Organic electronic device comprising a compound of formula (i), display device comprising the organic electronic device as well as compounds of formula (i) for use in organic electronic devices

Abstract

The present invention relates to a compound of formula (I) and an organic electronic device comprising a charge-generating layer comprising a compound of formula (I).

Description

[Technical Field]

[0001] This invention relates to an organic electronic device comprising a compound of formula (I) and a display device comprising the organic electronic device. This invention further relates to a novel compound of formula (I) that can be used in organic electronic devices. [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 an anode, a hole transport layer (HTL), an emitter layer (EML), an electron transport layer (ETL), and a cathode, sequentially stacked on a substrate. In this regard, the 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 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 their excited state to the ground state, light is emitted. The injection and flow of holes and electrons should be balanced so that OLEDs with the above structure have excellent efficiency and / or a long lifespan.

[0004] The performance of organic light-emitting diodes can be affected by the characteristics of the semiconductor layer, and especially by the characteristics of the compound of formula (I) contained in the semiconductor layer.

[0005] EP3382770A1 relates to an ink composition for forming an organic semiconductor layer, wherein the ink composition comprises: - at least one p-type dopant including electron-withdrawing groups; - at least one first auxiliary compound, wherein the first auxiliary compound is an aromatic nitrile compound, wherein the aromatic nitrile compound has about ≥1 to about ≤3 nitrile groups and a melting point of about <100°C, wherein the first auxiliary compound is different from the p-type dopant; and wherein the electron-withdrawing groups are fluorine, chlorine, bromine and / or nitrile.

[0006] US2010288362A1 provides an electronic device including an anode and a cathode, with at least two organic phototransducing units separated by an intermediate connection between the anode and the cathode. The intermediate connection sequentially includes: an organic p-type layer; an intermediate layer in direct contact with the organic p-type layer and comprising a compound having a HOMO of less than -3.0 eV and different from the organic compound in the organic p-type layer; and an n-type doped organic layer in direct contact with the intermediate layer and comprising a predominantly electron transport material and an organic n-dopant with a HOMO of not less than -4.5 eV. In one embodiment, the electronic device is a cascaded OLED.

[0007] WO2019168368A1 provides an organic light-emitting diode, comprising: a cathode, an anode, and a light-emitting layer provided between the cathode and the anode, wherein any one of the compounds represented by chemical formula 1, chemical formula 2, and chemical formula 3 is included between the anode and the light-emitting layer.

[0008] There is still a need to improve the performance of organic semiconductor materials, semiconductor layers and their organic electronic devices, in particular, to improve the stability of the operating voltage over time by improving the properties of the compounds contained therein. [Summary of the Invention]

[0009] The present invention provides an organic electronic device comprising: an anode layer, a cathode layer, and a charge generation layer, wherein the charge generation layer comprises a p-type charge generation layer and an n-type charge generation layer, wherein the p-type charge generation layer comprises a compound of formula (I) wherein A1 is selected from formula (II) X1 is selected from CR1 or N; X2 is selected from CR2 or N; X3 is selected from CR3 or N; X4 is selected from CR4 or N; X5 is selected from CR5 or N; R1, R2, R3, R4, and R5 (if present) are independently selected from CN, partially fluorinated or perfluorinated C1 to C8 alkyl groups, halogens, Cl, F, D, or H, wherein when any one of R1, R2, R3, R4, and R5 is present, the corresponding X1, X2, X3, X4, and X5 are not N; but provided that one of the following requirements a) to e) is satisfied: a) At least one of R1, R2, R3, R4 and R5 is independently selected from CN, partially fluorinated or perfluorinated C1 to C8 alkyl, halogen, Cl, F, and at least one of the remaining R1, R2, R3, R4 and R5 is selected from D or H; b) R1 or R2 is selected from CN or partially fluorinated or perfluorinated C1 to C8 alkyl, and at least one of the remaining R1 to R5 is independently selected from CN, partially fluorinated or perfluorinated C1 to C8 alkyl, halogen, Cl or F; c) R3 is selected from partially fluorinated or perfluorinated C1 to C8 alkyl, and at least one of R1, R2, R4 and R5 is independently selected from CN, partially fluorinated or perfluorinated C1 to C8 alkyl, halogen, Cl or F; d) At least two of R1 to R5 are independently selected from CN or partially fluorinated or perfluorinated C1 to C8 alkyl groups; or e) at least one of X1 to X5 is N, and at least two of X1 to X5 are selected from CR1 to CR5; A2 and A3 are independently selected from formula (III) (III) wherein Ar is independently selected from substituted or unsubstituted C6 to C18 aryl and substituted or unsubstituted C2 to C18 heteroaryl, wherein the substituent on Ar is independently selected from CN, partially or perfluorinated C1 to C6 alkyl, halogen, Cl, F, D; and R' is selected from Ar, substituted or unsubstituted C6 to C18 aryl or C3 to C18 heteroaryl, partially fluorinated or perfluorinated C1 to C8 alkyl, halogen, F or CN.

[0010] It should be noted that in this application and throughout the scope of the patent application, any of An, Bn, Rn, etc., always refers to the same part, unless otherwise stated.

[0011] In this specification, unless otherwise defined, “substituted” means substituted with deuterium, C1 to C12 alkyl and C1 to C12 alkoxy.

[0012] However, in this specification, "aryl-substituted" means substitution with one or more aryl groups, which themselves may be substituted with one or more aryl and / or heteroaryl groups.

[0013] Correspondingly, in this specification, "heteroaryl substituted" means substitution with one or more heteroaryl groups, which themselves may be substituted with one or more aryl and / or heteroaryl groups.

[0014] 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.

[0015] 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, and hexyl groups.

[0016] The term "cycloalkyl" refers to a saturated hydrocarbon group derived from a cycloalkane by taking a hydrogen atom from a ring atom included in the corresponding cycloalkane. Examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, adamantyl, and the like.

[0017] The term "heteroatom" is understood as a way in which 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.

[0018] In this specification, "aryl group" means a hydrocarbon group that can be extracted from a hydrogen atom of an aromatic ring in the corresponding aromatic hydrocarbon. An aromatic hydrocarbon means a hydrocarbon containing at least one aromatic ring or aromatic ring system. An aromatic ring or aromatic ring system means 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 multiple aromatic rings linked by single bonds, such as biphenyl; and polycyclic groups comprising fused rings, such as naphthyl or fumonisin-2-yl.

[0019] Similarly, under heteroaryl, it is particularly suitable to understand the derivation of a group derived from a cyclic hydrogen of a heterocyclic aromatic ring in a compound that includes at least one such ring.

[0020] 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 such ring.

[0021] The terms “fused aryl ring” or “condensed aryl ring” are understood as two aryl rings being considered as fused or condensed when they share at least two common sp2-hybridized carbon atoms.

[0022] In this specification, a single key refers to a direct key.

[0023] The term “n-type charge generation layer” is sometimes also referred to in the art as n-CGL or electron generation layer, and is intended to include both.

[0024] The term “p-type charge generation layer” is sometimes also referred to in the art as p-CGL or hole generation layer, and is intended to include both.

[0025] The terms “none,” “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.

[0026] The term “sandwiched in contact” refers to a three-layer arrangement in which the middle layer is in direct contact with two adjacent layers.

[0027] The terms “light-absorbing layer” and “light absorption layer” are used synonymously.

[0028] The terms “light-emitting layer”, “light emission layer” and “emission layer” are used synonymously.

[0029] The terms “OLED”, “organic light-emitting diode” and “organic light-emitting device” are used synonymously.

[0030] The terms “anode”, “anode layer” and “anode electrode” are used synonymously.

[0031] The terms “cathode”, “cathode layer” and “cathode electrode” are used synonymously.

[0032] 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 a hole formed in the anode to be easily injected into and transported in the emitter layer due to its conductivity, based on the highest occupied molecular orbital (HOMO) energy level.

[0033] Furthermore, the electronic properties refer to the following capabilities: receiving electrons when an electric field is applied; and, based on the lowest unoccupied molecular orbital (LUMO) energy level, due to conductivity, electrons formed in the cathode can be easily injected into and transported within the emitter layer. Advantageous effects

[0034] Surprisingly, it has been found that the organic electronic device according to the invention solves the problem that forms the basis of the invention by making the device in various forms, especially in terms of operating voltage during the service life, superior to the organic electroluminescent devices known in the art.

[0035] According to one embodiment of the present invention, the p-type charge generation layer includes compound (IV) of formula (IV), wherein B1 is selected from formula (V), B3 and B5 are Ar, and B2, B4 and B6 are R3.

[0036] According to one embodiment, the p-type charge generation layer includes a composition comprising a compound of formula (IV) and at least one compound of formula (IVa) to (IVd) (IVa)(IVb)(IVc)(IVd).

[0037] In cases where the p-type charge generation layer includes such a composition, throughout this application text, the term "compound of formula (I)" should also be intended to include the composition described above.

[0038] According to one embodiment of the present invention, in formula (II), at least two of the preconditions a) to e) are satisfied.

[0039] According to one embodiment of the present invention, in formula (II), R3 is selected from CN or partially fluorinated or perfluorinated C1 to C8 alkyl groups, and at least one of R1, R2, R4, and R5 is selected from H or D.

[0040] According to one embodiment of the present invention, R1 is preferably selected from perfluorinated C1 to C6 alkyl or CN, more preferably selected from perfluorinated C1 to C4 alkyl or CN, even more preferably CF3 or CN, and even more preferably CF3.

[0041] According to one embodiment of the present invention, R2 is preferably selected from perfluorinated C1 to C6 alkyl groups, more preferably from perfluorinated C1 to C4 alkyl groups, and even more preferably CF3.

[0042] According to one embodiment of the present invention, R3 is selected from CN, partially or fully fluorinated C1 to C4 alkyl, substituted or unsubstituted C6 to C12 aryl or C3 to C12 heteroaryl, wherein the substituent is selected from halogen, F, Cl, CN, partially or fully fluorinated C1 to C4 alkyl; more preferably, R3 is selected from CN, CF3 or F, and most preferably CN.

[0043] According to one embodiment of the present invention, one of R1 to R5 is selected from perfluorinated C1 to C6 alkyl or CN, more preferably from perfluorinated C1 to C4 alkyl or CN, even more preferably CF3 or CN, and at least three of R1 to R5 are F.

[0044] According to one embodiment of the present invention, both of R1 to R5 are independently selected from perfluorinated C1 to C6 alkyl or CN, more preferably from perfluorinated C1 to C4 alkyl or CN, even more preferably CF3 or CN, and at least two of R1 to R5 are F.

[0045] According to one embodiment of the present invention, one of R1 to R5 is selected from perfluorinated C1 to C6 alkyl or CN, more preferably from perfluorinated C1 to C4 alkyl or CN, even more preferably CF3 or CN, and at least one of X1 to X5 is N.

[0046] According to one embodiment of the present invention, both of R1 to R5 are independently selected from perfluorinated C1 to C6 alkyl or CN, more preferably from perfluorinated C1 to C4 alkyl or CN, even more preferably CF3 or CN, and at least two of X1 to X5 are N.

[0047] According to one embodiment of the present invention, in formula (II), R1 to R5 are independently selected from CN, partially fluorinated or perfluorinated C1 to C8 alkyl groups, halogens, Cl, and F.

[0048] According to one embodiment of the present invention, in formula (II), at least one of X1 to X5 is N, and at least one of R1 to R5 is selected from CN, partially fluorinated or perfluorinated C1 to C8 alkyl, halogen, Cl, F.

[0049] According to one embodiment of the present invention, R3 is selected from CN or partially fluorinated or perfluorinated C1 to C8 alkyl groups, and at least one of R1, R2, R4, and R5 is selected from H or D.

[0050] According to one embodiment of the present invention, R1 to R5 are not D or H.

[0051] According to one embodiment of the present invention, A2 and A3 are the same.

[0052] According to one embodiment of the present invention, at least one of A2 and A3 is the same as A1.

[0053] According to one embodiment of the present invention, A1 is different from A2 and / or A3.

[0054] According to one embodiment of the present invention, Ar is selected from substituted or unsubstituted C6 to C12 aryl and substituted or unsubstituted C3 to C12 heteroaryl, wherein the substituent on Ar is independently selected from CN, partially or perfluorinated C1 to C4 alkyl, halogen, F; preferably, Ar is selected from substituted phenyl, pyridyl, pyrimidinyl or triazine, wherein the substituent on Ar is independently selected from CN, CF3 or F.

[0055] According to one embodiment of the present invention, A2 is selected from formula (IIIa) and A3 is selected from formula (III).

[0056] According to an alternative embodiment of the present invention, A2 and A3 are independently selected from formula (IIIa).

[0057] According to one embodiment of the present invention, A1, A2 and A3 are selected to be the same.

[0058] According to one embodiment of the present invention, A2 and A3 are selected to be the same, and A1 is selected to be different from A2 and A3.

[0059] According to one embodiment of the present invention, A1 and A2 are selected to be the same, and A3 is selected to be different from A1 and A2.

[0060] According to one embodiment of the present invention, R' is CN.

[0061] According to one embodiment of the present invention, formula (II) is selected from groups including the following portions: , ...

[0062] According to one embodiment of the present invention, formula (II) is selected from groups including the following: , ...

[0063] According to one embodiment of the present invention, formula (II) is selected from groups including the following: , , , , , , , , , , , , , , , , , , , , , , and.

[0064] According to one embodiment of the present invention, formula (III) is selected from groups comprising the following parts: , ...

[0065] According to one embodiment of the present invention, formula (III) is selected from groups including the following: , , , , , , , , , , , , , , , , , and.

[0066] According to one embodiment of the present invention, the compound of formula (I) comprises fewer than nine CN groups selected from groups including the following portions, preferably fewer than eight CN groups.

[0067] According to one embodiment of the present invention, the compound of formula (I) comprises between three and eight CN groups, preferably between three and seven CN groups.

[0068] In particular, when the number of CN groups in the compound of formula (I) is selected within this range in vacuum thermal deposition, improved processing performance can be obtained.

[0069] According to one embodiment of the present invention, when the mixing function B3LYP and the 6-31G* basis set in the gas phase are applied and calculated by the suite program TURBOMOLE V6.5 (TURBOMOLE GmbH, Litzenhardtstrasse 19, 76135 Karlsruhe, Germany), the LUMO energy level of the compound of formula (I) is selected in the range of ≤-4.5 eV and ≥-5.8 eV, preferably in the range of ≤-4.6 eV and ≥-5.7 eV, also preferably in the range of ≤-4.7 eV and ≥-5.7 eV, and most preferably in the range of ≤-4.8 eV and ≥-5.7 eV.

[0070] According to one embodiment, the compound of formula (I) is selected from compounds A1 to A59. A 1 A 2 A 3 A1 A2 A3 A4 A5 A6 A7 A8 A9 A10 A11 A12 A13 A14 A15 A16 A17 A18 A19 A20 A21 A22 A23 A24 A25 A26 A27 A28 A29 A30 A31 A32 A33 A34 A35 A36 A37 A38 A39 A40 A41 A42 A43 A44 A45 A46 A47 A48 A49 A50 A51 A52 A53 A54 A55 A56 A57 A58 A59

[0071] This invention is further related to the compound of formula (I) as described in claim 1, wherein formula (II) is selected from the group consisting of: , , , , , , , , , , , , , , , , , , , , and.

[0072] According to one embodiment of the present invention, the p-type and / or n-charge generating layer and / or the compound of formula (I) is non-radioactive.

[0073] In the context of this specification, the terms “substantially non-emissive” or “non-emissive” mean that the compound or layer contributes less than 10%, preferably less than 5%, to the visible emission spectrum from the device. The visible emission spectrum is an emission spectrum with wavelengths of about ≥380 nm to about ≤780 nm.

[0074] According to one embodiment of the present invention, the p-type charge generation layer is positioned closer to the cathode layer than the n-type charge generation layer.

[0075] According to one embodiment of the present invention, the p-type charge-generating layer further comprises a substantially covalent matrix compound. The substantially covalent matrix compound

[0076] According to one embodiment, the substantially covalent matrix compound may be selected from at least one organic compound. The substantially covalent matrix may substantially consist of covalently bonded C, H, O, N, S, and optionally additionally include covalently bonded B, P, As, and / or Se.

[0077] According to one embodiment of the organic electronic device, the p-CGL may further include a substantially covalent matrix compound, wherein the substantially covalent matrix compound may be selected from organic compounds substantially composed of covalently bonded C, H, O, N, S, and optionally additionally include covalently bonded B, P, As and / or Se.

[0078] Further examples of organic compounds that include organometallic compounds comprising carbon-metal covalent bonds, metal complexes comprising organic ligands, and metal salts of organic acids as substantially covalent organic matrix compounds that can act as p-CGLs.

[0079] In one embodiment, the substantially covalent matrix compound lacks metal atoms, and most of its framework atoms may be selected from C, O, S, and N. Alternatively, the substantially covalent matrix compound lacks metal atoms, and most of its framework atoms may be selected from C and N.

[0080] According to one embodiment, the substantially covalent matrix compound may have a molecular weight Mw of ≥400 and ≤2000 g / mol, preferably ≥450 and ≤1500 g / mol, more preferably ≥500 and ≤1000 g / mol, additionally preferably ≥550 and ≤900 g / mol, and also preferably ≥600 and ≤800 g / mol.

[0081] Preferably, the substantially covalent matrix compound includes at least one aromatic amine moiety, replacing the diaryl amine moiety, replacing the triaryl amine moiety.

[0082] Preferably, the substantially covalent matrix compound is free of metal and / or ionic bonds. Compound of formula (VI) or compound of formula (VII)

[0083] According to another embodiment of the present invention, the substantially covalent matrix compound may include at least a monoarylamine compound, a diarylamine compound, a triarylamine compound, a compound of formula (VI) or a compound of formula (VII): (VI), (VII), wherein T1, T2, T3, T4 and T5 are independently selected from single bonds, phenylene, biphenylene, triphenylene or naphthenylene, preferably selected from single bonds or phenylene; T6 is phenylene, biphenylene, triphenylene or naphthenylene; 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 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 tetraphenanthrene, substituted or unsubstituted dibenzofuran, substituted or unsubstituted dibenzothiophene, substituted or unsubstituted dibenzopiperanone, substituted or unsubstituted carbazole, substituted 9-phenylcarbazole, substituted or unsubstituted aziridine, substituted or unsubstituted dibenzo[b,f]aziridine, etc. Substituted or unsubstituted 9,9'-spirobi[furan], substituted or unsubstituted spiro[furan-9,9'-dibenzopiperan], or substituted or unsubstituted aromatic fused ring systems (comprising at least three substituted or unsubstituted aromatic rings selected from the group consisting of: substituted or unsubstituted non-heterogeneous 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 furan, or fused ring systems (comprising 2 to 6 substituted or unsubstituted 5 to 7-membered rings), wherein the ring is 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-heterogeneous rings, (iv) 6-membered aromatic non-heterogeneous rings;The substituents of Ar1, Ar2, Ar3, Ar4, and Ar5 are selected from the group consisting of the following groups, which may be the same or different: 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 group includes: 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 heteroaryl group; a fused ring system comprising 2 to 6 unsubstituted 5 to 7-membered rings, wherein the ring is 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 may be 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 heteroaryl group.

[0084] According to an embodiment, T1, T2, T3, T4, and T5 may be independently selected from single bonds, extended phenyl groups, extended biphenyl groups, or extended triphenyl groups. According to an embodiment, T1, T2, T3, T4, and T5 may be independently selected from extended phenyl groups, extended biphenyl groups, or extended triphenyl groups, and one of T1, T2, T3, T4, and T5 is a single bond. According to an embodiment, T1, T2, T3, T4, and T5 may be independently selected from extended phenyl groups or extended biphenyl groups, and one of T1, T2, T3, T4, and T5 is a single bond. According to an embodiment, T1, T2, T3, T4, and T5 may be independently selected from extended phenyl groups or extended biphenyl groups, and two of T1, T2, T3, T4, and T5 are single bonds.

[0085] According to an embodiment, T1, T2, and T3 may be independently selected from phenylene, and one of T1, T2, and T3 is a single bond. According to an embodiment, T1, T2, and T3 may be independently selected from phenylene, and two of T1, T2, and T3 are single bonds.

[0086] According to an embodiment, T6 may be an extended phenyl group, an extended biphenyl group, or an extended triphenyl group. According to an embodiment, T6 may be an extended phenyl group. According to an embodiment, T6 may be an extended biphenyl group. According to an embodiment, T6 may be an extended triphenyl group.

[0087] According to the embodiment, Ar1, Ar2, Ar3, Ar4 and Ar5 can be independently selected from D1 to D16: (D1), (D2), (D3), (D4), (D5), (D6), (D7), (D8), (D9), (D10), (D11), (D12), (D13), (D14), (D15), (D16), where the asterisk "*" indicates the binding position.

[0088] According to the embodiment, Ar1, Ar2, Ar3, Ar4 and Ar5 may be independently selected from D1 to D15; alternatively, they may be selected from D1 to D10 and D13 to D15.

[0089] According to the implementation, Ar1, Ar2, Ar3, Ar4 and Ar5 can be independently selected from the group consisting of D1, D2, D5, D7, D9, D10, D13 to D16.

[0090] When Ar1, Ar2, Ar3, Ar4 and Ar5 are selected in this range, the rate start temperature can be in a range that is particularly suitable for mass production.

[0091] "Matrix compounds of formula (VI) or formula (VII)" may also be referred to as "hole transport compounds".

[0092] According to one embodiment, the substantially covalent matrix compound includes at least one naphthyl group, carbazole group, dibenzofuran group, dibenzothiophene group and / or substituted genoyl group, wherein the substituent is independently selected from methyl, phenyl or genoyl.

[0093] According to an embodiment of the electronic device, the matrix compound of formula (VI) or formula (VII) is selected from F1 to F18: (F1), (F2), (F3), (F4), (F5), (F6), (F7), (F8), (F9), (F10), (F11), (F12), (F13), (F14), (F15), (F16), (F17), (F18).

[0094] According to one embodiment of the present invention, the organic electronic device is an electroluminescent device, preferably an organic light-emitting diode.

[0095] The present invention further relates to a display device comprising an organic electronic device according to the present invention. p-type charge generation layer

[0096] The p-type charge-generating layer can be formed on the anode or cathode layer by vacuum deposition, spin coating, printing, casting, slot coating, Langmuir-Blodgett (LB) deposition, or similar methods. When the p-type charge-generating layer is formed using vacuum deposition, the deposition conditions can vary depending on the compound(s) used to form the layer and the desired structure and thermal properties of the layer. However, generally, conditions 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.

[0097] When spin coating or printing is used to form a p-type charge-generating layer, the coating conditions may vary depending on the desired structure and thermal properties of the compound(s) used to form the layer and the organic semiconductor layer. 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.

[0098] The thickness of the p-type charge generation layer can be in the range of about 1 nm to about 20 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.

[0099] According to one embodiment of the present invention, the p-type charge generation 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 ≥1 wt.-% to about ≤15 wt.-%, of a compound of formula (I), 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 ≤99 wt.-%, of a substantially covalent matrix compound; preferably, the wt.-% of the compound of formula (I) is lower than the wt.-% of the substantially covalent matrix compound; wherein the weight-% of the composition is based on the total weight of the p-type charge generation layer. n-type charge generation layer

[0100] As indicated, the charge generation layer may additionally include an n-type charge generation layer.

[0101] According to an embodiment of the present invention, the n-type charge generation layer may include an n-CGL matrix compound, preferably including at least one of C2 to C24N heteroaryl groups, or a P=X group, wherein X is O, P, or Se, and P=O is particularly preferred.

[0102] According to an embodiment of the present invention, at least one of the C2 to C24N-heteroaryl groups may be selected from compounds comprising at least one acridine group, preferably at least two acridine groups, and also preferably three acridine groups.

[0103] According to an embodiment of the present invention, the n-type charge generation layer may include an n-CGL matrix compound, the n-CGL matrix compound comprising at least one group selected from the list of the following: pyridine, pyrimidine, triazine, imidazole, benzimidazole, benzoxazole, quinone, benzoquinone, quinoline, benzoquinoline, acridine, phenoline, benzoacridine, dibenzoacridine.

[0104] According to an embodiment of the present invention, the n-type charge generation layer may include a metal dopant, wherein the metal dopant may be a metal selected from Li, Na, Cs, Mg, Ca, Sr, S or Yb, preferably selected from Li or Yb.

[0105] According to an embodiment of the present invention, the n-type charge generation layer and the p-type charge generation layer are in direct contact. Additional layers...

[0106] According to the present invention, in addition to the layers already mentioned above, the organic electronic device may also include other outer layers. Exemplary embodiments of each layer are described below: Substrate

[0107] The substrate can be any substrate commonly used in the manufacture of electronic devices such as organic light-emitting diodes. If light is emitted through the substrate, the substrate is a transparent or translucent material, such as a glass substrate or a transparent plastic substrate. If light is 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, or a silicon substrate. Anode layer

[0108] 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 a low work function material (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. Hole injection layer

[0109] Hole injection layers (HILs) can be formed on the anodic layer by vacuum deposition, spin coating, printing, casting, slot coating, Langmuir-Blodgett (LB) deposition, or similar methods. When the HIL is formed using vacuum deposition, the deposition conditions can vary depending on the compound used to form the HIL and the desired structure and thermal properties of the HIL. However, generally, conditions for vacuum deposition can include deposition temperatures from 100°C to 500°C, pressures from 10⁻⁸ to 10⁻³ Torr (1 Torr equals 133.322 Pa), and deposition rates from 0.1 to 10 nm / sec.

[0110] When the HIL is formed using spin coating or printing, the coating conditions may vary depending on the 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.

[0111] HIL can be formed from any compound commonly used to form HIL. Examples of compounds that can be used to form HIL include: phthalocyanine compounds (e.g., copper phthalocyanine (CuPc)), 4,4',4"-tris(3-methylphenylphenylamino)triphenylamine (m-MTDATA), TDATA, 2T-NATA, polyaniline / dodecylbenzenesulfonic acid (Pani / DBSA), poly(3,4-ethylenedioxythiophene) / poly(4-styrenesulfonate) (PEDOT / PSS), polyaniline / camphorsulfonic acid (Pani / CSA), and polyaniline / poly4-styrenesulfonic acid (PANI / PSS).

[0112] The HIL may include or may be composed of p-type dopants, and the p-type dopants may be selected from: tetrafluorotetracyanoquinone dimethyl ether (F4TCNQ), 2,2'-(perfluoronaphthalene-2,6-diethylenedimethyl ether)dimalonitrile or 2,2',2"-(cyclopropane-1,2,3-triethylenedimethyl ether)tris(2-(p-cyanotetrafluorophenyl)acetonitrile), but are not limited thereto. The HIL may be selected from hole transport matrix compounds doped with p-type dopants. A typical example of a known doped hole transport material is: tetrafluorotetracyanoquinone dimethyl ether (F4TCNQ), 2,2'-(perfluoronaphthalene-2,6-diethylenedimethyl ether)dimalonitrile, 2,2',2"-(cyclopropane-1,2,3-triethylenedimethyl ether)tris(2-(p-cyanotetrafluorophenyl)acetonitrile), 2,2',2"-(cyclopropane-1,2,3-triethylenedimethyl ether)tris(2-(p-cyanotetrafluorophenyl)acetonitrile), 2,2',2"-(perfluoronaphthalene-2,6-diethylenedimethyl ether)dimalonitrile, ... F4TCNQ-doped copper phthalocyanine (CuPc) (with a LUMO level of approximately -5.2 eV); F4TCNQ-doped zinc phthalocyanine (ZnPc) (HOMO = -5.2 eV); F4TCNQ-doped α-NPD (N,N'-bis(naphthyl-1-yl)-N,N'-bis(phenyl)-benzidine); α-NPD doped with 2,2'-(perfluoronaphthyl-2,6-diethylenediamine)dimalonitrile. The concentration of the p-type dopant can be selected from 1 to 20 wt.-%, more preferably from 3 wt.-% to 10 wt.-%.

[0113] However, according to a preferred embodiment of the present invention, HIL comprises compounds of formula (I) or (IV) as described above.

[0114] According to a preferred embodiment of the present invention, the HIL may include the same compound of formula (I) and / or (IV) as the p-type charge generation layer.

[0115] According to a preferred embodiment of the present invention, HIL may include substantially covalent matrix compounds as described above.

[0116] According to a preferred embodiment of the present invention, HIL may include compounds of formula (I) or (IV) as described above and compounds of formula (VI) or (VII) as described above.

[0117] According to a preferred embodiment of the present invention, the p-type charge generation layer and the hole injection layer may comprise the same substantially covalent matrix compound.

[0118] The thickness of the HIL can range from about 1 nm to about 100 nm, and for example, from about 1 nm to about 25 nm. When the thickness of the HIL is within this range, the HIL can exhibit excellent hole injection characteristics without substantial loss of driving voltage. Hole transport layer

[0119] Hole transport layers (HTLs) can be formed on HILs by vacuum deposition, spin coating, slot coating, printing, casting, Langmuir-Blodgett (LB) deposition, or similar methods. When an HTL is formed by vacuum deposition or spin coating, the deposition and coating conditions can be similar to those for HIL formation. However, the conditions for vacuum or solution deposition can vary depending on the compound used to form the HTL.

[0120] HTLs can be formed from any compound commonly used to form HTLs. Suitable compounds are disclosed, for example, in Yasuhiko Shirota and Hiroshi Kageyama, Chem. Rev. 2007, 107, 953-1010, which are incorporated herein by reference. Examples of compounds that can be used to form HTLs include: carbazole derivatives, such as N-phenylcarbazole or polyvinylcarbazole; benzidine derivatives, such as N,N'-bis(3-methylphenyl)-N,N'-diphenyl-[1,1-biphenyl]-4,4'-diamine (TPD), or N,N'-di(naphthyl-1-yl)-N,N'-diphenylbenzidine (alpha-NPD); and triphenylamine type compounds, such as 4,4',4"-tris(N-carbazolyl)triphenylamine (TCTA). In these compounds, TCTA can transport holes and inhibit exciton diffusion into the EML.

[0121] According to one embodiment of the present invention, the hole transport layer may include a substantially covalent matrix compound as described above.

[0122] According to one embodiment of the present invention, the hole transport layer may include compounds of formula (VI) or (VII) as described above.

[0123] According to a preferred embodiment of the present invention, the hole injection layer and the hole transport layer may include the same compound of formula (VI) or (VII) as described above.

[0124] According to a preferred embodiment of the present invention, the p-type charge generation layer, the hole injection layer and the hole transport layer may comprise the same substantially covalent matrix compound.

[0125] According to a preferred embodiment of the present invention, the p-type charge generation layer, the hole injection layer and the hole transport layer may include the same compound of formula (VI) or (VII) as described above.

[0126] The thickness of the HTL can 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 160 nm, further in the range of about 100 nm to about 160 nm, and further in the range of about 120 nm to about 140 nm. The preferred thickness of the HTL can be 170 nm to 200 nm.

[0127] 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

[0128] The function of the electron blocking layer (EBL) is to prevent electrons from transferring from the emitter layer to the hole transport layer, thus confining the electrons within the emitter layer. Therefore, efficiency, operating voltage, and / or service life are improved. Typically, the electron blocking layer comprises a triarylamine compound. Compared to the LUMO energy level of the hole transport layer, the triarylamine compound can have a LUMO energy level closer to the vacuum energy level. Compared to the HOMO energy level of the hole transport layer, the electron blocking layer can have a HOMO energy level further away from the vacuum energy level. The thickness of the electron blocking layer can be selected between 2 and 20 nm.

[0129] If the electron blocking layer has a high triplet energy level, it can also be described as a triplet control layer.

[0130] If a green or blue phosphorescent emitting layer is used, the function of the triplet control layer is to reduce triplet quenching. Therefore, a higher light emission efficiency from the phosphorescent emitting layer can be achieved. The triplet control layer is selected from triarylamine compounds having a triplet energy level higher than that of the phosphorescent emitter in the adjacent emitting layer. Suitable compounds (particularly triarylamine compounds) for use as triplet control layers are described in EP 2 722 908 A1. Photoactive Layer (PAL)

[0131] According to an embodiment of the present invention, the organic electronic device may further include a photoactive layer, wherein the photoactive layer is disposed between the anode layer and the cathode layer.

[0132] The photoactive layer converts current into photons, or photons into current.

[0133] PAL can be formed on HTL by vacuum deposition, spin coating, slot coating, printing, casting, LB deposition, or similar methods. When PAL is formed using vacuum deposition or spin coating, the deposition and coating conditions can be similar to those for HIL formation. However, the deposition and coating conditions may vary depending on the compound used to form PAL.

[0134] According to one embodiment of the present invention, the photoactive layer does not include the compound of formula (I).

[0135] This photoactive layer can be a light-emitting layer or a light-absorbing layer. Emitting Layer (EML)

[0136] According to an embodiment of the present invention, the organic electronic device may further include an emission layer, wherein the emission layer is disposed between the anode layer and the cathode layer.

[0137] EML can be formed on HTL by vacuum deposition, spin coating, slot coating, printing, casting, LB deposition, or similar methods. When EML 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 the EML.

[0138] According to one embodiment of the present invention, the emission layer does not include the compound of formula (I).

[0139] The emitter layer (EML) can be formed by a combination of a host and an emitter dopant. Examples of hosts are Alq3, 4,4'-N,N'-dicarbazole-biphenyl (CBP), poly(n-vinylcarbazole) (PVK), 9,10-bis(naphthyl-2-yl)anthracene (AND), 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)benzo-thiazolate)zinc (Zn(BTZ)2).

[0140] 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.

[0141] Examples of red emitter dopants include PtOEP, Ir(piq)3, and Btp2lr(acac), but are not limited thereto. These compounds are phosphorescent emitters; however, red fluorescent emitter dopants may also be used.

[0142] Examples of green phosphorescent emitter dopants are Ir(ppy)3 (ppy = phenylpyridine), Ir(ppy)2(acac), and Ir(mpyp)3.

[0143] Examples of blue phosphorescent emitter dopants are 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 blue phosphorescent emitter dopants.

[0144] The amount of emitter dopant can range from about 0.01 to about 50 parts by weight based on 100 parts by weight of the host. Alternatively, the 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)

[0145] 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 dopants, the HBL can also have triplet exciton blocking function.

[0146] HBL can also be referred to as auxiliary ETL or a-ETL.

[0147] 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 the HBL. Any compound commonly used to form HBL can be used. Examples of compounds used to form HBL include: diazole derivatives, triazole derivatives, phenocyanate derivatives, and azazine derivatives, preferably triazine or pyrimidine derivatives.

[0148] 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 properties without substantial loss of driving voltage. Electron Transport Layer (ETL)

[0149] The organic electronic device according to the present invention may further include an electron transport layer (ETL).

[0150] According to another embodiment of the present invention, the electron transport layer may further include an azazine compound, preferably a triazine compound or a pyrimidine compound.

[0151] In one embodiment, the electron transport layer may further include a dopant selected from alkali organic complexes (preferably LiQ).

[0152] 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 performance without substantial loss of driving voltage.

[0153] 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 include an azine compound. Preferably, the azine compound is a triazine compound.

[0154] According to an embodiment of the present invention, the n-type charge generation layer is sandwiched between the electron transport layer and the p-type charge generation layer.

[0155] According to an embodiment of the present invention, an n-type charge generation layer is sandwiched between an electron transport layer and a p-type charge generation layer in contact; wherein the n-type charge generation layer and / or the electron transport layer comprises an azazine compound. This results in exceptionally improved performance.

[0156] According to an embodiment of the present invention, an n-type charge generation layer is sandwiched between an electron transport layer and a p-type charge generation layer in contact; and an electron transport layer is sandwiched between a first emission layer and an n-type charge generation layer in contact; wherein the n-type charge generation layer and / or the electron transport layer comprises an azazine compound. This results in exceptionally improved performance.

[0157] According to an embodiment of the present invention, an n-type charge-generating layer is sandwiched between an electron transport layer and a p-type charge-generating layer; and an electron transport layer is sandwiched between a first emission layer and an n-type charge-generating layer; wherein the n-type charge-generating layer comprises a morpholine compound, and the electron transport layer comprises an azazine compound, preferably a triazine or pyrimidine compound. This results in exceptionally improved performance. Electron Injection Layer (EIL)

[0158] 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.

[0159] 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 properties without substantial loss of driving voltage. Cathode layer

[0160] The cathode layer is formed on the EIL, or optionally on an EIL. The cathode layer may be formed of a metal, alloy, conductive compound, or mixture thereof. The cathode electrode 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 electrode may be formed of a transparent conductive oxide such as ITO or IZO.

[0161] 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.

[0162] It should be understood that the cathode layer is not part of the electron injection layer or electron transport layer. Organic Light Emitting Diode (OLED)

[0163] The organic electronic device according to the present invention may be an organic light-emitting device.

[0164] According to one aspect of the present invention, an organic light-emitting diode (OLED) is provided, comprising: a substrate; an anode layer formed on the substrate; a charge-generating layer according to the present invention; at least one emission layer; and a cathode layer.

[0165] According to another aspect of the present invention, an organic light-emitting diode (OLED) is provided, comprising: a substrate; a cathode layer formed on the substrate; a charge-generating layer according to the present invention; at least a first and a second emitting layer; and a cathode layer, wherein the charge-generating layer is disposed between the first and the second emitting layers.

[0166] According to one aspect of the present invention, an organic light-emitting diode (OLED) is provided, comprising: a substrate; an anode layer formed on the substrate; an n-type charge generation layer; a p-type charge generation layer, including a compound of formula (I); a hole transport layer; an emission layer; an electron transport layer; and a cathode layer.

[0167] According to another aspect of the present invention, an OLED is provided, comprising: a substrate; an anode layer formed on the substrate; an n-type charge generating layer; a p-type charge generating layer comprising a compound of formula (I); a hole transport layer; an electron blocking layer; an emission layer; a hole blocking layer; an electron transport layer; and a cathode layer.

[0168] According to another aspect of the present invention, an OLED is provided, comprising: a substrate; an anode electrode formed on the substrate; an n-type charge generation layer; a p-type charge generation layer comprising a compound of formula (I); a hole transport layer; an electron blocking layer; an emission layer; a hole blocking layer; an electron transport layer; an electron injection layer; and a cathode electrode.

[0169] According to various embodiments of the present invention, OLED layers disposed between the aforementioned layers, on a substrate, or on a top electrode can be provided.

[0170] According to one embodiment, the OLED may include a layer structure of a substrate disposed adjacent to an anode electrode, the anode electrode being disposed adjacent to a first hole injection layer, the first hole injection layer being disposed adjacent to a first hole transport layer, the first hole transport layer being disposed adjacent to a first electron blocking layer, the first electron blocking layer being disposed adjacent to a first emitter layer, the first emitter layer being disposed adjacent to the first electron transport layer, the first electron transport layer being disposed adjacent to an n-type charge generation layer, the n-type charge generation layer being disposed adjacent to a hole generation layer, the hole generation layer being disposed adjacent to a second hole transport layer, the second hole transport layer being disposed adjacent to a second electron blocking layer, the second electron blocking layer being disposed adjacent to a second emitter layer, and an optional electron transport layer and / or an optional injection layer being disposed between the second emitter layer and the cathode electrode.

[0171] The organic semiconductor layer according to the present invention may be a first hole injection layer and / or a p-type charge generation layer. Organic electronic device

[0172] The organic electronic device according to the present invention may be a light-emitting device.

[0173] 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.

[0174] Suitable deposition methods include: - deposition by vacuum thermal evaporation; - deposition by solution treatment, preferably selected from spin coating, printing, casting; and / or - slot coating.

[0175] According to various embodiments of the present invention, a method is provided that uses: - a first deposition source to release a compound of formula (1) according to the present invention, and - a second deposition source to release a substantially covalent matrix compound; - a third deposition source to release an n-CGL matrix compound; - a fourth deposition source to release an n-CGL dopant; The method includes the step of forming a p-type charge generation layer; wherein for an organic light-emitting diode (OLED): - a p-type charge generation layer is formed by releasing a compound of formula (1) according to the present invention from a first deposition source and releasing a substantially covalent matrix compound from a second deposition source; The method includes the step of forming an n-type charge generation layer; wherein for an organic light-emitting diode (OLED): - an n-type charge generation layer is formed by releasing an n-CGL matrix compound according to the present invention from a third deposition source and releasing an n-CGL dopant from a fourth deposition source.

[0176] According to various embodiments of the present invention, the method may further include forming at least one layer on the anode electrode and forming an emission layer and an n-type charge generation layer between the anode electrode and the cathode layer, wherein the at least one layer on the anode electrode is selected from the group consisting of forming a hole transport layer or forming a hole blocking layer.

[0177] According to another aspect of the present invention, an electronic device is provided, comprising at least one organic light-emitting device according to any embodiment described in various parts of this application. Preferably, in one of the embodiments described in various parts of this application, the electronic device comprises an organic light-emitting diode. More preferably, the electronic device is a display device.

[0178] In the following, embodiments are described in more detail with reference to examples. However, this disclosure is not limited to the examples below. Exemplary features will now be explained in detail.

Implementation Method

[0180] The invention is further illustrated by the following examples, which are illustrative rather than restrictive.

[0181] Compound of formula (I) can be prepared as described in EP2180029A1 and WO2016097017A1. The calculated HOMO and LUMO...

[0182] HOMO and LUMO were calculated using the suite program TURBOMOLE V6.5 (TURBOMOLE GmbH, Litzenhardtstrasse 19, 76135 Karlsruhe, Germany). The optimal geometry of the molecular structure and the HOMO and LUMO energy levels were determined by applying the mixing function B3LYP and the 6-31G* basis set in the gas phase. If more than one configuration was feasible, the configuration with the lowest total energy was selected. General procedure for OLED manufacturing.

[0183] Regarding the OLED 100 including CGL, see Table 2. The glass substrate is cut into a size of 50 mm x 50 mm x 0.7 mm, ultrasonically cleaned with isopropyl alcohol for 5 minutes, followed by ultrasonic cleaning with pure water for 5 minutes, and then UV ozone cleaning for 30 minutes to prepare the substrate.

[0184] Then, an anode layer with a thickness of 100 nm is formed on the substrate by depositing Ag at a rate of 0.01 to 1 Å / s at 10-7 mbar.

[0185] Then, a hole injection layer (HIL) with a thickness of 10 nm is formed on the anode layer by co-deposition of a substantially covalent matrix compound and a p-dopant. The composition of the HIL is shown in Table 2.

[0186] Then, a first hole transport layer (HTL1) with a thickness of 34 nm is formed on the HIL by depositing a substantially covalent matrix compound. The composition of the HTL is shown in Table 2.

[0187] Then, an electron blocking layer (EBL) with a thickness of 5 nm is formed on HTL1 by depositing N-([1,1'-biphenyl]-4-yl)-9,9-diphenyl-N-(4-(triphenylsilyl)phenyl)-9H-furan-2-amine.

[0188] Then, an emission layer (EML) with a thickness of 20 nm was formed on the EBL by co-depositing 97 vol.-% H09 (Sun Fine Chemicals, Korea) as the EML body and 3 vol.-% BD200 (Sun Fine Chemicals, Korea) as the blue fluorescent dopant.

[0189] Then, a hole blocking layer (HBL) with a thickness of 5 nm is formed on the emission layer by depositing 2-(3'-(9,9-dimethyl-9H-furo-2-yl)-[1,1'-biphenyl]-3-yl)-4,6-diphenyl-1,3,5-triazine.

[0190] Then, an electron transport layer (ETL) with a thickness of 20 nm is formed on the hole blocking layer by co-depositing 50 wt.-% of 2-([1,1'-biphenyl]-4-yl)-4-(9,9-diphenyl-9H-furo-4-yl)-6-phenyl-1,3,5-triazine and 50 wt.-% of LiQ.

[0191] An n-CGL with a thickness of 10 nm was formed on an ETL by co-depositing 99 vol.-% of 2,2'-(1,3-epenylphenyl)bis[9-phenyl-1,10-phenanthroline] and 1 vol.-% of Li.

[0192] Then, p-CGL is formed on n-CGL by co-deposition of a substantially covalent matrix compound and a compound of formula (I). The composition and thickness of p-CGL are shown in Table 2.

[0193] Then, a second hole transport layer (HTL2) with a thickness of 81 nm was formed on p-CGL by depositing a substantially covalent matrix compound. The composition of HTL2 is shown in Table 2.

[0194] An electron injection layer (EIL) with a thickness of 2 nm was formed on HTL2 by depositing Yb.

[0195] A cathode layer with a thickness of 13 nm was formed on the EIL by co-depositing Ag:Mg (90:10 vol.-%) at a rate of 0.01 to 1 Å / s at 10-7 mbar.

[0196] Then, a capping layer with a thickness of 75 nm is formed on the cathode layer by depositing an F3 compound.

[0197] 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.

[0198] To evaluate the performance of the present invention 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. Furthermore, 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 Akkreditierungs-stelle (DAkkS)). The cd / A efficiency at 10 mA / cm² was determined by interpolating the luminance-voltage characteristics and current-voltage characteristics separately.

[0199] In the bottom-emitting device, the emission is primarily Lambertian emission and is quantified as a percentage of external quantum efficiency (EQE). To determine the efficiency EQE as a percentage, the light output of a calibrated photodiode is measured at 10 mA / cm².

[0200] In top-emitting devices, the emission is forward-directed non-Lambertian emission and is also highly dependent on the microcavity. Therefore, the efficiency EQE is higher compared to bottom-emitting devices. To determine the efficiency EQE as a percentage, the light output of a calibrated photodiode was measured at 10 mA / cm².

[0201] The lifespan LT of the device was measured and recorded in hours under ambient conditions (20°C) and 30 mA / cm² using a Keithley 2400 sourcemeter.

[0202] The brightness of the device is measured using a calibrated photodiode. The service life LT is defined as the time until the brightness of the device decreases to 97% of its initial value.

[0203] By measuring the difference in operating voltage between 1 hour and 50 hours at 30 mA / cm², the increase in operating voltage U over time is measured as "U increase (50-1 hour)". Technical effects of the present invention

[0204] The LUMO levels of Examples A1 to A59 and Comparative Example 1 (=C1) are shown in Table 1. Compounds with A1 to A3 = pentafluorophenyl and R' = CN were used as comparative compounds (referred to as C1).

[0205] The LUMO levels were calculated using the software suite TURBOMOLE V6.5 (TURBOMOLE GmbH, Litzenhardtstrasse 19, 76135 Karlsruhe, Germany) by applying the mixing function B3LYP and the 6-31G* basis set in the gas phase. Table 1: Calculated LUMO levels of compounds of formula (I) A 1 A 2 A 3 LUMO [eV] Compare compound 1 -4.58 A1 -4.79 A2 -4.75 A3 -4.92 A4 -4.82 A5 -4.83 A6 -4.95 A7 -5.12 A8 -5.51 A9 -4.91 A10 -5.10 A11 -5.36 A12 -5.32 A13 -5.09 A14 -5.07 A15 -5.00 A16 -5.25 A17 -5.18 A18 -5.20 A19 -5.12 A20 -5.23 A21 -5.07 A22 -5.07 A23 -5.19 A24 -5.06 A25 -5.10 A26 -5.28 A27 -5.10 A28 -4.98 A29 -5.15 A30 -5.23 A31 -5.34 A32 -5.10 A33 -5.03 A34 -5.36 A35 -5.36 A36 -5.33 A37 -5.34 A38 -5.51 A39 -5.31 A40 -5.29 A41 -4.99 A42 -5.12 A43 -5.16 A44 -5.33 A45 -5.21 A46 -5.07 A47 -4.71 A48 -4.73 A49 -4.71 A50 -5.50 A51 -4.91 A52 -4.66 A53 -4.95 A54 -5.33 A55 -5.58 A56 -5.36 A57 -5.50 A58 -4.96 A59 -5.61

[0206] Table 2 (see page 77) shows the configuration of several devices according to a comparative example and several embodiments of the present invention.

[0207] A compound having A1 to A3 = pentafluorophenyl and R' = CN was used as a comparative compound (referred to as C1).

[0208] In Comparative Example 1 and Examples 2 to 5, the hole injection layer includes compound C2. In C2, A1 to A3 are:

[0209] Especially in mobile devices, a low operating voltage U can be beneficial for reducing power consumption and improving battery life.

[0210] Especially in mobile devices, high external quantum efficiency (EQE) can be beneficial for reducing power consumption and improving battery life.

[0211] The improved service life LT and the improved voltage increase over time can be beneficial for the long service life of organic electronic devices.

[0212] The specific combinations of elements and features in the detailed embodiments above are merely exemplary; the interchange and substitution of such teachings with other teachings in this patent / application and in patents / applications incorporated by reference are also clearly conceived. As will be recognized by those skilled in the art, they will be able to conceive of changes, modifications and other implementations to the content described herein 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 the plural. The fact that certain measures are described in mutually different appendices does not imply that combinations of such 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 invention. Table 2: Organic electronic devices comprising a p-type charge generating layer (p-CGL), p-CGL comprising compounds of formula (I) and substantially organic matrix compounds. [Simplified Explanation of the Diagram]

[0179] The foregoing elements and the elements claimed and used in the embodiments according to the invention have no particular exceptions in terms of their size, shape, material selection and technical concept, so that selection criteria known in the relevant art can be applied 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 the respective drawings of preferred embodiments of the invention in an exemplary manner. However, any embodiment does not necessarily represent the full scope of the invention, and therefore, is used as a reference for the claims and is used to explain the scope of the invention herein. It should be understood that the foregoing general description and the following detailed description are exemplary and explanatory only, and are intended to provide further explanation of the claimed invention. FIG1 is a schematic cross-sectional view of an OLED including a charge-generating layer according to an exemplary embodiment of the invention. FIG2 is a schematic cross-sectional view of an OLED including a charge-generating layer according to an exemplary embodiment of the invention. In the following, the drawings are described in more detail with reference to examples. However, this disclosure is not limited to the following drawings. In this document, when a first element is 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 between them. When the first element is formed or disposed "directly" on or "above" the second element, no other elements are disposed between them. Figure 1 is a schematic cross-sectional view of an OLED 100 according to an exemplary embodiment of the present invention. Referring to Figure 1, the OLED 100 includes a substrate 110; an anode layer 120; a hole injection layer (HIL) 130; a first hole transport layer (HTL1) 140; an electron blocking layer (EBL) 145; an emission layer (EML) 150; a hole blocking layer (HBL) 155; an electron transport layer (ETL) 160; an n-type charge generation layer (n-CGL) 185; a p-type charge generation layer (p-GCL) 135, which may include a compound of formula (I); a second hole transport layer (HTL2) 141; and an electron injection layer (EIL) 180 and a cathode layer 190. The HIL may include a compound of formula (I). Figure 2 is a schematic cross-sectional view of a stacked OLED 100 according to another exemplary embodiment of the present invention. The difference between Figure 2 and Figure 1 is that the OLED 100 in Figure 1 further includes a second emission layer.Referring to Figure 2, the OLED 100 includes a substrate 110, an anode layer 120, a hole injection layer (HIL) 130, a first hole transport layer (HTL) 140, a first electron blocking layer (EBL) 145, a first emitter layer (EML) 150, a first hole blocking layer (HBL) 155, a first electron transport layer (ETL) 160, an n-type charge generation layer (n-CGL) 185, a p-type charge generation layer (p-GCL) 135 (which may include a compound of formula (I)), a second hole transport layer (HTL) 141, a second electron blocking layer (EBL) 146, a second emitter layer (EML) 151, a second hole blocking layer (EBL) 156, a second electron transport layer (ETL) 161, an electron injection layer (EIL) 180, and a cathode layer 190. The HIL may include a compound of formula (I). In the above description, the method of manufacturing the OLED 100 of the present invention begins with the formation of an anode layer 120 on a substrate 110, wherein the anode layer 120 is formed in the following order or reverse order: a hole injection layer 130, a first hole transport layer 140, an optional first electron blocking layer 145, a first emitter layer 150, an optional first hole blocking layer 155, an optional at least one first electron transport layer 160, an n-CGL 185, a p-CGL 135, a second hole transport layer 141, an optional second electron blocking layer 146, a second emitter layer 151, an optional second hole blocking layer 156, an optional at least one second electron transport layer 161, an optional electron injection layer (EIL) 180, and a cathode layer 190. Although not shown in Figures 1 and 2, a sealing layer and / or a capping layer may be further formed on the cathode layer 190 to seal the organic electronic device 100. Furthermore, various other modifications may be applied thereto. In the following, one or more exemplary embodiments of the present invention will be described in more detail with reference to the following examples. However, these examples are not intended to limit the purpose and scope of one or more exemplary embodiments of the present invention.

Claims

1. An organic electronic device, comprising: An anode layer, a cathode layer, and a charge-generating layer, wherein the charge-generating layer includes a p-type charge-generating layer and an n-type charge-generating layer, wherein the p-type charge-generating layer includes compound (I) of formula (I), wherein A1 is selected from formula (II); (II) X1 is selected from CR1 or N; X2 is selected from CR2 or N; X3 is selected from CR3 or N; X4 is selected from CR4 or N; X5 is selected from CR5 or N; R1, R2, R3, R4, and R5 (if present) are independently selected from CN, partially fluorinated or perfluorinated C1 to C8 alkyl, Cl, F, D, or H, wherein when any of R1, R2, R3, R4, and R5 is present, the corresponding X1, X2, X3, X4, and X5 are not N; provided that one of the following requirements a) to e) is satisfied: a) At least one of R1, R2, R3, R4, and R5 is independently selected from CN, partially fluorinated or perfluorinated C1 to C8 alkyl, Cl, or F, and at least one of the remaining R1, R2, R3, R4, and R5 is selected from D or H; b) R1 or R2 is selected from CN or partially fluorinated or perfluorinated C1 to C8 alkyl, and at least one of the remaining R1 to R5 is independently selected from CN, partially fluorinated or perfluorinated C1 to C8 alkyl, Cl, or F; c) R3 is selected from partially fluorinated or perfluorinated C1 to C8 alkyl, and at least one of R1, R2, R4, and R5 is independently selected from CN, partially fluorinated or perfluorinated C1 to C8 alkyl, Cl, or F; d) At least two of R1 to R5 are independently selected from CN or partially fluorinated or perfluorinated C1 to C8 alkyl; or e) at least one of X1 to X5 is N, and at least two of X1 to X5 are selected from CR1 to CR5; A2 and A3 are independently selected from formula (III) (III) wherein Ar is independently selected from substituted or unsubstituted C6 to C18 aryl and substituted or unsubstituted C2 to C18 heteroaryl, wherein the substituent on Ar is independently selected from CN, partially or perfluorinated C1 to C6 alkyl, Cl, F, D; and wherein the asterisk "*" indicates the binding position; R' is selected from Ar, substituted or unsubstituted C6 to C18 aryl or C3 to C18 heteroaryl, partially fluorinated or perfluorinated C1 to C8 alkyl, F or CN, wherein: The compounds of formula (I) exclude the following compounds: and.

2. The organic electronic device as claimed in claim 1, wherein the p-type charge generating layer comprises a compound of formula (IV) wherein B1 is selected from formula (V) and B3 and B5 are Ar, and B2, B4 and B6 are R'.

3. The organic electronic device as claimed in claim 1 or claim 2, wherein in formula (II), R3 is selected from CN or partially fluorinated or perfluorinated C1 to C8 alkyl groups, and at least one of R1, R2, R4, and R5 is selected from H or D.

4. The organic electronic device as claimed in claim 1 or claim 2, wherein in formula (II), at least one of X1 to X5 is N, and at least one of R1 to R5 is selected from CN, partially fluorinated or perfluorinated C1 to C8 alkyl, Cl, F.

5. The organic electronic device as claimed in claim 1 or claim 2, wherein in formula (II), R1 to R5 are independently selected from CN, partially fluorinated or perfluorinated C1 to C8 alkyl groups, Cl, and F.

6. The organic electronic device as claimed in claim 1 or claim 2, wherein A2 and A3 are the same.

7. The organic electronic device as claimed in claim 1 or claim 2, wherein A1 is different from A2 and / or A3.

8. The organic electronic device as claimed in claim 1 or claim 2, wherein the p-type charge generating layer comprises a composition comprising a compound of formula (IV) and at least one compound of formula (IVa) to (IVd).

9. The organic electronic device as claimed in claim 1 or claim 2, wherein the p-type charge generating layer further comprises a substantially covalent matrix compound.

10. The organic electronic device as claimed in claim 1 or claim 2, further comprising a hole injection layer, wherein the hole injection layer is disposed between the anode layer and the charge generation layer, and wherein the hole injection layer comprises a compound of formula (I) or (IV).

11. The organic electronic device as claimed in claim 1 or claim 2, wherein the p-type charge generation layer and the hole injection layer comprise the same compound of formula (I) or (IV).

12. The organic electronic device as claimed in claim 1 or claim 2, wherein the p-type charge generating layer and the hole injection layer comprise the same substantially covalent matrix compound.

13. The organic electronic device as claimed in any one of claims 1 or 2, wherein the organic electronic device is an electroluminescent device.

14. The organic electronic device as claimed in claim 1 or claim 2, wherein the organic electronic device is an organic light-emitting diode.

15. A display device comprising an organic electronic device as described in any one of claims 1 to 14.

16. A compound of formula (I) included in an organic electronic device as claimed in claim 1, wherein formula (II) is selected from the group consisting of: , ...

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