C(=O)R2, CN, Si(R2)3, P(=O)(R2)2, OR2, S(=O)R2, S(=O)2R2, substituted or unsubstituted linear alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted branched alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 20 carbon atoms, and substituted or unsubstituted alkenyl or ynyl groups having 2 to 20 carbon atoms. The following are included: substituted or unsubstituted alkoxy groups having 1 to 20 carbon atoms; substituted or unsubstituted aromatic ring systems having 6 to 40 aromatic ring atoms; substituted or unsubstituted heteroaromatic ring systems having 5 to 40 aromatic ring atoms; unsubstituted C6 to C18 aryl groups; unsubstituted C3 to C18 heteroaromatic groups; and fused ring systems comprising 2 to 6 unsubstituted 5 to 7-membered rings, wherein the 5 to 7-membered rings are selected from the group consisting of unsaturated 5 to 7-membered heterocycles, 5 to 6-membered aromatic heterocycles, unsaturated 5 to 7-membered non-heterocycles, and 6-membered aromatic non-heterocycles. R2 is selected from H, D, straight-chain alkyl groups having 1 to 6 carbon atoms, branched alkyl groups having 1 to 6 carbon atoms, cycloalkyl groups having 3 to 6 carbon atoms, alkenyl or ynyl groups having 2 to 6 carbon atoms, C6 to C18 aryl or C3 to C18 heteroaryl; wherein the compound of formula (III) or (IV) has a calculated HOMO in the range of <-4.79 eV and >6.5 eV; and wherein - the first anode sublayer comprises a first metal having a work function in the range of ≥4 and ≤6 eV, - the second anode sublayer comprises a transparent conductive oxide (TCO); and - the third anode sublayer preferably comprises a transparent conductive oxide, wherein the first anode sublayer is positioned closer to the substrate, the second anode sublayer is positioned closer to the hole injection layer; and the third anode sublayer is disposed between the substrate and the first anode sublayer. Anode layer;

[0060] The anode layer can be formed by deposition or sputtering of a material used to form the anode layer. The material used to form the anode layer can be a high work function material to promote hole injection. The anode material can also be selected from low work function materials (i.e., aluminum). The anode electrode can be a transparent or reflective electrode. Transparent conductive oxides, such as indium tin oxide (ITO), indium zinc oxide (IZO), tin dioxide (SnO2), aluminum zinc oxide (AlZO), and zinc oxide (ZnO), can be used to form the anode electrode. Metals (typically silver (Ag), gold (Au), or metal alloys) can also be used to form the anode layer.

[0061] According to one embodiment, the anode layer includes a first anode sublayer and a second anode sublayer, wherein - the first anode sublayer includes a first metal having a work function in the range of ≥4 and ≤6 eV, and - the second anode sublayer includes a transparent conductive oxide, preferably a TCO.

[0062] According to one embodiment, the anode layer includes a first anode sublayer and a second anode sublayer, wherein - the first anode sublayer includes a first metal having a work function in the range of ≥4 and ≤6 eV, and - the second anode sublayer includes a transparent conductive oxide, preferably ITO.

[0063] According to one embodiment, the anode layer may include a first anode sublayer, a second anode sublayer, and an optional third anode sublayer, wherein the first anode sublayer includes or is composed of Ag or Au, the second anode sublayer includes or is composed of ITO or IZO, and the third anode sublayer includes or is composed of ITO or IZO.

[0064] The anode layer of the organic electronic device further includes a third anode sublayer; wherein the third anode sublayer preferably includes a transparent conductive oxide, and wherein the third anode sublayer is disposed between the substrate and the first anode sublayer.

[0065] Preferably, the first anode sublayer may include or be composed of Ag, the second anode sublayer may include or be composed of ITO, and the third anode sublayer may include or be composed of ITO. Preferably, the transparent conductive oxides in the second and third anode sublayers may be the same. The transparent conductive oxide may be selected from the group consisting of indium tin oxide or indium zinc oxide, and more preferably indium tin oxide (ITO).

[0066] According to one embodiment, the anode layer may include a first anode sublayer, a second anode sublayer, and a third anode sublayer. The first anode sublayer comprises Ag or Au and has a thickness of 100 to 150 nm, the second anode sublayer comprises ITO or IZO and has a thickness of 3 to 20 nm, and the third anode sublayer comprises ITO or IZO and has a thickness of 3 to 20 nm. Formula I metal complex

[0067] According to one embodiment, the metal complex according to formula (I) is non-emissive.

[0068] According to one embodiment, n in formula (I) is an integer from 1 to 4, preferably from 1 to 3, and also preferably from 2 or 3. Preferably, m and n in formula (I) are the same and are integers from 1 to 4, preferably from 1 to 3, and also preferably from 2 or 3.

[0069] According to one embodiment, at least one or both of the B1 and B2 groups each include at least 1 to 5 substituents, preferably 2 to 4 or 2 to 3 substituents, wherein the substituents are independently selected from halogens, F, CF3, C2F5, C3F7, C4F9, OCF3, OC2F5 or CN. Formula Ia metal complex

[0070] According to one embodiment, the metal complex is selected from formula (Ia): (Ia), where M is a metal ion; n is the valence of M; m is n; B1 and B2 are independently selected from substituted C6 to C19 aryl groups, or substituted or unsubstituted C2 to C20 heteroaryl groups, wherein at least one of the substituents of the substituted C6 to C19 aryl groups or the substituted C2 to C20 heteroaryl groups is independently selected from halogens, Cl, F, CN, partially or perfluoro C1 to C8 alkyl groups, and partially or perfluoro C1 to C8 alkoxy groups.

[0071] According to one embodiment, at least one or both of the B1 and B2 groups each include at least 1 to 5 substituents, preferably 2 to 4 or 2 to 3 substituents, which are independently selected from halogens, F, CF3, C2F5, C3F7, C4F9, OCF3, OC2F5 or CN.

[0072] According to one embodiment, the metal complex of formula (I) is selected from compounds W1 to W12: (W1), (W2), (W3), (W4), (W5), (W6), (W7), (W8), (W9), (W10), (W11), (W12). The ligand L of formula (II)

[0073] According to one embodiment, the ligand L of formula (II) can be selected from G1 to G21: (G1), (G2), (G3), (G4), (G5), (G6), (G7), (G8), (G9), (G10), (G11), (G12), (G13), (G14), (G15), (G16), (G17), (G18), (G19), (G20), (G21).

[0074] According to one embodiment, L in formula (II) is selected from the group consisting of (G1) to (G13) and (G15) to (G21), and preferably from the group consisting of (G2), (G6), (G7), (G11), (G15), (G17), (G19) to (G21).

[0075] According to one embodiment, M is Ag, n is 1, m is 1, and L is selected from the group consisting of (G1) to (G13) and (G15) to (G21), preferably from the group consisting of (G1), (G3) to (G13) and (G15) to (G21).

[0076] According to one embodiment, M is Cu, n is 2, m is 2, and L is selected from the group consisting of (G1) to (G13) and (G15) to (G21), preferably from the group consisting of (G3) to (G13) and (G15) to (G21).

[0077] According to one embodiment, M is Li, Na, K, Rb, Cs, n is 1, m is 1, and L is selected from the group consisting of (G1) to (G13), (G15) to (G18) and (G20) to (G21), preferably selected from the group consisting of (G1), (G3) to (G13), (G15), (G16) and (G21).

[0078] According to one embodiment, M is Li, n is 1, m is 1, and L is selected from the group consisting of (G1) to (G13), (G15) to (G18) and (G20) to (G21), preferably from the group consisting of (G1), (G3) to (G13), (G15), (G16) and (G21).

[0079] In the metal complexes of formula (I) and (Ia), the negative charge may be partially or completely delocalized on the A1 and A2 groups, and optionally also partially or completely delocalized on the B1 and B2 groups. The M of the metal complexes of formula (I) or (Ia)

[0080] The metal complexes according to formula (I) or formula (Ia) are non-emissive.

[0081] In the context of this specification, the terms "substantially non-emissive" or "non-emissive" mean that the metal complex according to formula (I) contributes less than 10%, preferably less than 5%, to the visible emission spectrum from an organic electronic device (e.g., an OLED or a display device). The visible emission spectrum is an emission spectrum with a wavelength of about ≥380 nm to about ≤780 nm.

[0082] According to one embodiment of the present invention, the valence n of M in the metal complex of formula (I) or formula (Ia) is 1, 2, 3 or 4, preferably 1, 2 or 3, or more preferably 1 or 2.

[0083] The phrase “according to Allen’s electronegativity values” specifically refers to Allen, Leland C. (1989). “Electronegativity is the average single-electron energy of valence shell electrons in a ground-state free atom.” Journal of the American Chemical Society 111 (25): 9003-9014.

[0084] According to one embodiment, M in the metal complex of formula (I) or formula (Ia) may be selected from a metal ion having an electronegativity of less than 2.4 according to Allen's law. Preferably, M may be selected from an alkali metal, alkaline earth metal, rare earth metal, transition metal, or a metal with an atomic mass ≥ 24 Da. More preferably, M may be selected from a metal with an atomic mass ≥ 24 Da and M may have an oxidation number ≥ 2. More preferably, M may be selected from an alkali metal, alkaline earth metal, transition metal, or a group III or group V metal.

[0085] M in the metal complex of formula (I) or formula (Ia) may be selected from metal ions having an electronegativity of less than 2.4 according to Allen, preferably M is selected from alkali metals, alkaline earth metals, rare earth metals, transition metals, or group III or group V metals, more preferably M is selected from metals with an atomic mass ≥ 24 Da, and further preferably M is selected from metals with an atomic mass ≥ 24 Da and M has an oxidation number ≥ 2.

[0086] Alkali metals may be selected from the group including Li, Na, K, or Rb. Alkali earth metals may be selected from the group including Mg, Ca, Sr, or Ba. Transition metals may be selected from Sc, Y, La, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Co, Ni, Cu, Ag, Au, or Zn. Group III and Group V metals may be selected from the group including Bi and Al.

[0087] According to one embodiment of the present invention, M is selected from Li, Na, K, Mg, Mn, Cu, Zn, Ag; preferably, M is selected from Na, K, Mg, Mn, Cu, Zn, Ag; and even more preferably, M is selected from Cu and / or Ag, wherein if M is Cu, then n is 2.

[0088] According to one embodiment, the metal complex of formula (I) may be a Cu(II) metal complex, an Ag(I) metal complex or a Zn(II) metal complex, preferably a Cu(II) metal complex or an Ag(I) metal complex.

[0089] According to one embodiment, the metal complex of formula (I) may be a Cu(II) metal complex, an Ag(I) metal complex or a Li(I) metal complex.

[0090] According to one embodiment of the present invention, M is selected from alkali metals, alkaline earth metals, rare earth metals or transition metals. Optionally, M is selected from alkali metals, alkaline earth metals, transition metals or group III metals.

[0091] According to one embodiment of the present invention, M is not Li.

[0092] The metal complex of formula (I) may have a molecular weight Mw of ≥ 339 g / mol and ≤ 2000 g / mol, preferably ≥ 400 g / mol and ≤ 1500 g / mol, more preferably ≥ 450 g / mol and ≤ 1500 g / mol, and even more preferably ≥ 450 g / mol and ≤ 1400 g / mol. Compounds of formulas (III) and (IV)

[0093] Thus, the compounds of formula (III) and formula (IV) can have a rate start temperature suitable for mass production.

[0094] According to an embodiment of the organic electronic device, the hole injection layer comprises a compound of formula (III) or (IV): (III) or (IV), wherein T1, T2, T3, T4 and T5 may be independently selected from single bond, phenyl, biphenyl, triphenyl or naphthylmethylene, preferably single bond or phenyl; T6 is selected from substituted or unsubstituted phenyl, biphenyl, triphenyl or naphthylmethylene; wherein the substituent on the phenyl group is selected from C6 to C18 aryl, C3 to C18 heteroaryl, phenyl, biphenyl, carbazole, phenylcarbazole, preferably biphenyl or 9-phenylcarbazole; Ar1, Ar2, Ar3, Ar4, and Ar5 can be independently selected from: unsubstituted C6 to C20 aryl, or unsubstituted C3 to C20 heteroaryl, unsubstituted biphenyl, unsubstituted phenanthrene, substituted 9-phenanthrene, substituted 9,9-phenanthrene, unsubstituted phenanthrene, unsubstituted pyrene, unsubstituted perylene, unsubstituted triphenylene, unsubstituted tetraphenylene, unsubstituted tetraphenanthrene, unsubstituted dibenzofuran, unsubstituted dibenzofuran Thiophene, unsubstituted dibenzopiperanone, unsubstituted carbazole, unsubstituted 9-phenylcarbazole, unsubstituted aziridine, unsubstituted dibenzo[b,f]aziridine, unsubstituted 9,9'-spirodi[fu], substituted or unsubstituted 9,9'-spirodi[fu] having at least one fused aromatic ring, unsubstituted spiro[fu]-9,9'-dibenzopiperanone, substituted or unsubstituted aziridine comprising two aromatic 6-membered rings and two aromatic 5-membered rings, wherein at least one 5-membered ring comprises a heteroatom. The aromatic fused ring system comprises two aromatic 6-membered rings and two aromatic 5-membered rings, wherein at least one of the 5-membered rings comprises an O atom; or an unsubstituted aromatic fused ring system comprises at least three unsubstituted aromatic rings selected from the group consisting of: unsubstituted non-hetero-5-membered rings, unsubstituted hetero-5-membered rings, unsubstituted 6-membered rings and / or unsubstituted 7-membered rings, unsubstituted cyclopentadienyl rings, and substituted rings with cyclization. The substituted or unsubstituted heterocyclic system comprises 2 to 6 substituted or unsubstituted 5, 6 or 7-membered rings, or a fused ring system comprising 2 to 6 unsubstituted 5 to 7-membered rings, wherein the rings are selected from the group consisting of: (i) unsaturated 5 to 7-membered heterocycles, (ii) 5 to 6-membered aromatic heterocycles, (iii) unsaturated 5 to 7-membered non-heterocycles, and (iv) 6-membered aromatic non-heterocycles.

[0095] According to one embodiment of the organic electronic device, the hole injection layer comprises a compound of formula (III) or (IV): (III) or (IV), wherein T1, T2, T3, T4 and T5 may be independently selected from single bond, phenyl, biphenyl, triphenyl or naphthylmethylene, preferably single bond or phenyl; T6 is selected from substituted or unsubstituted phenyl, biphenyl, triphenyl or naphthylmethylene; wherein the substituent on the phenyl group is selected from C6 to C18 aryl, C3 to C18 heteroaryl, phenyl, biphenyl, carbazole, phenylcarbazole, preferably biphenyl or 9-phenylcarbazole; Ar1, Ar2, Ar3, Ar4, and Ar5 can be independently selected from: unsubstituted C6 to C20 aryl, or unsubstituted C3 to C20 heteroaryl, unsubstituted biphenyl, unsubstituted phenanthrene, substituted 9-phenanthrene, substituted 9,9-phenanthrene, unsubstituted phenanthrene, unsubstituted pyrene, unsubstituted perylene, unsubstituted triphenylene, unsubstituted tetraphenylene, unsubstituted tetraphenanthrene, unsubstituted dibenzofuran, unsubstituted dibenzothiophene, unsubstituted dibenzopiperan, unsubstituted carbazole, substituted 9-phenylcarbazole, unsubstituted aziridine, unsubstituted dibenzo[b,f]aziridine, unsubstituted 9,9'- aziridine -spirodi[fu], substituted or unsubstituted 9,9'-spirodi[fu] having at least one fused aromatic ring, unsubstituted spiro[fu-9,9'-dibenzopiperan], substituted or unsubstituted aromatic fused ring system comprising two aromatic 6-membered rings and two aromatic 5-membered rings wherein at least one 5-membered ring comprises a heteroatom, substituted or unsubstituted aromatic fused ring system comprising two aromatic 6-membered rings and two aromatic 5-membered rings wherein at least one 5-membered ring comprises an O atom, substituted or unsubstituted fu for a cyclized substituted or unsubstituted heterocyclic or non-heterocyclic system comprising 2 to 6 substituted or unsubstituted 5, 6 or 7-membered rings.

[0096] Thus, the compounds of formula (III) and formula (IV) can have a rate start temperature suitable for mass production.

[0097] Unless otherwise specified, the substituents of Ar1, Ar2, Ar3, Ar4 and Ar5 are selected from the group consisting of the same or different groups including: H, D, F, C(=O)R2, CN, Si(R2)3, P(=O)(R2)2, OR2, S(=O)R2, S(=O)2R2, substituted or unsubstituted linear alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted branched alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 20 carbon atoms, and substituted or unsubstituted alkenyl groups having 2 to 20 carbon atoms. R2 may be an alkynyl group, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aromatic ring system having 6 to 40 aromatic ring atoms, a substituted or unsubstituted heteroaromatic ring system having 5 to 40 aromatic ring atoms, an unsubstituted C6 to C18 aryl group, an unsubstituted C3 to C18 heteroaromatic group, or a fused ring system comprising 2 to 6 unsubstituted 5 to 7-membered rings selected from the group consisting of unsaturated 5 to 7-membered heterocycles, 5 to 6-membered aromatic heterocycles, unsaturated 5 to 7-membered non-heterocycles, and 6-membered aromatic non-heterocycles, wherein R2 is selected from H, D, a straight-chain alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an alkenyl or alkynyl group having 2 to 6 carbon atoms, a C6 to C18 aryl group, or a C3 to C18 heteroaromatic group.

[0098] According to one embodiment, T1, T2, T3, T4, and T5, or T1, T2, and T3, may be independently selected from single bonds, extended phenyl groups, extended biphenyl groups, or extended triphenyl groups. According to one embodiment, T1, T2, T3, T4, and T5, or T1, T2, and T3, may be independently selected from extended phenyl groups, extended biphenyl groups, or extended triphenyl groups, and one of T1, T2, T3, T4, and T5, or T1, T2, and T3, is a single bond. According to one embodiment, T1, T2, T3, T4, and T5, or T1, T2, and T3, may be independently selected from extended phenyl groups or extended biphenyl groups, and one of T1, T2, T3, T4, and T5, or T1, T2, and T3, is a single bond. According to one embodiment, T1, T2, T3, T4 and T5, or T1, T2 and T3, may be independently selected from phenyl or biphenyl, and two of T1, T2, T3, T4 and T5, or T1, T2 and T3, are single bonds.

[0099] According to one embodiment, T1, T2, T3, T4, and T5, or T1, T2, and T3, may be independently selected from phenylene oxides, and one of T1, T2, T3, T4, and T5, or T1, T2, and T3, is a single bond. According to one embodiment, T1, T2, T3, T4, and T5, or T1, T2, and T3, may be independently selected from phenylene oxides, and two of T1, T2, T3, T4, and T5, or T1, T2, and T3, are single bonds.

[0100] According to another embodiment, Ar1, Ar2, Ar3, Ar4 and Ar5, or Ar1, Ar2 and Ar3 are independently selected from D1 to D22: (D1), (D2), (D3), (D4), (D5), (D6), (D7), (D8), (D9), (D10), (D11), (D12), (D13), (D14), (D15), (D16), (D17), (D18), (D19), (D20), (D21), (D22), where the asterisk * represents the bond position.

[0101] According to one embodiment, Ar1, Ar2, Ar3, Ar4 and Ar5, or Ar1, Ar2 and Ar3 may be independently selected from D1 to D21; or selected from D1 to D13 and D15 to D21.

[0102] According to one embodiment, Ar1, Ar2, Ar3, Ar4 and Ar5, or Ar1, Ar2 and Ar3 may be independently selected from the group consisting of D1, D2, D5, D7, D9, D10 to D21.

[0103] When Ar1, Ar2, Ar3, Ar4 and Ar5, or Ar1, Ar2 and Ar3 are selected from a range particularly suitable for mass production, the rate start temperature may be within this range.

[0104] According to one embodiment, T6 is a substituted phenyl group, and the substituents on the phenyl group are selected from D1 to D21; preferably selected from D1, D2, D5, D10 to D13, D16, D17, D20.

[0105] "Compounds of formula (III) or formula (IV)" may also be called "hole transport compounds".

[0106] According to one embodiment, the compound of formula (III) or formula (IV) may include at least 1 to 6 substituted or unsubstituted aromatic fused ring systems, the aromatic fused ring systems including heteroaromatic rings.

[0107] According to one embodiment, the compound of formula (III) or formula (IV) may include at least 1 to 6 substituted or unsubstituted aromatic fused ring systems, the aromatic fused ring system including a heteroaromatic ring and at least 1 to 3 substituted or unsubstituted unsaturated 5 to 7-membered heterocycles; preferably including 2 to 5 substituted or unsubstituted aromatic fused ring systems including a heteroaromatic ring.

[0108] According to one embodiment, the compound of formula (III) or formula (IV) may comprise at least 1 to 6 substituted or unsubstituted aromatic fused ring systems, the aromatic fused ring system comprising a heteroaromatic ring and at least 1 to 3 substituted or unsubstituted unsaturated 5- to 7-membered heterocycles; preferably comprising 2 to 5 substituted or unsubstituted aromatic fused ring systems, the aromatic fused ring system comprising a heteroaromatic ring and at least 1 to 3 substituted or unsubstituted unsaturated 5- to 7-membered heterocycles; further preferably comprising 3 or 4 substituted or unsubstituted aromatic fused ring systems, the aromatic fused ring system comprising a heteroaromatic ring and optionally at least 1 to 3 substituted or unsubstituted unsaturated 5- to 7-membered heterocycles; and even more preferably comprising aromatic fused ring systems comprising unsubstituted and optionally at least 1 to 6 substituted or unsubstituted heterocycles. Heterocyclic rings consisting of three unsubstituted, unsaturated 5- to 7-membered rings.

[0109] According to one embodiment, the compound of formula (III) or formula (IV) may include at least 1 to 6 substituted or unsubstituted aromatic fused ring systems, preferably 2 to 5 substituted or unsubstituted aromatic fused ring systems, and more preferably 3 or 4 substituted or unsubstituted aromatic fused ring systems.

[0110] According to one embodiment, the compound of formula (III) or formula (IV) may include at least 1 to 6 substituted or unsubstituted aromatic fused ring systems, preferably 2 to 5 substituted or unsubstituted aromatic fused ring systems, and more preferably 3 or 4 substituted or unsubstituted aromatic fused ring systems, which include substituted or unsubstituted heteroaromatic rings.

[0111] According to one embodiment, the compound of formula (III) or formula (IV) may include at least 1 to 3 or 2 substituted or unsubstituted unsaturated 5 to 7-membered heterocycles.

[0112] According to one embodiment, the compound of formula (III) or formula (IV) may include at least 1 to 3 or 2 substituted or unsubstituted unsaturated 7-membered heterocycles.

[0113] According to one embodiment, the substituted or unsubstituted aromatic fused ring system of the matrix compound of formula (III) or formula (IV) may include at least 1 to 3 or 2 substituted or unsubstituted unsaturated 5 to 7-membered heterocycles.

[0114] According to one embodiment, the substituted or unsubstituted aromatic fused ring system of the compound of formula (III) or formula (IV) may include at least 1 to ≤ 3 or 2 substituted or unsubstituted unsaturated 7-membered heterocycles.

[0115] According to one embodiment, the compound of formula (III) or formula (IV) may include at least 1 to 6 substituted or unsubstituted aromatic fused ring systems, preferably 2 to 5 substituted or unsubstituted aromatic fused ring systems, and more preferably 3 or 4 substituted or unsubstituted aromatic fused ring systems, wherein the aromatic fused ring system includes a substituted or unsubstituted unsaturated 5 to 7-membered heterocycle.

[0116] According to one embodiment, the compound of formula (III) or formula (IV) may include at least 1 to 6 substituted or unsubstituted aromatic fused ring systems, preferably 2 to 5 substituted or unsubstituted aromatic fused ring systems, and more preferably 3 or 4 substituted or unsubstituted aromatic fused ring systems (which include substituted or unsubstituted heteroaromatic rings), wherein the aromatic fused ring system includes substituted or unsubstituted unsaturated 5 to 7-membered heterocycles.

[0117] According to one embodiment, the compound of formula (III) or formula (IV) may include at least 1 to 6 substituted or unsubstituted aromatic fused ring systems, preferably 2 to 5 substituted or unsubstituted aromatic fused ring systems, and more preferably 3 or 4 substituted or unsubstituted aromatic fused ring systems, wherein the aromatic fused ring system includes at least 1 to 3 or 2 substituted or unsubstituted unsaturated 5 to 7-membered heterocycles.

[0118] According to one embodiment, the compound of formula (III) or formula (IV) may include at least 1 to 6 substituted or unsubstituted aromatic fused ring systems, preferably 2 to 5 substituted or unsubstituted aromatic fused ring systems, and more preferably 3 or 4 substituted or unsubstituted aromatic fused ring systems (which include substituted or unsubstituted heteroaromatic rings), wherein the aromatic fused ring system includes at least 1 to 3 or 2 substituted or unsubstituted unsaturated 5 to 7-membered heterocycles.

[0119] According to one embodiment, a compound of formula (III) or formula (IV) may include: - a substituted or unsubstituted aromatic fused ring system having at least 2 to ≤ 6, preferably ≥ 3 to ≤ 5, or 4 fused aromatic rings, the fused aromatic rings being selected from the group consisting of substituted or unsubstituted non-heteroaromatic rings, substituted or unsubstituted hetero 5-membered rings, substituted or unsubstituted 6-membered rings and / or substituted or unsubstituted unsaturated 5 to 7-membered rings; or - an unsubstituted aromatic fused ring system having at least 2 to ≤ 6, preferably ≥ 3 to ≤ 5, or 4 fused aromatic rings, the fused aromatic rings being selected from the group consisting of unsubstituted non-heteroaromatic rings, unsubstituted hetero 5-membered rings, unsubstituted 6-membered rings and / or unsubstituted unsaturated 5 to 7-membered rings.

[0120] It should be noted here that the term "aromatic fused ring system" may include at least one aromatic ring and at least one substituted or unsubstituted unsaturated 5- to 7-membered ring. It should be noted here that the substituted or unsubstituted unsaturated 5- to 7-membered ring may not be an aromatic ring.

[0121] According to one embodiment, the compound of formula (III) or formula (IV) may include at least ≥ 1 to ≤ 6, preferably ≥ 2 to ≤ 5, or more preferably 3 or 4 substituted or unsubstituted aromatic fused ring systems having the following: - at least one unsaturated 5-membered ring, and / or - at least one unsaturated 6-membered ring, and / or - at least one unsaturated 7-membered ring; wherein preferably at least one unsaturated 5-membered ring and / or at least one unsaturated 7-membered ring includes at least 1 to 3 (preferably 1) heteroatoms.

[0122] According to one embodiment, the compound of formula (III) or formula (IV) may include at least ≥ 1 to ≤ 6, preferably ≥ 2 to ≤ 5, or more preferably 3 or 4 substituted or unsubstituted aromatic fused ring systems having the following: - at least one aromatic 5-membered ring, and / or - at least one aromatic 6-membered ring, and / or - at least one aromatic 7-membered ring; wherein preferably at least one aromatic 5-membered ring and / or at least one aromatic 7-membered ring includes at least 1 to 3 (preferably 1) heteroatoms; wherein the substituted or unsubstituted aromatic fused ring system includes at least ≥ 1 to ≤ 3 or 2 substituted or unsubstituted unsaturated 5- to 7-membered heterocycles.

[0123] According to one embodiment, the compound of formula (III) or formula (IV) may include: - at least ≥ 6 to ≤ 12, preferably ≥ 7 to ≤ 11, more preferably ≥ 8 to ≤ 10 or 9 aromatic rings; and / or - at least ≥ 4 to ≤ 11, preferably ≥ 5 to ≤ 10, more preferably ≥ 6 to ≤ 9 or even more preferably 7 or 8 non-heteroaromatic rings, preferably, the non-heteroaromatic rings are aromatic C6 rings; and / or - at least ≥ 1 to ≤ 4, preferably 2 or 3 aromatic 5-membered rings (preferably, heteroaromatic 5-membered rings); and / or - at least 1 or 2 unsaturated 5- to 7-membered heterocycles, preferably at least 1 or 2 unsaturated 7-membered heterocycles; - at least ≥ 6 to ≤ 12, preferably ≥ 7 to ≤ 11, more preferably ≥ 8 to ≤ The aromatic rings comprise 10 or 9 aromatic rings, wherein at least 4 to 11, preferably 5 to 10, further preferably 6 to 9, or even more preferably 7 or 8 are non-heteroaromatic rings, and at least 1 to 4, preferably 2 or 3 are heteroaromatic rings, wherein the total number of all non-heteroaromatic rings and heteroaromatic rings does not exceed 12 aromatic rings; and / or at least 6 to 12, preferably 7 to 11, further preferably 8 to 10 or 9 aromatic rings, wherein at least 4 to 11, preferably 5 to 10, further preferably 6 to 9, or even more preferably 7 or 8 are non-heteroaromatic rings, and at least 1 to 4, preferably 2 or 3 are heteroaromatic rings, wherein the total number of all non-heteroaromatic rings and heteroaromatic rings does not exceed 12 aromatic rings.

[0124] According to one embodiment, the compound of formula (III) or formula (IV) may include at least ≥ 1 to ≤ 6, preferably ≥ 2 to ≤ 5, or more preferably 3 or 4 substituted or unsubstituted aromatic fused ring systems having the following: - at least one aromatic 5-membered ring, and / or - at least one aromatic 6-membered ring, and / or - at least one aromatic 7-membered ring; wherein preferably, the at least one aromatic 5-membered ring and / or the at least one aromatic 7-membered ring includes at least 1 to 3 (preferably 1) heteroatoms; wherein the substituted or unsubstituted aromatic fused ring system optionally includes at least ≥ 1 to ≤ 3 or 2 substituted or unsubstituted unsaturated 5 to 7-membered heterocycles; and wherein the substituted or unsubstituted aromatic fused ring system includes heteroatoms selected from the group consisting of O, S, N, B, P or Si, preferably, the heteroatoms selected from the group consisting of O, S or N.

[0125] According to one embodiment, the compound of formula (III) or formula (IV) is selected from F1 to F19: (F1), (F2), (F3), (F4), (F5), (F6), (F7), (F8), (F9), (F10), (F11), (F12), (F13), (F14), (F15), (F16), (F17), (F18), (F19).

[0126] The hole injection layer may not contain HTM014, HTM081, HTM163, HTM222, EL-301, HTM226, HTM355, HTM133, HTM334, HTM604, and EL-22T. These abbreviations represent the names of manufacturers such as Merck or Lumtec.

[0127] According to one embodiment, the compound of formula (III) or formula (IV) may have a molecular weight of ≥ 400 and ≤ 2000 g / mol, preferably ≥ 450 and ≤ 1500 g / mol, further preferably ≥ 500 and ≤ 1000 g / mol, and even more preferably ≥ 550 and ≤ 900 g / mol.

[0128] In one embodiment, when measured under the same conditions, the HOMO energy level of the substantially covalent matrix compound may be more negative than that of N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-N-(4-(9-phenyl-9H-carbazole-3-yl)phenyl)-9H-furo-2-amine (CAS 1242056-42-3).

[0129] In one embodiment, when the HOMO level is calculated in the gas phase using TURBOMOLE V6.5 (TURBOMOLE GmbH, Litzenhardtstrasse 19, 76135 Karlsruhe, Germany) by applying the mixing function B3LYP with a 6-31G* basis set, the HOMO level of the substantially covalent matrix compound can be ≤ -4.8 eV, preferably ≤ -4.805 eV, preferably ≤ -4.815 eV; and > 6.5 eV.

[0130] In one embodiment, when the HOMO level is calculated in the gas phase using TURBOMOLE V6.5 (TURBOMOLE GmbH, Litzenhardtstrasse 19, 76135 Karlsruhe, Germany) by applying the mixing function B3LYP with a 6-31G* basis set, the HOMO level of the substantially covalent matrix compound can be selected in the range of <-4.79 eV and ≥-5.5 eV, or in the range of ≤-4.8 eV and ≥-5.3 eV, or in the range of ≤-4.8 eV and ≥-5.2 eV, or in the range of ≤-4.8 eV and ≥-5 eV, or in the range of <-4.8 eV and ≥-5 eV.

[0131] In one embodiment of the present invention, the substantially covalent matrix compound may lack alkoxy groups. Hole injection layer

[0132] The hole-injection layer (HIL) can be formed on the anodic layer by vacuum deposition, spin coating, printing, casting, slot coating, Langmuir-Broguet (LB) deposition, or similar methods. When the HIL is formed using vacuum deposition, the deposition conditions can vary depending on the hole-transporting compound used to form the HIL and the desired structure and thermal properties of the HIL. However, generally, the conditions used for vacuum deposition can include a deposition temperature of 100°C to 350°C, a pressure of 10⁻⁸ to 10⁻³ Torr (1 Torr equals 133.322 Pa), and a deposition rate of 0.1 to 10 nm / sec.

[0133] When the HIL is formed using spin coating or printing, the coating conditions may vary depending on the hole transport compound used to form the HIL and the desired structure and thermal properties of the HIL. For example, coating conditions may include a coating speed of about 2000 rpm to about 5000 rpm and a heat treatment temperature of about 80 °C to about 200 °C. After coating, heat treatment removes the solvent.

[0134] The thickness of the HIL can be in the range of about 1 nm to about 15 nm, and for example in the range of about 2 nm to about 15 nm, or alternatively in the range of about 2 nm to about 12 nm.

[0135] When the thickness of HIL is within this range, HIL can have excellent hole injection characteristics without substantial loss of driving voltage.

[0136] According to one embodiment of the present invention, the hole injection layer may include: - at least about ≥ 0.5 wt.-% to about ≤ 30 wt.-%, preferably about ≥ 0.5 wt.-% to about ≤ 20 wt.-%, and more preferably about ≥ 2 wt.-% to about ≤ 15 wt.-%, of a metal complex of formula (I) or formula (Ia), and - at least about ≥ 70 wt.-% to about ≤ 99.5 wt.-%, preferably about ≥ 80 wt.-% to about ≤ 99.5 wt.-%, and more preferably about ≥ 85 wt.-% to about ≤ 98 wt.-%, of a compound of formula (III) or formula (IV); preferably, the wt.-% of the metal complex of formula (I) or formula (Ia) is lower than the wt.-% of the compound of formula (III) or formula (IV); wherein the weight percentages of these components are based on the total weight of the hole injection layer.

[0137] According to one embodiment of the invention, the hole injection layer may include: - at least about ≥ 0.5 vol.-% to about ≤ 30 vol.-%, preferably about ≥ 0.5 vol.-% to about ≤ 20 vol.-%, and more preferably about ≥ 2 vol.-% to about ≤ 15 vol.-%, of a metal complex of formula (I) or formula (Ia), and - at least about ≥ 70 vol.-% to about ≤ 99.5 vol.-%, preferably about ≥ 80 vol.-% to about ≤ 99.5 vol.-%, and more preferably about ≥ 85 vol.-% to about ≤ 98 vol.-%. Preferably, the vol.-% of the metal complex of formula (I) or formula (Ia) is lower than the vol.-% of the compound of formula (III) or formula (IV); wherein the volume percentages of these components are based on the total volume of the hole injection layer.

[0138] According to an embodiment of an organic electronic device, the hole injection layer is non-emissive.

[0139] It should be understood that the hole injection layer is not part of the anode layer. Other layers...

[0140] According to the present invention, in addition to the layers mentioned above, organic electronic devices may include additional layers. Exemplary embodiments of each layer are described below: Substrate

[0141] The substrate can be any substrate commonly used in the manufacture of electronic devices such as organic light-emitting diodes. If light is to be emitted through the substrate, the substrate should be a transparent or translucent material, such as a glass substrate or a transparent plastic substrate. If light is to be emitted through the top surface, the substrate can be a transparent or opaque material, such as a glass substrate, a plastic substrate, a metal substrate, a silicon substrate, or a transistor backplane. Preferably, the substrate is a silicon substrate or a backplane for a display. Hole transport layer

[0142] According to one embodiment of an organic electronic device, the organic electronic device further includes a hole transport layer, wherein the hole transport layer is disposed between a hole injection layer and at least one emitter layer or a first emitter layer.

[0143] The hole transport layer may include a substantially covalent matrix compound. According to one embodiment, the substantially covalent matrix compound of the hole transport layer may be selected from at least one organic compound. The substantially covalent matrix may substantially consist of covalently bonded C, H, O, N, and S, and optionally also includes covalently bonded B, P, As, and / or Se.

[0144] According to one embodiment of the organic electronic device, the hole transport layer includes a matrix compound, wherein the matrix compound of the hole transport layer may be selected from an organic compound composed of covalently bonded C, H, O, N, S, or substantially composed of covalently bonded C, H, O, N, S, and optionally further comprising covalently bonded B, P, As, and / or Se.

[0145] According to one embodiment, the substantially covalent matrix compound of the hole transport layer may have a molecular weight of ≥ 400 and ≤ 2000 g / mol, preferably a molecular weight Mw of ≥ 450 and ≤ 1500 g / mol, further preferably a molecular weight of ≥ 500 and ≤ 1000 g / mol, and even more preferably a molecular weight of ≥ 550 and ≤ 900 g / mol.

[0146] According to one embodiment of the organic electronic device, the hole transport layer may include a matrix compound of formula (III) or formula (IV), preferably, the matrix compound in the hole transport layer and the hole injection layer are selected to be the same.

[0147] According to one embodiment of an organic electronic device, the hole transport layer comprises a compound according to formula (III) or formula (IV), preferably, the matrix compound in the hole transport layer and the hole injection layer are selected to be the same.

[0148] The hole transport layer may not include HTM014, HTM081, HTM163, HTM222, EL-301, HTM226, HTM355, HTM133, HTM334, HTM604, and EL-22T. These abbreviations represent the names of manufacturers such as Merck or Lumtec.

[0149] The hole transport layer (HTL) can be formed on the HIL by vacuum deposition, spin coating, slot coating, printing, casting, Langmuir-Blodgett (LB) deposition, or similar methods. When the HTL is formed by vacuum deposition or spin coating, the conditions used for deposition and coating can be similar to those used for the formation of the HIL. However, the conditions used for vacuum or solution deposition can vary depending on the hole transport compound used to form the HTL.

[0150] The thickness of the HTL may be in the range of about 5 nm to about 250 nm, preferably in the range of about 10 nm to about 200 nm, further in the range of about 20 nm to about 190 nm, further in the range of about 40 nm to about 180 nm, further in the range of about 60 nm to about 170 nm, further in the range of about 80 nm to about 200 nm, further in the range of about 100 nm to about 180 nm, and further in the range of about 110 nm to about 140 nm.

[0151] When the thickness of the HTL is within this range, the HTL can exhibit excellent hole transport characteristics without substantial loss of driving voltage. Electron blocking layer

[0152] The function of the electron blocking layer (EBL) is to prevent electrons from being transferred from the emitter layer to the hole transport layer, and thus confine the electrons within the emitter layer. This improves efficiency, operating voltage, and / or lifetime. Typically, the electron blocking layer comprises a triarylamine compound.

[0153] If the electron blocking layer has a high triplet energy level, it can also be described as a triplet control layer.

[0154] If a green or blue phosphorescent emitting layer is used, the function of the triplet control layer is to reduce triplet quenching. This allows for higher light emission efficiency from the phosphorescent emitting layer. The triplet control layer can be selected from a triarylamine compound having a triplet energy level higher than that of the phosphorescent emitter in the adjacent emitting layer.

[0155] The thickness of the electron blocking layer can be selected between 2 and 20 nm. Emitter Layer (EML)

[0156] At least one first emitter layer (EML), also referred to as the first emitter layer, can be formed on the HTL or EBL by vacuum deposition, spin coating, slot coating, printing, casting, LB deposition, or the like. When the EML is formed using vacuum deposition or spin coating, the conditions for deposition and coating can be similar to those for forming the HIL. However, the conditions for deposition and coating can vary depending on the compound used to form the EML.

[0157] According to the present invention, preferably, the organic electronic device includes an emission layer referred to as a "first emission layer". However, the organic electronic device may optionally include two emission layers, wherein the first layer is referred to as the first emission layer and the second layer is referred to as the second emission layer.

[0158] It may be specified that at least one of the emitter layers, also known as the first emitter layer, has no hole injection layer.

[0159] It may be specified that at least one emission layer does not include compounds of formula (III) or formula (IV).

[0160] At least one emitter layer (EML) may be formed by a combination of a host and an emitter dopant. Examples of hosts are Alq3, 4,4'-N,N'-dicarbazole-biphenyl (HTC-10), poly(n-vinylcarbazole) (PVK), 9,10-bis(naphthyl-2-yl)anthracene (ADN), 4,4',4''-tris(carbazole-9-yl)-triphenylamine (TCTA), 1,3,5-tris(N-phenylbenzimidazol-2-yl)benzene (TPBI), 3-tert-butyl-9,10-bis-2-naphthylanthracene (TBADN), stilbene aryl (DSA), and bis(2-(2-hydroxyphenyl)benzothiazolyl)zinc (Zn(BTZ)2).

[0161] The emitter dopant may be a phosphorescent or fluorescent emitter. Phosphorescent emitters and emitters that emit light via thermally activated delayed fluorescence (TADF) are preferred due to their higher efficiency. The emitter may be a small molecule or a polymer.

[0162] Examples of red emitter dopants include PtOEP, Ir(piq)3, and Btp2lr(acac), but are not limited thereto. These compounds are phosphorescent emitters; however, fluorescent red emitter dopants may also be used.

[0163] Examples of phosphorescent green emitter dopants are Ir(ppy)3 (ppy = phenylpyridine), Ir(ppy)2(acac), and Ir(mpyp)3.

[0164] Examples of phosphorescent blue emitter dopants include F2Irpic, (F2ppy)2Ir(tmd), and Ir(dfppz)3 and trifurfen. 4,4'-bis(4-diphenylaminostyryl)biphenyl (DPAVBi) and 2,5,8,11-tetra-tert-butylperylene (TBPe) are examples of phosphorescent blue emitter dopants.

[0165] Based on 100 parts by weight of the host, the amount of emitter dopant can range from about 0.01 to about 50 parts by weight. Alternatively, at least one emitter layer can be composed of a light-emitting polymer. The EML can have a thickness of about 10 nm to about 100 nm, for example, about 20 nm to about 60 nm. When the thickness of the EML is within this range, the EML can exhibit excellent light emission without substantial loss of driving voltage. Hole blocking layer (HBL)

[0166] The hole blocking layer (HBL) can be formed on the EML by vacuum deposition, spin coating, slot coating, printing, casting, LB deposition or similar methods to prevent holes from diffusing into the ETL. When the EML includes phosphorescent emitter dopants, the HBL can also have triplet exciton blocking functionality.

[0167] HBL can also be referred to as auxiliary ETL or a-ETL.

[0168] When HBL is formed using vacuum deposition or spin coating, the conditions for deposition and coating can be similar to those for forming HIL. However, the deposition and coating conditions can vary depending on the compound used to form HBL. Any compound commonly used to form HBL can be used. Examples of compounds used to form HBL include acediazole derivatives, triazole derivatives, phenobarbital derivatives, and triazine derivatives.

[0169] The HBL can have a thickness in the range of about 5 nm to about 100 nm, for example, in the range of about 10 nm to about 30 nm. When the thickness of the HBL is within this range, the HBL can have excellent hole blocking characteristics without substantial loss of driving voltage. Electron Transport Layer (ETL)

[0170] The organic electronic device according to the present invention may further include an electron transport layer (ETL).

[0171] According to another embodiment of the present invention, the electron transport layer may further include an azazine compound, preferably a triazine compound.

[0172] In one embodiment, the electron transport layer may further include a dopant selected from an alkaline organic complex (preferably LiQ).

[0173] The thickness of the ETL can be in the range of about 15 nm to about 50 nm, for example, in the range of about 20 nm to about 40 nm. When the thickness of the EIL is in this range, the ETL can have satisfactory electron injection characteristics without substantial loss of driving voltage.

[0174] According to another embodiment of the present invention, the organic electronic device may further include a hole-blocking layer and an electron transport layer, wherein the hole-blocking layer and the electron transport layer comprise an azazine compound. Preferably, the azazine compound is a triazine compound. Electron Injection Layer (EIL)

[0175] Optional EILs that facilitate electron injection from the cathode can be formed on the ETL, preferably directly on the electron transport layer. Examples of materials used to form EILs include lithium 8-hydroxyquinoline (LiQ), LiF, NaCl, CsF, Li₂O, BaO, Ca, Ba, Yb, and Mg, known in the art. The deposition and coating conditions for forming EILs are similar to those for forming HILs, but the deposition and coating conditions may vary depending on the material used to form the EIL.

[0176] The thickness of the EIL can be in the range of about 0.1 nm to about 10 nm, for example, in the range of about 0.5 nm to about 9 nm. When the thickness of the EIL is within this range, the EIL can have satisfactory electron injection characteristics without substantial loss of driving voltage. Cathode layer

[0177] The cathode layer is formed on the ETL, or optionally on the EIL. The cathode layer may be formed of a metal, alloy, conductive compound, or mixture thereof. The cathode layer may have a low work function. For example, the cathode layer may be formed of lithium (Li), magnesium (Mg), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), barium (Ba), ytterbium (Yb), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag), or the like. Alternatively, the cathode layer may be formed of a transparent conductive oxide such as ITO or IZO.

[0178] The thickness of the cathode layer can be in the range of about 5 nm to about 1000 nm, for example, in the range of about 10 nm to about 100 nm. When the thickness of the cathode layer is in the range of about 5 nm to about 50 nm, the cathode layer can be transparent or translucent, even if it is formed of metal or metal alloy.

[0179] It should be understood that the cathode layer is not part of the electron injection layer or the electron transport layer. Organic electronic devices

[0180] According to one embodiment of an organic electronic device, the hole injection layer may be configured to be in direct contact with a cathode layer, the cathode layer comprising at least a first cathode sublayer and a second cathode sublayer.

[0181] According to one embodiment of the present invention, the organic electronic device may include a hole injection layer comprising a metal complex of formula (I) or formula (Ia) and a compound of formula (III) or formula (IV), wherein M in formula (I) or formula (Ia) is selected from Li, Na, K, Cs, Mg, Mn, Cu, Zn or Ag, or Mg, Mn, Cu, Zn or Ag, or Cu, Zn or Ag.

[0182] According to another embodiment, the organic electronic device may be a light-emitting device or a display device.

[0183] According to one aspect of the present invention, an organic electronic device is provided, comprising: a substrate; an anode layer comprising at least two or more anode sublayers, the at least two or more anode sublayers comprising at least a first anode sublayer and a second anode layer formed on the substrate; a hole injection layer comprising a metal complex of formula (I) or (Ia) and a compound of formula (III) or (IV) according to the present invention; a hole transport layer; at least a first emission layer; an electron transport layer; and a cathode layer.

[0184] According to another aspect of the present invention, an organic electronic device is provided, comprising: a substrate; an anode layer comprising at least two or more anode sublayers, the at least two or more anode sublayers including a first anode sublayer and a second anode sublayer formed on the substrate; a hole injection layer comprising a compound of formula (III) or (IV) and a metal complex of formula (I) or (Ia); a hole transport layer; an electron blocking layer; at least a first emission layer; a hole blocking layer; an electron transport layer; and a cathode layer.

[0185] According to another aspect of the present invention, an organic electronic device is provided, comprising: a substrate; an anode layer comprising at least two or more anode sublayers, the at least two or more anode sublayers including a first anode sublayer and a second anode sublayer formed on the substrate, a hole injection layer comprising a compound of formula (III) or (IV) and a metal complex of formula (I) or (Ia), a hole transport layer, an electron blocking layer, at least a first emission layer, a hole blocking layer, an electron transport layer, an optional electron injection layer, and a cathode layer.

[0186] According to various embodiments of the present invention, additional layers may be provided between the above-described layers, on the substrate, or on the top electrode.

[0187] For example, the organic electronic device according to FIG. 5 can be formed by a method in which an anode layer (120) including at least a first anode sublayer (121) and a second anode sublayer (122), a hole injection layer (130) including a compound of formula (III) or (IV) and a metal complex of formula (I) or (Ia), a hole transport layer (140), a first emission layer (150), a hole blocking layer (155), an electron transport layer (160), and a cathode layer (190) are formed sequentially on a substrate (110). Manufacturing method

[0188] According to another aspect of the present invention, a method for manufacturing an organic electronic device is provided, the method using: - at least one deposition source, preferably two deposition sources, and more preferably at least three deposition sources.

[0189] Suitable deposition methods include: - deposition by vacuum thermal evaporation; - deposition by solution treatment, preferably selected from spin coating, printing, casting; and / or - slot coating.

[0190] According to various embodiments of the present invention, a method is provided that uses: - a first deposition source to release the compound of formula (III) or formula (IV) of the present invention, and - a second deposition source to release the metal complex of formula (I) or formula (Ia).

[0191] The method includes the step of forming a hole injection layer; thereby, for organic electronic devices: - forming a hole injection layer by releasing a compound of formula (III) or formula (IV) according to the invention from a first deposition source and releasing a metal complex of formula (I) or formula (Ia) from a second deposition source.

[0192] According to various embodiments of the present invention, the method may further include forming layers on the hole injection layer in the following order, at least one layer selected from the group consisting of: forming a hole transport layer, forming a hole blocking layer, forming a first emission layer, forming a hole blocking layer, forming an electron transport layer and / or forming an electron injection layer and / or forming a cathode layer.

[0193] According to various embodiments of the present invention, the method may further include the step of forming an organic electronic device, wherein - an anode layer comprising at least a first anode sublayer and a second anode sublayer is formed on a substrate; - a hole injection layer comprising a compound of formula (III) or (IV) and a metal complex of formula (I) or (Ia) according to the present invention is formed on the hole injection layer; - a hole transport layer is formed on the hole transport layer; - at least a first emitter layer is formed on the hole transport layer; - an electron transport layer is formed on the emitter layer, optionally a hole blocking layer and / or an electron transport layer are formed on the emitter layer; - finally, a cathode layer is formed; - an optional electron blocking layer is formed between the hole transport layer and the emitter layer in this order; - an optional electron injection layer is formed between the electron transport layer and the cathode layer.

[0194] According to various embodiments, an organic electronic device may have the following layer structure, wherein the layers have the following order: an anode layer including at least a first anode sublayer and a second anode sublayer, a hole injection layer including a compound of formula (III) or (IV) according to the invention and a metal complex of formula (I) or (Ia), a hole transport layer, an optional electron blocking layer, at least a first emission layer, an optional hole blocking layer, an electron transport layer, an optional electron injection layer, and a cathode layer.

[0195] According to one embodiment, the organic electronic device of the present invention is formed by depositing a hole injection layer in a vacuum.

[0196] According to another aspect, an electronic device is provided, comprising at least one organic light-emitting device according to any embodiment described throughout this application, preferably, the electronic device comprising an organic light-emitting diode of one of the embodiments described throughout this application. More preferably, the organic electronic device is a display device.

[0197] According to another aspect of the invention, a metal complex for use in an organic electronic device or a layer of an organic electronic device is provided, wherein the metal complex has the formula (I) where M is Ag(I) or Cu(II); N is the valence of M; m is n; and L is selected from G7, G15, G17, G19, G20 or G21 compounds: (G7), (G15), (G17), (G19), (G20), (G21); or M is Li, n is 1, m is 1, and L is selected from G2: (G2).

[0198] According to one aspect of the invention, M is Ag and n is 1 and / or M is Cu and n is 2; and L is selected from compounds of G7, G15, G17, G19, G20 or G21.

[0199] According to another aspect of the invention, M is Ag, n is 1 and L is selected from compounds of G7, G15, G17, G19, G20 or G21.

[0200] According to another aspect of the invention, M is Cu, n is 2 and L is selected from compounds of G7, G15, G17, G19, G20 or G21.

[0201] According to another aspect of the invention, M is Li, n is 1 and L is selected from G2:(G2).

[0202] In the following, embodiments are described in more detail with reference to examples. However, this disclosure is not limited to the following examples. Exemplary embodiments will now be referred to in detail.

Implementation Method

[0204] The present invention is further illustrated by the following examples, which are merely illustrative and not binding.

[0205] Metal complexes of formula (I) or (Ia) and compounds of formula (III) or (IV) can be prepared as described in the literature. Compounds of formula (I) and (Ia), wherein M is Ag(I): Several methods for preparing the compounds of the present invention are shown below, using the following general method A:

[0206] Sulfoamide ligands were synthesized using methods known in the literature.

[0207] The sulfonamide ligand was dissolved in methanol (approximately 5 ml / g) and 0.55 equivalents of silver carbonate were added. The reaction mixture was stirred overnight at room temperature. Excess silver carbonate was filtered off and washed with a small amount of methanol. The liquid phases were combined and the solvent was removed under reduced pressure. The remaining solid was dried under high vacuum. The crude substance was purified by sublimation under reduced pressure. Compounds of formula (I) and (Ia), wherein M is Cu(II): Several methods for preparing the compounds of the present invention are shown below, using the following general method B:

[0208] Sulfoamide ligands were synthesized using methods known in the literature.

[0209] The sulfonamide ligand was dissolved in water (approximately 10 ml / g) and 0.5 equivalents of copper acetate were added. The mixture was stirred until a clear blue solution was obtained. The solvent was removed under reduced pressure. Residual acetic acid was removed by repeated addition of toluene and the solvent was removed under reduced pressure. The crude substance was purified by sublimation. Compounds of formula (I) and (Ia), wherein M is Li(I): Several methods for preparing the compounds of the present invention are shown below, using the following general method C:

[0210] Sulfoamide ligands were synthesized using methods known in the literature.

[0211] The sulfonamide ligand was dissolved in methanol (approximately 5 ml / g), and 1.1 equivalents of lithium hydroxide were added. The reaction mixture was stirred overnight at room temperature. Excess lithium hydroxide was filtered off and washed with a small amount of methanol. The liquid phases were combined, and the solvent was removed under reduced pressure. The remaining solid was dried under high vacuum. The crude substance was purified by sublimation under reduced pressure. Rate start temperature

[0212] 100 mg of the compound was loaded into a VTE source to determine the rate onset temperature (TRO). A point source of organic material supplied by companies such as Kurt J. Lesker Company (www.lesker.com) or CreaPhys GmbH (http: / / www.creaphys.com) could be used as the VTE source. The VTE source was heated at a fixed rate of 15 K / min under a pressure below 10⁻⁵ mbar, and the temperature within the source was measured using a thermocouple. Evaporation of the compound was detected using a QCM detector, which detected compound deposition on a quartz crystal. The deposition rate on the quartz crystal was measured in Ångstrom / s. The deposition rate was plotted against the VTE source temperature to determine the rate onset temperature. Rate onset is the temperature at which significant deposition occurs on the QCM detector. For accurate results, the VTE source was heated and cooled three times, and only the results from the second and third cycles were used to determine the rate onset temperature.

[0213] To achieve good control over the evaporation rate of the compound, the rate-starting temperature can be in the range of 200 to 300˚C. If the rate-starting temperature is below 200˚C, evaporation may be too rapid and therefore difficult to control. If the rate-starting temperature is above 300˚C, the evaporation rate may be too low, which can lead to a short tact time, and decomposition of the metal complex in the VTE source may occur due to prolonged exposure to the elevated temperature.

[0214] Rate onset temperature is an indirect measure of a compound's volatility. The higher the rate onset temperature, the lower the volatility of the compound.

[0215] Table 1 shows the rate-on-temperature (TRO) of the metal complexes of formula (I). Table 1: Metal complexes of formula (I) name Chemical formula T RO ( o C) W1 262 W11 250 W2 245 W3 260 W4 255 W12 294 W5 224 W6 240 W7 230 W8 225 W9 235 W10 231

[0216] As shown in Table 1, the metal complex of formula (I) has a rate-starting temperature suitable for mass production of organic electronic devices. Calculated HOMO and LUMO

[0217] HOMO and LUMO were calculated using the software suite TURBOMOLE V6.5 (TURBOMOLE GmbH, Litzenhardtstrasse 19, 76135 Karlsruhe, Germany). The optimal geometry and LUMO energy levels for the HOMO and LUMO were determined by applying the mixing function B3LYP with a 6-31G* basis set in the gas phase. If more than one configuration was observed, the configuration with the lowest total energy was selected.

[0218] Table 2 shows the calculated HOMO level and rate onset temperature (TRO) of the matrix compound of formula (I). The HOMO level was calculated as described above. Table 2: Calculated HOMO levels of compounds of formula (III) or (IV) Chemical formula Calculated HOMO (mixing function B3LYP in the gas phase and 6-31G* basis set) [eV] F1 - 4.800 F2 - 4.800 F3 - 4.800 F4 - 4.806 F5 - 4.816 F6 - 4.818 F7 - 4.822 F8 - 4.822 F9 - 4.825 F10 - 4.832 F11 - 4.854 F12 - 4.876 F13 - 4.884 F14 - 4.904 F15 - 4.904 F16 - 4.927 F17 - 4.928 F18 - 4.960 F19 - 4.967 The general process for manufacturing OLEDs is a process for manufacturing organic electronic devices that include a hole injection layer comprising a metal complex and a matrix compound.

[0219] Regarding Examples 1 to 32 and Comparative Examples 1 to 6 in Table 3, a glass substrate having an anode layer (comprising a first anode sublayer of 120 nm Ag, a second anode sublayer of 8 nm ITO, and a third anode sublayer of 10 nm ITO) was cut to a size of 50 mm x 50 mm x 0.7 mm, ultrasonically cleaned with water for 60 minutes, and then ultrasonically cleaned with isopropanol for 20 minutes. The liquid film was removed in a nitrogen stream, followed by plasma treatment to prepare the anode layer. The plasma treatment was performed for 38 seconds at 80 W in an atmosphere containing 97.6 vol.-% nitrogen and 2.4 vol.-% oxygen.

[0220] Then, the compound of formula (III) or formula (IV) and the metal complex of formula (I) are co-deposited on the anode layer under vacuum to form a hole injection layer (HIL) with a thickness of 10 nm. The composition of the hole injection layer is shown in Table 3.

[0221] Then, the compound of formula (III) or (IV) is vacuum deposited onto the HIL to form the HTL. The compound of formula (III) or (IV) in the HTL is selected to be the same as the compound of formula (III) or (IV) in the HIL. The compounds of formula (III) or (IV) and the thickness of the HTL are shown in Table 3. The thickness of the HTL is adjusted in such a way that the CIE 1931 y-coordinate of the light emitted by the organic electronic device is in the range of 0.035 to 0.052.

[0222] Then, N-(4-(dibenzo[b,d]furan-4-yl)phenyl)-N-(4-(9-phenyl-9H-furan-9-yl)phenyl)-[1,1'-biphenyl]-4-amine (CAS 1824678-59-2) was vacuum deposited on HTL to form an electron blocking layer (EBL) with a thickness of 5 nm.

[0223] Then, 97 vol.-% H09, which is the main body of the EML, and 3 vol.-% BD200 (South Korean Sun Fine Chemical Co., Ltd.), which is a fluorescent blue emitter dopant, were deposited on the EBL to form a first blue emitting layer (EML) with a thickness of 20 nm.

[0224] Then, a hole blocking layer (HBL) with a thickness of 5 nm is formed by depositing 2-(3'-(9,9-dimethyl-9H-furo-2-yl)-[1,1'-biphenyl]-3-yl)-4,6-diphenyl-1,3,5-triazine on the emitter layer EML.

[0225] Then, an electron transport layer (ETL) with a thickness of 31 nm is formed on the hole blocking layer by depositing 50 wt.-% of 4'-(4-(4-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)naphth-1-yl)-[1,1'-biphenyl]-4-carboxynitrile and 50 wt.-% LiQ.

[0226] Then, Yb is deposited on the ETL to form an electron injection layer (EIL) with a thickness of 2 nm.

[0227] Then, Ag:Mg (90:10 vol.-%) was evaporated at 10-7 mbar at a rate of 0.01 to 1 Å / s to form a cathode layer with a thickness of 13 nm on the EIL.

[0228] Then, N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-N-(4-(9-phenyl-9H-carbazole-3-yl)phenyl)-9H-furan-2-amine is deposited on the cathode layer to form a capping layer with a thickness of 75 nm.

[0229] By encapsulating the device with a glass slide, the OLED stack is protected from environmental conditions. This forms a cavity that includes getter material for further protection.

[0230] To evaluate the performance of the present invention example compared to the prior art, current efficiency was measured at 20°C. Using a Keithley 2635 source measure unit, the current-voltage characteristics were determined by supplying voltage in V and measuring the current flowing through the device under test in mA. The voltage applied to the device varied in 0.1 V steps within the range of 0 V to 10 V. Similarly, the luminance-voltage characteristics and CIE coordinates were determined by measuring the luminance in cd / m² for each voltage value using an Instrument Systems CAS-140CT array spectrometer (calibrated by Deutsche Akkreditierungsstelle (DAkkS)). The cd / A efficiency at 10 mA / cm² was determined by interpolating the luminance-voltage characteristics and current-voltage characteristics separately.

[0231] In order to determine the EQE in % terms, the light output of the device was measured at 15 mA / cm2 using a calibrated optical diode.

[0232] The lifespan LT of the Keithley 2400 source meter was measured under environmental conditions (20°C) and 30 mA / cm², and recorded in hours.

[0233] The brightness of the device is measured using a calibrated optical diode. The lifespan LT is defined as the time until the brightness of the device decreases to 97% of its initial value.

[0234] To determine the voltage stability over a time period U (50h-1h), a current density of 30 mA / cm² was applied to the device. The operating voltage was measured after 1 hour and after 50 hours, and the voltage stability over the time period from 1 hour to 50 hours was calculated. The higher the absolute value of U (50h-1h), the worse the voltage stability over time. Technical Effects of the Invention

[0235] Table 3 shows data for organic electronic devices including a hole injection layer comprising a metal complex of various types (I) and a compound of various types (III) or (IV).

[0236] In Comparative Examples 1 and 2, the hole-injection layer comprised a metal complex LiTFSI (also known as bis(trifluoromethanesulfonyl)imine lithium). The LiTFSI was free of substituents B1 and B2. The rate-on temperature of the LiTFSI was 222 °C. The calculated HOMO of F1 was -4.8 eV, as shown in Table 2. At a doping concentration of 2 vol.-%, the operating voltage was 4.3 V, the EQE efficiency was 12.37%, the cd / A efficiency was 5.02 cd / A, and the voltage stability over time U (50 h–1 h) was 0.741 V. At a doping concentration of 4 vol.-%, the operating voltage increased to 4.06 V, and the voltage stability over time increased to 0.395 V. However, the efficiency decreased slightly to 12.21% and 4.94 cd / A, respectively.

[0237] In Example 1, the hole injection layer comprises a metal complex W1 at a concentration of 2 vol.%. The compound of Formula (III) is the same as that in Comparative Examples 1 and 2. Compared with Comparative Example 1, the operating voltage is improved. The efficiency is slightly lower at 11.97%. However, the voltage stability over time is significantly improved to 0.69 V.

[0238] In Examples 2 and 3, the hole injection layer includes a higher concentration of W1. Compared with Comparative Examples 1 to 3, the operating voltage, efficiency, and voltage stability over time are improved.

[0239] In Examples 4 to 6, the hole injection layer includes a metallic complex W5. Compared to Comparative Examples 1 to 3, the operating voltage, efficiency, and / or voltage stability over time are improved.

[0240] In Examples 7 to 12, the hole injection layer comprises compound F2 of formula (III). The calculated HOMO of F2 is -4.8 eV. As can be seen in Table 3, compared with Comparative Examples 1 to 3, there are improvements in operating voltage, efficiency, and / or voltage stability over time.

[0241] In Examples 13 to 18, the hole injection layer includes compound F7 of formula (III). The calculated HOMO of F7 is -4.822 eV. As can be seen in Table 3, compared with Comparative Examples 1 and 2, the operating voltage, efficiency, and / or voltage stability over time are improved. In addition, compared with Comparative Example 3, the operating voltage and voltage stability over time are improved. In Comparative Example 3, the metal complex of formula (I) has been replaced by LiTFSI.

[0242] In Examples 19 to 21, the hole injection layer comprises compound F11 of formula (III). The calculated HOMO of F11 is -4.854 eV. As can be seen in Table 3, compared with Comparative Example 4, there are improvements in operating voltage, efficiency, and / or voltage stability over time. In Comparative Example 4, the metal complex of formula (I) has been replaced by LiTFSI.

[0243] In Examples 22 to 24, the hole injection layer comprises compound F13 of formula (IV). The calculated HOMO of F13 is -4.884 eV. As can be seen in Table 3, compared to Comparative Example 5, there are improvements in operating voltage, efficiency, and / or voltage stability over time. In Comparative Example 5, the metal complex of formula (I) has been replaced by LiTFSI.

[0244] In Examples 25 to 27, the hole injection layer comprises compound F16 of formula (III). The calculated HOMO of F16 is -4.927 eV. As can be seen in Table 3, compared to Comparative Example 6, there are improvements in operating voltage, efficiency, and / or voltage stability over time. In Comparative Example 6, the metal complex of formula (I) has been replaced by LiTFSI.

[0245] In Examples 28 to 32, the hole injection layer comprises compound F6 of formula (III). The calculated HOMO of F6 is -4.818 eV. As can be seen in Table 3, compared with Comparative Examples 1 to 3, there are improvements in operating voltage, efficiency, and / or voltage stability over time. In Comparative Examples 1 to 3, the metal complex of formula (I) has been replaced by LiTFSI.

[0246] In summary, significant improvements in performance (particularly operating voltage), efficiency, and / or voltage stability over time can be achieved in the organic electronic devices according to the present invention.

[0247] In particular, improved performance according to the invention can be obtained at doping concentrations of 2 vol.-% or less for the metal complex of formula (I). Because the metal complex of formula (I) can be deposited at a lower rate, a lower doping concentration may be beneficial.

[0248] Lowering the operating voltage helps reduce power consumption and extend battery life, especially in mobile devices.

[0249] Improved EQE and / or cd / A efficiency helps reduce power consumption and increase battery life, especially in mobile devices.

[0250] Improved voltage stability over time is beneficial to the long-term stability of organic electronic devices. Table 3: Performance of organic electronic devices including hole-injection layers, wherein the hole-injection layers include metal complexes of formula (I) and compounds of formula (III) or (IV). Metal complex of formula (I) Concentration (vol.-%) of metal complex of formula (I) Compounds of formula (III) or (IV) Concentration (vol.-%) of compounds of formula (III) or (IV) thickness Hole transport layer (nm) Operating voltage U (V) at 15 mA / cm² EQE (%) at 15 mA / cm² cd / A efficiency at 15 mA / cm² U(50h–1h) (V) at 30 mA / cm² Comparative Example 1 LiTFSI 2 F1 98 123 4.30 12.37 5.02 0.741 Comparative Example 2 LiTFSI 4 F1 96 123 4.06 12.21 4.94 0.395 Example 1 W1 2 F1 98 123 4.08 11.97 4.96 0.069 Example 2 W1 4 F1 96 123 3.89 12.04 4.98 0.035 Example 3 W1 8 F1 92 123 3.77 12.57 5.15 0.030 Example 4 W5 2 F1 98 123 3.86 12.14 5.03 0.290 Example 5 W5 4 F1 96 123 3.78 12.61 5.20 0.065 Example 6 W5 8 F1 92 123 3.78 12.48 5.14 0.027 Example 7 W1 2 F2 98 126 3.69 13.02 6.84 0.001 Example 8 W1 4 F2 96 126 3.62 12.96 6.78 0.011 Example 9 W1 8 F2 92 126 3.61 12.83 6.71 0.007 Example 10 W5 2 F2 98 126 3.63 12.84 6.52 0.133 Example 11 W5 4 F2 96 126 3.62 12.70 6.54 0.020 Example 12 W5 8 F2 92 126 3.62 12.69 6.51 0.014 Example 13 W1 2 F7 98 127 3.99 14.25 6.05 0.121 Example 14 W1 4 F7 96 127 3.87 14.40 6.08 0.037 Example 15 W1 8 F7 92 127 3.82 14.91 6.25 0.020 Example 16 W5 2 F7 98 127 3.83 15.81 8.15 0.229 Example 17 W5 4 F7 96 127 3.82 15.56 7.94 0.045 Example 18 W5 8 F7 92 127 3.82 15.64 7.90 0.029 Comparative Example 3 LiTFSI 4 F7 96 127 3.96 15.56 7.43 0.278 Example 19 W1 4 F11 96 124 3.62 12.33 5.84 0.047 Example 20 W1 8 F11 92 124 3.61 12.33 5.59 0.039 Example 21 W1 12 F11 88 124 3.61 12.32 5.91 0.039 Comparative Example 4 LiTFSI 4 F11 96 124 3.88 12.19 5.77 0.194 Example 22 W1 4 F13 96 125 3.73 13.12 7.07 0.184 Example 23 W1 8 F13 92 125 3.71 13.15 7.06 0.124 Example 24 W1 12 F13 88 125 3.72 13.12 7.06 0.12 Comparative Example 5 LiTFSI 4 F13 96 125 4.15 12.97 6.64 0.756 Example 25 W1 4 F16 96 127 3.92 12.15 5.15 0.085 Example 26 W1 8 F16 92 127 3.80 12.03 5.08 0.082 Example 27 W1 12 F16 88 127 3.79 12.00 5.03 0.073 Comparative Example 6 LiTFSI 4 F16 96 127 4.55 11.70 4.84 0.587 Example 28 W1 4 F6 96 126 3.72 13.90 6.92 0.061 Example 29 W1 8 F6 92 126 3.67 13.88 6.87 0.049 Example 30 W12 5 F6 95 126 3.69 13.75 6.85 0.056 Example 31 W12 10 F6 90 126 3.65 13.92 6.88 0.034 Example 32 W12 14 F6 86 126 3.63 13.93 6.84 0.034

[0251] The specific combinations of elements and features in the detailed embodiments described above are merely exemplary; it is also clearly conceived that these teachings in this and in the patents / applications incorporated herein by reference be interchanged and substituted with other teachings. As will be understood by those skilled in the art, changes, modifications and other implementations of the content described herein can be conceived without departing from the spirit and scope of the claimed invention. Therefore, the foregoing description is merely illustrative and not intended to be limiting. In the claims, the term "comprising" does not exclude other elements or steps, and the indefinite articles "a" or "an" do not exclude a plurality. The fact that certain measures are described in mutually different appendices does not indicate that combinations of these measures cannot be used advantageously. The scope of the invention is defined in the following claims and their equivalents. Furthermore, the element symbols used in the description and claims do not limit the scope of the claimed invention. [Simplified Explanation of the Diagram]

[0203] The foregoing elements, the claimed elements, and the elements used according to the invention in the described embodiments have no particular exceptions in terms of their size, shape, material selection, and technical concept, allowing for the application of selection criteria known in the relevant art without limitation. Additional details, features, and advantages of the object of the invention are disclosed in the appendices and in the following description, which shows, in an exemplary manner, preferred embodiments of the invention. However, any embodiment does not necessarily represent the full scope of the invention, and therefore, reference is made to the claims and this document to explain the scope of the invention. It should be understood that the foregoing general description and the following detailed description are merely exemplary and explanatory, and are intended to provide further explanation of the claimed invention. Figures 1 to 7 Figure 1 is a schematic cross-sectional view of an organic electronic device according to an exemplary embodiment of the invention; Figure 2 is a schematic cross-sectional view of an organic electronic device according to an exemplary embodiment of the invention; Figure 3 is a schematic cross-sectional view of an organic electronic device according to an exemplary embodiment of the invention; Figure 4 is a schematic cross-sectional view of an organic electronic device according to an exemplary embodiment of the invention; Figure 5 is a schematic cross-sectional view of an organic electronic device according to an exemplary embodiment of the invention; Figure 6 is a schematic cross-sectional view of an organic electronic device according to an exemplary embodiment of the invention; Figure 7 is a schematic cross-sectional view of an organic electronic device according to an exemplary embodiment of the invention. In the following description, Figures 1 through 7 will be explained in more detail with reference to the examples. However, the disclosure is not limited to the following figures. In this document, when a first element is referred to as being formed or disposed "on" or "above" a second element, the first element may be disposed directly on the second element, or one or more other elements may be disposed therebetween. When a first element is referred to as being "directly" formed or disposed "on" or "above" a second element, no other elements are disposed between them. Figure 1 is a schematic cross-sectional view of an organic electronic device (100) according to an exemplary embodiment of the present invention. The organic electronic device (100) includes a substrate (110), an anode layer (120), and a hole injection layer (HIL) (130). The HIL (130) is disposed on the anode layer (120). A hole transport layer (140), a first emission layer (EML) (150), and a cathode layer (190) are disposed on the HIL (130). Figure 2 is a schematic cross-sectional view of an organic electronic device (100) according to an exemplary embodiment of the present invention. The organic electronic device (100) includes a substrate (110), an anode layer (120) including a first anode sublayer (121) and a second anode sublayer (122), and a hole injection layer (HIL) (130). The HIL (130) is disposed on the anode layer (120) including the first anode sublayer (121) and the second anode sublayer (122). Above the HIL (130), a hole transport layer (140), a first emission layer (EML) (150), and a cathode layer (190) are disposed.Figure 3 is a schematic cross-sectional view of an organic electronic device (100) according to an exemplary embodiment of the present invention. The organic electronic device (100) includes a substrate (110), an anode layer (120) including a first anode sublayer (121), a second anode sublayer (122), and a third anode sublayer (123), and a hole injection layer (HIL) (130). The HIL (130) is disposed on the anode layer (120). A hole transport layer (140), a first emission layer (EML) (150), and a cathode layer (190) are disposed on the HIL (130). Figure 4 is a schematic cross-sectional view of an organic electronic device (100) according to an exemplary embodiment of the present invention. The organic electronic device (100) includes a substrate (110), an anode layer (120) including a first anode sublayer (121) and a second anode sublayer (122), and a hole injection layer (HIL) (130). The HIL (130) is disposed on the anode layer (120). A hole transport layer (140), a first emitter layer (EML) (150), a hole blocking layer (EBL) (155), an electron transport layer (ETL) (160), and a cathode layer (190) are disposed on the HIL (130). FIG5 is a schematic cross-sectional view of an organic electronic device (100) according to an exemplary embodiment of the present invention. The organic electronic device (100) includes a substrate (110), an anode layer (120) including a first anode sublayer (121), a second anode sublayer (122), and a third anode sublayer (123), and a hole injection layer (HIL) (130). The HIL (130) is disposed on the anode layer (120). A hole transport layer (140), a first emitter layer (EML) (150), a hole blocking layer (EBL) (155), an electron transport layer (ETL) (160), and a cathode layer (190) are disposed on the HIL (130). Figure 6 is a schematic cross-sectional view of an organic electronic device (100) according to an exemplary embodiment of the present invention. The organic electronic device (100) includes a substrate (110), an anode layer (120) including a first anode sublayer (121), a second anode sublayer (122), and a third anode sublayer (123), and a hole injection layer (HIL) (130). The HIL (130) is disposed on the anode layer (120). Above the HIL (130), a hole transport layer (140), an electron blocking layer (EBL) (145), a first emitter layer (EML) (150), a hole blocking layer (EBL) (155), an electron transport layer (ETL) (160), and a cathode layer (190) are disposed. Figure 7 is a schematic cross-sectional view of an organic electronic device (100) according to an exemplary embodiment of the present invention.The organic electronic device (100) includes a substrate (110), an anode layer (120) including a first anode sublayer (121), a second anode sublayer (122), and a third anode sublayer (123), and a hole injection layer (HIL) (130). The HIL (130) is disposed on the anode layer (120). Above the HIL (130), a hole transport layer (140), an electron blocking layer (EBL) (145), a first emitter layer (EML) (150), a hole blocking layer (EBL) (155), an electron transport layer (ETL) (160), an electron injection layer (180), and a cathode layer (190) are disposed. Although not shown in Figures 1 to 7, a capping layer and / or sealing layer may be further formed on the cathode electrode 190 to seal the organic electronic device 100. In addition, various other modifications may be applied thereto. In the following, embodiments will be described in more detail with reference to the following examples. However, this disclosure is not limited to the following examples.

Claims

1. An organic electronic device comprising a substrate, an anode layer, a cathode layer, at least one emitter layer, and at least one or more hole injection layers, wherein the hole injection layers are disposed between the anode layer and the at least one emitter layer, and wherein the hole injection layers comprise: - A metal complex having formula (I): (I) where M is a metal ion; n is the valence of M; m is n; L is a ligand (II) of formula (II), where A1 and A2 are SO2; X is N; B1 and B2 are independently selected from substituted C6 to C19 aryl groups, the C6 to C19 aryl groups comprising 2 to 4 substituents, the 2 to 4 substituents being independently selected from the group consisting of halogens, CF3, C2F5, C3F7, C4F9, OCF3, OC2F5, and CN; and - A compound of formula (III) or (IV): (III) or (IV), where T1, T2, T3, T4, and T5 are independently selected from a single bond, phenyl, biphenyl, triphenyl, or naphthylmethylene; T6 is selected from substituted or unsubstituted phenyl, biphenyl, triphenyl, or naphthylmethylene, wherein the substituents on the phenyl group are selected from C6 to C18 aryl, C3 to C18 heteroaryl, phenyl, biphenyl, carbazole, and phenylcarbazole.Ar1, Ar2, Ar3, Ar4, and Ar5 are independently selected from: substituted or unsubstituted C6 to C20 aryl groups, or substituted or unsubstituted C3 to C20 heteroaryl groups, substituted or unsubstituted biphenyls, substituted or unsubstituted phenanthrene, substituted or unsubstituted 9-phenanthrene, substituted 9,9-phenanthrene, substituted or unsubstituted naphthalene, substituted or unsubstituted anthracene, substituted or unsubstituted phenanthrene, substituted or unsubstituted pyrene, substituted or unsubstituted perylene, substituted or unsubstituted triphenylene, substituted or unsubstituted tetraphenylene, substituted or unsubstituted tetraphenylene, substituted or unsubstituted tetraphenylene, substituted... Substituted or unsubstituted dibenzofuran, substituted or unsubstituted dibenzothiophene, substituted or unsubstituted dibenzopiperan, substituted or unsubstituted carbazole, substituted 9-phenylcarbazole, substituted or unsubstituted aziridine, substituted or unsubstituted dibenzo[b,f]aziridine, substituted or unsubstituted 9,9'-spirodi[fu], substituted or unsubstituted 9,9'-spirodi[fu] having at least one fused aromatic ring, substituted or unsubstituted spiro[fu]-9,9'-dibenzopiperan], comprising two aromatic 6-membered rings and two aromatic 5-membered rings, wherein at least one 5-membered ring is present. The ring includes a substituted or unsubstituted aromatic fused ring system comprising a heteroatom, a substituted or unsubstituted aromatic fused ring system comprising two aromatic 6-membered rings and two aromatic 5-membered rings, wherein at least one 5-membered ring comprises an O atom, or a substituted or unsubstituted aromatic fused ring system comprising at least three substituted or unsubstituted aromatic rings selected from the group consisting of: substituted or unsubstituted non-hetero-5-membered rings, substituted or unsubstituted hetero-5-membered rings, substituted or unsubstituted 6-membered rings and / or substituted or unsubstituted 7-membered rings, etc. Substituted or unsubstituted cyclohexane, substituted or unsubstituted heterocyclic or non-heterocyclic system comprising 2 to 6 substituted or unsubstituted 5, 6 or 7-membered rings, or a fused ring system comprising 2 to 6 substituted or unsubstituted 5 to 7-membered rings, wherein the substituted or unsubstituted 5 to 7-membered rings are selected from the group consisting of: (i) unsaturated 5 to 7-membered heterocyclic rings, (ii) 5 to 6-membered aromatic heterocyclic rings, (iii) unsaturated 5 to 7-membered non-heterocyclic rings, and (iv) 6-membered aromatic non-heterocyclic rings.The substituents of Ar1, Ar2, Ar3, Ar4, and Ar5 are selected from the group consisting of the same or different groups including: H, D, F, C(=O)R2, CN, Si(R2)3, P(=O)(R2)2, OR2, S(=O)R2, S(=O)2R2, substituted or unsubstituted linear alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted branched alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 20 carbon atoms, and substituted or unsubstituted alkenyl or ynyl groups having 2 to 20 carbon atoms. The following are included: substituted or unsubstituted alkoxy groups having 1 to 20 carbon atoms; substituted or unsubstituted aromatic ring systems having 6 to 40 aromatic ring atoms; substituted or unsubstituted heteroaromatic ring systems having 5 to 40 aromatic ring atoms; unsubstituted C6 to C18 aryl groups; unsubstituted C3 to C18 heteroaromatic groups; and fused ring systems comprising 2 to 6 unsubstituted 5 to 7-membered rings, wherein the 5 to 7-membered rings are selected from the group consisting of unsaturated 5 to 7-membered heterocycles, 5 to 6-membered aromatic heterocycles, unsaturated 5 to 7-membered non-heterocycles, and 6-membered aromatic non-heterocycles. R2 is selected from H, D, straight-chain alkyl groups having 1 to 6 carbon atoms, branched alkyl groups having 1 to 6 carbon atoms, cycloalkyl groups having 3 to 6 carbon atoms, alkenyl or ynyl groups having 2 to 6 carbon atoms, C6 to C18 aryl or C3 to C18 heteroaryl groups; wherein the compound of formula (III) or (IV) has a calculated HOMO in the range of <-4.79 eV and >6.5 eV.

2. The organic electronic device as claimed in claim 1, wherein the following compounds E1 to E5 are excluded: (E1), (E2), (E3), (E4), (E5).

3. The organic electronic device as claimed in claim 1, wherein the anode layer comprises a first anode sublayer and a second anode sublayer, wherein - the first anode sublayer comprises a first metal having a work function in the range of ≥4 and ≤6 eV, and - the second anode sublayer comprises a transparent conductive oxide or ITO.

4. The organic electronic device as claimed in claim 1, wherein the M of the metal complex of formula (I) is selected from a metal ion, an alkali metal, an alkaline earth metal, a rare earth metal, a transition metal, or a group III or group V metal, a metal with an atomic mass ≥ 24 Da, or a metal with an atomic mass ≥ 24 Da and M having an oxidation number ≥ 2, wherein the corresponding metal in the metal ion has an electronegativity of less than 2.4 according to Allen.

5. The organic electronic device as claimed in claim 1, wherein the metal complex of formula (I) has a molecular weight of ≥ 339 and ≤ 2000 g / mol.

6. The organic electronic device as claimed in claim 1, wherein the anode layer of the organic electronic device further includes a third anode sublayer.

7. The organic electronic device as claimed in claim 1, wherein the compounds of formula (III) and (IV) have a molecular weight of ≥ 400 and ≤ 2000 g / mol.

8. The organic electronic device as claimed in claim 1, wherein Ar1, Ar2, Ar3, Ar4 and Ar5 are independently selected from D1 to D22: (D1), (D2), (D3), (D4), (D5), (D6), (D7), (D8), (D9), (D10), (D11), (D12), (D13), (D14), (D15), (D16), (D17), (D18), (D19), (D20), (D21), (D22), where an asterisk * represents a bond position.

9. The organic electronic device as claimed in claim 1, wherein the compounds of formula (III) and formula (IV) are selected from F1 to F19: (F1), (F2), (F3), (F4), (F5), (F6), (F7), (F8), (F9), (F10), (F11), (F12), (F13), (F14), (F15), (F16), (F17), (F18), (F19).

10. The organic electronic device as claimed in claim 1, wherein m and n in formula (I) are the same and are an integer from 1 to 4.

11. The organic electronic device as claimed in claim 1, wherein the metal complex is selected from formula (Ia): (Ia), wherein M is a metal ion; n is the valence of M; m is n; B1 and B2 are independently selected from substituted C6 to C19 aryl groups, or substituted or unsubstituted C2 to C20 heteroaryl groups, wherein at least one of the substituents of the substituted C6 to C19 aryl group or the substituted C2 to C20 heteroaryl group is independently selected from halogen, CN, partially or perfluoro C1 to C8 alkyl, partially or perfluoro C1 to C8 alkoxy.

12. The organic electronic device as claimed in claim 1, wherein the halogen is F.

13. The organic electronic device as claimed in claim 11, wherein the halogen is Cl or F.

14. The organic electronic device as claimed in claim 1, wherein the ligands of formula (II) are independently selected from G1 to G21: (G1), (G2), (G3), (G4), (G5), (G6), (G7), (G8), (G9), (G10), (G11), (G12), (G13), (G14), (G15), (G16), (G17), (G18), (G19), (G20), (G21).

15. The organic electronic device as claimed in claim 1, wherein the metal complex of formula (I) is selected from a compound W1 to W12: (W1), (W2), (W3), (W4), (W5), (W6), (W7), (W8), (W9), (W10), (W11), (W12).

16. The organic electronic device as claimed in claim 1, wherein the organic electronic device further includes a hole transport layer, wherein the hole transport layer is disposed between the hole injection layer and the at least one emitter layer or the first emitter layer.

17. The organic electronic device as claimed in claim 16, wherein the hole transport layer comprises a matrix compound according to formula (III) or (IV).

18. The organic electronic device as claimed in claim 17, wherein the matrix compound in the hole injection layer and the hole transport layer is selected as the same compound.

19. The organic electronic device as claimed in claim 1, wherein the organic electronic device is a light-emitting device or a display device.

20. A metal complex for use in an organic electronic device or in a layer of an organic electronic device, wherein the metal complex has the formula (I): (I) where M is silver (I) or copper (II); n is the valence of M; m is n; and L is a compound selected from G7, G15, G17, G19, G20 or G21: (G7), (G15), (G17), (G19), (G20), (G21); or M is Li, n is 1, m is 1, and L is selected from G2: (G2).

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