ORGANIC ELECTRONIC DEVICES COMPRISING HOLE INJECTION LAYERS COMPRISING HOLE TRANSPORT COMPOUNDS - Patent application

Abstract

The present invention relates to an organic electronic device comprising an anode layer, a cathode layer and a hole injection layer, wherein the hole injection layer is disposed between the anode layer and the cathode layer, and the hole injection layer comprises a hole transport compound and a metal complex.

Description

Detailed Description of the Invention

[0001] [Technical field] The present invention relates to an organic electronic device comprising an anode layer, a cathode layer and a hole injection layer, the hole injection layer comprising a hole transport compound.

[0002] [Background technology] Organic electronic devices (e.g., organic light-emitting diodes (OLEDs)) are self-emitting devices that have a wide viewing angle, excellent contrast, rapid response, high brightness, excellent operating voltage performance, and color reproducibility. A typical OLED includes an anode layer, a hole injection layer (HIL), a hole transport layer (HTL), an emission layer (EML), an electron transport layer (ETL), and a cathode layer, which are successively stacked on a substrate. Here, the HIL, HTL, EML, and ETL are thin films formed from organic compounds.

[0003] When voltage is applied to the anode and cathode, holes injected from the anode migrate to the EML through the HIL and HTL, and electrons injected from the cathode migrate to the EML through the ETL. The holes and electrons recombine in the EML to generate excitons. When the excitons fall from the excited state to the ground state, light is emitted. The injection and outflow of holes and electrons must be balanced, so that OLEDs with the above-mentioned structure have low operating voltages, excellent efficiency and / or long lifetimes.

[0004] The performance of an organic light-emitting diode can be influenced by the performance of the hole injection layer, among others, the performance of the hole transport compound and the metal complex contained in the hole injection layer.

[0005] WO2017029370 relates to metal amides of the general formula Ia and their use as hole injection layers (HILs) for organic light emitting diodes (OLEDs), as well as methods for producing organic light emitting diodes (OLEDs) comprising a hole injection layer comprising a metal amide of the general formula Ia. WO2017029370 discloses a hole transport layer that may further comprise a triarylamine compound having the formula VIIa:

[0006] [ka]

[0007] WO2017029366 relates to a hole injection layer for an OLED comprising a triarylamine compound doped with a charge-neutral metal amide compound, the hole injection layer having a thickness of at least about ≧20 nm to about ≦1000 nm, the charge-neutral metal amide compound having formula Ia. WO2017029366 discloses a hole injection layer (HIL) comprising a triarylamine compound having formula VIIa:

[0008] [ka]

[0009] WO2017102861 relates to an organic electronic device (10) comprising at least one organic layer (3) having a fluorinated sulfonamide metal salt of the following formula 1: (1) where M is either a divalent metal with an atomic mass of more than 26 g / mol or a metal with a higher valence, or a monovalent metal with an atomic mass of 39 g / mol or more, where 1≦n≦7, and R1, R2 are each independently selected from the group comprising fluorine-substituted aryl radicals, fluorine-substituted alkyl radicals, and fluorine-substituted arylalkyl radicals. The material of the matrix is ​​a hole transport material.

[0010] WO2017178473A1 relates to an organic electronic component (100) including a stack (S1) of a first organic functional layer, a stack (S2) of a second organic functional layer, and a charge carrier generation layer (5) disposed therebetween. The charge carrier generation layer (5) includes an n-conducting region (5b), a doped organic p-doped region (5a), and an intermediate region (5c) having a layer thickness of 0.1 nm to 20 nm disposed therebetween. The doped organic p-doped region (5a) includes a fluorinated sulfonimide metal salt of the following formula 1 as a p-dopant, where M is either a divalent metal having an atomic mass of more than 26 g / mol or a metal with a higher valence, or a monovalent metal having an atomic mass of 39 g / mol or more. wherein 1≦n≦7, and R1, R2 are each independently selected from the group consisting of a fluorine-substituted aryl radical, a fluorine-substituted alkyl radical, and a fluorine-substituted arylalkyl radical.

[0011] There remains a need to improve the performance of organic electronic devices by providing hole injection layers with improved performance, particularly by achieving improved operating voltages through improvements in the hole injection layer and the performance of the organic electronic device.

[0012] Moreover, a need remains to provide a hole injection layer that allows injection into an adjacent layer that contains a compound having a HOMO level further away from the vacuum level.

[0013] A further object is to provide a hole injection layer comprising a compound that can be deposited by vacuum thermal evaporation under conditions suitable for mass production.

[0014] [Disclosure] One aspect of the invention is an organic electronic device comprising an anode layer, a cathode layer and a hole injection layer, the hole injection layer being disposed between the anode layer and the cathode layer, the hole injection layer comprising a hole transport compound and a metal complex, wherein: said hole transport compound comprises a covalently bonded atom selected from: covalently bound C, H, O, N, Si and / or S; or covalently bound C, H, O, N, B, and P, and Where: the hole transport compound has a molecular weight Mw of ≧400 g / mol and ≦2000 g / mol, the HOMO level of said hole transport compound is further away from the vacuum level than the HOMO level of N4,N4'''-di(naphthalen-1-yl)-N4,N4'''-diphenyl-[1,1':4',1'':4'',1'''-quaterphenyl]-4,4'''-diamine measured under the same conditions; and said metal complex having the formula (II):

[0015] [ka]

[0016] During the ceremony, M is a metal ion; n is the valence of M, and n is an integer from 1 to 4; L is a ligand containing at least two carbon atoms; and wherein the hole injection layer is disposed adjacent to the anode layer.

[0017] In one embodiment, the organic electronic device comprises an anode layer, a cathode layer, and a hole injection layer, the hole injection layer being disposed between the anode layer and the cathode layer, the hole injection layer comprising a hole transport compound and a metal complex, wherein: said hole transport compound comprises a covalently bonded atom selected from: covalently bound C, H, O, N, Si and / or S; or covalently bound C, H, O, N, B, and P, and Where: the hole transport compound has a molecular weight Mw of ≧400 g / mol and ≦2000 g / mol, the HOMO level of said hole transport compound is further away from the vacuum level than the HOMO level of N4,N4'''-di(naphthalen-1-yl)-N4,N4'''-diphenyl-[1,1':4',1'':4'',1'''-quaterphenyl]-4,4'''-diamine measured under the same conditions; and The metal complex has the formula (II):

[0018] [ka]

[0019] Where: said metal complex has a molecular weight Mw of ≧400 g / mol and ≦2000 g / mol, M is a metal ion; n is the valence of M, and n is an integer from 1 to 4; L is a ligand containing at least two carbon atoms; and wherein the hole injection layer is disposed adjacent to the anode layer; and wherein optionally the hole transport compound is a triarylamine hole transport compound; wherein the aryl substituent is attached to the tertiary amine by a single bond, and excludes the aryl substituent forming part of a heterocycle.

[0020] Examples of triarylamine hole transport compounds in the present invention include N,N,N',N'-tetrakis(4-methylphenyl)-benzidine, N4,N4,N4',N4'-tetra(biphenyl-4-yl)biphenyl-4,4'-diamine, biphenyl-4-yl(9,9-diphenyl-9H-fluoren-2-yl)-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]-amine, N,N'-bis(naphthalen-1-yl)-N,N'-bis(phenyl)-benzidine, N1,N3-di([1,1'-biphenyl]-4-yl)-5-(9,9-dimethyl-9H-fluoren-2-yl)- N,N'-((9H-fluorene-9,9-diyl)bis(4,1-phenylene))bis(N-([1,1'-biphenyl]-4-yl)-[1,1'-biphenyl]-4-amine), N4,N4''-di(naphthalen-1-yl)-N4,N4''-diphenyl-[1,1':4',1''-terphenyl]-4,4''-diamine (CAS 139255-16-6), 4,4'-bis-(N-(1-naphthyl)-N-phenyl-amino)-quaterphenyl (CAS 650609-47-5), 4,4',4''-tris(carbazol-9-yl)-triphenylamine.

[0021] In one embodiment, the organic electronic device comprises an anode layer, a cathode layer, and a hole injection layer, the hole injection layer being disposed between the anode layer and the cathode layer, the hole injection layer comprising a hole transport compound and a metal complex, wherein: said hole transport compound comprises a covalently bonded atom selected from: covalently bound C, H, O, N, Si and / or S; or covalently bound C, H, O, N, B, and P, and Where: the hole transport compound has a molecular weight Mw of ≧400 g / mol and ≦2000 g / mol, the HOMO level of said hole transport compound is further away from the vacuum level than the HOMO level of N4,N4'''-di(naphthalen-1-yl)-N4,N4'''-diphenyl-[1,1':4',1'':4'',1'''-quaterphenyl]-4,4'''-diamine measured under the same conditions; and said metal complex having the formula (II):

[0022] [ka]

[0023] Where: said metal complex has a molecular weight Mw of ≧400 g / mol and ≦2000 g / mol, M is a metal ion; n is the valence of M, and n is an integer from 1 to 4; L is a ligand containing at least two carbon atoms; and wherein the hole injection layer is disposed adjacent to the anode layer; and wherein optionally the hole transport compound is a triarylamine hole transport compound; wherein the aryl substituent is attached to the tertiary amine by a single bond and excludes the aryl substituent forming part of a heterocycle; and 3 Hole transport compounds having hybridized carbon atoms are excluded.

[0024] The term "HOMO level" should be understood to mean the highest occupied molecular orbital and is measured in eV (electron volts).

[0025] The term "HOMO level further away from the vacuum level" is understood to mean that the absolute value of the HOMO level is higher than the absolute value of the HOMO level of the reference compound. For example, the term "further away from the vacuum level than the HOMO level of N4,N4'''-di(naphthalen-1-yl)-N4,N4'''-diphenyl-[1,1':4',1'':4'',1'''-quaterphenyl]-4,4'''-diamine" is understood to mean that the absolute value of the HOMO level of the organic matrix compound (OMC) is higher than the HOMO level of N4,N4'''-di(naphthalen-1-yl)-N4,N4'''-diphenyl-[1,1':4',1'':4'',1'''-quaterphenyl]-4,4'''-diamine.

[0026] The term "absolute value" is understood to mean the value without the "-" sign. In one embodiment of the present invention, the HOMO level of the hole transport compound may be calculated by quantum mechanical methods.

[0027] When the HOMO level of a hole-transporting compound is calculated by this method, the HOMO level of the hole-transporting compound is lower than the HOMO level of N4,N4'''-di(naphthalen-1-yl)-N4,N4'''-diphenyl-[1,1':4',1'':4'',1'''-quaterphenyl]-4,4'''-diamine.

[0028] When the HOMO level of a hole-transporting compound is calculated by the method, the absolute value of the HOMO level of the hole-transporting compound is higher than the absolute value of the HOMO level of N4,N4'''-di(naphthalen-1-yl)-N4,N4'''-diphenyl-[1,1':4',1'':4'',1'''-quaterphenyl]-4,4'''-diamine.

[0029] In one embodiment of the present invention, the HOMO levels of hole transporting compounds are calculated using the program package TURBOMOLE V6.5, available from TURBOMOLE GmbH, Litzenhardtstrasse 19, 76135 Karlsruhe, Germany.

[0030] When calculated by this method, the HOMO level of N4,N4'''-di(naphthalen-1-yl)-N4,N4'''-diphenyl-[1,1':4',1'':4'',1'''-quaterphenyl]-4,4'''-diamine is -4.85 eV. When the HOMO levels are calculated by this method, the hole transport compounds of the prior art have the following HOMO levels: For comparison, the HOMO levels calculated from the redox potentials are also provided.

[0031] [Table 1] JPEG0007644768000007.jpg230169JPEG0007644768000008.jpg228169JPEG0007644768000009.jpg129169

[0032] When the HOMO level is far from the vacuum level, it may no longer be feasible to accurately measure the redox potential, and therefore, unless otherwise stated, HOMO levels are measured herein by quantum mechanical methods.

[0033] Note that the ligand L carries a negative charge.

[0034] In one embodiment, the ligand L has one negative charge, in other words, the ligand L is a monoanion.

[0035] In one embodiment, the negative charge of the ligand L may correspond to the valence of the metal ion M.

[0036] In another aspect, an organic electronic device includes an anode layer, a cathode layer, and a hole injection layer, the hole injection layer being disposed between the anode layer and the cathode layer, the hole injection layer comprising a hole transport compound and a metal complex, wherein: said hole transport compound has the formula (I):

[0037] [ka]

[0038] During the ceremony, k, m, q, and r are each independently selected from 0, 1, or 2; p is 1, 2 or 3; 2≦k+m+q+r+p≦11, Ar 1 ~Ar 6 are independently a substituted or unsubstituted unsaturated 5- to 7-membered heterocycle, a substituted or unsubstituted C6-C 30 Aryl, substituted or unsubstituted C3-C 30 heteroaryl, substituted or unsubstituted fluorene, or a fused ring system containing 2 to 6 substituted or unsubstituted 5 to 7 membered rings, the rings being 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) fused ring systems containing 6 membered aromatic non-heterocycles; preferably, independently, substituted or unsubstituted biphenylene, substituted or unsubstituted fluorene, 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 tetracene, substituted or unsubstituted tetraphene, substituted or unsubstituted dibenzo furan, substituted or unsubstituted dibenzothiophene, substituted or unsubstituted xanthene, substituted or unsubstituted carbazole, substituted or unsubstituted azepine, substituted or unsubstituted dibenzo[b,f]azepine, 9,9'-spirobi[fluorene], substituted or unsubstituted spiro[fluorene-9,9'-xanthene], substituted or unsubstituted 9,14-dihydrodibenzo[2,3:6,7]azepino[4,5-b]indole, or a substituted or unsubstituted aromatic fused ring system comprising at least three substituted or unsubstituted aromatic rings selected from the group comprising a substituted or unsubstituted non-hetero 5-membered ring, a substituted or unsubstituted hetero 5-membered ring, a substituted or unsubstituted 6-membered ring, and / or a substituted or unsubstituted 7-membered ring; wherein the substituents are H, D, C1-C 12 Alkyl, unsubstituted C6-C 18 Aryl, unsubstituted C3-C 18 heteroaryl, a fused ring system containing 2 to 6 unsubstituted 5- to 7-membered rings, the rings being selected from the group consisting of unsaturated 5- to 7-membered heterocyclic rings, 5- to 6-membered aromatic heterocyclic rings, unsaturated 5- to 7-membered non-heterocyclic rings, and 6-membered aromatic non-heterocyclic rings; and The metal complex has the formula (II):

[0039] [ka]

[0040] Where: M is a metal ion; n is the valence of M, and n is an integer from 1 to 4; L is a ligand containing at least two carbon atoms; and The hole injection layer is disposed adjacent to the anode layer.

[0041] In one embodiment, the organic electronic device comprises an anode layer, a cathode layer, and a hole injection layer, the hole injection layer being disposed between the anode layer and the cathode layer, the hole injection layer comprising a hole transport compound and a metal complex, wherein: said hole transport compound has the formula (I):

[0042] [ka]

[0043] During the ceremony, k, m, q, and r are each independently selected from 0, 1, or 2; p is 1, 2 or 3; 2≦k+m+q+r+p≦11, Ar 1 ~Ar 6are independently a substituted or unsubstituted unsaturated 5- to 7-membered heterocycle, a substituted or unsubstituted C6-C 30 Aryl, substituted or unsubstituted C3-C 30 heteroaryl, substituted or unsubstituted fluorene, or a fused ring system containing 2 to 6 substituted or unsubstituted 5 to 7 membered rings, the rings being 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) fused ring systems containing 6 membered aromatic non-heterocycles; preferably, independently, substituted or unsubstituted biphenylene, substituted or unsubstituted fluorene, 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 tetracene, substituted or unsubstituted tetraphene, substituted or unsubstituted dibenzo furan, substituted or unsubstituted dibenzothiophene, substituted or unsubstituted xanthene, substituted or unsubstituted carbazole, substituted or unsubstituted azepine, substituted or unsubstituted dibenzo[b,f]azepine, 9,9'-spirobi[fluorene], substituted or unsubstituted spiro[fluorene-9,9'-xanthene], substituted or unsubstituted 9,14-dihydrodibenzo[2,3:6,7]azepino[4,5-b]indole, or a substituted or unsubstituted aromatic fused ring system comprising at least three substituted or unsubstituted aromatic rings selected from the group comprising a substituted or unsubstituted non-hetero 5-membered ring, a substituted or unsubstituted hetero 5-membered ring, a substituted or unsubstituted 6-membered ring, and / or a substituted or unsubstituted 7-membered ring; wherein the substituents are H, D, C1-C 12 Alkyl, unsubstituted C6-C 18 Aryl, unsubstituted C3-C 18 heteroaryl, a fused ring system containing 2 to 6 unsubstituted 5- to 7-membered rings, the rings being selected from the group consisting of unsaturated 5- to 7-membered heterocyclic rings, 5- to 6-membered aromatic heterocyclic rings, unsaturated 5- to 7-membered non-heterocyclic rings, and 6-membered aromatic non-heterocyclic rings; and The metal complex has the formula (II):

[0044] [ka]

[0045] The metal complex has a molecular weight Mw of ≧400 g / mol and ≦2000 g / mol; M is a metal ion; n is the valence of M, and n is an integer from 1 to 4; L is a ligand containing at least two carbon atoms; and wherein the hole injection layer is disposed adjacent to the anode layer; and wherein optionally the hole transport compound is a triarylamine hole transport compound; wherein the aryl substituent is attached to the tertiary amine by a single bond, and wherein the aryl substituent forms part of a heterocycle is excluded.

[0046] In one embodiment, the organic electronic device comprises an anode layer, a cathode layer, and a hole injection layer, the hole injection layer being disposed between the anode layer and the cathode layer, the hole injection layer comprising a hole transport compound and a metal complex, wherein: the hole transport compound has a molecular weight Mw of ≧400 g / mol and ≦2000 g / mol, the hole transport compound has the formula (I):

[0047] [ka]

[0048] During the ceremony, k, m, q, and r are each independently selected from 0, 1, or 2; p is 1, 2 or 3; 2≦k+m+q+r+p≦11, Ar 1 ~Ar 6are independently a substituted or unsubstituted unsaturated 5- to 7-membered heterocycle, a substituted or unsubstituted C6-C 30 Aryl, substituted or unsubstituted C3-C 30 heteroaryl, substituted or unsubstituted fluorene, or a fused ring system containing 2 to 6 substituted or unsubstituted 5 to 7 membered rings, the rings being 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) fused ring systems containing 6 membered aromatic non-heterocycles; preferably, independently, substituted or unsubstituted biphenylene, substituted or unsubstituted fluorene, 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 tetracene, substituted or unsubstituted tetraphene, substituted or unsubstituted dibenzo furan, substituted or unsubstituted dibenzothiophene, substituted or unsubstituted xanthene, substituted or unsubstituted carbazole, substituted or unsubstituted azepine, substituted or unsubstituted dibenzo[b,f]azepine, 9,9'-spirobi[fluorene], substituted or unsubstituted spiro[fluorene-9,9'-xanthene], substituted or unsubstituted 9,14-dihydrodibenzo[2,3:6,7]azepino[4,5-b]indole, or a substituted or unsubstituted aromatic fused ring system comprising at least three substituted or unsubstituted aromatic rings selected from the group comprising a substituted or unsubstituted non-hetero 5-membered ring, a substituted or unsubstituted hetero 5-membered ring, a substituted or unsubstituted 6-membered ring, and / or a substituted or unsubstituted 7-membered ring; wherein the substituents are H, D, C1-C 12 Alkyl, unsubstituted C6-C 18 Aryl, unsubstituted C3-C 18 heteroaryl, a fused ring system containing 2 to 6 unsubstituted 5- to 7-membered rings, the rings being selected from the group consisting of unsaturated 5- to 7-membered heterocyclic rings, 5- to 6-membered aromatic heterocyclic rings, unsaturated 5- to 7-membered non-heterocyclic rings, and 6-membered aromatic non-heterocyclic rings; and The metal complex has the formula (II):

[0049] [ka]

[0050] During the ceremony, said metal complex has a molecular weight Mw of ≧400 g / mol and ≦2000 g / mol, M is a metal ion; n is the valence of M, and n is an integer from 1 to 4; L is a ligand containing at least two carbon atoms; and the hole injection layer is disposed adjacent to the anode layer; and wherein optionally the hole transport compound is a triarylamine hole transport compound; wherein the aryl substituent is attached to the tertiary amine by a single bond, and wherein the aryl substituent forms part of a heterocycle is excluded.

[0051] In one embodiment, the organic electronic device comprises an anode layer, a cathode layer, and a hole injection layer, the hole injection layer being disposed between the anode layer and the cathode layer, the hole injection layer comprising a hole transport compound and a metal complex, wherein: the hole transport compound has a molecular weight Mw of ≧400 g / mol and ≦2000 g / mol, the hole transport compound has the formula (I):

[0052] [ka]

[0053] During the ceremony, k, m, q, and r are each independently selected from 0, 1, or 2; p is 1, 2 or 3; 2≦k+m+q+r+p≦11, Ar 1 ~Ar 6are independently a substituted or unsubstituted unsaturated 5- to 7-membered heterocycle, a substituted or unsubstituted C6-C 30 Aryl, substituted or unsubstituted C3-C 30 heteroaryl, substituted or unsubstituted fluorene, or a fused ring system containing 2 to 6 substituted or unsubstituted 5 to 7 membered rings, the rings being 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) fused ring systems containing 6 membered aromatic non-heterocycles; preferably, independently, substituted or unsubstituted biphenylene, substituted or unsubstituted fluorene, 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 tetracene, substituted or unsubstituted tetraphene, substituted or unsubstituted dibenzo furan, substituted or unsubstituted dibenzothiophene, substituted or unsubstituted xanthene, substituted or unsubstituted carbazole, substituted or unsubstituted azepine, substituted or unsubstituted dibenzo[b,f]azepine, 9,9'-spirobi[fluorene], substituted or unsubstituted spiro[fluorene-9,9'-xanthene], substituted or unsubstituted 9,14-dihydrodibenzo[2,3:6,7]azepino[4,5-b]indole, or a substituted or unsubstituted aromatic fused ring system comprising at least three substituted or unsubstituted aromatic rings selected from the group comprising a substituted or unsubstituted non-hetero 5-membered ring, a substituted or unsubstituted hetero 5-membered ring, a substituted or unsubstituted 6-membered ring, and / or a substituted or unsubstituted 7-membered ring; wherein the substituents are H, D, C1-C 12 Alkyl, unsubstituted C6-C 18 Aryl, unsubstituted C3-C 18 heteroaryl, a fused ring system containing 2 to 6 unsubstituted 5- to 7-membered rings, the rings being selected from the group consisting of unsaturated 5- to 7-membered heterocyclic rings, 5- to 6-membered aromatic heterocyclic rings, unsaturated 5- to 7-membered non-heterocyclic rings, and 6-membered aromatic non-heterocyclic rings; and The metal complex has the formula (II):

[0054] [ka]

[0055] During the ceremony, said metal complex has a molecular weight Mw of ≧400 g / mol and ≦2000 g / mol, M is a metal ion; n is the valence of M, and n is an integer from 1 to 4; L is a ligand containing at least two carbon atoms; and the hole injection layer is disposed adjacent to the anode layer; and wherein optionally the hole transport compound is a triarylamine hole transport compound; wherein said aryl substituent is attached to the tertiary amine by a single bond, and said aryl substituent forming part of a heterocycle is excluded; Here, sp 3 Hole transport compounds having hybridized carbon atoms are excluded.

[0056] In one embodiment, triarylamine hole transport compounds (wherein the aryl substituent is attached to the tertiary amine by a single bond and the tertiary amine to which the aryl substituent is attached is not part of a heterocycle) may be excluded and / or sp 3 Hole transport compounds having hybridized carbon may be excluded.

[0057] In one embodiment, the hole transport compounds and / or metal complexes of formula (II) that are phosphorescent emitting compounds are excluded.

[0058] In one embodiment, triarylamine hole transport compounds (wherein the aryl substituent is attached to a tertiary amine by a single bond and the tertiary amine to which the aryl substituent is attached is not part of a heterocycle) may be excluded, and hole transport compounds that are phosphorescent emitting compounds are excluded.

[0059] In one embodiment, triarylamine hole transport compounds (wherein the aryl substituent is attached to the tertiary amine by a single bond and the tertiary amine to which the aryl substituent is attached is not part of a heterocycle) may be excluded, sp 3 Hole transporting compounds having hybridized carbon may be excluded, and hole transporting compounds that are phosphorescent emitting compounds may be excluded.

[0060] In one embodiment, the organic electronic device comprises an anode layer, a cathode layer, and a hole injection layer, the hole injection layer being disposed between the anode layer and the cathode layer, the hole injection layer comprising a hole transport compound and a metal complex, wherein: the hole transport compound has the formula (I):

[0061] [ka]

[0062] During the ceremony, k, m, q, and r are each independently selected from 0, 1, or 2; p is 1, 2 or 3; 2≦k+m+q+r+p≦11, Ar 1 ~Ar 6 are independently a substituted or unsubstituted unsaturated 5- to 7-membered heterocycle, a substituted or unsubstituted C6-C 30 Aryl, substituted or unsubstituted C3-C 30 heteroaryl, substituted or unsubstituted fluorene, or a fused ring system containing 2 to 6 substituted or unsubstituted 5- to 7-membered rings, the rings being 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, (iv) 6-membered aromatic non-heterocyclic rings; wherein the substituents are H, D, C1-C 12 Alkyl, unsubstituted C6-C 18 Aryl, unsubstituted C3-C 18heteroaryl, a fused ring system containing 2 to 6 unsubstituted 5- to 7-membered rings, the rings being selected from the group consisting of unsaturated 5- to 7-membered heterocyclic rings, 5- to 6-membered aromatic heterocyclic rings, unsaturated 5- to 7-membered non-heterocyclic rings, and 6-membered aromatic non-heterocyclic rings; and The metal complex has the formula (II):

[0063] [ka]

[0064] Where: M is a metal ion; n is the valence of M, and n is an integer from 1 to 4; L is a ligand containing at least two carbon atoms; and The hole injection layer is disposed adjacent to the anode layer.

[0065] In another embodiment, the hole transport compound or the hole transport compound of formula (I) may be a covalent hole transport compound.

[0066] In one embodiment, n may be an integer of 1 to 4, preferably 1 to 3, and more preferably 2 or 3.

[0067] Note that k, m, q, and r represent the number of substituents on adjacent Ar moieties. For example, compound F7 of formula (I):

[0068] [ka]

[0069] (F7) is Ar 3 = phenylene, k = 0, m = 0, q = 0, r = 0 and p = 3; Where:

[0070] [ka]

[0071] In one embodiment, the hole injection layer is non-emissive.

[0072] In one embodiment of the invention, the hole injection layer, and / or the hole transport compound of formula (I), and / or the metal complex of formula (II) are non-emissive.

[0073] In the context of this specification, the term "essentially non-emissive" or "non-emissive" means that the contribution of said hole transport compound, metal complex and / or layer (e.g., hole injection layer) to the visible emission spectrum from an organic electronic device (e.g., an OLED or display device) is less than 10%, preferably less than 5%. The visible emission spectrum is an emission spectrum having a wavelength of about ≧380 nm to about ≦780 nm.

[0074] Unless otherwise indicated, throughout this application and the claims, any Ar 1 ~Ar 6 etc., refer to the same part.

[0075] In this specification, unless otherwise specified, "substituted" means any of H, deuterium, C-C 12 Alkyl, unsubstituted C6-C 18 Aryl and unsubstituted C3-C 18 It refers to those substituted by heteroaryl.

[0076] In the present specification, unless otherwise specified, an 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. The following is an example of a substituted C6 aryl group having 4 phenyl groups:

[0077] [ka]

[0078] However, as used herein, "aryl substituted" refers to substitution with one or more aryl groups. The aryl groups themselves may be substituted with one or more aryl and / or heteroaryl groups.

[0079] Similarly, as used herein, "heteroaryl substituted" refers to substitution with one or more heteroaryl groups. The heteroaryl groups may themselves be substituted with one or more aryl and / or heteroaryl groups.

[0080] In this specification, unless otherwise specified, "alkyl group" refers to a saturated aliphatic hydrocarbyl group. An alkyl group is a C-C 12 It may be an alkyl group. More specifically, the alkyl group may be a C1-C 10 It may be an alkyl group or a C1-C6 alkyl group. For example, the C1-C4 alkyl group contains 1 to 4 carbons in the alkyl chain and may be selected from methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl.

[0081] Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a branched pentyl group, and a hexyl group.

[0082] The term "cycloalkyl" refers to a saturated hydrocarbyl group derived from a cycloalkane by formal abstraction of a hydrogen atom from a ring atom of the corresponding cycloalkane. Examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, adamantyl, and the like.

[0083] The term "hetero" is to be understood as a state in which at least one carbon atom in a structure that can be formed by covalently bonded carbon atoms is replaced by another polyvalent atom. Preferably, the heteroatom is selected from B, Si, N, P, O, S, more preferably, the heteroatom is selected from N, P, O, S.

[0084] Preferred examples of hole transport compounds that may be covalent hole transport compounds include organic compounds that consist primarily of covalently bonded C, H, O, N, and S. The organic compounds may also optionally contain covalently bonded B, P, or Si. In one embodiment, the hole transport compounds that may be covalent compounds may be free of metal atoms and have a majority of their backbone atoms selected from C, O, S, and N. Alternatively, the hole transport compounds that may be covalent compounds may be free of metal atoms and have a majority of their backbone atoms selected from C and N.

[0085] As used herein, "aryl group" and "aromatic ring" refer to a hydrocarbyl group that can be generated by formally abstracting one hydrogen atom from an aromatic ring in a corresponding aromatic hydrocarbon. An aromatic hydrocarbon refers to a hydrocarbon that contains 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, which includes a conjugated system of delocalized electrons that satisfies the Hückel rule. Examples of aryl groups include monocyclic groups (e.g., phenyl or tolyl), polycyclic groups that include multiple aromatic rings connected by single bonds (e.g., biphenyl), and polycyclic groups that include fused rings (e.g., naphthyl or fluorenyl).

[0086] Similarly, under "heteroaryl" and "heteroaromatic compound" it is to be understood that groups derived by the formal abstraction of a ring hydrogen from a heteroaromatic ring in a compound containing at least one such ring are particularly preferred.

[0087] The term "non-heterocyclic" should be understood to mean a ring or ring system that does not contain a heteroatom as a ring member.

[0088] The term "heterocycle" is understood to mean a heterocycle containing at least one ring containing one or more heteroatoms. A heterocycle containing more than one ring means that all rings contain heteroatoms or that at least one ring contains heteroatoms and at least one ring contains only C atoms and does not contain heteroatoms.

[0089] Under heterocycloalkyl, it should be understood that particularly preferred are groups derived by the formal abstraction of one ring hydrogen from a saturated cycloalkyl ring in a compound containing at least one such ring.

[0090] The term "fused aryl rings" or "condensed aryl rings" refers to a ring in which two aryl rings share at least two common sp 2 It is understood that when they share a hybridized carbon atom, they are considered to be fused or condensed.

[0091] The term "fused ring system" should be understood to mean a ring system in which two or more rings have at least two atoms in common.

[0092] The term "5-, 6- or 7-membered ring" is understood to mean a ring containing 5, 6 or 7 atoms, which may be selected from C and one or more heteroatoms.

[0093] As used herein, a single bond refers to a direct bond.

[0094] In the context of this invention, "different" means that the compounds do not have the same chemical structure.

[0095] The terms "free of," "does not contain," and "does not comprise" do not exclude impurities that may be present in the hole transport compound prior to deposition. The impurities have no technical impact with respect to the objectives achieved by the present invention.

[0096] The term "adjacent to" should be understood to mean that the distance between the layers may be less than 2 nm or that adjacently disposed layers are in contact with one another. The term "sandwiched in contact" refers to a three-layer arrangement in which a middle layer is in direct contact with two adjacent layers.

[0097] The terms "light-absorbing layer" and "light absorption layer" are used interchangeably.

[0098] The terms "light-emitting layer," "light emission layer," and "emission layer" are used interchangeably.

[0099] The terms "OLED," "organic light emitting diode," and "organic light emitting device" are used interchangeably.

[0100] The terms "anode," "anode layer," and "anode electrode" are used interchangeably.

[0101] The terms "cathode," "cathode layer," and "cathode electrode" are used interchangeably.

[0102] The term "hole injection layer" is understood to mean a layer that improves charge injection from the anode layer into a further layer in an organic electronic device or from a further layer of an organic electronic device into the anode.

[0103] The term "hole transport layer" is understood to mean a layer which transports holes between a hole injection layer and a further layer which is arranged between the hole injection layer and the cathode layer.

[0104] The operating voltage U is measured in volts.

[0105] In this specification, the hole performance refers to the ability to donate electrons to form holes when an electric field is applied, and refers to the ease with which holes formed in the anode are injected into and transported through the light-emitting layer due to the conductive performance according to the highest occupied molecular orbital (HOMO) level.

[0106] Furthermore, the electronic performance refers to the ability to receive electrons when an electric field is applied, and the conductive performance according to the lowest occupied molecular orbital (LUMO) level indicates that electrons formed in the cathode are easily injected into the light-emitting layer and transported through the light-emitting layer.

[0107] [Advantageous Effects] Surprisingly, it has been found that an organic electronic device according to the invention solves the problem underlying the invention by making the organic electronic device (e.g. an organic light emitting diode) superior in various aspects to organic electronic devices known in the art (in particular with regard to operating voltage).

[0108] It has further been found that the problem underlying the present invention can be solved by providing compounds suitable for deposition by vacuum thermal evaporation under conditions suitable for mass production. In particular, the rate onset temperature of the hole transport compounds and metal complexes of the present invention can be in a range suitable for mass production.

[0109] In one embodiment, the HOMO level of the hole transport compound or hole transport compound of Formula (I) is further away from the vacuum level than the HOMO level of N4,N4'''-di(naphthalen-1-yl)-N4,N4'''-diphenyl-[1,1':4',1'':4'',1'''-quaterphenyl]-4,4'''-diamine (-4.85 eV, calculated according to the methods described herein) when measured under the same conditions.

[0110] Preferably, the HOMO level of the hole transport compound or hole transport compound of formula (I) is further away from the vacuum level than the HOMO level of N,N'-((9H-fluorene-9,9-diyl)bis(4,1-phenylene))bis(N-([1,1'-biphenyl]-4-yl)-[1,1'-biphenyl]-4-amine) (-4.86 eV, calculated according to the method described herein); alternatively, the HOMO level of the hole transport compound or hole transport compound of formula (I) is further away from the vacuum level than the HOMO level of 9-phenyl-10-(3',4',5'-triphenyl- or the HOMO level of the hole transport compound or the hole transport compound of formula (I) is the same as or further from the vacuum level than the HOMO level of tris(4-(9H-carbazol-9-yl)phenyl)amine (−5.09 eV, calculated by the methods described herein).

[0111] In one embodiment, the HOMO level of the hole transport compound or hole transport compound of formula (I) is further away from the vacuum level than the HOMO level of N4,N4'''-di(naphthalen-1-yl)-N4,N4'''-diphenyl-[1,1':4',1'':4''1'''-quaterphenyl]-4,4'''-diamine and is the same as the HOMO level of 4,4',4''-(1,3,5-benzenetriyl)tris[dibenzothiophene] when measured under the same conditions; or closer to the vacuum level than the HOMO level of said hole transport compound or hole transport compound of formula (I); preferably, the HOMO level of said hole transport compound or hole transport compound of formula (I) is further away from the vacuum level than the HOMO level of N,N'-((9H-fluorene-9,9-diyl)bis(4,1-phenylene))bis(N-([1,1'-biphenyl]-4-yl)-[1,1'-biphenyl]-4-amine) and is equal to or closer to the HOMO level of 4,4',4''-(1,3,5-benzenetriyl)tris[dibenzothiophene]. or closer to the vacuum level than the HOMO level of the hole transport compound or the hole transport compound of formula (I) is the same as the HOMO level of 9-phenyl-10-(3',4',5'-triphenyl-[1,1':2',1''-terphenyl]-3-yl)anthracene or is further away from the vacuum level than the HOMO level of the hole transport compound or the hole transport compound of formula (I) is the same as the HOMO level of 4,4',4''-(1,3,5-benzenetriyl)tris[dibenzothiophene] or closer to the vacuum level than the HOMO level of the hole transporting compound or hole transporting compound of formula (I) is further away from the vacuum level than the HOMO level of tris(4-(9H-carbazol-9-yl)phenyl)amine and is the same as or closer to the vacuum level than the HOMO level of 4,4',4''-(1,3,5-benzenetriyl)tris[dibenzothiophene] (-5.67 eV, calculated by the methods described herein).

[0112] The term "HOMO level closer to the vacuum level" should be understood to mean that the absolute value of the HOMO level is lower than the absolute value of the HOMO level of the reference compound. For example, the term "closer to the vacuum level than the HOMO level of 4,4',4''-(1,3,5-benzenetriyl)tris[dibenzothiophene]" should be understood to mean that the absolute value of the HOMO level of the organic matrix compound (OMC) is lower than the HOMO level of 4,4',4''-(1,3,5-benzenetriyl)tris[dibenzothiophene].

[0113] In one embodiment, the HOMO level of the hole transport compound or hole transport compound of formula (I) is further away from the vacuum level than the HOMO level of N4,N4'''-di(naphthalen-1-yl)-N4,N4'''-diphenyl-[1,1':4',1'':4'',1'''-quaterphenyl]-4,4'''-diamine, when measured under the same conditions; where N4,N4'''-di(naphthalen-1-yl)-N4,N4'''-diphenyl-[1,1':4',1'':4'',1'''-quaterphenyl]-4,4'''-diamine the HOMO level of N,N'-((9H-fluorene-9,9-diyl)bis(4,1-phenylene))bis(N-([1,1'-biphenyl]-4-yl)-[1,1'-biphenyl]-4-amine) is -4.85 eV; preferably, the HOMO level of the hole transport compound or the hole transport compound of formula (I) is further away from the vacuum level than the HOMO level of N,N'-((9H-fluorene-9,9-diyl)bis(4,1-phenylene))bis(N-([1,1'-biphenyl]-4-yl)-[1,1'-biphenyl]-4-amine) when measured under the same conditions; the HOMO level of the hole transport compound or the hole transport compound of formula (I) is the same as or further away from the vacuum level than the HOMO level of 9-phenyl-10-(3',4',5'-triphenyl-[1,1':2',1''-terphenyl]-3-yl)anthracene, where 9-phenyl-10-(3',4',5'-triphenyl-[1,1':2',1''-terphenyl]-3-yl)anthracene has a HOMO level of -4.86 eV; the HOMO level of 1,1':2',1''-triphenyl-3-yl)anthracene is -5.04 eV; or the HOMO level of the hole transporting compound or the hole transporting compound of formula (I) is the same as or further away from the vacuum level than the HOMO level of tris(4-(9H-carbazol-9-yl)phenyl)amine, which has a HOMO level of -5.09 eV.

[0114] Hole transport compounds that may be suitably used (for example as a matrix material in a hole injection layer of an organic electronic device) may have the formula (I):

[0115] [ka]

[0116] During the ceremony, k, m, q, r may be independently selected from 0, 1 or 2; p is 1, 2 or 3; 2≦k+m+q+r+p≦11, Ar 1 ~Ar 6 are independently a substituted or unsubstituted unsaturated 5- to 7-membered heterocycle, a substituted or unsubstituted C6-C 30 Aryl, substituted or unsubstituted C3-C 30 heteroaryl, substituted or unsubstituted fluorene, or a fused ring system containing 2 to 6 substituted or unsubstituted 5- to 7-membered rings, the rings being 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; wherein the substituents are H, D, C1-C 12 Alkyl, unsubstituted C6-C 18 Aryl, unsubstituted C3-C 18 Heteroaryl, a fused ring system containing 2 to 6 unsubstituted 5- to 7-membered rings, the rings being selected from the group consisting of an unsaturated 5- to 7-membered heterocyclic ring, a 5- to 6-membered aromatic heterocyclic ring, an unsaturated 5- to 7-membered non-heterocyclic ring, and a fused ring system containing a 6-membered aromatic non-heterocyclic ring.

[0117] In one embodiment, Ar 1 ~Ar 6are independently substituted or unsubstituted biphenylene, substituted or unsubstituted fluorene, 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 tetracene, substituted or unsubstituted tetraphene, substituted or unsubstituted dibenzofuran, substituted or unsubstituted dibenzothiophene, substituted or unsubstituted xanthene, substituted or unsubstituted carbazole, substituted or unsubstituted azepine, substituted or unsubstituted dibenzo[b,f]azepine, 9,9'-spirobi[fluorene], substituted or unsubstituted spiro[fluorene-9,9'-xanthene], substituted or unsubstituted 9,14-dihydrodibenzo[2,3:6,7]azepino[4,5-b]indole, or a substituted or unsubstituted aromatic fused ring system comprising at least three substituted or unsubstituted aromatic rings selected from the group comprising a substituted or unsubstituted non-hetero 5-membered ring, a substituted or unsubstituted hetero 5-membered ring, a substituted or unsubstituted 6-membered ring, and / or a substituted or unsubstituted 7-membered ring; wherein the substituents are H, D, C1-C 12 Alkyl, unsubstituted C6-C 18 Aryl, unsubstituted C3-C 18 Heteroaryl, a fused ring system containing 2 to 6 unsubstituted 5- to 7-membered rings, the rings being selected from the group consisting of an unsaturated 5- to 7-membered heterocyclic ring, a 5- to 6-membered aromatic heterocyclic ring, an unsaturated 5- to 7-membered non-heterocyclic ring, and a fused ring system containing a 6-membered aromatic non-heterocyclic ring.

[0118] In one embodiment, the hole transport compound of formula (I) can have a molecular weight Mw of ≧400 g / mol and ≦2000 g / mol, preferably a molecular weight Mw of ≧450 g / mol and ≦1500 g / mol, more preferably a molecular weight Mw of ≧500 g / mol and ≦1000 g / mol, even more preferably a molecular weight Mw of ≧550 g / mol and ≦900 g / mol, and particularly preferably a molecular weight Mw of ≧600 g / mol and ≦800 g / mol.

[0119] In one embodiment, the HOMO level of the hole transport compound or hole transport compound of formula (I) can be less than -4.85 eV, preferably less than -4.86 eV, preferably less than -4.9 eV, alternatively less than -4.95 eV, alternatively less than -5 eV, alternatively less than -5.05 eV, alternatively less than -5.09 eV.

[0120] In an embodiment, the HOMO level of the hole transport compound or hole transport compound of formula (I) can be less than -4.85 eV and greater than -7 eV, preferably less than -4.86 eV and greater than -7 eV, more preferably less than -4.9 eV and greater than -7 eV, alternatively less than -4.95 eV and greater than -7 eV, alternatively less than -5 eV and greater than -7 eV, alternatively less than -5.05 eV and greater than -7 eV, alternatively less than -5.09 eV and greater than -7 eV.

[0121] In an embodiment, the HOMO level of the hole transport compound or hole transport compound of formula (I) can be less than -4.85 eV and greater than -6.5 eV, preferably less than -4.86 eV and greater than -6.5 eV, more preferably less than -4.9 eV and greater than -6.5 eV, alternatively less than -4.95 eV and greater than -6.5 eV, alternatively less than -5 eV and greater than -6.5 eV, alternatively less than -5.05 eV and greater than -6.5 eV, alternatively less than -5.09 eV and greater than -6.5 eV.

[0122] In an embodiment, the HOMO level of the hole transport compound or hole transport compound of formula (I) can be less than -4.85 eV and greater than -6 eV, preferably less than -4.86 eV and greater than -6.5 eV, more preferably less than -4.9 eV and greater than -6 eV, alternatively less than -4.95 eV and greater than -6 eV, alternatively less than -5 eV and greater than -6 eV, alternatively less than -5.05 eV and greater than -6 eV, alternatively less than -5.09 eV and greater than -6 eV.

[0123] In one embodiment, the hole transport compound or hole transport compounds of Formula (I) can include at least ≧1 to ≦6 substituted or unsubstituted aromatic fused ring systems including heterocyclic aromatic rings.

[0124] In one embodiment, the hole transport compound or hole transport compound of Formula (I) can include at least ≧1 to ≦6 substituted or unsubstituted aromatic fused ring systems containing heterocyclic aromatic rings, and at least ≧1 to ≦3 substituted or unsubstituted unsaturated 5-7 membered heterocycles, preferably ≧2 to ≦5 substituted or unsubstituted aromatic fused ring systems containing heterocyclic aromatic rings.

[0125] In one embodiment, the hole transport compound or hole transport compound of formula (I) can include at least ≧1 to ≦6 substituted or unsubstituted aromatic fused ring systems containing a heterocyclic aromatic ring and at least ≧1 to ≦3 substituted or unsubstituted unsaturated 5-7 membered heterocycles, preferably ≧2 to ≦5 substituted or unsubstituted aromatic fused ring systems containing a heterocyclic aromatic ring and at least ≧1 to ≦3 substituted or unsubstituted unsaturated 5-7 membered heterocycles, more preferably 3 or 4 substituted or unsubstituted aromatic fused ring systems containing a heterocyclic aromatic ring and optionally at least ≧1 to ≦3 substituted or unsubstituted unsaturated 5-7 membered heterocycles, particularly preferably the aromatic fused ring system containing a heterocyclic aromatic ring is unsubstituted and can optionally include at least ≧1 to ≦3 unsubstituted unsaturated 5-7 membered heterocycles.

[0126] In one embodiment, the hole transport compound or hole transport compound of Formula (I) can 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.

[0127] In one embodiment, the hole transport compound or hole transport compound of Formula (I) can contain 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, including substituted or unsubstituted heterocyclic aromatic rings.

[0128] In one embodiment, the hole transport compound or hole transport compounds of formula (I) can include at least ≧1 and ≦3 or 2 substituted or unsubstituted unsaturated 5-7 membered heterocycles.

[0129] In one embodiment, the hole transport compound or hole transport compounds of formula (I) can include at least ≧1 to ≦3 or 2 substituted or unsubstituted unsaturated seven-membered heterocycles.

[0130] In one embodiment, the hole transport compound or the substituted or unsubstituted aromatic fused ring system of the hole transport compound of Formula (I) can include at least ≧1 and ≦3 or 2 substituted or unsubstituted unsaturated 5-7 membered heterocycles.

[0131] In one embodiment, the hole transport compound or the substituted or unsubstituted aromatic fused ring system of the hole transport compound of Formula (I) can include at least ≧1 to ≦3 or 2 substituted or unsubstituted unsaturated seven-membered heterocycles.

[0132] In one embodiment, the hole transport compound or hole transport compound of Formula (I) can comprise 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, where the aromatic fused ring systems comprise a substituted or unsubstituted unsaturated 5-7 membered heterocycle.

[0133] In one embodiment, the hole transport compound or hole transport compound of Formula (I) can 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, including a substituted or unsubstituted heterocyclic aromatic ring, where the aromatic fused ring system includes a substituted or unsubstituted unsaturated 5-7 membered heterocycle.

[0134] In one embodiment, the hole transport compound or hole transport compound of Formula (I) can 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, where the aromatic fused ring systems include at least ≧1 to ≦3 or 2 substituted or unsubstituted unsaturated 5-7 membered heterocycles.

[0135] In one embodiment, the hole transport compound or hole transport compound of Formula (I) can 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, including a substituted or unsubstituted heterocyclic aromatic ring, wherein the aromatic fused ring system includes at least ≧1 to ≦3 or 2 substituted or unsubstituted unsaturated 5- to 7-membered heterocycles.

[0136] In one embodiment, the hole transport compound or hole transport compounds of formula (I) can include: a substituted or unsubstituted aromatic fused ring system having at least ≧2 to ≦6, preferably ≧3 to ≦5, or 4 fused aromatic rings selected from the group consisting of a substituted or unsubstituted non-heterocyclic aromatic ring, a substituted or unsubstituted 5-membered heterocyclic ring, a substituted or unsubstituted 6-membered ring, and / or a substituted or unsubstituted unsaturated 5- to 7-membered heterocyclic ring, or - an unsubstituted aromatic fused ring system having at least ≧2 to ≦6, preferably ≧3 to ≦5 or 4 fused aromatic rings selected from the group consisting of unsubstituted non-heterocyclic aromatic rings, unsubstituted 5-membered heterocyclic rings, unsubstituted 6-membered rings, and / or unsubstituted unsaturated 5- to 7-membered heterocyclic rings.

[0137] It should be noted 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, where the substituted or unsubstituted unsaturated 5- to 7-membered ring does not have to be an aromatic ring.

[0138] In one embodiment, the hole transport compound or hole transport compounds of formula (I) can include at least ≧1 to ≦6, preferably ≧2 to ≦5, and more preferably 3 or 4, substituted or unsubstituted aromatic fused ring systems having: at least one unsaturated five-membered ring, and / or at least one unsaturated 6-membered ring, and / or at least one unsaturated 7-membered ring; where preferably at least one unsaturated 5-membered ring and / or at least one unsaturated 7-membered ring contains at least 1 to 3, preferably 1, heteroatom.

[0139] In one embodiment, the hole transport compound or hole transport compounds of formula (I) can include at least ≧1 to ≦6, preferably ≧2 to ≦5, and more preferably 3 or 4, substituted or unsubstituted aromatic fused ring systems having: at least one aromatic five-membered ring, and / or at least one aromatic six-membered ring, and / or at least one aromatic 7-membered ring; preferably at least one unsaturated 5-membered ring and / or at least one aromatic 7-membered ring contains at least 1 to 3, preferably 1, heteroatom; Here, the substituted or unsubstituted aromatic fused ring system contains at least ≧1 to ≦3, or 2, substituted or unsubstituted unsaturated 5- to 7-membered heterocycles.

[0140] In one embodiment, the hole transport compound or hole transport compounds of formula (I) can 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, particularly preferably 7 or 8 non-heterocyclic aromatic rings, preferably the non-heterocyclic aromatic rings are aromatic C6 rings; and / or at least ≧1 to ≦4, preferably 2 or 3, five-membered aromatic rings, preferably heteroaromatic five-membered rings; and / or at least one or two unsaturated 5- to 7-membered heterocyclic rings, preferably at least one or two unsaturated 7-membered heterocyclic rings; at least ≧6 to ≦12, preferably ≧7 to ≦11, and more preferably ≧8 to ≦10 or 9 aromatic rings, at least ≧4 to ≦11, preferably ≧5 to ≦10, more preferably ≧6 to ≦9, particularly preferably 7 or 8, are non-heterocyclic aromatic rings; and at least ≧1 and ≦4, preferably 2 or 3, aromatic rings are heterocyclic aromatic rings, wherein the total number of non-heterocyclic aromatic rings and heterocyclic aromatic rings does not exceed 12 aromatic rings; and / or at least ≧6 to ≦12, preferably ≧7 to ≦11, more preferably ≧8 to ≦10 or 9 aromatic rings, At least ≧4 to ≦11, preferably ≧5 to ≦10, more preferably ≧6 to ≦9, particularly preferably 7 or 8, are non-heterocyclic aromatic rings; and at least ≧1 and ≦4, preferably 2 or 3, aromatic rings are heterocyclic aromatic rings, wherein the total number of non-heterocyclic aromatic rings and heterocyclic aromatic rings does not exceed 12 aromatic rings; and The hole transport compound or hole transport compounds of formula I contain at least ≧1 to ≦4, preferably 2 or 3, five-membered aromatic rings, preferably heteroaromatic five-membered rings, and / or The hole transport compound or hole transport compounds of formula (I) contain at least one or two unsaturated 5- to 7-membered heterocycles, preferably at least one or two unsaturated 7-membered heterocycles.

[0141] In an embodiment, the hole transport compound or the hole transport compound of formula (I) may comprise a heteroatom, which may be selected from the group comprising O, S, N, B or P, preferably, the heteroatom may be selected from the group comprising O, S or N.

[0142] In one embodiment, the hole transport compound or hole transport compounds of formula (I) can include at least ≧1 to ≦6, preferably ≧2 to ≦5, and more preferably 3 or 4, substituted or unsubstituted aromatic fused ring systems having: at least one aromatic five-membered ring, and / or at least one aromatic six-membered ring, and / or at least one aromatic 7-membered ring; where preferably at least one aromatic 5-membered ring and / or at least one aromatic 7-membered ring contains at least 1 to 3, preferably 1, heteroatom; wherein the substituted or unsubstituted aromatic fused ring system optionally comprises at least ≧1 to ≦3 or 2 substituted or unsubstituted unsaturated 5-7 membered heterocycles; wherein the substituted or unsubstituted aromatic fused ring system comprises a heteroatom, which may be selected from the group comprising O, S, N, B, P or Si, preferably, the heteroatom may be selected from the group comprising O, S or N.

[0143] In one embodiment, the hole transport compound or the hole transport compound of formula (I) may be free of heteroatoms that are not part of an aromatic ring and / or heteroatoms that are not part of an unsaturated seven-membered ring, and preferably, the hole transport compound or the hole transport compound of formula (I) may be free of N atoms, except for N atoms that are part of an aromatic ring or N atoms that are part of an unsaturated seven-membered ring.

[0144] In one embodiment, the hole transport compound includes two carbazole groups, at least one dibenzofuran group, at least one dibenzothiophene group, and / or at least one anthracene group.

[0145] In one embodiment, the hole transport compound includes two carbazole groups, one to three dibenzofuran groups, one to three dibenzothiophene groups, and / or one to two anthracene groups.

[0146] In one embodiment, for the hole transport compound of formula (I): Ar 3 may be selected from D1 to D17, preferably D1 to D6 and D16:

[0147] [ka]

[0148] In one embodiment, Ar 1 may be selected from D7 to D15 and D17. 2 may be selected from D1 to D6, D7 to D15 and D17. 4 may be selected from D1 to D6, D7 to D15 and D17. 5 may be selected from D1 to D6, D7 to D15 and D17. 6 may be selected from D7 to D15 and D17.

[0149] In one embodiment, for the hole transport compound of formula (I): Ar 3 may be selected from D1 to D17, preferably D1 to D6 and D16:

[0150] [ka]

[0151] Ar 1 is selected from D7 to D15 and D17 when m>0 and k>0, is selected from D7 to D15 and D17 when k>0 and m=0, and is selected from D1 to D6 when k>1; Ar 2is selected from D1 to D6 if m>0 and k>0; or is selected from D7 to D15 and D17 if m>0 and k=0; Ar 4 is selected from D1 to D6 if q>0, and is selected from D1 to D6 if q=0 and r>0; is selected from D7 to D15 and D17 if q=0 and r=0; Ar 5 is selected from D1 to D6 if q>0 and r>0, and is selected from D7 to D15 and D17 if q>0 and r=0; Ar 6 is selected from D7 to D15 and D17 when r>0, q>0, is selected from D7 to D15 and D17 when r>0, q=0, is selected from D7 to D15 and D17, and is selected from D1 to D6 when r>1.

[0152] In one embodiment, in formula (I), Ar 3 The groups are selected from anthracene, carbazole, dibenzothiophene, and / or dibenzofuran.

[0153] In one embodiment, in formula (I), Ar 3 The group is selected to be anthracene.

[0154] In one embodiment, in formula (I), Ar 3 The groups are selected from carbazole, dibenzothiophene, and / or dibenzofuran.

[0155] In one embodiment, the hole transport compound or hole transport compounds of formula (I) can be selected from F1-F13:

[0156] [ka] JPEG0007644768000027.jpg123169

[0157] Preferably, the hole transport compound is free of metals and / or ionic bonds.

[0158] The hole injection layer and / or hole transport compound may include, but are not limited to, HTM014, HTM081, HTM163, HTM222, EL-301, HTM226, HTM355, HTM133, HTM334, HTM604, and EL-22T. Abbreviations indicate the manufacturer's name (e.g., Merck or Lumtec).

[0159] The hole injection layer and / or hole transport compound may be N,N'-bis(naphthalen-1-yl)-N,N'-bis(phenyl)-9,9-dimethyl-fluorene, N,N'-bis(3-methylphenyl)-N,N'-bis(phenyl)-9,9-dimethyl-fluorene, N,N'-bis(naphthalen-1-yl)-N,N'-bis(phenyl)-9,9-dimethylfluorene, N,N'-bis(naphthalen-1-yl)-N,N'-bis(phenyl)-2,2-dimethylbenzidine, N,N'-bis(3-methylphenyl)-N,N'-bis(phenyl). -9,9-spirobifluorene, 2,2',7,7'-tetrakis(N,N-diphenylamino)-9,9'-spirobifluorene, N,N'-bis(naphthalen-1-yl)-N,N'-bis(phenyl)-benzidine, N,N'-bis(naphthalen-2-yl)-N,N'-bis(phenyl)-benzidine, N,N'-bis(3-methylphenyl)-N,N'-bis(phenyl)-benzidine, N,N'-bis(3-methylphenyl)-N,N'-bis(phenyl)-9,9-dimethyl-fluorene, N,N'-bis(naphthalen-1-yl) -N,N'-bis(phenyl)-9,9-spirobifluorene, di-[4-(N,N-ditolyl-amino)-phenyl]-cyclohexane, 2,2',7,7'-tetra(N,N-di-tolyl)amino-spiro-bifluorene, 9,9-bis[4-(N,N-bis-biphenyl-4-yl-amino)phenyl]-9H-fluorene, 2,2',7,7'-tetrakis(N,N-naphthalenyl(phenyl)-amino]-9,9'-spirobifluorene, 2,7-bis(N,N-bis(9,9-spiro-bifluoren-2-yl)-amino)-9,9' -spirobifluorene, 2,2'-bis(N,N-bis(biphenyl-4-yl)amino]-9,9'-spirobifluorene, N,N'-bis(phenanthren-9-yl)-N,N'-bis(phenyl)-benzidine, N,N,N',N'-tetra-naphthalen-2-yl)-benzidine, 2,2'-bis(N,N-di-phenyl-amino)-9,9-spirobifluorene, 9,9-bis[4-(N,N-bis-naphthalen-2-yl-amino)phenyl]-9H-fluorene, 9,9-bis[4-(N,N'-bis-naphthalen-2-yl-N,N'-bis(phenylamino)-phenyl]-9H-fluorene, titanium oxide phthalocyanine, copper phthalocyanine, 2,3,5,6 tetrafluoro 7,7,8,8, tetracyanoquinodimethane, 4,4'4''-tris(N-3-methylphenyl-N-phenyl-amino)triphenylamine, 4,4'4''-tris(N-(2-naphthyl)-N-phenyl-amino)triphenylamine, 4,4',4''-tris(N-(1-naphthyl)-N-phenyl-amino)triphenylamine, N,N-triphenylamine, 4,4',4''-tris(N,N-diphenyl-amino)triphenylamine, pyrazino[2,3-f][1,10]phenanthroline-2,3-dicarbonitrile, N,N,N',N'-tetrakis(4-methoxyphenyl)benzidine, HTM014, HTM081, HTM163, HTM222, EL-301, HTM226, HTM355, HTM133, HTM334, HTM604, and EL-22T. Abbreviations indicate the name of the manufacturer (e.g., Merck or Lumtec).

[0160] Metal complexes of formula (II) The metal complex of formula (II) is non-emissive. In the context of this specification, the term "essentially non-emissive" or "non-emissive" means that the contribution of the metal complex of formula (II) to the visible emission spectrum from an organic electronic device (e.g., an OLED or a display device) is less than 10% relative to the visible emission spectrum, preferably less than 5%. The visible emission spectrum is an emission spectrum having a wavelength of about ≧380 nm to about ≦780 nm.

[0161] In one embodiment, the metal ion M of formula (II) may be selected from metal ions, where the corresponding metal has an electronegativity of arene of less than 2.4, preferably M may be selected from alkali metals, alkaline earth metals, rare earth metals or transition metals, more preferably M may be selected from metals with atomic mass ≧24 Da, particularly preferably M may be selected from metals with atomic mass ≧24 Da and M may have an oxidation number ≧2.

[0162] The term "Allen's electronegativity" refers specifically to Allen, Leland C (1989). "Electronegativity is the average one-electron energy of a valence shell electron in a free atom in the ground state." (See Journal of American Chemical Society 111 (25): 9003-9014) In one embodiment of the present invention, the valence n of M is 1 or 2.

[0163] In one embodiment of the present invention, M may be selected from metal ions whose corresponding metals have an electronegativity of the arene less than 2.4, preferably less than 2, more preferably less than 1.9, and the valence n of M is 1 or 2.

[0164] In one embodiment of the invention, M is selected from an alkali metal, an alkaline earth metal, a rare earth metal, or a transition metal; alternatively, M is selected from an alkali metal, an alkaline earth metal, a transition metal, or a main group metal of period 4 or a main group metal of period 5.

[0165] In one embodiment of the invention, M is selected from Li, Na, K, Cs, Mg, Mn, Cu, Zn, Ag, Bi and Mo; preferably, M is selected from Na, K, Cs, Mg, Mn, Cu, Zn and Ag; more preferably, M is selected from Na, K, Mg, Mn, Cu, Zn and Ag, where n is 2 when M is Cu.

[0166] In one embodiment of the present invention, M is not Li.

[0167] In one embodiment of the present invention, M is not Li or K.

[0168] In one embodiment of the present invention, M is not Ag.

[0169] In one embodiment of the present invention, M is not Cu.

[0170] In one embodiment of the present invention, M is not Mo.

[0171] In one embodiment of the present invention, M is not Ir and / or Pt.

[0172] In another embodiment, the metal complex of formula (II) may have a molecular weight Mw of ≧287 g / mol and ≦2000 g / mol, preferably a molecular weight Mw of ≧400 g / mol and ≦1500 g / mol, more preferably a molecular weight Mw of ≧580 g / mol and ≦1500 g / mol, particularly preferably a molecular weight Mw of ≧580 g / mol and ≦1400 g / mol.

[0173] In another embodiment, the metal complex of formula (II) may have a molecular weight Mw of ≧400 g / mol and ≦2000 g / mol, preferably a molecular weight Mw of ≧400 g / mol and ≦1500 g / mol, more preferably a molecular weight Mw of ≧580 g / mol and ≦1500 g / mol, particularly preferably a molecular weight Mw of ≧580 g / mol and ≦1400 g / mol.

[0174] In another embodiment, the ligand L of formula (II), also referred to as L, may be selected from the group comprising: at least 3 carbon atoms, or at least 4 carbon atoms, and / or at least 2 oxygen atoms or 1 oxygen atom and 1 nitrogen atom, 2 to 4 oxygen atoms, 2 to 4 oxygen atoms and 0 to 2 nitrogen atoms, and / or - at least one or more groups selected from halogen, F, CN, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C1-C6 alkoxy, or two or more groups selected from halogen, F, CN, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C1-C6 alkoxy, at least one or more groups selected from halogen, F, CN, substituted C1-C6 alkyl, substituted C1-C6 alkoxy, or two or more groups selected from halogen, F, CN, perfluorinated C1-C6 alkyl, perfluorinated C1-C6 alkoxy, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C6-C12 Aryl and / or substituted or unsubstituted C3-C 12 one or more groups selected from heteroaryl, wherein the substituent is D, C6 aryl, C3-C9 heteroaryl, C1-C6 alkyl, C1-C6 alkoxy, C3-C6 branched alkyl, C3-C6 cyclic alkyl, C3-C6 branched alkoxy, C3-C6 cyclic alkoxy, partially or fully fluorinated C1-C 16 Alkyl, partially or fully fluorinated C1-C 16 Alkoxy, partially or fully deuterated C1-C6 alkyl, partially or fully deuterated C1-C6 alkoxy, COR 6 , COOR 6 , halogen, F or CN; Here, R 6 is C6 aryl, C3-C9 heteroaryl, C1-C6 alkyl, C1-C6 alkoxy, C3-C6 branched alkyl, C3-C6 cyclic alkyl, C3-C6 branched alkoxy, C3-C6 cyclic alkoxy, partially or fully fluorinated C1-C 16 Alkyl, partially or fully fluorinated C1-C 16 alkoxy, partially or fully deuterated C1-C6 alkyl, partially or fully deuterated C1-C6 alkoxy.

[0175] In another embodiment, the ligand L of formula (II) is selected from the group consisting of at least 2 carbon atoms, alternatively at least 3 carbon atoms, at least 1 oxygen atom, at least 2 oxygen atoms, at least 1 oxygen atom and / or nitrogen atom, 1 nitrogen atom and at least 2 oxygen atoms, at least 2 carbon atoms and at least 1 oxygen atom, at least 2 carbon atoms and 2 oxygen atoms or 1 oxygen atom and 1 nitrogen atom; halogen, F, CN, substituted or unsubstituted C1-C6 alkyl ... or at least one group selected from halogen, F, CN, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C1-C6 alkoxy; or at least one group selected from halogen, F, CN, substituted C1-C6 alkyl, substituted C1-C6 alkoxy; or at least one group selected from halogen, F, CN, substituted C1-C6 alkyl, substituted C1-C6 alkoxy; or at least two groups selected from halogen, F, CN, perfluorinated C1-C6 alkyl, perfluorinated C1-C6 alkoxy; or at least two groups selected from substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C6-C 12 Aryl and / or substituted or unsubstituted C3-C 12 one or more groups selected from heteroaryl; wherein the substituent is D, C6 aryl, C3-C9 heteroaryl, C1-C6 alkyl, C1-C6 alkoxy, C3-C6 branched alkyl, C3-C6 cyclic alkyl, C3-C6 branched alkoxy, C3-C6 cyclic alkoxy, partially or fully fluorinated C1-C 16 Alkyl, partially or fully fluorinated C1-C 16 Alkoxy, partially or fully deuterated C1-C6 alkyl, partially or fully deuterated C1-C6 alkoxy, COR 6 , COOR 6 , halogen, F or CN; Here, R 6 is C6 aryl, C3-C9 heteroaryl, C1-C6 alkyl, C1-C6 alkoxy, C3-C6 branched alkyl, C3-C6 cyclic alkyl, C3-C6 branched alkoxy, C3-C6 cyclic alkoxy, partially or fully fluorinated C1-C 16Alkyl, partially or fully fluorinated C1-C 16 alkoxy, partially or fully deuterated C1-C6 alkyl, partially or fully deuterated C1-C6 alkoxy.

[0176] In another embodiment, the ligand L of formula (II) may be selected from the group including F, CN, perfluorinated C1-C6 alkyl, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C1-C6 alkoxy.

[0177] The substituents are D, C6 aryl, C3-C9 heteroaryl, C1-C6 alkyl, C1-C6 alkoxy, C3-C6 branched alkyl, C3-C6 cyclic alkyl, C3-C6 branched alkoxy, C3-C6 cyclic alkoxy, partially or fully fluorinated C1-C 16 Alkyl, partially or fully fluorinated C1-C 16 Alkoxy, partially or fully deuterated C1-C6 alkyl, partially or fully deuterated C1-C6 alkoxy, COR 6 , COOR 6 , halogen, F or CN; Here, R 6 is C6 aryl, C3-C9 heteroaryl, C1-C6 alkyl, C1-C6 alkoxy, C3-C6 branched alkyl, C3-C6 cyclic alkyl, C3-C6 branched alkoxy, C3-C6 cyclic alkoxy, partially or fully fluorinated C1-C 16 Alkyl, partially or fully fluorinated C1-C 16 alkoxy, partially or fully deuterated C1-C6 alkyl, partially or fully deuterated C1-C6 alkoxy.

[0178] In another embodiment, the ligand L does not contain a sulfur atom.

[0179] In another embodiment, the ligand L does not contain a sulfur atom or a phthalocyanine group.

[0180] In another embodiment, the ligands L of formula (II) may be independently selected from G1 to G64, preferably G1 to G62:

[0181] [ka] JPEG0007644768000029.jpg224169JPEG0007644768000030.jpg199169JPEG0007644768000031.jpg209169JPEG0007644768000032.jpg251169

[0182] Preferably, L is selected from (G2) to (G59), or L is selected from (G2) to (G52).

[0183] In another embodiment, L is selected from (G1)-(G52) and (G60)-(G64).

[0184] In another embodiment, L is selected from (G1)-(G52) and (G60)-(G62).

[0185] The negative charge in the metal complex of formula (II) may be partially or completely delocalized on the ligands L.

[0186] Metal complexes of formula (IIa) to (IIe) In one embodiment, the metal complex may be selected from the following formulae (IIa) to (IIe), with formulae (IIa) to (IId) being preferred:

[0187] [ka]

[0188] Where: M is a metal ion; n is the valence of M; A 1 and A 2 are independently substituted or unsubstituted C1-C12 Alkyl, substituted or unsubstituted C6-C 12 Aryl, substituted or unsubstituted C3-C 12 heteroaryl; A 3 is H, D, substituted or unsubstituted C1-C 12 Alkyl, substituted or unsubstituted C6-C 12 Aryl, substituted or unsubstituted C3-C 12 heteroaryl; Here, A 1 and A 2 and / or A 3 The substituents are independently selected from D, C6 aryl, C3-C9 heteroaryl, C1-C6 alkyl, C1-C6 alkoxy, C3-C6 branched alkyl, C3-C6 cyclic alkyl, C3-C6 branched alkoxy, C3-C6 cyclic alkoxy, partially or fully fluorinated C1-C 16 Alkyl, partially or fully fluorinated C1-C 16 Alkoxy, partially or fully deuterated C1-C6 alkyl, partially or fully deuterated C1-C6 alkoxy, COR 1 , COOR 1 , halogen, F or CN; R 1 is C6 aryl, C3-C9 heteroaryl, C1-C6 alkyl, C1-C6 alkoxy, C3-C6 branched alkyl, C3-C6 cyclic alkyl, C3-C6 branched alkoxy, C3-C6 cyclic alkoxy, partially or fully fluorinated C1-C 16 Alkyl, partially or fully fluorinated C1-C 16 Alkoxy, partially or fully deuterated C1-C6 alkyl, partially or fully deuterated C1-C 16 It may be selected from alkoxy.

[0189] The negative charge in the metal complexes of formula (IIa), formula (IIb), formula (IIc) and / or formula (IId) is formed by the carbon atoms and heteroatoms and the A 1 and / or A 2 and / or A 3 The nucleophilic substance may be partially or completely delocalized on the surface.

[0190] In one embodiment, A 1 and A 2 and / or A 3 At least one of A contains a substituent. 1 and A 2 and / or A 3 At least one of the substituents is independently selected from C3-C9 heteroaryl, C1-C6 alkoxy, C3-C6 branched alkoxy, C3-C6 cyclic alkoxy, partially or fully fluorinated C1-C 16 Alkyl, partially or fully fluorinated C1-C 16 Alkoxy, partially or fully deuterated C1-C6 alkoxy, COR 1 , COOR 1 , halogen, F or CN; preferably, A 1 and A 2 and / or A 3 at least one of contains at least two substituents; Here, A 1 and A 2 and / or A 3 The substituents are independently selected from C3-C9 heteroaryl, C1-C6 alkoxy, C3-C6 branched alkoxy, C3-C6 cyclic alkoxy, partially or fully fluorinated C1-C 16 Alkyl, partially or fully fluorinated C1-C 16 Alkoxy, partially or fully deuterated C1-C6 alkoxy, COR 1 , COOR 1 , halogen, F or CN; more preferably, A 1 and A 2 and / or A 3 may contain at least one substituent independently selected from halogen, F, CF3, C2F5, C3F7, C4F9, OCF3, OC2F5 or CN; particularly preferably, A 1 and A 2 may include at least two substituents independently selected from halogen, F, CF3, C2F5, C3F7, C4F9, OCF3, OC2F5, or CN.

[0191] In one embodiment of the present invention, 1 and A 2 and / or A 3 are, independently, CF3, C2F5, C3F7, C4F9, and C5F 11 , C6F 13 and / or phenyl substituted by 2 to 5 groups independently selected from F or CF; or C2F5, C3F7, C4F9, C5F 11 , C6F 13 and / or phenyl substituted by 2 to 5 groups independently selected from F or CF; or CF, C2F5, C3F7, C4F9, C5F 11 , C6F 13 or phenyl substituted by 0-2 CF3 groups and / or 0-5 F atoms.

[0192] In one embodiment of the invention, the metal complex may be selected from: - of formula (IIa), in which M is selected from alkali metals, alkaline earth metals, transition metals or rare earth metals; and / or - of formula (IIb), in which M is selected from alkali metals, alkaline earth metals, transition metals or rare earth metals; and / or - Formula (IIc), where M is selected from alkali metals, alkaline earth metals or main group metals.

[0193] In one embodiment of the invention, the metal complex may be selected from: - of formula (IIa), in which M is selected from alkali metals, alkaline earth metals, transition metals or rare earth metals; and / or - of formula (IIb), in which M is selected from alkali metals, alkaline earth metals, transition metals or rare earth metals; and / or - of formula (IId), in which M is selected from alkali metals, alkaline earth metals, transition metals or rare earth metals; and / or Formula (IIe), in which M is selected from alkali metals, alkaline earth metals, transition metals or rare earth metals.

[0194] In one embodiment of the present invention, the metal complex may be selected from formula (IIa) or formula (IIb): wherein M is selected from a metal ion, the corresponding metal having an electronegativity of arene less than 2.4, preferably M is selected from an alkali metal, an alkaline earth metal, a rare earth metal or a transition metal, more preferably M is selected from a metal having an atomic mass ≧24 Da, particularly preferably M is selected from a metal having an atomic mass ≧24 Da and M has an oxidation number ≧2; and / or formula (IIc), wherein M is selected from Bi.

[0195] Particularly preferred are metal complexes of the formula:

[0196] [ka] JPEG0007644768000035.jpg237169JPEG0007644768000036.jpg247169

[0197] In one embodiment, the metal complex may be free of bis(trifluoromethane)sulfonimide (TFSI), which may make the metal complex particularly suitable for mass production of organic electronic devices.

[0198] Hole injection layer In another embodiment, the hole injection layer may include a hole transport compound and a metal complex: wherein said hole transport compound has formula (I):

[0199] [ka]

[0200] During the ceremony, k, m, q, r may be independently selected from 0, 1 or 2; p is 1, 2 or 3; where 2≦k+m+q+r+p≦11, Ar 1 ~Ar 6 are independently a substituted or unsubstituted unsaturated 5- to 7-membered heterocycle, a substituted or unsubstituted C6-C 30 Aryl, substituted or unsubstituted C3-C 30 heteroaryl, substituted or unsubstituted fluorene, or a fused ring system containing 2 to 6 substituted or unsubstituted 5- to 7-membered rings, the rings being 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, (iv) 6-membered aromatic non-heterocyclic rings; Ar when k=1 2 , Ar 3 , Ar when q=1 4 , Ar when r=1 5 are independently a substituted or unsubstituted unsaturated 5- to 7-membered heterocycle, a substituted or unsubstituted C6-C 30 Arylene, substituted or unsubstituted C3-C 30Heteroarylene, substituted or unsubstituted biphenylene, substituted or unsubstituted fluorene, 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 tetracene, substituted or unsubstituted tetraphene, substituted or unsubstituted dibenzofuran, substituted or unsubstituted dibenzothiophene, substituted or unsubstituted xanthene, substituted or unsubstituted carbazole, substituted or unsubstituted azepine, substituted or unsubstituted diphenylene, substituted or unsubstituted cyclohexyl ether ... benzo[b,f]azepine, 9,9'-spirobi[fluorene], substituted or unsubstituted spiro[fluorene-9,9'-xanthene], substituted or unsubstituted 9,14-dihydrodibenzo[2,3:6,7]azepino[4,5-b]indole, or substituted or unsubstituted aromatic fused ring systems comprising at least three, preferably three to six, substituted or unsubstituted aromatic rings selected from the group comprising substituted or unsubstituted non-hetero 5-membered ring, substituted or unsubstituted hetero 5-membered ring, substituted or unsubstituted 6-membered ring, and / or substituted or unsubstituted 7-membered ring; Ar when k=0 2 , Ar where m=0 and k=0 3 , Ar where q=0 and r=0 4 , Ar when r=0 5 are independently a substituted or unsubstituted unsaturated 5- to 7-membered heterocycle, a substituted or unsubstituted C6-C 30 Aryl, substituted or unsubstituted C3-C 30Heteroaryl, substituted or unsubstituted biphenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted naphthalenyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted pyrenyl, substituted or unsubstituted perylenyl, substituted or unsubstituted triphenylenyl, substituted or unsubstituted tetracenyl, substituted or unsubstituted tetraphenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted xanthenyl, substituted or unsubstituted carbazole, substituted or unsubstituted azepine, substituted or unsubstituted may be selected from substituted dibenzo[b,f]azepines, 9,9'-spirobi[fluorenyl], substituted or unsubstituted spiro[fluorenyl-9,9'-xanthene], substituted or unsubstituted 9,14-dihydrodibenzo[2,3:6,7]azepino[4,5-b]indoles, or substituted or unsubstituted aromatic fused ring systems comprising at least three, preferably three to six, substituted or unsubstituted aromatic rings selected from the group comprising 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; wherein the substituents are H, D, C1-C 12 Alkyl, unsubstituted C6-C 18 Aryl or unsubstituted C3-C 18 Heteroaryl; The metal complex has the formula (II):

[0201] [ka]

[0202] Where: M is a metal ion; n is the valence of M, and n is an integer from 1 to 4; L is a ligand containing at least two carbon atoms.

[0203] Preferably, the hole injection layer does not comprise ionic liquids, metal phthalocyanines, CuPc, HAT-CN, pyrazino[2,3-f][1,10]phenanthroline-2,3-dicarbonitrile, F4TCNQ, metal fluorides and / or metal oxides, and the metal in said metal oxides is selected from Re and / or Mo. This allows the hole injection layer to be deposited under conditions suitable for mass production.

[0204] Organic Electronic Devices In one embodiment, the hole injection layer is disposed in direct contact with the anode layer.

[0205] In one embodiment, the organic electronic device may further include at least one photoactive layer, the photoactive layer being disposed between the hole injection layer and the cathode layer.

[0206] In one embodiment, the organic electronic device may further include at least one photoactive layer disposed between the hole injection layer and the cathode layer, the hole injection layer being disposed in direct contact with the anode layer.

[0207] In one embodiment, an organic electronic device may include at least one photoactive layer, which may be an emissive layer.

[0208] In one embodiment, an organic electronic device may include a hole injection layer, where the hole injection layer includes a first sublayer comprising a metal complex of Formula (II) and a second sublayer comprising a hole transport compound or a hole transport compound of Formula (I), where the first sublayer may be disposed closer to the anode layer and the second sublayer may be disposed closer to the cathode layer.

[0209] In one embodiment, an organic electronic device comprises a hole injection layer comprising a first sublayer consisting of a metal complex of formula (II) and a second sublayer comprising a hole transport compound or a hole transport compound of formula (I), wherein the first sublayer is disposed closer to the anode layer and the second sublayer is disposed closer to the cathode layer.

[0210] In the context of this specification, the term "consisting essentially of" specifically means and / or includes a proportion of ≧90% (volume / volume), more preferably ≧95% (volume / volume), and most preferably ≧99% (volume / volume).

[0211] In one embodiment of the present invention, an organic electronic device may include a hole injection layer comprising a first sublayer of a metal complex of formula (II) and a second sublayer comprising a hole transport compound or a hole transport compound of formula (I), the first sublayer being disposed closer to the anode layer and the second sublayer being disposed closer to the cathode layer, wherein M in formula (II) is selected from Li, Na, K, Cs, Mg, Mn, Cu, Zn, Ag, Bi and Mo, or selected from Mg, Mn, Cu, Zn, Ag, Bi and Mo, or selected from Cu, Zn, Ag or Bi.

[0212] In one embodiment, an organic electronic device may comprise a hole injection layer comprising a first sublayer comprising a metal complex of Formula (II) and a second sublayer comprising a hole transport compound or a hole transport compound of Formula (I) and a metal complex, wherein the first sublayer is disposed closer to the anode layer and the second sublayer is disposed closer to the cathode layer.

[0213] In one embodiment, an organic electronic device may comprise a hole injection layer comprising a first sublayer comprising a metal complex of Formula (II) and a second sublayer comprising a hole transport compound or a hole transport compound of Formula (I) and a metal complex of Formula (II), wherein the first sublayer is disposed closer to the anode layer and the second sublayer is disposed closer to the cathode layer.

[0214] In another embodiment, the organic electronic device may be a light emitting device, a thin film transistor, a battery, a display device or a photovoltaic cell, preferably a light emitting device and / or a display device.

[0215] The hole injection layer (HIL) can be formed on the anode layer by vacuum deposition, spin coating, printing, casting, slot-die coating, Langmuir-Blodgett (LB) deposition, and the like. When vacuum deposition is used to form the HIL, the deposition conditions can vary depending on the hole transport compound used to form the HIL, as well as the desired structure and thermal performance of the HIL. However, typically, the conditions for vacuum deposition include a deposition temperature of 100°C to 350°C, a deposition pressure of 10 -8 ~10 -3 Torr (1 Torr equals 133.322 Pa) and a deposition rate of 0.1-10 nm / sec.

[0216] When the HIL is formed using spin coating or printing, the coating conditions can vary depending on the hole transport compound used to form the HIL and the desired structure and thermal performance of the HIL. For example, the coating conditions can 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, the solvent is removed by heat treatment.

[0217] The HIL may be formed by any hole transport compound of formula (I) and a metal complex of formula (II), (IIa), (IIb), (IIc), (IId) and (IIe), preferably (II), (IIa) to (IId).

[0218] The thickness of the HIL can range from about 1 nm to about 15 nm, for example, from about 2 nm to about 12 nm, or from about 3 nm to about 10 nm.

[0219] If the thickness of the HIL is within this range, the HIL can have excellent hole injection performance without a substantial penalty in operating voltage.

[0220] In one embodiment of the present invention, the hole injection layer may comprise: at least about ≧5% to about ≦90% by weight, preferably about ≧30% to about ≦80% by weight, more preferably about ≧40% to about 80% by weight, and even more preferably about ≧50% to about 80% by weight of a hole transport compound or a hole transport compound of formula (I), at least about ≧10 wt% to about ≦95 wt%, preferably about ≧20 wt% to about ≦70 wt%, more preferably about ≧20 wt% to about ≦60 wt%, and even more preferably about ≧20 wt% to about ≦50 wt% of the metal complex of Formula (II), (IIa), (IIb), (IIc), (IId) and (IIe), preferably Formula (II), (IIa) to (IId); preferably the weight % of the metal complex of Formula (II), (IIa), (IIb), (IIc), (IId) and (IIe), preferably Formula (II), (IIa) to (IId), is lower than the weight % of the hole transport compound or the hole transport compound of Formula (I); wherein the weight % of the components is based on the total weight of the hole injection layer.

[0221] In one embodiment of the present invention, the hole injection layer comprises: at least about ≧5% to about ≦90% by volume, preferably about ≧30% to about ≦80% by volume, more preferably about ≧40% to about ≦80% by volume, and even more preferably about ≧50% to about ≦80% by volume of a hole transport compound or a hole transport compound of formula (I), at least about ≧10% to about ≦95% by volume, preferably about ≧20% to about ≦70% by volume, more preferably about ≧20% to about ≦60% by volume, and even more preferably ≧20% to about ≦50% by volume of the metal complex of Formula (II), (IIa), (IIb), (IIc), (IId), and (IIe), preferably Formula (II), (IIa) to (IId); preferably the volume % of the metal complex of Formula (II), (IIa), (IIb), (IIc), (IId), and (IIe), preferably Formula (II), (IIa) to (IId), is lower than the volume % of the hole transport compound or the hole transport compound of Formula (I); wherein the weight % of the components is based on the total weight of the hole injection layer.

[0222] Further layers According to the present invention, the organic electronic device may include additional layers in addition to those mentioned above, exemplary embodiments of each of which are described below.

[0223] substrate The substrate can be any substrate commonly used in the manufacture of electronic devices (e.g., organic light-emitting diodes). If the light is emitted through the substrate, the substrate must be a transparent or semi-transparent material (e.g., a glass substrate or a transparent plastic substrate). If the light is emitted through the top surface, the substrate can be both a transparent and a non-transparent material (e.g., a glass substrate, a plastic substrate, a metal substrate, or a silicon substrate).

[0224] anode layer The anode layer may be formed by evaporating or sputtering the material used to form the anode layer. The material used to form the anode layer may be a high work function material. This facilitates hole injection. The anode material may also be selected from low work function materials (e.g., aluminum). The anode layer may be a transparent electrode or a reflective electrode. Transparent conductive oxides (e.g., indium tin oxide (ITO), indium zinc oxide (IZO), tin dioxide (SnO2), aluminum zinc oxide (AlZO) and zinc oxide (ZnO)) may be used to form the anode layer. The anode layer may be formed using a metal (typically silver (Ag), gold (Au) or a metal alloy).

[0225] Hole transport layer In one embodiment, the organic electronic device may further include a hole transport layer, where the hole transport layer may be disposed between the hole injection layer and the cathode layer, and the optional hole transport layer may be disposed between the hole injection layer and the at least one photoactive layer or the at least one light-emitting layer.

[0226] In one embodiment, the organic electronic device may comprise a hole transport layer, wherein the hole transport layer comprises a hole transport compound according to claim 1 or a hole transport compound of formula (I), preferably, the hole transport compounds in the hole injection layer and in the hole transport layer may be selected to be the same.

[0227] In another embodiment, the organic electronic device may include a hole transport layer, wherein the hole transport layer may include a hole transport compound or a hole transport compound of Formula (I); the hole transport compounds or the hole transport compounds of Formula (I) in the hole injection layer and in the hole transport layer may be selected to be the same.

[0228] In one embodiment, the hole transport layer may comprise a hole transport compound or a hole transport compound of formula (I); the hole transport compounds or the hole transport compounds of formula (I) in the hole injection layer and in the hole transport layer are selected the same, and the hole transport compound or the hole transport compound of formula (I) may be free of heteroatoms that are not part of an aromatic ring and / or a heteroatom that is not part of an unsaturated seven-membered ring, preferably the hole transport compound or the hole transport compound of formula (I) may be free of N atoms, except for N atoms that are part of an aromatic ring or N atoms that are part of an unsaturated seven-membered ring.

[0229] In one embodiment, the hole transport layer may comprise a hole transport compound or a hole transport compound of Formula (I); the hole transport compounds or the hole transport compounds of Formula (I) in the hole injection layer and in the hole transport layer are selected to be the same, and the hole transport compound comprises two carbazole groups, at least one dibenzofuran group, at least one dibenzothiophene group, and / or at least one anthracene group.

[0230] In one embodiment, the hole transport layer may comprise a hole transport compound or a hole transport compound of Formula (I); the hole transport compounds or the hole transport compounds of Formula (I) in the hole injection layer and the hole transport layer are selected to be the same, and the hole transport compound comprises two carbazole groups, one to three dibenzofuran groups, one to three dibenzothiophene groups, and / or one to two anthracene groups.

[0231] In one embodiment, the hole transport layer may comprise a hole transport compound or a hole transport compound of formula (I); the hole transport compounds or the hole transport compounds of formula (I) in the hole injection layer and in the hole transport layer are selected to be the same, and for the hole transport compound of formula (I): -Ar 3 may be selected from D1 to D15, preferably D1 to D6:

[0232] [ka]

[0233] In one embodiment, Ar 1 may be selected from D7 to D13. 2 may be selected from D1 to D6 or D7 to D13. 4 may be selected from D1 to D6 or D7 to D13. 5 may be selected from D1 to D6 or D7 to D13. 6 may be selected from D7 to D13.

[0234] In one embodiment, the hole transport layer may comprise a hole transport compound or a hole transport compound of formula (I); the hole transport compounds or the hole transport compounds of formula (I) in the hole injection layer and in the hole transport layer are selected to be the same, and for the hole transport compound of formula (I): Ar 3 may be selected from D1 to D15, preferably D1 to D6:

[0235] [ka]

[0236] Ar 1 may be selected from D7 to D15 when m>0 and k>0, may be selected from D7 to D15 when k>0 and m=0, and may be selected from D1 to D6 when k>1; Ar 2 may be selected from D1 to D6 if m>0 and k>0, and may be selected from D7 to D15 if m>0 and k=0; Ar 4 may be selected from D1 to D6 if q>0, may be selected from D1 to D6 if q=0 and r>0; may be selected from D7 to D15 if q=0 and r=0; Ar 5 may be selected from D1 to D6 if q>0 and r>0, and may be selected from D7 to D15 if q>0 and r=0; Ar 6 When r>0, q>0, it can be selected from D7 to D15, when r>0, q=0, it can be selected from D7 to D15, and when r>1, it can be selected from D1 to D6.

[0237] In one embodiment, the hole transport layer may comprise a hole transport compound or a hole transport compound of formula (I); the hole transport compounds or the hole transport compounds of formula (I) in the hole injection layer and in the hole transport layer are selected to be the same, and the hole transport compound or the hole transport compound of formula (I) may be selected from F1 to F13:

[0238] [ka] JPEG0007644768000042.jpg126169

[0239] The hole transport layer may not include HTM014, HTM081, HTM163, HTM222, EL-301, HTM226, HTM355, HTM133, HTM334, HTM604, and EL-22T. Abbreviations indicate the manufacturer's name (e.g., Merck or Lumtec).

[0240] The hole transport layer is made of N,N'-bis(naphthalene-1-yl)-N,N'-bis(phenyl)-9,9-dimethyl-fluorene, N,N'-bis(3-methylphenyl)-N,N'-bis(phenyl)-9,9-dimethyl-fluorene, N,N'-bis(naphthalene-1-yl)-N,N'-bis(phenyl)-9,9-dimethyl-fluorene, N,N'-bis(naphthalene-1-yl)-N,N'-bis(phenyl)-2,2-dimethylbenzidine, N,N'-bis(3-methylphenyl)-N,N'-bis(phenyl)-9,9-spirobifurane, fluorene, 2,2',7,7'-tetrakis(N,N-diphenylamino)-9,9'-spirobifluorene, N,N'-bis(naphthalen-1-yl)-N,N'-bis(phenyl)-benzidine, N,N'-bis(naphthalen-2-yl)-N,N'-bis(phenyl)-benzidine, N,N'-bis(3-methylphenyl)-N,N'-bis(phenyl)-benzidine, N,N'-bis(3-methylphenyl)-N,N'-bis(phenyl)-9,9-dimethyl-fluorene, N,N'-bis(naphthalen-1-yl)-N,N'-bifluorene bis(phenyl)-9,9-spirobifluorene, di-[4-(N,N-ditolyl-amino)-phenyl]-cyclohexane, 2,2',7,7'-tetra(N,N-diitolyl)amino-spiro-bifluorene, 9,9-bis[4-(N,N-bis-biphenyl-4-yl-amino)phenyl]-9H-fluorene, 2,2',7,7'-tetrakis(N,N-naphthalenyl(phenyl)-amino]-9,9'-spirobifluorene, 2,7-bis(N,N-bis(9,9-spiro-bifluoren-2-yl)-amino]-9,9'-spiro Bifluorene, 2,2'-bis(N,N-bis(biphenyl-4-yl)amino]-9,9'-spirobifluorene, N,N'-bis(phenanthren-9-yl)-N,N'-bis(phenyl)-benzidine, N,N,N',N'-tetra-naphthalen-2-yl)-benzidine, 2,2'-bis(N,N-di-phenyl-amino)-9,9-spirobifluorene, 9,9-bis[4-(N,N-bis-naphthalen-2-yl-amino)phenyl]-9H-fluorene, 9,9-bis[4-(N,N'-bis-naphthalen-2-yl-N,N'-bis(phenylamino)-phenyl]-9H-fluorene, titanium oxide phthalocyanine, copper phthalocyanine, 2,3,5,6 tetrafluoro 7,7,8,8, tetracyanoquinodimethane, 4,4'4''-tris(N-(3-methylphenyl-N-phenyl-amino)triphenylamine, 4,4'4''-tris(N-(2-naphthyl)-N-phenyl-amino)triphenylamine, 4,4',4''-tris(N-(1-naphthyl)-N-phenyl-amino)triphenylamine The following may be excluded: 4,4',4''-tris(N,N-diphenyl-amino)triphenylamine, pyrazino[2,3-f][1,10]phenanthroline-2,3-dicarbonitrile, N,N,N',N'-tetrakis(4-methoxyphenyl)benzidine, HTM014, HTM081, HTM163, HTM222, EL-301, HTM226, HTM355, HTM133, HTM334, HTM604 and EL-22T. Abbreviations indicate the name of the manufacturer (e.g., Merck or Lumtec).

[0241] The hole transport layer (HTL) can be formed on the HIL by vacuum deposition, spin coating, slot-die coating, printing, casting, Langmuir-Blodgett (LB) deposition, etc. When forming the HTL by vacuum deposition or spin coating, the deposition and coating conditions may be the same as those for the HIL formation. However, the vacuum deposition or solution deposition conditions may vary depending on the hole transport compound used to form the HTL.

[0242] The thickness of the HTL can be in the range of about 5 nm to about 250 nm, preferably about 10 nm to about 200 nm, further about 20 nm to about 190 nm, further about 40 nm to about 180 nm, further about 60 nm to about 170 nm, further about 80 nm to about 200 nm, further about 100 nm to about 180 nm, further about 120 nm to about 170 nm.

[0243] If the thickness of the HIL is within this range, the HTL can have excellent hole transport performance without a substantial penalty in operating voltage.

[0244] electron blocking layer The function of the electron blocking layer (EBL) is to prevent electrons from migrating from the emissive layer to the hole transport layer, thereby confining the electrons to the emissive layer, which may improve efficiency, operating voltage, and / or lifetime. Typically, the electron blocking layer comprises a triarylamine compound.

[0245] When the electron blocking layer has a high triplet level, it can be described as a triplet control layer.

[0246] The function of the triplet control layer is to reduce triplet quenching when a phosphorescent green or blue emitting layer is used, thereby increasing the efficiency of emission from the phosphorescent emitting layer. The triplet control layer may be selected from triarylamine compounds having a triplet level higher than the triplet level of the phosphorescent emitter in the adjacent emitting layer.

[0247] The thickness of the electron blocking layer can be selected between 2 nm and 20 nm.

[0248] Photoactive layer (PAL) The photoactive layer converts electrical current into photons or photons into electrical current.

[0249] The PAL can be formed on the HTL by vacuum deposition, spin coating, slot-die coating, printing, casting, LB deposition, etc. When the PAL is formed using vacuum deposition or spin coating, the deposition and coating conditions can be the same as those for the HIL formation. However, the deposition and coating conditions can vary depending on the compounds used to form the PAL.

[0250] It may be provided that the photoactive layer does not comprise a compound of formula (I).

[0251] The photoactive layer may be a light-emitting layer or a light-absorbing layer.

[0252] Emitting layer (EML) The EML can be formed on the HTL or EBL by vacuum deposition, spin coating, slot-die coating, printing, casting, LB deposition, etc. When the EML is formed using vacuum deposition or spin coating, the deposition and coating conditions can be the same as those for the HIL formation. However, the deposition and coating conditions can vary depending on the compounds used to form the EML.

[0253] It may be provided that the light-emitting layer does not comprise a compound of formula (I).

[0254] The light-emitting layer (EML) can be formed by combining a host and a light-emitting dopant. Examples of hosts include Alq3, 4,4'-N,N'-dicarbazole-biphenyl (HTC-10), poly(N-vinylcarbazole) (PVK), 9,10-di(naphthalene-2-yl)anthracene (ADN), 4,4',4''-tris(carbazol-9-yl)-triphenylamine (TCTA), 1,3,5-tris(N-phenylbenzimidazol-2-yl)benzene (TPBI), 3-tert-butyl-9,10-di-2-naphthylanthracene (TBADN), distyrylarylene (DSA), and bis(2-(2-hydroxyphenyl)benzo-thiazolate)zinc (Zn(BTZ)2).

[0255] The emissive dopant may be a phosphorescent or fluorescent emitter. Phosphorescent emitters and emitters that emit light via a thermally activated delayed fluorescence (TADF) mechanism may be preferred due to their higher efficiency. The emitter may be a small molecule or a polymer.

[0256] Examples of red-emitting dopants include, but are not limited to, PtOEP, Ir(piq)3, and Btp2lr(acac). These compounds are phosphorescent emitters, although fluorescent red-emitting dopants can also be used.

[0257] Examples of phosphorescent green-emitting dopants include Ir(ppy)3 (ppy=phenylpyridine), Ir(ppy)2(acac), and Ir(mpyp)3.

[0258] Examples of phosphorescent blue-emitting dopants include F2Irpic, (F2ppy)2Ir(tmd) and Ir(dfppz)3 and ter-fluorene. 4.4'-Bis(4-diphenylamiostyryl)biphenyl (DPAVBi), 2,5,8,11-tetra-tert-butylperylene (TBPe) are examples of fluorescent blue-emitting dopants.

[0259] The amount of the emitting dopant may range from about 0.01 parts by weight to about 50 parts by weight based on 100 parts by weight of the host. Alternatively, the emitting layer may be made of a emitting polymer. The EML may have a thickness of about 10 nm to about 100 nm (e.g., about 20 nm to about 60 nm). When the thickness of the EML is within this range, the EML may have excellent luminescence without a substantial penalty in operating voltage.

[0260] Hole Blocking Layer (HBL) A hole-blocking layer (HBL) can be formed on the EML to prevent holes from diffusing into the ETL by using vacuum deposition, spin-coating, slot-die coating, printing, casting, LB deposition, etc. If the EML contains a phosphorescent dopant, the HBL can also have a triplet exciton blocking function.

[0261] The HBL may also be referred to as an auxiliary ETL or a-ETL.

[0262] When the HBL is formed using vacuum deposition or spin coating, the deposition and coating conditions may be the same as those for the HIL formation. However, the deposition and coating conditions may vary depending on the compound used to form the HBL. Any compound commonly used to form the HBL can be used. Examples of compounds that form the HBL include oxadiazole derivatives, triazole derivatives, phenanthroline derivatives, and triazine derivatives.

[0263] The HBL can have a thickness in the range of about 5 nm to about 100 nm (e.g., about 10 nm to about 30 nm). When the thickness of the HBL is within this range, the HBL can have excellent hole blocking performance without a substantial penalty in operating voltage.

[0264] Electron transport layer (ETL) The organic electronic device according to the present invention may further comprise an electron transport layer (ETL).

[0265] In another embodiment of the present invention, the electron transport layer may further comprise an azine compound, preferably a triazine compound.

[0266] In one embodiment, the electron transport layer may further comprise a dopant selected from alkali organic complexes, preferably LiQ.

[0267] The thickness of the ETL can be in the range of about 15 nm to about 50 nm (e.g., in the range of about 20 nm to about 40 nm). When the thickness of the ETL is within this range, the ETL can have satisfactory electron injection performance without a substantial penalty in operating voltage.

[0268] In another embodiment of the invention, the organic electronic device may further comprise a hole blocking layer and an electron transport layer, the hole blocking layer and the electron transport layer comprising an azine compound. Preferably, the azine compound is a triazine compound.

[0269] Electron injection layer (EIL) Any EIL that can facilitate the injection of electrons from the cathode can be formed on the ETL, preferably directly on the electron transport layer. Examples of materials for forming the EIL include lithium 8-hydroxyquinolinolate (LiQ), LiF, NaCl, CsF, Li2O, BaO, Ca, Ba, Yb, Mg, which are known in the art. The deposition and coating conditions for forming the EIL are the same as those for forming the HIL, but the deposition and coating conditions can vary depending on the materials used to form the EIL.

[0270] The thickness of the EIL can be in the range of about 0.1 nm to about 10 nm (e.g., 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 performance without imparting a substantial penalty in operating voltage.

[0271] Cathode Layer A cathode layer is formed on the ETL or on any EIL. The cathode layer can be formed of a metal, an alloy, a conductive compound, or a mixture thereof. The cathode layer can have a low work function. For example, the cathode layer can be formed of lithium (Li), magnesium (Mg), aluminum (Al), aluminum (Al)-lithium (Li), calcium (Ca), barium (Ba), ytterbium (Yb), magnesium (Mg)-indium (In), magnesium (Mg)-silver (Ag), etc. Alternatively, the cathode layer can be formed of a transparent conductive oxide (e.g., ITO or IZO).

[0272] The thickness of the cathode layer can be in the range of about 5 nm to about 1000 nm (e.g., in the range of about 10 nm to about 100 nm). When the thickness of the cathode layer is within the range of about 5 nm to about 50 nm, the cathode layer can be transparent or translucent even if it is formed from a metal or a metal alloy.

[0273] It should be understood that the cathode layer is not part of the electron injection layer or the electron transport layer.

[0274] Organic Light Emitting Diode (OLED) The organic electronic device according to the present invention may be an organic light emitting device.

[0275] In one aspect of the present invention, there is provided an organic light emitting diode (OLED) comprising: a substrate; an anode layer formed on the substrate; a hole injection layer comprising a hole transport compound or a hole transport compound of Formula (I) and a metal complex of Formula (II), a hole transport layer, an emissive layer, an electron transport layer, and a cathode layer.

[0276] In another aspect of the invention, there is provided an OLED comprising: a substrate; an anode layer formed on the substrate; and a hole-injection layer, a hole-transport layer, an emissive layer, a hole-blocking layer, an electron-transport layer, an electron-injection layer, and a cathode layer of the invention, the hole-transport layer comprising a first sublayer and a second sublayer. wherein the first sublayer is disposed adjacent to the anode layer and the second sublayer is disposed adjacent to the hole transport layer; wherein the first sublayer comprises or consists of a metal complex of formula (II) and the second sublayer comprises or consists of a hole transport compound of formula (I).

[0277] In another embodiment of the present invention, there is provided an OLED that includes: a substrate; an anode layer formed on the substrate; a hole injection layer comprising a hole transport compound or a hole transport compound of Formula (I) and a metal complex of Formula (II), a hole transport layer, an electron blocking layer, an emissive layer, a hole blocking layer, an electron transport layer, and a cathode layer.

[0278] In another aspect of the invention, there is provided an OLED comprising: a substrate; an anode layer formed on the substrate; a hole-injection layer, a hole-transport layer, an electron-blocking layer, an emissive layer, a hole-blocking layer, an electron-transport layer, an electron-injection layer, and a cathode layer of the invention, the hole-injection layer comprising a first sublayer and a second sublayer; wherein the first sublayer is disposed adjacent to the anode layer and the second sublayer is disposed adjacent to the hole transport layer; wherein the first sublayer comprises or consists of a metal complex of formula (II) and the second sublayer comprises or consists of a hole transport compound of formula (I).

[0279] In another embodiment of the present invention, there is provided an OLED that includes: a substrate; an anode layer formed on the substrate; a hole injection layer comprising a hole transport compound or a hole transport compound of Formula (I) and a metal complex of Formula (II), a hole transport layer, an electron blocking layer, an emissive layer, a hole blocking layer, an electron transport layer, an electron injection layer, and a cathode layer.

[0280] In another aspect of the invention, there is provided an OLED comprising: a substrate; an anode layer formed on the substrate; a hole-injection layer, a hole-transport layer, an electron-blocking layer, an emissive layer, a hole-blocking layer, an electron-transport layer, an electron-injection layer, and a cathode layer of the invention, the hole-injection layer comprising a first sublayer and a second sublayer; wherein the first sublayer is disposed adjacent to the anode layer and the second sublayer is disposed adjacent to the hole transport layer; wherein the first sublayer comprises or consists of a metal complex of formula (II) and the second sublayer comprises or consists of a hole transport compound of formula (I).

[0281] In various embodiments of the present invention, an OLED layer may be provided, disposed between the layers described above, on the substrate, or on the top electrode.

[0282] For example, the OLED depicted in FIG. 2 may be formed by a method in which the following layers are formed successively on a substrate (110), in that order: an anode layer (120), a hole injection layer (130) comprising a hole transport compound or a hole transport compound of Formula (I) and a metal complex of Formula (II), a hole transport layer (140), an electron blocking layer (145), an emissive layer (150), a hole blocking layer (155), an electron transport layer (160), an electron injection layer (180), and a cathode layer (190).

[0283] Manufacturing method In another aspect of the invention, there is provided a method of manufacturing an organic electronic device, the method comprising: at least one deposition source, preferably two deposition sources, more preferably at least three deposition sources.

[0284] Methods of deposition that may be suitable include: -Deposition by vacuum thermal evaporation; - deposition by solution processing, preferably said processing may be selected from spin-coating, printing, casting; and / or -Slot die coating.

[0285] In various embodiments of the present invention, methods are provided that utilize: a first deposition source for releasing a hole transport compound of formula (I) of the present invention, and - a second deposition source for releasing the metal complex of formula (II).

[0286] A method for forming a hole injection layer for an organic light emitting diode (OLED), comprising the steps of: The hole injection layer is formed by releasing a hole transport compound of formula (I) of the present invention from a first deposition source and releasing a metal complex of formula (II) from a second deposition source.

[0287] In various embodiments of the invention, the method may further comprise forming at least one layer on the hole injection layer selected from the group consisting of forming a hole transport layer, forming a hole blocking layer, forming an emissive layer, forming a hole blocking layer, forming an electron transport layer and / or forming an electron injection layer and / or forming a cathode layer.

[0288] In various embodiments of the present invention, the method may further include forming an organic light emitting diode (OLED); -An anode layer is formed on the substrate, - forming on said anode layer a hole injection layer comprising a hole transport compound of formula (I) and a metal complex of formula (II), a hole transport layer is formed on said hole injection layer comprising a hole transport compound of formula (I) and a metal complex of formula (II), a light-emitting layer is formed on the hole transport layer; an electron transport layer is formed on the light-emitting layer, and optionally a hole blocking layer is formed on the light-emitting layer; -Finally, a cathode layer is formed, Optionally, a hole blocking layer is formed between the hole injection layer and the light emitting layer, Optionally, an electron injection layer is formed between said electron transport layer and said cathode layer.

[0289] In various embodiments, the OLED may have the following layer structure, with the layers in the following order: an anode layer, a hole injection layer comprising a hole transport compound or a hole transport compound of formula (I) and a metal complex of formula (II), a hole transport layer, an optional electron blocking layer, a light-emitting layer, an optional hole blocking layer, an electron transport layer, an optional electron injection layer, and a cathode layer.

[0290] In one embodiment, the organic electronic device of the present invention is formed by vacuum deposition of the hole injection layer and the cathode layer.

[0291] In another aspect, there is provided an electronic device comprising at least one organic light emitting device of any of the embodiments described throughout this application, preferably the electronic device comprises an organic light emitting diode of an embodiment described throughout this application, more preferably the organic electronic device is a display device.

[0292] The following examples are provided to further illustrate and explain the embodiments in detail, but the invention is not limited to the following examples. Reference will now be made in detail to the illustrative embodiments.

[0293] Description of the drawings The aforementioned components, as well as the claimed components and components used according to the invention in the described embodiments, are not subject to any special exceptions with regard to their size, shape, material selection and technical concept, and, as a consequence, selection criteria known in the relevant fields can be applied without limitation.

[0294] Further details, features and advantages of the object are disclosed in the dependent claims and in the following description of each drawing in an exemplary manner showing preferred embodiments of the present invention. However, any embodiment does not necessarily represent the full scope, and therefore, reference is made to the claims and this specification to interpret the scope. It should be understood that both the foregoing summary and the following detailed description are exemplary and explanatory only, and are intended to provide further explanation of the invention as claimed.

[0295] FIG. 1 is a schematic cross-sectional view of an organic electronic device according to an exemplary embodiment of the present invention; FIG. 2 is a schematic cross-sectional view of an organic light-emitting diode (OLED) according to an exemplary embodiment of the present invention; FIG. 3 is a schematic cross-sectional view of an OLED according to an exemplary embodiment of the present invention.

[0296] In the following the drawings are explained in more detail by way of examples, but the invention is not limited to the drawings.

[0297] As used herein, when a first element is referred to as being formed or disposed "on" or "onto" a second element, the first element can be disposed directly on the second element, or one or more other elements can be disposed therebetween. When a first element is referred to as being formed or disposed "directly on" or "directly onto" a second element, no other elements are disposed therebetween.

[0298] 1 is a schematic cross-sectional view of an organic electronic device 100 in accordance with 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 photoactive layer (PAL) 170 and a cathode layer 190 are disposed on the HIL 130.

[0299] The hole injection layer (HIL) 130 may include a first sublayer and a second sublayer, where the first sublayer is disposed on the anode and the second sublayer is disposed on the first sublayer, and the photoactive layer (PAL) 170 is disposed on the second sublayer.

[0300] 2 is a schematic cross-sectional view of an organic light-emitting diode (OLED) 100 according to an exemplary embodiment of the present invention. The OLED 100 includes a substrate 110, an anode layer 120, and a hole injection layer (HIL) 130, which is disposed on the anode layer 120. Disposed on the HIL 130 are a hole transport layer (HTL) 140, an emissive layer (EML) 150, an electron transport layer (ETL) 160, an electron injection layer (EIL) 180, and a cathode layer 190. Instead of the single electron transport layer 160, an electron transport stack (ETL) may optionally be used.

[0301] The hole injection layer (HIL) 130 may include a first sublayer and a second sublayer, where the first sublayer is disposed on the anode and the second sublayer is disposed on the first sublayer, and the hole transport layer (HTL) 140 is disposed on the second sublayer.

[0302] 3 is a schematic cross-sectional view of an OLED 100 according to another exemplary embodiment of the present invention. FIG. 2 differs from FIG. 1 in that the OLED 100 in FIG. 2 includes an electron blocking layer (EBL) 145 and a hole blocking layer (HBL) 155.

[0303] Referring to FIG. 3, an OLED 100 includes a substrate 110, an anode layer 120, a hole injection layer (HIL) 130, a hole transport layer (HTL) 140, an electron blocking layer (EBL) 145, an emissive layer (EML) 150, a hole blocking layer (HBL) 155, an electron transport layer (ETL) 160, an electron injection layer (EIL) 180, and a cathode layer 190.

[0304] 1, 2 and 3, a sealing layer may be further formed on the cathode layer 190 to seal the organic electronic device 100. In addition, various other modifications may be applied.

[0305] The following examples are provided to further explain the embodiments in detail, but the present invention is not limited to these examples.

[0306] Detailed Description The invention is further illustrated by the following examples, which are merely illustrative and non-binding.

[0307] The hole transport compounds and the hole transport compounds of formula (I) and metal complexes of formula (II) can be prepared as described in the literature.

[0308] Rate onset temperature Speed ​​starting temperature (T RO ) is measured by loading 100 mg of the hole transport compound into the VTE source. As the VTE source, a point source of organic material can be used as supplied by Kurt J. Lesker Company (www.lesker.com) or CreaPhys GmbH (http: / / www.creaphys.com). The VTE source is a 10 -5It is heated at a constant rate of 15 K / min at a pressure of less than mbar and the temperature in the source is measured using a thermocouple. The evaporation of the hole transport compound is detected by a QCM detector which detects the deposition of the hole transport compound onto the detector quartz crystal. The deposition rate on the quartz is measured in angstroms / second. The deposition rate is plotted against the VTE source temperature to determine the rate onset temperature. The rate onset is the temperature at which noticeable deposition onto the QCM detector occurs. For accurate results, the VTE source is heated and cooled three times and only the second and third test results are used to determine the rate onset temperature.

[0309] To achieve good control of the evaporation rate of the metal complex of formula (II), the rate onset temperature may be in the range of ≧110° C. to ≦300° C., preferably ≧115° C. to ≦290° C. If the rate onset temperature is too low, the evaporation may be too rapid and difficult to control. If the rate onset temperature is too high, the evaporation rate may be too slow, resulting in low tact times and / or decomposition of the metal complex of formula (II) in the VTE source may occur due to prolonged exposure to high temperatures.

[0310] To achieve good control of the evaporation rate of the hole transport compound of the present invention, the rate onset temperature can be in the range of 120° C. to 300° C. If the rate onset temperature is too low, the evaporation may be too rapid and difficult to control. If the rate onset temperature is too high, the evaporation rate may be too slow, resulting in a low tact time.

[0311] The rate onset temperature is an indirect measure of the volatility of a compound: the higher the rate onset temperature, the less volatile the compound.

[0312] HOMO and LUMO The HOMO and LUMO levels are calculated using the program package TURBOMOLE V6.5 (TURBOMOLE GmbH, Litzenhardtstrasse 19, 76135 Karlsruhe, Germany). The optimized geometries of the molecular structures as well as the HOMO and LUMO levels are calculated using the 6-31G* It is determined by applying the hybrid functional B3LYP with basis set. If more than one conformation is feasible, the conformation with the lowest total energy may be selected. HOMO and LUMO levels are reported in electron volts (eV).

[0313] General Procedure for the Fabrication of an OLED Comprising a Hole Injection Layer and an Emitting Layer Comprising a Fluorescent Blue Emitter For OLEDs, see Examples 1 to 11 and Comparative Examples 1 to 3 in Tables 3 and 4. 2 The glass substrate was cut into a size of 50 mm x 50 mm x 0.7 mm. It was ultrasonically cleaned with isopropyl alcohol for 5 minutes, then ultrasonically cleaned with pure water for 5 minutes, and again cleaned with ultraviolet ozone for 30 minutes to prepare an anode layer.

[0314] Then, 70% by volume of the hole transport compound and 30% by volume of the metal complex were co-deposited on the anode layer in vacuum to form a hole injection layer (HIL) having a thickness of 10 nm. The composition of the hole injection layer is shown in Tables 3 and 4. In Comparative Examples 1 to 3, 70% by volume of the hole transport compound and 30% by volume of HAT-CN were co-deposited on the anode layer in vacuum to form a HIL having a thickness of 10 nm.

[0315] Then, a hole transport compound was vacuum-deposited on the HIL to form a HTL with a thickness of 128 nm. The hole transport compound in the HTL is selected to be the same as the hole transport compound in the HIL. The hole transport compounds are shown in Tables 3 and 4.

[0316] Then, N,N-bis(4-(dibenzo[b,d]furan-4-yl)phenyl)-[1,1′:4′,1″-terphenyl]-4-amine (CAS 1198399-61-9) was vacuum evaporated onto the HTL to form an electron blocking layer (EBL) with a thickness of 5 nm.

[0317] Then, 97 vol. % of HTC-6 as the EML host and 3 vol. % of BD200 (Sun Fine Chemicals, Korea) as the fluorescent blue-emitting dopant were evaporated onto the EBL to form a blue-emitting EML with a thickness of 20 nm.

[0318] Next, 2-(3′-(9,9-dimethyl-9H-fluoren-2-yl)-[1,1′-biphenyl]-3-yl)-4,6-diphenyl-1,3,5-triazine was evaporated onto the emissive layer EML to form a hole blocking layer with a thickness of 5 nm.

[0319] Then, 50 wt % of 4'-(4-(4-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)naphthalen-1-yl)-[1,1'-biphenyl]-4-carbonitrile and 50 wt % of LiQ were evaporated to form an electron transport layer having a thickness of 31 nm on the hole blocking layer.

[0320] Next, 10 -7 Al was evaporated at a rate of 0.01 Å / s to 1 Å / s at mbar to form a cathode layer having a thickness of 100 nm on the electron transport layer.

[0321] The OLED stack was protected from ambient conditions by encapsulating the device with a glass slide, which creates a cavity containing a getter material for further protection.

[0322] General Procedure for the Fabrication of an OLED Comprising a Hole Injection Layer and an Emitting Layer Comprising a Phosphorescent Green Emitter For OLEDs, see Examples 12 and 13 and Comparative Examples 4 and 5 in Table 5, and a 15 Ω / cm OLED with 90 nm ITO (available from Corning Incorporated) 2 The glass substrate was cut to a size of 50 mm × 50 mm × 0.7 mm. It was ultrasonically cleaned with isopropyl alcohol for 5 minutes, then ultrasonically cleaned with pure water for 5 minutes, and again cleaned with ultraviolet ozone for 30 minutes to prepare an anode layer.

[0323] Then, 70% by volume of the hole transport compound and 30% by volume of the metal complex were co-deposited on the anode layer in vacuum to form a hole injection layer (HIL) having a thickness of 10 nm. The composition of the hole injection layer is shown in Table 5. In Comparative Examples 4 and 5, 70% by volume of the hole transport compound and 30% by volume of HAT-CN were deposited on the anode layer to form a HIL having a thickness of 10 nm.

[0324] Then, a hole transport compound was vacuum-deposited on the HIL to form a HTL with a thickness of 165 nm. The hole transport compound in the HTL is selected to be the same as the hole transport compound in the HIL. The hole transport compound is shown in Table 5.

[0325] Then, 90 vol. % of GH-1 as the EML host and 10 vol. % of GD-1 as the phosphorescent green emitter dopant were co-evaporated in vacuum onto the HTL to form a green-emitting EML with a thickness of 40 nm. The formulas of GH-1 and GD-1 are shown below:

[0326] [ka]

[0327] Next, 2,4-diphenyl-6-(3'-(triphenylen-2-yl)-[1,1'-biphenyl]-3-yl)-1,3,5-triazine was evaporated onto the emitting layer EML to form a hole blocking layer with a thickness of 25 nm.

[0328] Then, 99 vol. % 3-phenyl-3H-benzo[b]dinaphtho[2,1-d:1′,2′-f]phosphepine-3-oxide and 1 vol. % Yb were evaporated to form an electron transport layer having a thickness of 10 nm on the hole blocking layer.

[0329] Next, 10 -7 Al was evaporated at a rate of 0.01-1 Å / s at mbar to form a cathode layer having a thickness of 100 nm on the electron transport layer.

[0330] The OLED stack is protected from ambient conditions by encapsulating the device with a glass slide, which creates a cavity that contains a getter material for further protection.

[0331] General Procedure for the Fabrication of an OLED Containing a Hole Injection Layer Comprising a First Sublayer and a Second Sublayer For OLEDs, see Examples 14 to 28 and Comparative Examples 6 to 11 in Table 6. 2 The glass substrate was cut into a size of 50 mm x 50 mm x 0.7 mm. It was ultrasonically cleaned with isopropyl alcohol for 5 minutes, then cleaned with pure water for 5 minutes, and again cleaned with ultraviolet ozone for 30 minutes to prepare an anode layer.

[0332] Then, a hole injection layer including a first sublayer and a second sublayer was vacuum-deposited on the anode layer. First, a metal complex was vacuum-deposited on the anode layer to form a first sublayer having a thickness of 3 nm or 5 nm (see Table 6). In Comparative Examples 6 to 11, HAT-CN was vapor-deposited on the anode layer to form a first sublayer having a thickness of 3 nm or 5 nm (see Table 6).

[0333] A hole transporting compound was then vacuum deposited onto the first sublayer to form a second sublayer having a thickness of 7 nm or 5 nm (see Table 6).

[0334] A hole transport compound was then vacuum deposited onto the hole injection layer to form the HTL. The hole transport compound in the HTL was chosen to be the same as the hole transport compound in the HIL (see Table 6). The thickness was chosen such that the thickness of the second sublayer and the thickness of the HTL added up to a total of 128 nm.

[0335] Then, N,N-bis(4-(dibenzo[b,d]furan-4-yl)phenyl)-[1,1′:4′,1″-terphenyl]-4-amine (CAS 1198399-61-9) was vacuum evaporated onto the HTL to form an electron blocking layer (EBL) with a thickness of 5 nm.

[0336] Then, 97 vol. % of HTC-6 as the EML host and 3 vol. % of BD200 (Sun Fine Chemicals, Korea) as the fluorescent blue-emitting dopant were evaporated onto the EBL to form a blue-emitting EML with a thickness of 20 nm.

[0337] Next, 2-(3′-(9,9-dimethyl-9H-fluoren-2-yl)-[1,1′-biphenyl]-3-yl)-4,6-diphenyl-1,3,5-triazine was evaporated onto the light-emitting layer EML to form a hole-blocking layer having a thickness of 5 nm.

[0338] Then, an electron transport layer having a thickness of 31 nm was formed on the hole blocking layer by evaporating 50 wt % of 4'-(4-(4-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)naphthalen-1-yl)-[1,1'-biphenyl]-4-carbonitrile and 50 wt % of LiQ.

[0339] Next, 10 -7 Al was evaporated at a rate of 0.01-1 Å / s at mbar to form a cathode layer having a thickness of 100 nm on the electron transport layer.

[0340] The OLED stack is protected from ambient conditions by encapsulating the device with a glass slide, which creates a cavity that may contain a getter material for further protection.

[0341] To evaluate the performance of embodiments of the present invention compared to the prior art, the current efficiency is measured at 20°C. The current-voltage characteristics are measured using a Keithley 2635 source measure unit by sourcing an operating voltage U in V and measuring the current in mA through the device under test. The voltage applied to the device is varied in the range 0V to 10V in steps of 0.1V. The measurement was stopped at 10V to protect the instrument from damage.

[0342] [Technical effect] To examine the utility of the hole injection layer of the present invention, preferred materials were tested in view of their physical performance (see Tables 1 and 2).

[0343] The program TURBOMOLE V6.5 (TURBOMOLE GmbH, Litzenhardtstrasse 19, 76135 Karlsruhe, Germany) and the rate onset temperature T RO The HOMO levels calculated using the method are shown in Table 1.

[0344] [Table 2] JPEG0007644768000045.jpg218169JPEG0007644768000046.jpg180169

[0345] As can be seen from Table 1, the hole transport compounds had a rate onset temperature suitable for mass production of organic electronic devices.

[0346] Table 2 shows the rate onset temperature T RO is shown.

[0347] [Table 3] JPEG0007644768000048.jpg199169JPEG0007644768000049.jpg216169JPEG0007644768000050.jpg67169

[0348] As can be seen from Table 2, the metal complexes of formula (II) had a rate onset temperature suitable for mass production of organic electronic devices.

[0349] Table 3 shows the light emission at 10 mA / cm for an OLED comprising a fluorescent blue emitter and a hole injection layer comprising 70% by volume of HTC-10 and 30% by volume of a metal complex of formula (II). 2 The operating voltage is shown at 1000 V. HTC-10 has a HOMO level of −5.30 eV.

[0350] [Table 4]

[0351] In Comparative Example 1, the state of the art material HAT-CN was used at a concentration of 30% by volume. HAT-CN has the formula shown below:

[0352] [ka]

[0353] HAT-CN has a HOMO of -8.83 eV. The operating voltage is over 10 V.

[0354] In Example 1, the hole injection layer contains Cu(TFSI)2 as the metal complex. The operating voltage is substantially improved to 6.9V.

[0355] In Example 2, the hole injection layer contains a different Cu(II) complex, namely MC-24. Compared to Example 1, the TFSI ligand is replaced by an amide ligand containing one trifluoromethyl and one substituted aryl group. The operating voltage is further improved to 6.3 V.

[0356] In Example 3, the hole injection layer contains MC-6. Compared to Example 1, the Cu(II) cations are replaced by Mn(II) cations. Compared to Example 1, the operating voltage is improved from 6.9V to 5.3V.

[0357] In Example 4, the hole injection layer contains a Mg complex. Compared with Example 2, the Cu(II) cation is replaced by the Mg(II) cation. The operating voltage is improved from 6.3V to 5.4V.

[0358] In Example 5, the hole injection layer contains a Zn(II) complex. Compared to Example 4, the Mg(II) cation is replaced by a Zn(II) cation, and the amide ligand is replaced by a ligand containing an N-aryl group. The operating voltage is still within the range that allows mass production.

[0359] Table 4 shows the results of the emission spectra of 10 mA / cm2 in an OLED comprising a fluorescent blue emitter and a hole injection layer comprising 70% by volume of a hole transport compound and 30% by volume of a metal complex of formula (II). 2 The operating voltage is shown.

[0360] [Table 5]

[0361] In Comparative Example 2, the hole injection layer contains a hole transport compound HTC-5 and 30 volume % of HAT-CN. HAT-CN does not contain a metal complex. HTC-5 contains an anthracene group. The HOMO level of HTC-5 is -5.10 eV. The operating voltage is more than 10 V.

[0362] In Comparative Example 3, the hole injection layer contains the hole transport compound HTC-13 and 30% by volume of HAT-CN. HTC-13 contains three dibenzofuranyl groups. The HOMO level is -5.67 eV, and thus is further away from the vacuum level than Comparative Example 2. The operating voltage is more than 10 V.

[0363] In Example 6, the hole injection layer comprises HTC-5 and metal complex MC-29. The operating voltage is substantially reduced to 4.1 V.

[0364] In Example 7, the hole injection layer comprises HTC-6 and metal complex MC-29. HTC-6 comprises anthracene and dibenzofuranyl groups. The HOMO level is -5.13 eV, and is therefore further away from the vacuum level than Comparative Example 2. The operating voltage remains unchanged at 4.1 V.

[0365] In Example 8, the hole injection layer comprises HTC-7 and metal complex MC-29. HTC-7 comprises anthracene and dibenzofuran groups. The HOMO level is -5.13 eV, and is therefore further away from the vacuum level than in Example 6. The operating voltage is a little higher than in Example 7. However, the operating voltage is substantially lower than in Comparative Example 2.

[0366] In Example 9, the hole injection layer comprises HTC-9 and metal complex MC-29. HTC-9 comprises a dibenzoacridine group and a carbazole group. The HOMO level is -5.28 eV, and is therefore further away from the vacuum level than in Example 6. The operating voltage is a little higher than in Example 8. However, the operating voltage is substantially lower than in Comparative Example 2.

[0367] In Example 10, the hole injection layer comprises HTC-10 and metal complex MC-29. HTC-10 comprises two carbazole groups. The HOMO level is -5.30 eV, and is therefore further away from the vacuum level than in Example 9. However, the operating voltage is substantially reduced compared to Comparative Example 2.

[0368] In Example 11, the hole injection layer comprises HTC-13 and metal complex MC-29. HTC-13 comprises three dibenzofuranyl groups. The HOMO level is -5.67 eV, and is therefore further away from the vacuum level than in Example 6. The operating voltage is a little higher than in Example 10. However, the operating voltage is substantially lower than in Comparative Example 2.

[0369] Table 5 shows the emission spectra of 10 mA / cm2 for an OLED comprising a phosphorescent green emitter and a hole injection layer comprising a hole transport compound and 30% by volume of a metal complex of formula (II). 2 The operating voltage at is shown.

[0370] [Table 6]

[0371] In Comparative Example 4, the hole injection layer includes a hole transport compound HTC-5 and 30% by volume of HAT-CN. HTC-5 includes an anthracene group. The HOMO level of HTC-5 is -5.10 eV. The operating voltage is more than 10V.

[0372] In Example 12, the hole injection layer comprises HTC-5 and metal complex MC-29. The operating voltage is substantially reduced to 4.1 V.

[0373] In Comparative Example 5, the hole injection layer contains a hole transport compound HTC-10 and 30 volume % of HAT-CN. HTC-10 contains two carbazole groups. The HOMO level of HTC-10 is -5.30 eV. The operating voltage is more than 10 V.

[0374] In Example 13, the hole injection layer comprises HTC-10 and metal complex MC-29. The operating voltage is substantially reduced to 6.3 V.

[0375] Table 6 shows the results for the 10 mA / cm OLED with a fluorescent blue emitter and a hole injection layer. 2 An operating voltage of 0.05 V is shown, where the hole injection layer comprises a first sublayer of a metal complex of formula (II) and a second sublayer of a hole transport compound.

[0376] In Comparative Example 6, the first sublayer contains HAT-CN as the state-of-the-art hole injection material, with a thickness of 3 nm. The second sublayer contains hole transport compound HTC-6. The operating voltage is over 10V.

[0377] In Comparative Example 7, the first sublayer contains HAT-CN and the second sublayer contains the hole transport compound HTC-7. The operating voltage is greater than 10V.

[0378] In Comparative Example 8, the first sublayer contains HAT-CN and the second sublayer contains the hole transport compound HTC-10. The operating voltage is greater than 10V.

[0379] In Example 14, the first sublayer contains metal complex MC-29 with a thickness of 3 nm. The second sublayer contains hole transport compound HTC-6. The operating voltage is 4.0 V, which is a substantial improvement over Comparative Example 6.

[0380] In Examples 15-17, the first sublayer is the same as in Example 14. The second sublayer contains a series of hole transport compounds with HOMO levels further away from the vacuum level than HTC-6. In all Examples, the operating voltage is substantially improved over Comparative Examples 6, 7 and 8.

[0381] In Examples 18-20, the first sublayer comprises metal complex MC-27. MC-27 differs from MC-29 in terms of metal cation and ligand (see Table 2). The second sublayer comprises a range of hole transport compounds. In all Examples, the operating voltage is substantially improved over Comparative Examples 6, 7 and 8.

[0382] In Example 21, the first sublayer comprises metal complex MC-30. MC-30 differs from MC-29 in terms of metal cation and ligand (see Table 2). The second sublayer comprises HTC-7. The operating voltage is 6.6V, which is an improvement over Comparative Example 7.

[0383] In Comparative Examples 9-11, the first sublayer contains HAT-CN as the state-of-the-art hole injection material with a thickness of 5 nm. The second sublayer contains a range of hole transport compounds. The operating voltage is over 10V.

[0384] In Example 22, the first sublayer comprises metal complex MC-29 having a thickness of 5 nm. The second sublayer comprises hole transport compound HTC-6. The operating voltage is 4.0 V, which is a substantial improvement over Comparative Example 9. The performance is comparable to Example 14.

[0385] In Examples 23-25, the first sublayer is the same as in Example 22. The second sublayer contains various hole transport compounds with HOMO levels further away from the vacuum level than HTC-6. In all Examples, the operating voltage is substantially improved over Comparative Examples 9, 10 and 11.

[0386] In Examples 26 and 27, the first sublayer comprises metal complex MC-27. MC-27 differs from MC-29 in terms of metal cation and ligand (see Table 2). The second sublayer comprises a different hole transport compound. In all Examples, the operating voltage is substantially improved over Comparative Examples 9, 10 and 11.

[0387] In Example 28, the first sublayer comprises metal complex MC-30. MC-30 differs from MC-29 in terms of metal cation and ligand (see Table 2). The second sublayer comprises HTC-7. The operating voltage is 5.4V, which is an improvement over Comparative Example 10.

[0388] In summary, substantial improvements in operating voltage have been achieved for OLEDs including the hole injection layer of the present invention.

[0389] Lower operating voltages can be beneficial in reducing power consumption and improving battery life, especially in mobile devices.

[0390] [Table 7] JPEG0007644768000056.jpg238169JPEG0007644768000057.jpg193169

[0391] The particular combinations of elements and features in the above detailed embodiments are merely illustrative; it is expressly contemplated to interchange and replace these teachings with other teachings in the teachings and patents / applications incorporated by reference. As those skilled in the art will recognize, variations, modifications and other embodiments of what is described herein may occur to those skilled in the art without departing from the spirit and scope of the invention as claimed. Therefore, the foregoing description is merely illustrative and is not intended to be limiting. In the claims, the term "comprising" does not exclude other elements or steps, and the indefinite article "a" or "an" does not exclude a plural state. The mere fact that certain measures are recited in mutually different dependent claims does not indicate that a combination of these measures cannot be used to advantage. The scope of the invention is defined in the following claims and their equivalents. Moreover, the reference signs used in the description and claims do not limit the scope of the invention as claimed. [Brief description of the drawings]

[0392] [Figure 1] 1 is a schematic cross-sectional view of an organic electronic device according to an exemplary embodiment of the present invention. [Diagram 2] 1 is a schematic cross-sectional view of an organic light emitting diode (OLED) according to an exemplary embodiment of the present invention. [Diagram 3] 1 is a schematic cross-sectional view of an OLED according to an exemplary embodiment of the present invention.

Claims

1. 1. An organic electronic device comprising an anode layer, a cathode layer and a hole injection layer, the hole injection layer is disposed between the anode layer and the cathode layer; the hole injection layer comprises a hole transport compound and a metal complex; said hole transport compound has the formula (I): 【Chemistry 1】 During the ceremony, k, m, q, and r are each independently 0, 1, or 2; p is 1, 2 or 3; 2≦k+m+q+r+p≦11, Ar １ ~Ar ６ are independently a substituted or unsubstituted unsaturated 5- to 7-membered heterocycle, a substituted or unsubstituted C ６ -C ３０ Aryl, substituted or unsubstituted C ３ -C ３０ heteroaryl, substituted or unsubstituted fluorene, or a fused ring system comprising from two to six substituted or unsubstituted 5- to 7-membered rings, the rings being selected from the group comprising: (i) an unsaturated 5- to 7-membered heterocyclic ring, (ii) a 5- to 6-membered aromatic heterocyclic ring, (iii) an unsaturated 5- to 7-membered non-heterocyclic ring, (iv) a fused ring system comprising a 6-membered aromatic non-heterocyclic ring; Here, the substituents contained in Ar 1 to Ar 6 are H, D, C, １ -C １２ Alkyl, unsubstituted C ６ -C １８ Aryl, unsubstituted C ３ -C １８ heteroaryl, a fused ring system comprising from two to six unsubstituted 5- to 7-membered rings, the rings being selected from the group comprising an unsaturated 5- to 7-membered heterocyclic ring, a 5- to 6-membered aromatic heterocyclic ring, an unsaturated 5- to 7-membered non-heterocyclic ring, and a 6-membered aromatic non-heterocyclic ring; and said metal complex having the formula (II): 【Chemistry 2】 During the ceremony, M is a metal ion; n is the valence of M, n is an integer from 1 to 4, L is a ligand containing at least 2 carbon atoms; The metal complex of formula (II) has a molecular weight Mw of ≧400 g / mol and ≦1500 g / mol; and The hole injection layer is disposed adjacent to the anode layer.

2. 2. The organic electronic device of claim 1, wherein the HOMO level of the hole transporting compound is further away from the vacuum level than the HOMO level of N4,N4'''-di(naphthalen-1-yl)-N4,N4'''-diphenyl-[1,1':4',1'':4'',1'''-quaterphenyl]-4,4'''-diamine measured under the same conditions.

3. The organic electronic device of claim 1 , wherein the hole injection layer is non-emissive.

4. The organic electronic device of claim 1, wherein the hole transport compound of formula (I) has a molecular weight Mw of ≧400 g / mol and ≦2000 g / mol.

5. 2. The organic electronic device of claim 1, wherein M is selected from the group comprising: a metal ion whose corresponding metal has an arene electronegativity value less than 2.4; an alkali metal, an alkaline earth metal, a rare earth metal or a transition metal; a metal with an atomic mass > 24 Da; a metal whose atomic mass > 24 Da and M is an oxidation number > 2.

6. 2. The organic electronic device of claim 1, wherein L is selected from the group comprising: at least 3 carbon atoms, or at least 4 carbon atoms, and / or at least 2 oxygen atoms, or 1 oxygen atom and 1 nitrogen atom; 2 to 4 oxygen atoms; 2 to 4 oxygen atoms and 0 to 2 nitrogen atoms; and / or - halogen, F, CN, substituted or unsubstituted C １ -C ６ Alkyl, substituted or unsubstituted C １ -C ６ At least one group selected from alkoxy; or halogen, F, CN, substituted or unsubstituted C １ -C ６ Alkyl, substituted or unsubstituted C １ -C ６ two or more groups selected from alkoxy; halogen, F, CN, substituted C １ -C ６ Alkyl, substituted C １ -C ６ one or more groups selected from alkoxy; or halogen, F, CN, perfluorinated C １ -C ６ Alkyl, Perfluorinated C １ -C ６ two or more groups selected from alkoxy; substituted or unsubstituted C １ -C ６ Alkyl, substituted or unsubstituted C ６ -C １２ Aryl and / or substituted or unsubstituted C ３ -C １２ At least one group selected from heteroaryl, Here, the substituents contained in L are D, C ６ Aryl, C ３ -C ９ Heteroaryl, C １ -C ６ Alkyl, C １ -C ６ Alkoxy, C ３ -C ６ Branched alkyl, C ３ -C ６ Cyclic alkyl, C ３ -C ６ Branched Alkoxy, C ３ -C ６ Cyclic alkoxy, partially or fully fluorinated C １ -C １６ Alkyl, partially or fully fluorinated C １ -C １６ Alkoxy, partially or fully deuterated C １ -C ６ Alkyl, partially or fully deuterated C １ -C ６ Alkoxy, COR ６ , COOR ６ , halogen, F or CN; Here, R ６ is C ６ Aryl, C ３ -C ９ Heteroaryl, C １ -C ６ Alkyl, C １ -C ６ Alkoxy, C ３ -C ６ Branched alkyl, C ３ -C ６ Cyclic alkyl, C ３ -C ６ Branched Alkoxy, C ３ -C ６ Cyclic alkoxy, partially or fully fluorinated C １ -C １６ Alkyl, partially or fully fluorinated C １ -C １６ Alkoxy, partially or fully deuterated C １ -C ６ Alkyl, partially or fully deuterated C １ -C ６ alkoxy.

7. The organic electronic device of claim 1 , wherein the metal complex of formula (II) is non-emissive.

8. the hole injection layer comprises a hole transport compound and a metal complex; The hole transport compound has the formula (I): 【Chemistry 3】 During the ceremony, k, m, q, and r are each independently 0, 1, or 2; p is 1, 2 or 3; 2≦k+m+q+r+p≦11, Ar １ ~Ar ６ are independently a substituted or unsubstituted unsaturated 5- to 7-membered heterocycle, a substituted or unsubstituted C ６ -C ３０ Aryl, substituted or unsubstituted C ３ -C ３０ heteroaryl, substituted or unsubstituted fluorene, or a fused ring system comprising from two to six substituted or unsubstituted 5- to 7-membered rings, the rings being selected from the group comprising: (i) an unsaturated 5- to 7-membered heterocyclic ring, (ii) a 5- to 6-membered aromatic heterocyclic ring, (iii) an unsaturated 5- to 7-membered non-heterocyclic ring, (iv) a fused ring system comprising a 6-membered aromatic non-heterocyclic ring; Ar when k=1 ２ , Ar ３ , Ar when q=1 ４ , Ar when r=1 ５ are independently a substituted or unsubstituted unsaturated 5- to 7-membered heterocycle, a substituted or unsubstituted C ６ -C ３０ Arylene, substituted or unsubstituted C ３ -C ３０ Heteroarylene, substituted or unsubstituted biphenylene, substituted or unsubstituted fluorene, 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 tetracene, substituted or unsubstituted tetraphene, substituted or unsubstituted dibenzofuran, substituted or unsubstituted dibenzothiophene, substituted or unsubstituted xanthene, substituted or unsubstituted carbazole, substituted or unsubstituted azepine, substituted or unsubstituted aryl, substituted or unsubstituted aryl, substituted or unsubstituted aryl, substituted or unsubstituted aryl, substituted or unsubstituted aryl, substituted or unsubstituted aryl is selected from unsubstituted dibenzo[b,f]azepine, 9,9'-spirobi[fluorene], substituted or unsubstituted spiro[fluorene-9,9'-xanthene], substituted or unsubstituted 9,14-dihydrodibenzo[2,3:6,7]azepino[4,5-b]indole, or a substituted or unsubstituted aromatic fused ring system comprising at least three substituted or unsubstituted aromatic rings selected from the group comprising a substituted or unsubstituted non-hetero 5-membered ring, a substituted or unsubstituted hetero 5-membered ring, a substituted or unsubstituted 6-membered ring, and / or a substituted or unsubstituted 7-membered ring; Ar when k=0 ２ , Ar when m=0 and k=0 ３ , Ar when q=0 and r=0 ４ , Ar when r=0 ５ are independently a substituted or unsubstituted unsaturated 5- to 7-membered heterocycle, a substituted or unsubstituted C ６ -C ３０ Aryl, substituted or unsubstituted C ３ -C ３０ Heteroaryl, substituted or unsubstituted biphenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted naphthalenyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted pyrenyl, substituted or unsubstituted perylenyl, substituted or unsubstituted triphenylenyl, substituted or unsubstituted tetracenyl, substituted or unsubstituted tetraphenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted xanthenyl, substituted or unsubstituted carbazole, substituted or unsubstituted azepine, substituted or unsubstituted aryl, substituted or unsubstituted aryl, substituted or unsubstituted aryl, substituted or unsubstituted aryl, substituted or unsubstituted aryl, substituted or unsubstituted aryl substituted or unsubstituted dibenzo[b,f]azepine, 9,9'-spirobi[fluorenyl], substituted or unsubstituted spiro[fluorenyl-9,9'-xanthene], substituted or unsubstituted 9,14-dihydrodibenzo[2,3:6,7]azepino[4,5-b]indole, or a substituted or unsubstituted aromatic fused ring system comprising at least three substituted or unsubstituted aromatic rings selected from the group comprising a substituted or unsubstituted non-hetero 5-membered ring, a substituted or unsubstituted hetero 5-membered ring, a substituted or unsubstituted 6-membered ring, and / or a substituted or unsubstituted 7-membered ring; Here, the substituents contained in Ar 1 to Ar 6 are H, D, C, １ -C １２ Alkyl, unsubstituted C ６ -C １８ Aryl or unsubstituted C ３ -C １８ heteroaryl; and The organic electronic device of claim 1 , wherein the metal complex has the formula (II):

9. the hole transport compound is selected from the group of compounds comprising at least ≧1 to ≦6 substituted or unsubstituted aromatic fused ring systems containing heterocyclic aromatic rings; at least ≧1 to ≦3 substituted or unsubstituted unsaturated 5- to 7-membered heterocyclic rings, ≧2 to ≦5 substituted or unsubstituted aromatic fused ring systems containing heterocyclic aromatic rings; at least ≧1 to ≦3 substituted or unsubstituted unsaturated 5- to 7-membered heterocyclic rings, 3 or 4 substituted or unsubstituted aromatic fused ring systems containing heterocyclic aromatic rings; at least ≧1 to ≦3 substituted or unsubstituted unsaturated 5- to 7-membered heterocyclic rings, 2. The organic electronic device of claim 1, wherein the aromatic fused ring system containing the heterocyclic aromatic ring is unsubstituted or is at least ≧1 and ≦3 unsubstituted unsaturated 5-7 membered heterocyclic rings.

10. 2. The organic electronic device of claim 1, wherein the hole transport compound of claim 1 is selected from the group of compounds comprising a substituted or unsubstituted aromatic fused ring system having at least ≧2 to ≦6 fused aromatic rings selected from the group comprising a substituted or unsubstituted non-heterocyclic aromatic ring, a substituted or unsubstituted 5-membered heterocyclic ring, a substituted or unsubstituted 6-membered ring, and / or a substituted or unsubstituted unsaturated 5-7 membered heterocyclic ring, an unsubstituted aromatic fused ring system having at least ≧2 to ≦6 fused aromatic rings selected from the group comprising an unsubstituted non-heterocyclic aromatic ring, an unsubstituted 5-membered heterocyclic ring, an unsubstituted 6-membered ring, and an unsubstituted unsaturated 5-7 membered heterocyclic ring.

11. 2. The organic electronic device of claim 1 , wherein the hole transport compound of claim 1 is selected from the group of compounds containing at least ≧1 to ≦6 substituted or unsubstituted aromatic fused ring systems having at least one unsaturated 5-membered ring, at least one unsaturated 6-membered ring, at least one unsaturated 7-membered ring, at least one unsaturated 5-membered ring, or at least one unsaturated 7-membered ring containing at least 1 to 3 heteroatoms.

12. The hole transport compound of claim 1 is selected from the group of compounds including: at least ≧6 and ≦12 aromatic rings, at least ≧4 and ≦11 non-heterocyclic aromatic rings, at least ≧1 and ≦4 aromatic 5-membered rings, at least 1 or 2 unsaturated 5- to 7-membered heterocycles, at least ≧6 to ≦12 aromatic rings, among which at least ≧4 and ≦≦11 are non-heterocyclic aromatic rings; and at least ≧1 and ≦4 aromatic rings are heterocyclic aromatic rings, and the total number of non-heterocyclic aromatic rings and heterocyclic aromatic rings does not exceed 12 aromatic rings; at least ≧6 to ≦12 aromatic rings, among which at least ≧4 and ≦≦11 are non-heterocyclic aromatic rings; and at least ≧1 and ≦4 aromatic rings are heterocyclic aromatic rings, the total number of non-heterocyclic aromatic rings and heterocyclic aromatic rings does not exceed 12 aromatic rings; and The organic electronic device of claim 1 or 2, wherein the hole transport compound comprises at least ≧1 to ≦4 aromatic five-membered rings.

13. In formula (I): Ar ３ is selected from D1 to D17: 【Chemistry 4】 Ar １ is selected from D7 to D15 and D17 when m>0 and k>0, is selected from D7 to D15 and D17 when k>0 and m=0, and is selected from D1 to D6 when k>1; Ar ２ is selected from D1 to D6 when m>0 and k>0, and is selected from D7 to D15 and D17 when m>0 and k=0; Ar ４ is selected from D1 to D6 when q>0, from D1 to D6 when q=0 and r>0, and from D7 to D15 and D17 when q=0 and r=0; Ar ５ is selected from D1 to D6 when q>0 and r>0, and is selected from D7 to D15 and D17 when q>0 and r=0; Ar ６ is selected from D7 to D15 and D17 when r>0, q>0, is selected from D7 to D15 and D17 when r>0, q=0, and is selected from D1 to D6 when r>1.

14. The organic electronic device of claim 1, wherein the hole transport compound of formula (I) is selected from F1 to F13: 【Chemistry 5】 【change】

15. 2. The organic electronic device of claim 1, wherein n is an integer from 1 to 4.

16. The organic electronic device of claim 1, wherein the metal complex may be selected from the following formulae (IIa) to (IIe): 【Chemistry 6】 During the ceremony, M is a metal ion; n is the valence of M, n is an integer from 1 to 4; A １ and A ２ is independently a substituted or unsubstituted C １ -C １２ Alkyl, substituted or unsubstituted C ６ -C １２ Aryl, substituted or unsubstituted C ３ -C １２ heteroaryl; A ３ is H, D, substituted or unsubstituted C １ -C １２ alkyl, substituted or unsubstituted C ６ -C １２ Aryl, substituted or unsubstituted C ３ -C １２ heteroaryl; Here, A １ and A ２ And / or A ３ The substituents contained in are independently D, C ６ Aryl, C ３ -C ９ Heteroaryl, C １ -C ６ Alkyl, C １ -C ６ Alkoxy, C ３ -C ６ Branched alkyl, C ３ -C ６ Cyclic alkyl, C ３ -C ６ Branched Alkoxy, C ３ -C ６ Cyclic alkoxy, partially or fully fluorinated C １ -C １６ Alkyl, partially or fully fluorinated C １ -C １６ Alkoxy, partially or fully deuterated C １ -C ６ Alkyl, partially or fully deuterated C １ -C ６ Alkoxy, COR １ , COOR １ , halogen, F or CN; Here, R １ is C ６ Aryl, C ３ -C ９ Heteroaryl, C １ -C ６ Alkyl, C １ -C ６ Alkoxy, C ３ -C ６ Branched alkyl, C ３ -C ６ Cyclic alkyl, C ３ -C ６ Branched Alkoxy, C ３ -C ６ Cyclic alkoxy, partially or fully fluorinated C １ -C １６ Alkyl, partially or fully fluorinated C １ -C １６ Alkoxy, partially or fully deuterated C １ -C ６ Alkyl, partially or fully deuterated C １ -C １６ alkoxy.

17. A １ and A ２ And / or A ３ is selected from the group consisting of: A １ and A ２ And / or A ３ At least one of A contains a substituent. １ and A ２ And / or A ３ At least one of said substituents is independently ３ -C ９ Heteroaryl, C １ -C ６ Alkoxy, C ３ -C ６ Branched Alkoxy, C ３ -C ６ Cyclic alkoxy, partially or fully fluorinated C １ -C １６ Alkyl, partially or fully fluorinated C １ -C １６ Alkoxy, partially or fully deuterated C １ -C ６ Alkoxy, COR １ , COOR １ , halogen, F or CN; A １ and A ２ And / or A ３ At least one of A contains at least two substituents, １ and A ２ And / or A ３ The substituents in are independently selected from the group consisting of ３ -C ９ Heteroaryl, C １ -C ６ Alkoxy, C ３ -C ６ Branched Alkoxy, C ３ -C ６ Cyclic alkoxy, partially or fully fluorinated C １ -C １６ Alkyl, partially or fully fluorinated C １ -C １６ Alkoxy, partially or fully deuterated C １ -C ６ Alkoxy, COR １ , COOR １ 17. The organic electronic device of claim 16, wherein said halogen is selected from the group consisting of F and CN.

18. The organic electronic device of claim 1 or 17, wherein L is independently selected from G1 to G64: 【Chemistry 7】 【change】 【change】 【change】 【change】

19. The organic electronic device further comprises at least one photoactive layer; The organic electronic device of claim 1 , wherein the photoactive layer is disposed between the hole injection layer and the cathode layer.

20. The organic electronic device of claim 1 , wherein the at least one photoactive layer is a light-emitting layer.

21. the hole injection layer comprises a first sublayer comprising the metal complex of formula (II) and a second sublayer comprising a hole transport compound of formula (I), The organic electronic device of claim 1 , wherein the first sublayer is disposed closer to the anode layer and the second sublayer is disposed closer to the cathode layer.

22. the hole injection layer comprises a first sublayer consisting of the metal complex of formula (II) and a second sublayer comprising a hole transport compound of formula (I), The organic electronic device of claim 1 , wherein the first sublayer is disposed closer to the anode layer and the second sublayer is disposed closer to the cathode layer.

23. the hole injection layer comprises a first sublayer comprising the metal complex of formula (II) and a second sublayer comprising the hole transport compound of formula (I) and the metal complex; The organic electronic device of claim 1 , wherein the first sublayer is disposed closer to the anode layer and the second sublayer is disposed closer to the cathode layer.

24. The organic electronic device further comprises a hole transport layer; 2. The organic electronic device of claim 1 , wherein the hole transport layer is disposed between the hole injection layer and the cathode layer, or the hole transport layer is disposed between the hole injection layer and the at least one photoactive layer or the at least one light-emitting layer.

25. 25. The organic electronic device of claim 24, wherein the hole transport layer comprises the hole transport compound of claim 1.

26. 26. An organic electronic device according to claim 24 or 25, wherein the hole transport compound of formula (I) is selected to be the same in the hole injection layer and in the hole transport layer.

27. The organic electronic device of claim 1 , wherein the electronic device is a light-emitting device, a thin film transistor, a display device, or a photovoltaic cell.

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