Organic electronic devices containing hole injection layers with hole transport compounds

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 wherein the hole injection layer comprises a hole transport compound and a metal complex.

Description

Technical Field

[0001] 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 comprises a hole transport compound. Background Technology

[0002] Organic electronic devices, such as organic light-emitting diodes (OLEDs), are self-emissive, possessing wide viewing angles, excellent contrast ratios, rapid response times, high brightness, superior operating voltage characteristics, and excellent color reproduction. A typical OLED comprises an anode, a hole injection layer (HIL), a hole transport layer (HTL), an emissive layer (EML), an electron transport layer (ETL), and a cathode layer, which are sequentially stacked on a substrate. In this regard, the HIL, HTL, EML, and ETL are thin films formed from organic compounds.

[0003] When a voltage is applied to the anode and cathode, holes injected from the anode move to the EML via the HIL and HTL, while electrons injected from the cathode move to the EML via the ETL. Holes and electrons recombine in the EML to generate excitons. Light emission occurs when the excitons transition from the excited state to the ground state. The injection and flow of holes and electrons should be balanced so that OLEDs with the above structure exhibit low operating voltage, excellent efficiency, and / or long lifetime.

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

[0005] WO2017029370 relates to a metal amide of general formula Ia and its use as a hole injection layer (HIL) in an organic light-emitting diode (OLED), and a method for manufacturing an OLED comprising a hole injection layer containing a metal amide of general formula Ia. The hole transport layer disclosed in WO2017029370 may further comprise a triarylamine compound having formula VIIa.

[0006]

[0007] WO2017029366 relates to a hole injection layer for OLEDs comprising a triarylamine compound doped with an electrically neutral metal amide compound, characterized in that the thickness of the hole injection layer is at least about ≥20 nm to about ≤1000 nm and the electrically neutral metal amide compound has formula Ia. WO2017029366 discloses a hole injection layer (HIL) comprising a triarylamine compound having formula VIIa:

[0008]

[0009] WO2017102861 relates to an organic electronic device (10) comprising at least one organic layer (3), said organic layer having a fluorinated sulfonamide metal salt of formula 1: (1), wherein M is a divalent or higher-order metal with an atomic mass greater than 26 g / mol or a monovalent metal with an atomic mass greater than or equal to 39 g / mol, wherein 1 ≤ n ≤ 7, and wherein R1 and R2 are independently selected from fluorinated aryl groups, fluorinated alkyl groups, and fluorinated aryl-alkyl groups. The matrix material is a hole transport material.

[0010] WO2017178473A1 relates to an organic electronic device (100) comprising a first organic functional layer stack (S1) and a second organic functional layer stack (S2) and a charge carrier generating layer (5) disposed therebetween. The charge carrier generating layer (5) has an n-type conducting region (5b), a doped organic p-type doped region (5a), and an intermediate region (5c) disposed therebetween with a layer thickness of 0.1 nm to 20 nm, wherein the doped organic p-type doped region (5a) has a fluorinated sulfonylimide metal salt of Formula 1 as a p-type dopant, wherein M is a divalent or higher-order metal with an atomic mass greater than 26 g / mol or a monovalent metal with an atomic mass greater than or equal to 39 g / mol, wherein 1 ≤ n ≤ 7, and wherein R1 and R2 are independent of each other and selected from fluorinated aryl groups, fluorinated alkyl groups, and fluorinated arylalkyl groups.

[0011] There is still a need to improve the performance of organic electronic devices by providing improved hole injection layers, particularly by improving the characteristics of both the hole injection layer and the organic electronic devices to achieve improved operating voltage.

[0012] In addition, a hole injection layer is still required that can inject adjacent layers containing compounds whose HOMO energy levels are further away from the vacuum energy level.

[0013] Another objective is to provide a hole injection layer containing a compound that can be deposited by vacuum thermal evaporation under conditions suitable for large-scale production. Summary of the Invention

[0014] One aspect of the present invention provides 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 wherein the hole injection layer comprises a hole transport compound and a metal complex, wherein...

[0015] - The hole transport compound comprises covalently bonded atoms selected from the following:

[0016] Covalently bonded C, H, O, N, Si and / or S; or

[0017] Covalently bonded C, H, O, N, B, and P, and

[0018] in

[0019] - The molecular weight (Mw) of the hole transport compound is ≥400 and ≤2000 g / mol.

[0020] - When determined under the same conditions, the HOMO level of the hole-transporting compound is further from the vacuum level than the HOMO level of N4,N4”'-di(naphthyl-1-yl)-N4,N4”'-diphenyl-[1,1':4',1”:4”,1”'-tetraphenyl]-4,4”'-diamine; and

[0021] -The metal complex has formula (II):

[0022]

[0023] in

[0024] M is a metal ion.

[0025] n is the valence of M, where n is an integer from 1 to 4.

[0026] L is a ligand containing at least two carbon atoms; and

[0027] The hole injection layer is arranged adjacent to the anode layer.

[0028] According to one embodiment, the organic electronic device includes 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 wherein the hole injection layer includes a hole transport compound and a metal complex, wherein...

[0029] - The hole transport compound comprises covalently bonded atoms selected from the following:

[0030] Covalently bonded C, H, O, N, Si and / or S; or

[0031] Covalently bonded C, H, O, N, B, and P, and

[0032] in

[0033] - The molecular weight (Mw) of the hole transport compound is ≥400 and ≤2000 g / mol.

[0034] - When determined under the same conditions, the HOMO level of the hole-transporting compound is further from the vacuum level than the HOMO level of N4,N4”'-di(naphthyl-1-yl)-N4,N4”'-diphenyl-[1,1':4',1”:4”,1”'-tetraphenyl]-4,4”'-diamine; and

[0035] -The metal complex has formula (II):

[0036]

[0037] in

[0038] - The molecular weight Mw of the metal complex is ≥400 g / mol and ≤2000 g / mol;

[0039] M is a metal ion.

[0040] n is the valence of M, where n is an integer from 1 to 4.

[0041] L is a ligand containing at least two carbon atoms; and

[0042] The hole injection layer is arranged adjacent to the anode layer; and

[0043] Optionally, the hole-transporting compound is a triarylamine hole-transporting compound, wherein the aryl substituent is bonded to the tertiary amine via a single bond and wherein aryl substituents that form part of a heterocycle are excluded.

[0044] The triarylamine hole-transporting compounds in the sense of this invention are, for example, N,N,N',N'-tetra(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(naphthyl-1-yl)-N,N'-bis(phenyl)-benzidine, N1,N3-bis([1,1'-biphenyl]-4-yl)-5-(9,9-dimethyl-9H-fluoren-2-yl)-N1,N3-bis(3,5-dimethylphenyl)phenyl-1,3-diamine, N1,N3-Di([1,1'-biphenyl]-4-yl)-5-(9,9-dimethyl-9H-fluorene-2-yl)-N1,N3-diphenylmethylphenyl-1,3-diamine, N,N'-((9H-fluorene-9,9-diyl)bis(4,1-phenyleneyl))bis(N-([1,1'-biphenyl]-4-yl)-[1,1'-biphenyl]-4-amine), N4,N4”-Di(naphthyl-1-yl)-N4,N4”-Diphenyl-[1,1':4',1”-terphenyl]-4,4”-diamine (CAS139255-16-6), 4,4'-bis-(N-(1-naphthyl)-N-phenyl-amino)-tetraphenyl (CAS 650609-47-5), 4,4',4”-tris(carbazole-9-yl)-triphenylamine.

[0045] According to one embodiment, the organic electronic device includes 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 wherein the hole injection layer includes a hole transport compound and a metal complex, wherein...

[0046] - The hole transport compound comprises covalently bonded atoms selected from the following:

[0047] Covalently bonded C, H, O, N, Si and / or S; or

[0048] Covalently bonded C, H, O, N, B, and P, and

[0049] in

[0050] - The molecular weight Mw of the hole transport compound is ≥400 g / mol and ≤2000 g / mol;

[0051] - When determined under the same conditions, the HOMO level of the hole-transporting compound is further from the vacuum level than the HOMO level of N4,N4”'-di(naphthyl-1-yl)-N4,N4”'-diphenyl-[1,1':4',1”:4”,1”'-tetraphenyl]-4,4”'-diamine; and

[0052] -The metal complex has formula (II):

[0053]

[0054] in

[0055] - The molecular weight Mw of the metal complex is ≥400 g / mol and ≤2000 g / mol;

[0056] M is a metal ion.

[0057] n is the valence of M, where n is an integer from 1 to 4.

[0058] L is a ligand containing at least two carbon atoms; and

[0059] The hole injection layer is arranged adjacent to the anode layer; and

[0060] Optionally, the hole-transporting compound is a triarylamine hole-transporting compound, wherein the aryl substituent is bonded to the tertiary amine via a single bond and wherein aryl substituents forming part of a heterocycle are excluded; and wherein sp... 3 Hole-transporting compounds of hybrid carbon atoms.

[0061] The term "HOMO level" is understood to refer to the highest occupied molecular orbital and is determined in eV (electron volts).

[0062] The term "HOMO level further from the vacuum level" is understood to mean that the absolute value of the HOMO level is higher than that of the reference compound. For example, the term "far from the vacuum level than the HOMO level of N4,N4”'-di(naphthyl-1-yl)-N4,N4”'-diphenyl-[1,1':4',1”:4”,1”'-tetraphenyl]-4,4”'-diamine" is understood to mean that the absolute value of the HOMO level of the organic matrix compound (OMC) is higher than that of the HOMO level of N4,N4”'-di(naphthyl-1-yl)-N4,N4”'-diphenyl-[1,1':4',1”:4”,1”'-tetraphenyl]-4,4”'-diamine".

[0063] The term "absolute value" is understood to refer to a value without a "-" sign. According to one embodiment of the invention, the HOMO energy level of a hole-transporting compound can be calculated using quantum mechanical methods.

[0064] If the HOMO level of a hole-transporting compound is calculated using this method, then the HOMO level of the hole-transporting compound is less than the HOMO level of N4,N4”'-di(naphthyl-1-yl)-N4,N4”'-diphenyl-[1,1':4',1”:4”,1”'-tetraphenyl]-4,4”'-diamine.

[0065] If the HOMO level of a hole-transporting compound is calculated using this 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(naphthyl-1-yl)-N4,N4”'-diphenyl-[1,1':4',1”:4”,1”'-tetraphenyl]-4,4”'-diamine.

[0066] According to one embodiment of the invention, the HOMO level of the hole transport compound is calculated using the package TURBOMOLEV6.5, which is available from TURBOMOLE GmbH, Litzenhardtstrasse 19, 76135 Karlsruhe, Germany.

[0067] If calculated using this method, the HOMO level of N4,N4”'-di(naphthyl-1-yl)-N4,N4”'-diphenyl-[1,1':4',1”:4”,1”'-tetraphenyl]-4,4”'-diamine is -4.85 eV. The HOMO levels of hole-transporting compounds in the prior art, calculated using this method, are as follows. For comparison, HOMO levels calculated from redox potentials are also provided.

[0068]

[0069]

[0070]

[0071] If the HOMO level is far from the vacuum level, accurate measurement of the redox potential may no longer be feasible. Therefore, in this specification, unless otherwise stated, the HOMO level is determined by quantum mechanical methods.

[0072] It should be noted that the ligand L has a negative charge.

[0073] According to one implementation, ligand L has a negative charge; in other words, ligand L is a monoanion.

[0074] According to one implementation, the negative charge of ligand L can correspond to the valence of metal ion M.

[0075] Another aspect is 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 wherein the hole injection layer comprises a hole transport compound and a metal complex, wherein

[0076] -The hole transport compound has formula (I):

[0077] (Ar 1 ) k —(Ar 2 ) m —Ar 3 —(Ar 4 ) p —(Ar 5 ) q —(Ar 6 ) r (I),

[0078] in

[0079] k, m, q, r are each independently selected from 0, 1, or 2.

[0080] p is 1, 2, or 3.

[0081] Where 2≤k+m+q+r+p≤11,

[0082] Ar 1 To Ar 6 Independently selected from: heterocycles with substituted or unsubstituted unsaturated 5- to 7-membered rings, substituted or unsubstituted C6 to C6 rings. 30 Aryl, substituted or unsubstituted C3 to C4 30The ring is a heteroaryl group, a substituted or unsubstituted fluorene, or a fused ring system comprising 2 to 6 substituted or unsubstituted 5- to 7-membered rings, wherein the rings are selected from: (i) unsaturated 5- to 7-membered heterocycles, (ii) 5- to 6-membered aromatic heterocycles, (iii) unsaturated 5- to 7-membered non-heterocycles, and (iv) 6-membered aromatic non-heterocycles; preferably independently selected from: substituted or unsubstituted biphenylide, 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 biphenylide, substituted or unsubstituted tetraphenyl, substituted or unsubstituted benzo[a]anthracene, substituted or unsubstituted dibenzofuran, substituted or Unsubstituted dibenzothiophene, substituted or unsubstituted xanthane, substituted or unsubstituted carbazole, substituted or unsubstituted azaheptanyl, substituted or unsubstituted dibenzo[b,f]zaheptanyl, 9,9'-spirobis[fluorene], substituted or unsubstituted spiro[fluorene-9,9'-xanthane], substituted or unsubstituted 9,14-dihydrodibenzo[2,3:6,7]zaheptanyl[4,5-b]indole, or substituted or unsubstituted aromatic fused ring systems comprising at least three substituted or unsubstituted aromatic rings selected from substituted or unsubstituted non-heterocyclic rings, substituted or unsubstituted heterocyclic 5-membered rings, substituted or unsubstituted 6-membered rings, and / or substituted or unsubstituted 7-membered rings.

[0083] The substituents are selected from: H, D, C1 to C 12 Alkyl, unsubstituted C6 to C6 18 Aryl, unsubstituted C3 to C 18 Heteroaryl groups comprised of fused ring systems containing 2 to 6 unsubstituted 5- to 7-membered rings, wherein the rings are selected from unsaturated 5- to 7-membered heterocycles, 5- to 6-membered aromatic heterocycles, unsaturated 5- to 7-membered non-heterocycles, and 6-membered aromatic non-heterocycles; and

[0084] -The metal complex has formula (II):

[0085]

[0086] in

[0087] M is a metal ion.

[0088] n is the valence of M, where n is an integer from 1 to 4.

[0089] L is a ligand containing at least two carbon atoms; and

[0090] The hole injection layer is arranged adjacent to the anode layer.

[0091] According to one embodiment, the organic electronic device includes 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 wherein the hole injection layer includes a hole transport compound and a metal complex, wherein...

[0092] -The hole transport compound has formula (I):

[0093] (Ar 1 ) k —(Ar 2 ) m —Ar 3 —(Ar 4 ) p —(Ar 5 ) q —(Ar 6 ) r (I),

[0094] in

[0095] k, m, q, r are each independently selected from 0, 1, or 2.

[0096] p is 1, 2, or 3.

[0097] Where 2≤k+m+q+r+p≤11,

[0098] Ar 1 To Ar 6 Independently selected from: heterocycles with substituted or unsubstituted unsaturated 5- to 7-membered rings, substituted or unsubstituted C6 to C6 rings. 30 Aryl, substituted or unsubstituted C3 to C4 30The ring is a heteroaryl group, a substituted or unsubstituted fluorene, or a fused ring system comprising 2 to 6 substituted or unsubstituted 5- to 7-membered rings, wherein the rings are selected from: (i) unsaturated 5- to 7-membered heterocycles, (ii) 5- to 6-membered aromatic heterocycles, (iii) unsaturated 5- to 7-membered non-heterocycles, and (iv) 6-membered aromatic non-heterocycles; preferably independently selected from: substituted or unsubstituted biphenylide, 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 biphenylide, substituted or unsubstituted tetraphenyl, substituted or unsubstituted benzo[a]anthracene, substituted or unsubstituted dibenzofuran, substituted or Unsubstituted dibenzothiophene, substituted or unsubstituted xanthane, substituted or unsubstituted carbazole, substituted or unsubstituted azaheptanyl, substituted or unsubstituted dibenzo[b,f]zaheptanyl, 9,9'-spirobis[fluorene], substituted or unsubstituted spiro[fluorene-9,9'-xanthane], substituted or unsubstituted 9,14-dihydrodibenzo[2,3:6,7]zaheptanyl[4,5-b]indole, or substituted or unsubstituted aromatic fused ring systems comprising at least three substituted or unsubstituted aromatic rings selected from substituted or unsubstituted non-heterocyclic rings, substituted or unsubstituted heterocyclic 5-membered rings, substituted or unsubstituted 6-membered rings, and / or substituted or unsubstituted 7-membered rings.

[0099] The substituents are selected from: H, D, C1 to C 12 Alkyl, unsubstituted C6 to C6 18 Aryl, unsubstituted C3 to C 18 Heteroaryl groups comprised of fused ring systems containing 2 to 6 unsubstituted 5- to 7-membered rings, wherein the rings are selected from unsaturated 5- to 7-membered heterocycles, 5- to 6-membered aromatic heterocycles, unsaturated 5- to 7-membered non-heterocycles, and 6-membered aromatic non-heterocycles; and

[0100] -The metal complex has formula (II):

[0101]

[0102] in

[0103] - The molecular weight Mw of the metal complex is ≥400 g / mol and ≤2000 g / mol;

[0104] M is a metal ion.

[0105] n is the valence of M, where n is an integer from 1 to 4.

[0106] L is a ligand containing at least two carbon atoms; and

[0107] The hole injection layer is arranged adjacent to the anode layer; and

[0108] Optionally, the hole-transporting compound is a triarylamine hole-transporting compound, wherein the aryl substituent is bonded to the tertiary amine via a single bond and wherein aryl substituents that form part of a heterocycle are excluded.

[0109] According to one embodiment, the organic electronic device includes 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 wherein the hole injection layer includes a hole transport compound and a metal complex, wherein...

[0110] - The hole transport compound has a molecular weight Mw of ≥400 g / mol and ≤2000 g / mol and has formula (I):

[0111] (Ar 1 ) k —(Ar 2 ) m —Ar 3 —(Ar 4 ) p —(Ar 5 ) q —(Ar 6 ) r (I),

[0112] in

[0113] k, m, q, r are each independently selected from 0, 1, or 2.

[0114] p is 1, 2, or 3.

[0115] Where 2≤k+m+q+r+p≤11,

[0116] Ar 1 To Ar 6 Independently selected from: heterocycles with substituted or unsubstituted unsaturated 5- to 7-membered rings, substituted or unsubstituted C6 to C6 rings. 30 Aryl, substituted or unsubstituted C3 to C4 30The ring is a heteroaryl group, a substituted or unsubstituted fluorene, or a fused ring system comprising 2 to 6 substituted or unsubstituted 5- to 7-membered rings, wherein the rings are selected from: (i) unsaturated 5- to 7-membered heterocycles, (ii) 5- to 6-membered aromatic heterocycles, (iii) unsaturated 5- to 7-membered non-heterocycles, and (iv) 6-membered aromatic non-heterocycles; preferably independently selected from: substituted or unsubstituted biphenylide, 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 biphenylide, substituted or unsubstituted tetraphenyl, substituted or unsubstituted benzo[a]anthracene, substituted or unsubstituted dibenzofuran, substituted or Unsubstituted dibenzothiophene, substituted or unsubstituted xanthane, substituted or unsubstituted carbazole, substituted or unsubstituted azaheptanyl, substituted or unsubstituted dibenzo[b,f]zaheptanyl, 9,9'-spirobis[fluorene], substituted or unsubstituted spiro[fluorene-9,9'-xanthane], substituted or unsubstituted 9,14-dihydrodibenzo[2,3:6,7]zaheptanyl[4,5-b]indole, or substituted or unsubstituted aromatic fused ring systems comprising at least three substituted or unsubstituted aromatic rings selected from substituted or unsubstituted non-heterocyclic rings, substituted or unsubstituted heterocyclic 5-membered rings, substituted or unsubstituted 6-membered rings, and / or substituted or unsubstituted 7-membered rings.

[0117] The substituents are selected from: H, D, C1 to C 12 Alkyl, unsubstituted C6 to C6 18 Aryl, unsubstituted C3 to C 18 A heteroaryl group comprising a fused ring system of 2 to 6 unsubstituted 5- to 7-membered rings, wherein the rings are selected from: unsaturated 5- to 7-membered heterocycles, 5- to 6-membered aromatic heterocycles, unsaturated 5- to 7-membered non-heterocycles, and 6-membered aromatic non-heterocycles; and

[0118] -The metal complex has formula (II):

[0119]

[0120] in

[0121] - The molecular weight Mw of the metal complex is ≥400 and ≤2000 g / mol.

[0122] M is a metal ion.

[0123] n is the valence of M, where n is an integer from 1 to 4.

[0124] L is a ligand containing at least two carbon atoms; and

[0125] The hole injection layer is arranged adjacent to the anode layer; and

[0126] Optionally, the hole-transporting compound is a triarylamine hole-transporting compound, wherein the aryl substituent is bonded to the tertiary amine via a single bond and wherein aryl substituents that form part of a heterocycle are excluded.

[0127] According to one embodiment, the organic electronic device includes 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 wherein the hole injection layer includes a hole transport compound and a metal complex, wherein...

[0128] - The hole transport compound has a molecular weight Mw of ≥400 g / mol and ≤2000 g / mol and has formula (I):

[0129] (Ar 1 ) k —(Ar 2 ) m —Ar 3 —(Ar 4 ) p —(Ar 5 ) q —(Ar 6 ) r (I),

[0130] in

[0131] k, m, q, r are each independently selected from 0, 1, or 2.

[0132] p is 1, 2, or 3.

[0133] Where 2≤k+m+q+r+p≤11,

[0134] Ar 1 To Ar 6 Independently selected from: heterocycles with substituted or unsubstituted unsaturated 5- to 7-membered rings, substituted or unsubstituted C6 to C6 rings. 30 Aryl, substituted or unsubstituted C3 to C4 30The ring is a heteroaryl group, a substituted or unsubstituted fluorene, or a fused ring system comprising 2 to 6 substituted or unsubstituted 5- to 7-membered rings, wherein the rings are selected from: (i) unsaturated 5- to 7-membered heterocycles, (ii) 5- to 6-membered aromatic heterocycles, (iii) unsaturated 5- to 7-membered non-heterocycles, and (iv) 6-membered aromatic non-heterocycles; preferably independently selected from: substituted or unsubstituted biphenylide, 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 biphenylide, substituted or unsubstituted tetraphenyl, substituted or unsubstituted benzo[a]anthracene, substituted or unsubstituted dibenzofuran, substituted or Unsubstituted dibenzothiophene, substituted or unsubstituted xanthane, substituted or unsubstituted carbazole, substituted or unsubstituted azaheptanyl, substituted or unsubstituted dibenzo[b,f]zaheptanyl, 9,9'-spirobis[fluorene], substituted or unsubstituted spiro[fluorene-9,9'-xanthane], substituted or unsubstituted 9,14-dihydrodibenzo[2,3:6,7]zaheptanyl[4,5-b]indole, or substituted or unsubstituted aromatic fused ring systems comprising at least three substituted or unsubstituted aromatic rings selected from substituted or unsubstituted non-heterocyclic rings, substituted or unsubstituted heterocyclic 5-membered rings, substituted or unsubstituted 6-membered rings, and / or substituted or unsubstituted 7-membered rings.

[0135] The substituents are selected from: H, D, C1 to C 12 Alkyl, unsubstituted C6 to C6 18 Aryl, unsubstituted C3 to C 18 A heteroaryl group comprising a fused ring system of 2 to 6 unsubstituted 5- to 7-membered rings, wherein the rings are selected from: unsaturated 5- to 7-membered heterocycles, 5- to 6-membered aromatic heterocycles, unsaturated 5- to 7-membered non-heterocycles, and 6-membered aromatic non-heterocycles; and

[0136] -The metal complex has formula (II):

[0137]

[0138] in

[0139] The molecular weight (Mw) of the metal complex is ≥400 and ≤2000 g / mol.

[0140] M is a metal ion.

[0141] n is the valence of M, where n is an integer from 1 to 4.

[0142] L is a ligand containing at least two carbon atoms; and

[0143] The hole injection layer is arranged adjacent to the anode layer; and

[0144] Optionally, the hole-transporting compound is a triarylamine hole-transporting compound, wherein the aryl substituent is bonded to the tertiary amine via a single bond and wherein aryl substituents forming part of a heterocycle are excluded; and wherein sp... 3 Hole-transporting compounds of hybrid carbon atoms.

[0145] According to one embodiment, triarylamine hole-transporting compounds described below can be excluded if: the aryl substituent is bonded to a tertiary amine via a single bond and the tertiary amine to which the aryl substituent is bonded is not part of a heterocycle; and / or compounds having sp... 3 Hole transport compounds of hybrid carbon.

[0146] According to one embodiment, hole transport compounds and / or metal complexes of formula (II) are excluded as phosphorescent luminescent compounds.

[0147] According to one embodiment, the following triarylamine hole-transporting compounds can be excluded: wherein the aryl substituent is bonded to the tertiary amine via a single bond and wherein the tertiary amine bonded to the aryl substituent is not part of a heterocycle, and hole-transporting compounds that are phosphorescent emitters can be excluded.

[0148] According to one embodiment, triarylamine hole-transporting compounds described below can be excluded: wherein the aryl substituent is bonded to the tertiary amine via a single bond and wherein the tertiary amine to which the aryl substituent is bonded is not part of a heterocycle, and wherein compounds with sp... 3 Hole transport compounds of hybrid carbon and hole transport compounds that can be excluded as phosphorescent emitters.

[0149] According to one embodiment, the organic electronic device includes 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 wherein the hole injection layer includes a hole transport compound and a metal complex, wherein...

[0150] -The hole transport compound has formula (I):

[0151] (Ar 1 ) k —(Ar 2 ) m —Ar 3 —(Ar 4 ) p —(Ar 5 ) q —(Ar 6 ) r (I),

[0152] in

[0153] k, m, q, and r can be independently selected from 0, 1, or 2.

[0154] p is 1, 2, or 3.

[0155] Where 2≤k+m+q+r+p≤11,

[0156] Ar 1 To Ar 6 It can be independently selected from: substituted or unsubstituted unsaturated 5- to 7-membered heterocycles, substituted or unsubstituted C6 to C6 rings. 30 Aryl, substituted or unsubstituted C3 to C4 30 The rings are selected from: (i) heterocyclic rings with unsaturated 5 to 7-membered rings, (ii) aromatic heterocyclic rings with 5 to 6 members, (iii) non-heterocyclic rings with unsaturated 5 to 7-membered rings, and (iv) aromatic non-heterocyclic rings with 6-membered rings.

[0157] The substituents are selected from: H, D, C1 to C 12 Alkyl, unsubstituted C6 to C6 18 Aryl, unsubstituted C3 to C 18 A heteroaryl group comprising a fused ring system of 2 to 6 unsubstituted 5- to 7-membered rings, wherein the rings are selected from: unsaturated 5- to 7-membered heterocycles, 5- to 6-membered aromatic heterocycles, unsaturated 5- to 7-membered non-heterocycles, and 6-membered aromatic non-heterocycles; and

[0158] -The metal complex has formula (II):

[0159]

[0160] in

[0161] M is a metal ion.

[0162] n is the valence of M, where n is an integer from 1 to 4.

[0163] L is a ligand containing at least two carbon atoms; and

[0164] The hole injection layer is arranged adjacent to the anode layer.

[0165] According to another aspect, the hole transport compound or the hole transport compound according to formula (I) can be a covalent hole transport compound.

[0166] According to one implementation, n can be an integer from 1 to 4, preferably from 1 to 3, and also preferably 2 or 3.

[0167] It should be noted that k, m, q, and r represent the substituent numbers of adjacent Ar moieties. For example, compound F7 according to formula (I):

[0168] By Ar 3 =Benzene group, represented by k, m, q and r = 0 and p = 3, where

[0169] According to one embodiment, the hole injection layer does not emit light.

[0170] According to one embodiment of the present invention, the hole injection layer and / or the hole transport compound of formula (I) and / or the metal complex of formula (II) are non-luminescent.

[0171] In the context of this specification, the terms "substantially non-luminescent" or "non-luminescent" are used.

[0172] This means that the hole transport compound, metal complex, and / or layer, such as a hole injection layer, contributes less than 10%, preferably less than 5%, to the visible light emission spectrum of the organic electronic device (e.g., OLED or display device). The visible light emission spectrum is an emission spectrum with a wavelength of about ≥380 nm to about ≤780 nm.

[0173] It should be noted that throughout the application, any Ar 1 To Ar 6 "etc." always refers to the same part unless otherwise noted.

[0174] In this specification, unless otherwise defined, "replaced" means replaced by H, deuterium, Cl to C 12 Alkyl, unsubstituted C6 to C 18 aryl, and unsubstituted C3 to C 18 Hybridized aryl groups.

[0175] In this specification, unless otherwise defined, an aryl group having at least six C ring atoms may be substituted with one, two, three, four, or five substituents. For example, a substituted C6 aryl group may have one, two, three, four, or five phenyl substituents. Below is an example of a substituted C6 aryl group having four phenyl groups:

[0176]

[0177] However, in this specification, "aryl-substituted" means substituted by one or more aryl groups, and the aryl group itself may be substituted by one or more aryl and / or heteroaryl groups.

[0178] Accordingly, in this specification, "heteroaryl substituted" means substituted by one or more heteroaryl groups, and the heteroaryl group itself may be substituted by one or more aryl and / or heteroaryl groups.

[0179] In this specification, unless otherwise defined, "alkyl group" refers to a saturated aliphatic hydrocarbon group. Alkyl groups can be C1 to C2. 12 Alkyl groups. More specifically, the alkyl groups can be C1 to C2. 10 Alkyl groups or C1 to C6 alkyl groups. For example, C1 to C4 alkyl groups contain 1 to 4 carbons in the alkyl chain and can be selected from methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl.

[0180] Specific examples of the alkyl group may be methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, branched pentyl group, and hexyl group.

[0181] The term "cycloalkyl" refers to a saturated hydrocarbon group derived from a cycloalkane by formally isolating a hydrogen atom from the ring atoms contained in the respective cycloalkane. Examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, adamantyl, and so on.

[0182] The term "heteroatom" is understood as the replacement of at least one carbon atom with another polyvalent atom in a structure that can be formed from covalently bonded carbon atoms. Preferably, the heteroatom is selected from B, Si, N, P, O, and S; more preferably, it is selected from N, P, O, and S.

[0183] Preferred examples of hole-transporting compounds, which may be covalent hole-transporting compounds, are organic compounds primarily composed of covalently bonded C, H, O, N, and S, optionally also containing covalently bonded B, P, or Si. In one embodiment, the hole-transporting compound, which may be a covalent compound, does not contain metal atoms, and most of its framework atoms may be selected from C, O, S, and N. Alternatively, the covalent compound does not contain metal atoms, and most of its framework atoms may be selected from C and N.

[0184] In this specification, "aryl group" and "aromatic ring" refer to hydrocarbon groups that can be produced by formally isolating a hydrogen atom from the aromatic ring of the corresponding aromatic hydrocarbon. An aromatic hydrocarbon is a hydrocarbon containing at least one aromatic ring or aromatic ring system. An aromatic ring or aromatic ring system is a planar ring or ring system covalently bonded to a carbon atom, wherein the planar ring or ring system includes a conjugated system of delocalized electrons satisfying Hückel's rule. Examples of aryl groups include monocyclic groups such as phenyl or tolyl, polycyclic groups containing multiple aromatic rings linked by single bonds such as biphenyl, and polycyclic groups containing fused rings such as naphthyl or fluorenyl.

[0185] Similarly, "heteroaryl" and "heteroaromatic" are particularly well understood as groups derived by formally isolating a cyclic hydrogen atom from a heterocyclic aromatic ring in a compound containing at least one heterocyclic aromatic ring.

[0186] The term "non-heterocyclic" is understood to refer to a ring or ring system that does not contain heteroatoms as ring members.

[0187] The term "heterocycle" is understood to mean that the heterocycle contains 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 without heteroatoms.

[0188] Heterocyclic alkyl groups are particularly well understood as groups derived by formally isolating a cyclic hydrogen from a saturated cyclic alkyl ring in a compound containing at least one saturated cyclic alkyl ring.

[0189] The terms "fused aryl ring" or "condensed aryl ring" are understood as follows: when two aryl rings share at least two common sp... 2 When carbon atoms are hybridized, they are considered to be either fused or condensed.

[0190] The term "fused ring system" is understood to refer to a ring system in which two or more rings share at least two atoms.

[0191] The term "5-, 6-, or 7-membered ring" is understood to refer to a ring containing 5, 6, or 7 atoms. The atoms may be selected from carbon and one or more heteroatoms.

[0192] In this specification, a single key refers to a direct key.

[0193] In the context of this invention, "different" means that the compounds do not have the same chemical structure.

[0194] The terms "without," "containing," and "not including" do not exclude impurities that may be present in the hole transport compound prior to deposition. Impurities have no technical effect on the objectives of this invention.

[0195] The term "proximity" is understood to mean that the distance between layers can be less than 2 nm or that adjacent layers are in contact with each other. The term "contact sandwich" refers to a three-layer arrangement in which the middle layer is in direct contact with the two adjacent layers.

[0196] The terms "light-absorbing layer" and "light-absorbing layer" are used synonymously.

[0197] The terms “light-emitting layer,” “light-emitting layer,” and “emitting layer” are used synonymously.

[0198] The terms “OLED,” “organic light-emitting diode,” and “organic light-emitting device” are used synonymously.

[0199] The terms anode, anode layer, and anode electrode are used synonymously.

[0200] The terms cathode, cathode layer, and cathode electrode are used synonymously.

[0201] The term "hole injection layer" is understood to refer to a layer that improves the injection of charge from the anode layer into other layers of an organic electronic device or from other layers of an organic electronic device into the anode.

[0202] The term "hole transport layer" is understood to refer to the layer that transports holes between the hole injection layer and other layers arranged between the hole injection layer and the cathode layer.

[0203] The operating voltage U is measured in volts.

[0204] In this specification, hole characteristics refer to the ability to supply electrons to form holes when an electric field is applied, and due to the conductivity characteristics based on the highest occupied molecular orbital (HOMO) energy level, holes formed in the anode can be easily injected into the light-emitting layer and transported in the light-emitting layer.

[0205] In addition, electronic properties refer to the ability to accept electrons when an electric field is applied, and due to the conductivity of the lowest unoccupied molecular orbital (LUMO) energy level, electrons formed in the cathode can be easily injected into the light-emitting layer and transported in the light-emitting layer.

[0206] Beneficial effects

[0207] It has been surprisingly discovered that the organic electronic device according to the invention solves the fundamental problem of the invention by enabling organic electronic devices, such as organic light-emitting diodes, to be superior to known organic electronic devices in the art in several respects, particularly in terms of operating voltage.

[0208] Furthermore, the fundamental problem of the present invention can be solved by providing compounds that are suitable for deposition via vacuum thermal evaporation under conditions suitable for large-scale production. In particular, the standard onset temperatures of the hole-transporting compounds and metal complexes of the present invention are within a range suitable for large-scale production.

[0209] According to one embodiment, when determined under the same conditions, 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 N4,N4”'-di(naphthyl-1-yl)-N4,N4”'-diphenyl-[1,1':4',1”:4”,1”'-tetraphenyl]-4,4”'-diamine (-4.85 eV, calculated by the method described herein).

[0210] Preferably, the HOMO level of the hole-transporting compound or the hole-transporting compound of formula (I) is further from the vacuum level than the HOMO level of N,N'-((9H-fluorene-9,9-diyl)bis(4,1-phenyleneyl))bis(N-([1,1'-biphenyl]-4-yl)-[1,1'-biphenyl]-4-amine) (-4.86 eV, calculated using the method described herein); or, the HOMO level of the hole-transporting compound or the hole-transporting compound of formula (I) is closer to the vacuum level than the HOMO level of 9-phenyl- The HOMO level of 10-(3',4',5'-triphenyl-[1,1':2',1”-terphenyl]-3-yl)anthracene (-5.04 eV, calculated as described in this specification) is the same as or further from the vacuum level; or, the HOMO level of the hole-transporting compound or the hole-transporting compound of formula (I) is the same as or further from the vacuum level of tris(4-(9H-carbazole-9-yl)phenyl)amine (-5.09 eV, calculated as described in this specification).

[0211] According to one embodiment, when determined under the same conditions, 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 N4,N4”'-di(naphthyl-1-yl)-N4,N4”'-diphenyl-[1,1':4',1”:4”,1”'-tetraphenyl]-4,4”'-diamine, and is more similar to 4,4',4”-(1,3,5-phenyltriyl)tri [Dibenzothiophene] is the same as or closer to the vacuum energy level; preferably, the HOMO energy level of the hole-transporting compound or the hole-transporting compound of formula (I) is further away from the vacuum energy level than the HOMO energy level of N,N'-((9H-fluorene-9,9-diyl)bis(4,1-phenyleneyl))bis(N-([1,1'-biphenyl]-4-yl)-[1,1'-biphenyl]-4-amine), and is similar to that of 4,4',4”-(1,3,5 -benzyl)tri[dibenzothiophene] is the same as or closer to the vacuum level; or, the HOMO level of the hole-transporting compound or the hole-transporting compound of formula (I) is the same as or further from the vacuum level of the HOMO level of 9-phenyl-10-(3',4',5'-triphenyl-[1,1':2',1”-terphenyl]-3-yl)anthracene, and is the same as or further from the vacuum level of 4,4',4”-(1,3,5-benzyl)tri[dibenzothiophene] The hole transport compound or the hole transport compound of formula (I) has a HOMO level that is the same as or closer to 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 4,4',4”-(1,3,5-phenyltriyl)tris[dibenzothiophene] (-5.67 eV, calculated as described in this specification).

[0212] The term "HOMO level closer to the vacuum level" is 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-phenyltriyl)tri[dibenzothiophene]" is 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-phenyltriyl)tri[dibenzothiophene].

[0213] According to one embodiment, when determined under the same conditions, the HOMO level of the hole transport compound or the hole transport compound of formula (I) is further from the vacuum level than the HOMO level of N4,N4”'-di(naphthyl-1-yl)-N4,N4”'-diphenyl-[1,1':4',1”:4”,1”'-tetraphenyl]-4,4”'-diamine; wherein the N4,N4”'-di(naphthyl-1-yl)-N4,N4”'-diphenyl-[1,1':4',1”:4”:4”:4”: The HOMO level of [4,1”'-tetraphenyl]-4,4”'-diamine is -4.85 eV; preferably, when determined under the same conditions, the HOMO level of the hole-transporting compound or the hole-transporting compound of formula (I) is further from the vacuum level than the HOMO level of N,N'-((9H-fluorene-9,9-diyl)bis(4,1-phenyleneyl))bis(N-([1,1'-biphenyl]-4-yl)-[1,1'-biphenyl]-4-amine); wherein the N,N'-((9H-fluorene-9,9-diyl)bis(4,1-phenyleneyl))bis(N-([1,1'-biphenyl]-4-yl)-[1,1'-biphenyl]-4-amine) The HOMO level of H-fluorene-9,9-diyl)bis(4,1-phenylene))bis(N-([1,1'-biphenyl]-4-yl)-[1,1'-biphenyl]-4-amine) is -4.86 eV; or, the HOMO level of the hole-transporting compound or the hole-transporting compound of formula (I) is the same as or further from the vacuum level than the HOMO level of 9-phenyl-10-(3',4',5'-triphenyl-[1,1':2',1”-triphenyl]-3-yl)anthracene, wherein the The HOMO level of the 9-phenyl-10-(3',4',5'-triphenyl-[1,1':2',1”-terphenyl]-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-carbazole-9-yl)phenyl)amine, wherein the HOMO level of tris(4-(9H-carbazole-9-yl)phenyl)amine is -5.09 eV.

[0214] Hole transport compounds suitable for use as matrix materials in hole injection layers of, for example, organic electronic devices, may have formula (I):

[0215] (Ar1 ) k —(Ar 2 ) m —Ar 3 —(Ar 4 ) p —(Ar 5 ) q —(Ar 6 ) r (I),

[0216] in

[0217] k, m, q, and r can be independently selected from 0, 1, or 2.

[0218] p is 1, 2, or 3.

[0219] Where 2≤k+m+q+r+p≤11,

[0220] Ar 1 To Ar 6 It can be independently selected from: substituted or unsubstituted unsaturated 5- to 7-membered heterocycles, substituted or unsubstituted C6 to C6 rings. 30 Aryl, substituted or unsubstituted C3 to C4 30 The rings are selected from: (i) heterocyclic rings with unsaturated 5 to 7-membered rings, (ii) aromatic heterocyclic rings with 5 to 6 members, (iii) non-heterocyclic rings with unsaturated 5 to 7-membered rings, and (iv) aromatic non-heterocyclic rings with 6-membered rings.

[0221] The substituents are selected from: H, D, C1 to C 12 Alkyl, unsubstituted C6 to C6 18 Aryl, unsubstituted C3 to C 18 Heteroaryl groups comprise fused ring systems of 2 to 6 unsubstituted 5- to 7-membered rings, wherein the rings are selected from: unsaturated 5- to 7-membered heterocycles, 5- to 6-membered aromatic heterocycles, unsaturated 5- to 7-membered non-heterocycles, and 6-membered aromatic non-heterocycles.

[0222] According to one implementation, Ar 1 To Ar 6It can be independently selected from: substituted or unsubstituted biphenylide, 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 biphenylide, substituted or unsubstituted tetraphenyl, substituted or unsubstituted benzo[anthracene], substituted or unsubstituted dibenzofuran, substituted or unsubstituted dibenzothiophene, substituted or unsubstituted xanthan, substituted or unsubstituted carbazole, substituted or unsubstituted azaheptan, substituted or unsubstituted dibenzo[ [b,f]-aza-heptanyl, 9,9'-spirobis[fluorene], substituted or unsubstituted spiro[fluorene-9,9'-xanton], substituted or unsubstituted 9,14-dihydrodibenzo[2,3:6,7]aza-heptanyl[4,5-b]indole, or substituted or unsubstituted aromatic fused ring systems comprising at least three substituted or unsubstituted aromatic rings selected from substituted or unsubstituted non-heterocyclic rings, substituted or unsubstituted heterocyclic 5-membered rings, substituted or unsubstituted 6-membered rings, and / or substituted or unsubstituted 7-membered rings.

[0223] The substituents are selected from: H, D, C1 to C 12 Alkyl, unsubstituted C6 to C6 18 Aryl, unsubstituted C3 to C 18 Heteroaryl groups comprise fused ring systems of 2 to 6 unsubstituted 5- to 7-membered rings, wherein the rings are selected from: unsaturated 5- to 7-membered heterocycles, 5- to 6-membered aromatic heterocycles, unsaturated 5- to 7-membered non-heterocycles, and 6-membered aromatic non-heterocycles.

[0224] According to one embodiment, the molecular weight Mw of the hole transport compound of formula (I) can be ≥400 and ≤2000 g / mol, preferably ≥450 and ≤1500 g / mol, further preferably ≥500 and ≤1000 g / mol, even more preferably ≥550 and ≤900 g / mol, and even more preferably ≥600 and ≤800 g / mol.

[0225] According to one embodiment, the HOMO level of the hole transport compound or the hole transport compound of formula (I) may be less than -4.85 eV, preferably less than -4.86 eV, more preferably less than -4.9 eV, or less than -4.95 eV, or less than -5 eV, or less than -5.05 eV, or less than -5.09 eV.

[0226] According to one embodiment, the HOMO level of the hole transport compound or the hole transport compound of formula (I) may 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, or less than -4.95 eV and greater than -7 eV, or less than -5 eV and greater than -7 eV, or less than -5.05 eV and greater than -7 eV, or less than -5.09 eV and greater than -7 eV.

[0227] According to one embodiment, the HOMO energy level of the hole transport compound or the hole transport compound of formula (I) may 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, or less than -4.95 eV and greater than -6.5 eV, or less than -5 eV and greater than -6.5 eV, or less than -5.05 eV and greater than -6.5 eV, or less than -5.09 eV and greater than -6.5 eV.

[0228] According to one embodiment, the HOMO level of the hole transport compound or the hole transport compound of formula (I) may 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, or less than -4.95 eV and greater than -6 eV, or less than -5 eV and greater than -6 eV, or less than -5.05 eV and greater than -6 eV, or less than -5.09 eV and greater than -6 eV.

[0229] According to one embodiment, the hole transport compound or the hole transport compound of formula (I) may comprise at least 1 to 6 substituted or unsubstituted aromatic fused ring systems containing heteroaromatic rings.

[0230] According to one embodiment, the hole transport compound or the hole transport compound of formula (I) may comprise at least 1 to 6 substituted or unsubstituted aromatic fused ring systems containing heteroaromatic rings and at least 1 to 3 substituted or unsubstituted unsaturated 5- to 7-membered heterocycles, preferably 2 to 5 substituted or unsubstituted aromatic fused ring systems containing heteroaromatic rings.

[0231] According to one embodiment, the hole transport compound or the hole transport compound of formula (I) may comprise at least 1 to 6 substituted or unsubstituted aromatic fused ring systems containing heteroaromatic rings and at least 1 to 3 substituted or unsubstituted unsaturated 5 to 7-membered heterocycles, preferably 2 to 5 substituted or unsubstituted aromatic fused ring systems containing heteroaromatic rings and at least 1 to 3 substituted or unsubstituted unsaturated 5 to 7-membered heterocycles, more preferably 3 or 4 substituted or unsubstituted aromatic fused ring systems containing heteroaromatic rings and optionally at least 1 to 3 substituted or unsubstituted unsaturated 5 to 7-membered heterocycles, and even more preferably the aromatic fused ring system containing heteroaromatic rings is unsubstituted and optionally at least 1 to 3 unsubstituted unsaturated 5 to 7-membered heterocycles.

[0232] According to one embodiment, the hole transport compound or the hole transport compound of formula (I) may 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.

[0233] According to one embodiment, the hole transport compound or the hole transport compound of formula (I) may 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, wherein the aromatic fused ring system comprises substituted or unsubstituted heteroaromatic rings.

[0234] According to one embodiment, the hole transport compound or the hole transport compound of formula (I) may contain at least 1 to 3 or 2 substituted or unsubstituted unsaturated 5 to 7-membered heterocycles.

[0235] According to one embodiment, the hole transport compound or the hole transport compound of formula (I) may contain at least 1 to 3 or 2 heterocycles of substituted or unsubstituted unsaturated 7-membered rings.

[0236] According to one embodiment, the substituted or unsubstituted aromatic fused ring system of the hole transport compound or the hole transport compound of formula (I) may contain at least 1 to 3 or 2 substituted or unsubstituted unsaturated 5 to 7-membered heterocycles.

[0237] According to one embodiment, the substituted or unsubstituted aromatic fused ring system of the hole transport compound or the hole transport compound of formula (I) may contain at least 1 to ≤3 or 2 substituted or unsubstituted unsaturated 7-membered rings of heterocyclic rings.

[0238] According to one embodiment, the hole transport compound or the hole transport compound of formula (I) may 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, wherein the aromatic fused ring system comprises a heterocyclic ring of a substituted or unsubstituted unsaturated 5 to 7-membered ring.

[0239] According to one embodiment, the hole transport compound or the hole transport compound of formula (I) may 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, wherein the aromatic fused ring system comprises substituted or unsubstituted heteroaromatic rings, and wherein the aromatic fused ring system comprises substituted or unsubstituted unsaturated 5- to 7-membered heterocyclic rings.

[0240] According to one embodiment, the hole transport compound or the hole transport compound of formula (I) may 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, wherein the aromatic fused ring system comprises at least 1 to 3 or 2 substituted or unsubstituted unsaturated 5 to 7-membered heterocycles.

[0241] According to one embodiment, the hole transport compound or the hole transport compound of formula (I) may 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, wherein the aromatic fused ring system comprises substituted or unsubstituted heteroaromatic rings, and wherein the aromatic fused ring system comprises at least 1 to 3 or 2 substituted or unsubstituted unsaturated 5 to 7-membered heterocyclic rings.

[0242] According to one embodiment, the hole transport compound or the hole transport compound of formula (I) may comprise:

[0243] - A substituted or unsubstituted aromatic fused ring system having at least 2 to ≤6, preferably 3 to ≤5, or 4 fused aromatic rings, said aromatic fused ring system being selected from substituted or unsubstituted non-heteroaromatic rings, substituted or unsubstituted heterocyclic 5-membered rings, substituted or unsubstituted 6-membered rings, and / or heterocyclic rings with substituted or unsubstituted unsaturated 5- to 7-membered rings; or

[0244] - An unsubstituted aromatic fused ring system having at least 2 to 6, preferably 3 to 5, or 4 fused aromatic rings, said aromatic fused ring system being selected from unsubstituted non-heteroaromatic rings, unsubstituted hetero 5-membered rings, unsubstituted 6-membered rings, and / or unsubstituted unsaturated 5- to 7-membered rings.

[0245] It should be noted here that the term "aromatic fused ring system" may include at least one aromatic ring and at least one substituted or unsubstituted unsaturated 5- to 7-membered ring. It should also be noted here that the substituted or unsubstituted unsaturated 5- to 7-membered ring may not be an aromatic ring.

[0246] According to one embodiment, the hole-transporting compound or the hole-transporting compound of formula (I) may comprise at least 1 to 6, preferably 2 to 5, or more preferably 3 or 4 substituted or unsubstituted aromatic fused ring systems, wherein the aromatic fused ring system has:

[0247] - At least one unsaturated 5-membered ring, and / or

[0248] - At least one unsaturated 6-membered ring, and / or

[0249] - At least one unsaturated 7-membered ring; wherein preferably at least one unsaturated 5-membered ring and / or at least one unsaturated 7-membered ring contains at least 1 to 3, preferably 1, heteroatom.

[0250] According to one embodiment, the hole-transporting compound or the hole-transporting compound of formula (I) may comprise at least 1 to 6, preferably 2 to 5, or more preferably 3 or 4 substituted or unsubstituted aromatic fused ring systems, wherein the aromatic fused ring system has:

[0251] - At least one aromatic 5-membered ring, and / or

[0252] - At least one aromatic 6-membered ring, and / or

[0253] - At least one aromatic 7-membered ring; wherein preferably at least one aromatic 5-membered ring and / or at least one aromatic 7-membered ring contains at least 1 to 3, preferably 1, heteroatom;

[0254] The substituted or unsubstituted aromatic fused ring system comprises at least 1 to ≤3 or 2 substituted or unsubstituted unsaturated 5 to 7-membered heterocycles.

[0255] According to one embodiment, the hole transport compound or the hole transport compound of formula (I) may comprise:

[0256] - At least 6 to 12, preferably 7 to 11, and more preferably 8 to 10 or 9 aromatic rings; and / or

[0257] - At least 4 to 11, preferably 5 to 10, more preferably 6 to 9, or even more preferably 7 or 8 non-heterotropic aromatic rings, preferably said non-heterotropic aromatic rings are aromatic C6 rings; and / or

[0258] - At least 1 to 4, preferably 2 or 3, aromatic 5-membered rings, preferably heteroaromatic 5-membered rings; and / or

[0259] - At least one or two heterocyclic rings with unsaturated 5- or 7-membered rings, preferably at least one or two heterocyclic rings with unsaturated 7-membered rings;

[0260] - At least 6 to 12, preferably 7 to 11, and more preferably 8 to 10 or 9 aromatic rings, wherein...

[0261] At least 4 to 11, preferably 5 to 10, further preferably 6 to 9, or even more preferably 7 or 8, are non-heteroaromatic rings, and

[0262] At least 1 to 4, preferably 2 or 3, aromatic rings are heterocyclic aromatic rings, wherein the total number of non-heterocyclic and heterocyclic aromatic rings does not exceed 12 aromatic rings; and / or

[0263] - At least 6 to 12, preferably 7 to 11, more preferably 8 to 10, or 9 aromatic rings, wherein...

[0264] At least 4 to 11, preferably 5 to 10, further preferably 6 to 9, or even more preferably 7 or 8, are non-heteroaromatic rings, and

[0265] At least 1 to 4, preferably 2 or 3, aromatic rings are heteroaromatic rings, wherein the total number of non-heteroaromatic rings and heteroaromatic rings does not exceed 12 aromatic rings; and the hole transport compound or the hole transport compound according to formula (I) contains at least 1 to 4, preferably 2 or 3, aromatic 5-membered rings, preferably heteroaromatic 5-membered rings, and / or

[0266] The hole transport compound or the hole transport compound according to formula (I) comprises at least one or two heterocyclic rings with unsaturated 5- or 7-membered rings, preferably at least one or two heterocyclic rings with unsaturated 7-membered rings.

[0267] According to one embodiment, the hole transport compound or the hole transport compound of formula (I) may contain heteroatoms, which may be selected from O, S, N, B or P, preferably from O, S or N.

[0268] According to one embodiment, the hole-transporting compound or the hole-transporting compound of formula (I) may comprise at least 1 to 6, preferably 2 to 5, or more preferably 3 or 4 substituted or unsubstituted aromatic fused ring systems, wherein the aromatic fused ring system has:

[0269] - At least one aromatic 5-membered ring, and / or

[0270] - At least one aromatic 6-membered ring, and / or

[0271] - At least one aromatic 7-membered ring; wherein preferably at least one aromatic 5-membered ring and / or at least one aromatic 7-membered ring contains at least 1 to 3, preferably 1, heteroatom;

[0272] The substituted or unsubstituted aromatic fused ring system optionally comprises at least 1 to 3 or 2 substituted or unsubstituted unsaturated 5 to 7-membered heterocycles; and the substituted or unsubstituted aromatic fused ring system comprises heteroatoms, which may be selected from O, S, N, B, P or Si, preferably from O, S or N.

[0273] According to one embodiment, the hole transport compound or the hole transport compound of formula (I) may not contain heteroatoms that are not part of an aromatic ring and / or an unsaturated 7-membered ring. Preferably, the hole transport compound or the hole transport compound of formula (I) may not contain N atoms except for N atoms that are part of an aromatic ring or an unsaturated 7-membered ring.

[0274] According to one embodiment, 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.

[0275] According to one embodiment, 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.

[0276] According to one embodiment, for the hole transport compound according to formula (I):

[0277] -Ar 3 Options are available from D1 to D17, with D1 to D6 and D16 being preferred:

[0278]

[0279] According to one implementation, Ar 1 Selectable from D7 to D15 and D17. Ar 2 Options can be selected from D1 to D6, or D7 to D15 and D17. Ar 4 Options can be selected from D1 to D6, or D7 to D15 and D17. Ar 5 Options can be selected from D1 to D6, or D7 to D15 and D17. Ar 6 Selectable from D7 to D15 and D17.

[0280] According to one embodiment, for the hole transport compound according to formula (I):

[0281] -Ar 3 Options are available from D1 to D17, with D1 to D6 and D16 being preferred:

[0282]

[0283] If m>0 and k>0, then Ar 1 Selected from D7 to D15 and D17, or if k>0 and m=0, then Ar 1 Selected from D7 to D15 and D17, or if k>1, then Ar 1 Selected from D1 to D6;

[0284] If m>0 and k>0, then Ar 2 Selected from D1 to D6; or if m>0 and k=0, then Ar 2 Selected from D7 to D15 and D17;

[0285] If q > 0, then Ar 4 Selected from D1 to D6, or if q = 0 and r > 0, then Ar 4 Selected from D1 to D6; or if q and r = 0, then Ar 4 Selected from D7 to D15 and D17;

[0286] If q > 0 and r > 0, then Ar 5 Selected from D1 to D6, or if q>0 and r=0, then Ar 5 Selected from D7 to D15 and D17;

[0287] If r>0, q>0, then Ar 6 Selected from D7 to D15 and D17, or if r > 0, q = 0, then Ar 6 Selected from D7 to D15 and D17, or if r>1, then Ar 6 Selected from D1 to D6.

[0288] According to one implementation, in formula (I), Ar 3 The group is selected from anthracene, carbazole, dibenzothiophene and / or dibenzofuran.

[0289] According to one implementation, in formula (I), Ar 3 The group is selected from anthracene.

[0290] According to one implementation, in formula (I), Ar 3 The group is selected from carbazole, dibenzothiophene and / or dibenzofuran.

[0291] According to one embodiment, the hole transport compound or the hole transport compound according to formula (I) may be selected from F1 to F13:

[0292]

[0293]

[0294] Preferably, the hole transport compound does not contain metal and / or ionic bonds.

[0295] The hole injection layer and / or hole transport compound may not contain HTM014, HTM081, HTM163, HTM222, EL-301, HTM226, HTM355, HTM133, HTM334, HTM604, and EL-22T. Abbreviations indicate the manufacturer's name, such as Merck or Lumtec.

[0296] The hole injection layer and / or hole transport compound may be free of N,N'-bis(naphthyl-1-yl)-N,N'-bis(phenyl)-9,9-dimethylfluorene, N,N'-bis(3-methylphenyl)-N,N'-bis(phenyl)-9,9-dimethylfluorene, N,N'-bis(naphthyl-1-yl)-N,N'-bis(phenyl)-9,9-dimethylfluorene, N,N'-bis(naphthyl-1-yl)-N,N'-bis(phenyl)-2,2-dimethylbenzidine, N,N'-bis(3-methylphenyl)-N,N'-bis(phenyl)-9,9-spirodifluorene, 2,2',7,7'-tetra(N,N-diphenylamino)-9,9'-spirodifluorene, N,N '-bis(naphthyl-1-yl)-N,N'-bis(phenyl)-benzidine, N,N'-bis(naphthyl-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-dimethylfluorene, N,N'-bis(naphthyl-1-yl)-N,N'-bis(phenyl)-9,9-spirodifluorene, di-[4-(N,N-xylyl-amino)-phenyl]cyclohexane, 2,2',7,7'-tetra(N,N-xylyl)amino-spirodifluorene, 9,9-bis[4-(N,N-bis-biphenyl-4-yl-amino] [Phenylacetyl]-9H-fluorene, 2,2',7,7'-tetra(N,N-naphthyl(phenyl)-amino]-9,9'-spirodifluorene, 2,7-bis(N,N-bis(9,9-spirodifluorene-2-yl)-amino]-9,9'-spirodifluorene, 2,2'-bis(N,N-bis(biphenyl-4-yl)amino]-9,9'-spirodifluorene, N,N'-bis(phenanthrene-9-yl)-N,N'-bis(phenyl)-benzidine, N,N,N',N'-tetra-naphthyl-2-yl)-benzidine, 2,2'-bis(N,N-diphenyl-amino)-9,9-spirodifluorene, 9,9-bis[4-(N,N-bis-naphthyl-2-yl-amino)phenyl]-9H-fluorene, 9,9 -Bis[4-(N,N'-bis-naphthyl-2-yl-N,N'-bis-phenyl-amino)-phenyl]-9H-fluorene, titanium phthalocyanine oxide, copper phthalocyanine, 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinone dimethyl ether, 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, 4,4',4"-tris(N,N-diphenyl-amino)triphenylamine, pyrazino[2,3-f][1,10]phenanthroline-2,3-dicarboxynitrile, N,N,N',N'-Tetra(4-methoxyphenyl)benzidine, HTM014, HTM081, HTM163, HTM222, EL-301, HTM226, HTM355, HTM133, HTM334, HTM604, and EL-22T. The abbreviations indicate the manufacturer's name, such as Merck or Lumtec.

[0297] Metal complex of formula (II)

[0298] The metal complex according to formula (II) is non-luminescent. In the context of this specification, the terms "substantially non-luminescent" or "non-luminescent" mean that the metal complex according to formula (II) contributes less than 10%, preferably less than 5%, to the visible light emission spectrum of an organic electronic device (e.g., an OLED or display device). The visible light emission spectrum is an emission spectrum with wavelengths from about ≥380 nm to about ≤780 nm.

[0299] According to one embodiment, the metal ion M in formula (II) can be selected from metal ions, wherein the electronegativity value of the corresponding metal according to Allen is less than 2.4. Preferably, M can be selected from alkali metals, alkaline earth metals, rare earth metals or transition metals. More preferably, M can be selected from metals with an atomic mass ≥ 24 Da. Even more preferably, M can be selected from metals with an atomic mass ≥ 24 Da and the oxidation number of M is ≥ 2.

[0300] The term “according to Allen’s electronegativity values” is especially relevant to Allen, Leland C. (1989). “Electronegativity is the average one-electron energy of the valence-shell electrons in ground-state free atoms”. Journal of the American Chemical Society 111(25):9003-9014.

[0301] According to one embodiment of the present invention, the valence n of M is 1 or 2.

[0302] According to one embodiment of the invention, M is selected from metal ions, wherein the electronegativity of the corresponding metal according to Allen is less than 2.4, preferably less than 2, more preferably less than 1.9, and the valence n of M is 1 or 2.

[0303] According to one embodiment of the present invention, M is selected from alkali metals, alkaline earth metals, rare earth metals or transition metals, or M is selected from alkali metals, alkaline earth metals, transition metals or Group 4 or 5 metals.

[0304] According to one embodiment of the present 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; even more preferably, M is selected from Na, K, Mg, Mn, Cu, Zn and Ag, wherein if M is Cu, then n is 2.

[0305] According to one embodiment of the present invention, M is not Li.

[0306] According to one embodiment of the present invention, M is neither Li nor K.

[0307] According to one embodiment of the present invention, M is not Ag.

[0308] According to one embodiment of the present invention, M is not Cu.

[0309] According to one embodiment of the present invention, M is not Mo.

[0310] According to one embodiment of the present invention, M is not Ir and / or Pt.

[0311] According to another embodiment, the molecular weight Mw of the metal complex according to formula (II) can be ≥287 and ≤2000 g / mol, preferably ≥400 and ≤1500 g / mol, further preferably ≥580 and ≤1500 g / mol, and even more preferably ≥580 and ≤1400 g / mol.

[0312] According to another embodiment, the molecular weight Mw of the metal complex according to formula (II) can be ≥400 g / mol and ≤2000 g / mol, preferably ≥400 g / mol and ≤1500 g / mol, further preferably ≥580 g / mol and ≤1500 g / mol, and even more preferably ≥580 g / mol and ≤1400 g / mol.

[0313] According to another embodiment, the ligand L in formula (II), also referred to as L, may be selected from a group containing the following substances:

[0314] - At least three carbon atoms, or at least four carbon atoms, and / or

[0315] - at least two oxygen atoms or one oxygen atom and one nitrogen atom, two to four oxygen atoms, two to four oxygen atoms and zero to two nitrogen atoms, and / or

[0316] - At least one or more groups selected from the following: halogen, F, CN, substituted or unsubstituted C1 to C6 alkyl, substituted or unsubstituted C1 to C6 alkoxy; or two or more groups selected from the following: halogen, F, CN, substituted or unsubstituted C1 to C6 alkyl, substituted or unsubstituted C1 to C6 alkoxy; at least one or more groups selected from the following: halogen, F, CN, substituted C1 to C6 alkyl, substituted C1 to C6 alkoxy; or two or more groups selected from the following: halogen, F, CN, perfluorinated C1 to C6 alkyl, perfluorinated C1 to C6 alkoxy; or one or more groups selected from the following: substituted or unsubstituted C1 to C6 alkyl, substituted or unsubstituted C6 to C6 alkyl; 12 aryl, and / or substituted or unsubstituted C3 to C4 12 Mixed aromatics;

[0317] The substituents are selected from: D, C6 aryl, C3 to C9 heteroaryl, C1 to C6 alkyl, C1 to C6 alkoxy, C3 to C6 branched alkyl, C3 to C6 cyclic alkyl, C3 to C6 branched alkoxy, C3 to C6 cyclic alkoxy, partially or perfluorinated C1 to C6 alkyl groups. 16 Alkyl, partially or perfluorinated C1 to C2 16 Alkoxy, partially or fully deuterated C1 to C6 alkyl, partially or fully deuterated C1 to C6 alkoxy, COR 6 COOR 6 ,halogen

[0318] Elements, F, or CN;

[0319] Where R 6 Selectable from: C6 aryl, C3 to C9 heteroaryl, C1 to C6 alkyl, C1 to C6 alkoxy, C3 to C6 branched alkyl, C3 to C6 cyclic alkyl, C3 to C6 branched alkoxy, C3 to C6 cyclic alkoxy, partially or perfluorinated C1 to C 16 Alkyl, partially or perfluorinated C1 to C2 16 Alkoxy, partially or fully deuterated C1 to C6 alkyl, partially or fully deuterated C1 to C6 alkoxy.

[0320] According to another embodiment, the ligand L in formula (II) may be selected from a group comprising: at least two carbon atoms, or at least three carbon atoms, at least one oxygen atom, at least two oxygen atoms, at least one oxygen atom and / or a nitrogen atom, one nitrogen atom and at least two oxygen atoms, at least two carbon atoms and at least one oxygen atom, at least two carbon atoms and two oxygen atoms or one oxygen atom and one nitrogen atom, at least one or more groups selected from: halogen, F, CN, substituted or unsubstituted C1 to C6 alkyl, substituted or unsubstituted C1 to C6 alkoxy; Or two or more groups selected from the following: halogen, F, CN, substituted or unsubstituted C1 to C6 alkyl, substituted or unsubstituted C1 to C6 alkoxy; or at least one group selected from the following: halogen, F, CN, substituted C1 to C6 alkyl, substituted C1 to C6 alkoxy; or two or more groups selected from the following: halogen, F, CN, perfluorinated C1 to C6 alkyl, perfluorinated C1 to C6 alkoxy; or one or more groups selected from the following: substituted or unsubstituted C1 to C6 alkyl, substituted or unsubstituted C6 to C6 alkyl; or at least one group ... 12 aryl, and / or substituted or unsubstituted C3 to C4 12 Mixed aromatics;

[0321] The substituents are selected from: D, C6 aryl, C3 to C9 heteroaryl, C1 to C6 alkyl, C1 to C6 alkoxy, C3 to C6 branched alkyl, C3 to C6 cyclic alkyl, C3 to C6 branched alkoxy, C3 to C6 cyclic alkoxy, partially or perfluorinated C1 to C6 alkyl groups. 16 Alkyl, partially or perfluorinated C1 to C2 16 Alkoxy, partially or fully deuterated C1 to C6 alkyl, partially or fully deuterated C1 to C6 alkoxy, COR 6 COOR 6 ,halogen

[0322] Elements, F, or CN;

[0323] Where R 6 Selectable from: C6 aryl, C3 to C9 heteroaryl, C1 to C6 alkyl, C1 to C6 alkoxy, C3 to C6 branched alkyl, C3 to C6 cyclic alkyl, C3 to C6 branched alkoxy, C3 to C6 cyclic alkoxy, partially or perfluorinated C1 to C 16 Alkyl, partially or perfluorinated C1 to C2 16 Alkoxy, partially or fully deuterated C1 to C6 alkyl, partially or fully deuterated C1 to C6 alkoxy.

[0324] According to another embodiment, the ligand L in formula (II) may be selected from: F, CN, perfluorinated C1 to C6 alkyl, substituted or unsubstituted C1 to C6 alkyl, substituted or unsubstituted C1 to C6 alkoxy.

[0325] The substituent may be selected from: D, C6 aryl, C3 to C9 heteroaryl, C1 to C6 alkyl, C1 to C6 alkoxy, C3 to C6 branched alkyl, C3 to C6 cyclic alkyl, C3 to C6 branched alkoxy, C3 to C6 cyclic alkoxy, partially or perfluorinated C1 to C6 alkyl groups. 16 Alkyl, partially or perfluorinated C1 to C2 16 Alkoxy, partially or fully deuterated C1 to C6 alkyl, partially or fully deuterated C1 to C6 alkoxy, COR 6 COOR 6 Halogen, F, or CN

[0326] Where R 6 Selectable from: C6 aryl, C3 to C9 heteroaryl, C1 to C6 alkyl, C1 to C6 alkoxy, C3 to C6 branched alkyl, C3 to C6 cyclic alkyl, C3 to C6 branched alkoxy, C3 to C6 cyclic alkoxy, partially or perfluorinated C1 to C 16 Alkyl, partially or perfluorinated C1 to C2 16 Alkoxy, partially or fully deuterated C1 to C6 alkyl, partially or fully deuterated C1 to C6 alkoxy.

[0327] According to another embodiment, ligand L does not contain sulfur atoms.

[0328] According to another embodiment, ligand L does not contain sulfur atoms or phthalocyanine groups.

[0329] According to another embodiment, the ligand L in formula (II) can be independently selected from G1 to G64, wherein G1 to G62 are preferred:

[0330]

[0331]

[0332]

[0333]

[0334]

[0335] Preferably, L is selected from (G2) to (G59), or L is selected from (G2) to (G52).

[0336] According to another embodiment, L is selected from (G1) to (G52) and (G60) to (G64).

[0337] According to another embodiment, L is selected from (G1) to (G52) and (G60) to (G62).

[0338] The negative charge in the metal complex of formula (II) can be partially or completely delocalized on ligand L.

[0339] Metal complexes of formulas (IIa) to (IIe)

[0340] According to one embodiment, the metal complex may be selected from formulas (IIa) to (IIe), wherein formulas (IIa) to (IId) are preferred:

[0341]

[0342] in

[0343] M is a metal ion;

[0344] n is the valence of M;

[0345] A 1 and A 2 It can be independently selected from substituted or unsubstituted C1 to C1. 12 Alkyl, substituted or unsubstituted C6 to C 12 Aryl, substituted or unsubstituted C3 to C 12 Mixed aromatics;

[0346] A 3 Selected from H, D, substituted or unsubstituted C1 to C2 12 Alkyl, substituted or unsubstituted C6 to C 12 Aryl, substituted or unsubstituted C3 to C 12 Mixed aromatics;

[0347] in

[0348] A 1 and A 2 and / or A 3 The substituents may be independently selected from: D, C6 aryl, C3 to C9 heteroaryl, C1 to C6 alkyl, C1 to C6 alkoxy, C3 to C6 branched alkyl, C3 to C6 cyclic alkyl, C3 to C6 branched alkoxy, C3 to C6 cyclic alkoxy, partially or perfluorinated C1 to C6 alkyl groups. 16 Alkyl, partially or perfluorinated C1 to C2 16 Alkoxy, partially or fully deuterated C1 to C6 alkyl, partially or fully deuterated C1 to C6 alkoxy, COR 1 COOR 1 halogen, F, or CN, where

[0349] R 1Selectable from: C6 aryl, C3 to C9 heteroaryl, C1 to C6 alkyl, C1 to C6 alkoxy, C3 to C6 branched alkyl, C3 to C6 cyclic alkyl, C3 to C6 branched alkoxy, C3 to C6 cyclic alkoxy, partially or perfluorinated C1 to C 16 Alkyl, partially or perfluorinated C1 to C2 16 Alkoxy, partially or fully deuterated C1 to C6 alkyl, partially or fully deuterated C1 to C6 alkoxy.

[0350] The negative charge in the metal complexes of formulas (IIa), (IIb), (IIc) and / or (IId) can be present in carbon atoms and heteroatoms as well as A atoms. 1 and / or A 2 and / or A 3 The upper part or the entire domain is off-domain.

[0351] According to one implementation, A 1 and A 2 and / or A 3 At least one of them may contain a substituent, wherein A 1 and A 2 and / or A 3 At least one of the substituents may be independently selected from: C3 to C9 heteroaryl, C1 to C6 alkoxy, C3 to C6 branched alkoxy, C3 to C6 cyclic alkoxy, partially or perfluorinated C1 to C 16 Alkyl, partially or perfluorinated C1 to C2 16 Alkoxy groups, partially or fully deuterated C1 to C6 alkoxy groups, COR 1 COOR 1 Halogen, F, or CN; preferably A 1 and A 2 and / or A 3 At least one of them contains at least two substituents, wherein A 1 and A 2 and / or A 3 The substituents on the [structure] may be independently selected from: C3 to C9 heteroaryl, C1 to C6 alkoxy, C3 to C6 branched alkoxy, C3 to C6 cyclic alkoxy, partially or perfluorinated C1 to C [structure]. 16 Alkyl, partially or perfluorinated C1 to C2 16 Alkoxy groups, partially or fully deuterated C1 to C6 alkoxy groups, COR 1 COOR 1 Halogen, F, or CN; A is further preferred. 1 and A 2 and / or A 3It may contain at least one substituent independently selected from: halogen, F, CF3, C2F5, C3F7, C4F9, OCF3, OC2F5, or CN; more preferably A. 1 and A 2 It may contain at least two independent substituents selected from the following: halogen, F, CF3, C2F5, C3F7, C4F9, OCF3, OC2F5 or CN.

[0352] According to one embodiment of the present invention, A 1 and A 2 and / or A 3 It can be independently selected from: CF3, C2F5, C3F7, C4F9, C5F 11 C6F 13 And / or phenyl groups substituted with two to five independently selected groups chosen from F or CF3, or C2F5, C3F7, C4F9, C5F 11 C6F 13 And / or phenyl groups substituted with two to five independently selected groups chosen from F or CF3, or CF3, C2F5, C3F7, C4F9, C5F 11 C6F 13 Or a phenyl group substituted with zero to two CF3 groups and / or zero to five F atoms.

[0353] According to one embodiment of the present invention, the metal complex may be selected from...

[0354] - Formula (IIa), wherein M is selected from alkali metals, alkaline earth metals, transition metals, or rare earth metals; and / or

[0355] - Formula (IIb), wherein M is selected from alkali metals, alkaline earth metals, transition metals, or rare earth metals; and / or

[0356] - Formula (IIc), where M is selected from alkali metals, alkaline earth metals or main group metals.

[0357] According to one embodiment of the present invention, the metal complex may be selected from...

[0358] - Formula (IIa), wherein M is selected from alkali metals, alkaline earth metals, transition metals, or rare earth metals; and / or

[0359] - Formula (IIb), wherein M is selected from alkali metals, alkaline earth metals, transition metals, or rare earth metals; and / or

[0360] - Formula (IId), where M is selected from alkali metals, alkaline earth metals, transition metals or rare earth metals;

[0361] and / or

[0362] - Formula (IIe), where M is selected from alkali metals, alkaline earth metals, transition metals or rare earth metals.

[0363] According to one embodiment of the present invention, the metal complex may be selected from formula (IIa) or (IIb).

[0364] Wherein M is selected from metal ions, wherein the electronegativity of the corresponding metal according to Allen is less than 2.4, preferably M is selected from alkali metals, alkaline earth metals, rare earth metals or transition metals, further preferably M is selected from metals with an atomic mass ≥ 24 Da, even more preferably M is selected from metals with an atomic mass ≥ 24 Da and the oxidation number of M is ≥ 2; and / or formula (IIc), wherein M is selected from Bi.

[0365] The following metal complexes are particularly preferred:

[0366] LiTFSI

[0367] K TFSI

[0368] Cs TFSI

[0369] Ag TFSI

[0370] Mg(TFSI)2

[0371] Mn(TFSI)2

[0372] Sc(TFSI)3

[0373] Mg[N(SO2 i C3F7)2]2

[0374] Zn[N(SO2 i C3F7)2]2

[0375] Ag[N(SO2 i C3F7)2]

[0376] Ag[N(SO2C3F7)2]

[0377] Ag[N(SO2C4F9)2]

[0378] Ag[N(SO2CF3)(SO2C4F9)]

[0379] Cu[N(SO2 i C3F7)2]2

[0380] Cu[N(SO2C3F7)2]2

[0381] Cu[N(SO2CF3)(SO2C4F9)]2

[0382] Mg[N(SO2CF3)(SO2C4F9)]2

[0383] Mn[N(SO2CF3)(SO2C4F9)]2

[0384] Cu[N(SO2CH3)(SO2C4F9)]2

[0385] Ag[N(SO2CH3)(SO2C4F9)]

[0386]

[0387]

[0388]

[0389] According to one embodiment, the metal complex may be free of bis(trifluoromethane)sulfonylimide (TFSI). Therefore, the metal complex is particularly suitable for the large-scale production of organic electronic devices.

[0390] Hole injection layer

[0391] According to another embodiment, the hole injection layer may comprise a hole transport compound and a metal complex:

[0392] -The hole transport compound described herein has formula (I):

[0393] (Ar 1 ) k —(Ar 2 ) m —Ar 3 —(Ar 4 ) p —(Ar 5 ) q —(Ar 6 ) r (I),

[0394] in

[0395] k, m, q, and r can be independently selected from 0, 1, or 2.

[0396] p is 1, 2, or 3.

[0397] Where 2≤k+m+q+r+p≤11,

[0398] Ar 1 To Ar 6 It can be independently selected from: substituted or unsubstituted unsaturated 5- to 7-membered heterocycles, substituted or unsubstituted C6 to C6 rings. 30 Aryl, substituted or unsubstituted C3 to C430 The rings are selected from: (i) heterocyclic rings with unsaturated 5 to 7-membered rings, (ii) aromatic heterocyclic rings with 5 to 6 members, (iii) non-heterocyclic rings with unsaturated 5 to 7-membered rings, and (iv) aromatic non-heterocyclic rings with 6-membered rings.

[0399] Ar when k=1 2 Ar 3 Ar when q=1 4 Ar when r=1 5 Can be selected independently from:

[0400] Substituted or unsubstituted unsaturated 5- to 7-membered heterocycles, substituted or unsubstituted C6 to C6 rings. 30 Aranediol, substituted or unsubstituted C3 to C4 30 Heteroarylene groups, substituted or unsubstituted biphenylidene, 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 biphenylidene, substituted or unsubstituted tetraphenyl, substituted or unsubstituted benzo[b,f]anthracene, substituted or unsubstituted dibenzofuran, substituted or unsubstituted dibenzothiophene, substituted or unsubstituted xanthones, substituted or unsubstituted carbazole, substituted or unsubstituted azaheptanyl, substituted or unsubstituted dibenzo[b,f] Azaheptanyl, 9,9'-spirobis[fluorene], substituted or unsubstituted spiro[fluorene-9,9'-xanton], substituted or unsubstituted 9,14-dihydrodibenzo[2,3:6,7]zaheptanyl[4,5-b]indole, or a substituted or unsubstituted aromatic fused ring system comprising at least three, preferably three to six, substituted or unsubstituted aromatic rings selected from: substituted or unsubstituted non-heterocyclic rings, substituted or unsubstituted heterocyclic 5-membered rings, substituted or unsubstituted 6-membered rings and / or substituted or unsubstituted 7-membered rings;

[0401] Ar when k=0 2 Ar when m=0 and k=0 3 Ar when q and r = 0 4 Ar when r=0 5 Can be selected independently from:

[0402] Substituted or unsubstituted unsaturated 5- to 7-membered heterocycles, substituted or unsubstituted C6 to C6 rings. 30 Aryl, substituted or unsubstituted C3 to C4 30Heteroaryl, substituted or unsubstituted biphenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthrayl, substituted or unsubstituted phenanthyl, substituted or unsubstituted pyrene, substituted or unsubstituted peryl, substituted or unsubstituted triphenylimide, substituted or unsubstituted tetraphenyl, substituted or unsubstituted benzoanthrayl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophene, substituted or unsubstituted xanthonyl, substituted or unsubstituted carbazole, substituted or unsubstituted azaheptanyl, substituted or unsubstituted diphenyl Benzo[b,f]azacycloheptanyl, 9,9'-spirobis[fluorenyl], substituted or unsubstituted spiro[fluorenyl-9,9'-xanton], substituted or unsubstituted 9,14-dihydrodibenzo[2,3:6,7]azacycloheptanyl[4,5-b]indole, or a substituted or unsubstituted aromatic fused ring system comprising at least three, preferably three to six, substituted or unsubstituted aromatic rings selected from substituted or unsubstituted non-heterocyclic rings, substituted or unsubstituted heterocyclic 5-membered rings, substituted or unsubstituted 6-membered rings and / or substituted or unsubstituted 7-membered rings;

[0403] The substituents are selected from: H, D, C1 to C 12 Alkyl, unsubstituted C6 to C6 18 aryl, or unsubstituted C3 to C 18 Mixed aromatics;

[0404] -The metal complex described therein has formula (II):

[0405]

[0406] in

[0407] M is a metal ion.

[0408] n is the valence of M, where n is an integer from 1 to 4.

[0409] L is a ligand containing at least two carbon atoms.

[0410] Preferably, the hole injection layer is free of ionic liquids, metal phthalocyanines, CuPc, HAT-CN, pyrazino[2,3-f][1,10]phenanthroline-2,3-dicarboxynitrile, F4TCNQ, metal fluorides, and / or metal oxides, wherein the metal in the metal oxide is selected from Re and / or Mo. Thus, the hole injection layer can be deposited under conditions suitable for large-scale production.

[0411] Organic electronic devices

[0412] According to one embodiment, the hole injection layer is arranged to be in direct contact with the anode layer.

[0413] According to one embodiment, the organic electronic device may further include at least one photoactive layer disposed between the hole injection layer and the cathode layer.

[0414] According to one embodiment, the organic electronic device may further include at least one photoactive layer disposed between the hole injection layer and the cathode layer and the hole injection layer being arranged to be in direct contact with the anode layer.

[0415] According to one embodiment, the organic electronic device may include at least one photoactive layer, which may be a light-emitting layer.

[0416] According to one embodiment, the organic electronic device may include a hole injection layer, wherein the hole injection layer comprises a first sublayer containing a metal complex of formula (II) and a second sublayer containing the hole transport compound or the hole transport compound of formula (I), wherein the first sublayer may be arranged closer to the anode layer and the second sublayer is arranged closer to the cathode layer.

[0417] According to one embodiment, the organic electronic device may include a hole injection layer comprising a first sublayer consisting of a metal complex of formula (II) and a second sublayer containing the hole transport compound or a hole transport compound according to formula (I), wherein the first sublayer is arranged closer to the anode layer and the second sublayer is arranged closer to the cathode layer.

[0418] In the context of this specification, the term "consistently composed of" specifically refers to and / or includes concentrations of ≥90% (vol / vol), more preferably ≥95% (vol / vol), and most preferably ≥99% (vol / vol).

[0419] According to one embodiment of the present invention, the organic electronic device may include a hole injection layer comprising a first sublayer composed of a metal complex of formula (II) and a second sublayer containing the hole transport compound or a hole transport compound according to formula (I), wherein the first sublayer is arranged closer to the anode layer and the second sublayer is arranged closer to the cathode layer, wherein in formula (II), M is selected from Li, Na, K, Cs, Mg, Mn, Cu, Zn, Ag, Bi and Mo, or Mg, Mn, Cu, Zn, Ag, Bi and Mo, or Cu, Zn, Ag or Bi.

[0420] According to one embodiment, the organic electronic device may include a hole injection layer comprising a first sublayer containing a metal complex of formula (II) and a second sublayer containing the hole transport compound or the hole transport compound of formula (I) and the metal complex, wherein the first sublayer is arranged closer to the anode layer and the second sublayer is arranged closer to the cathode layer.

[0421] According to one embodiment, the organic electronic device may include a hole injection layer comprising a first sublayer containing a metal complex of formula (II) and a second sublayer containing the hole transport compound or a hole transport compound of formula (I) and a metal complex of formula (II), wherein the first sublayer is arranged closer to the anode layer and the second sublayer is arranged closer to the cathode layer.

[0422] According to 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, and preferably a light-emitting device and / or a display device.

[0423] Hole-injected layers (HILs) can be formed on the anolyte layer via vacuum deposition, spin coating, printing, casting, slot die coating, Langmuir-Blodgett (LB) deposition, and other methods. When using vacuum deposition to form HILs, the deposition conditions can vary depending on the hole transport compound used to form the HIL and the desired HIL structure and thermal properties. However, generally, vacuum deposition conditions can include deposition temperatures ranging from 100°C to 350°C and pressures of 10... -8 Up to 10 -3 Torr (1 Torr equals 133.322 Pa) and deposition rates of 0.1 to 10 nm / s.

[0424] When spin coating or printing is used to form HILs, the coating conditions can vary depending on the compound used to form the HIL and the desired HIL structure and thermal properties. For example, coating conditions may include a coating speed of about 2000 rpm to about 5000 rpm and a heat treatment temperature of about 80°C to about 200°C. The heat treatment removes the solvent after coating.

[0425] HIL can be formed from any hole transport compound of formula (I) and metal complexes of formulas (II), (IIa), (IIb), (IIc), (IId) and (IIe), and preferably (II), (IIa) to (IId).

[0426] The thickness of HIL can range from about 1 nm to about 15 nm, for example from about 1 nm to about 25 nm, or from about 3 nm to about 10 nm.

[0427] When the thickness of HIL is within this range, HIL can have excellent hole injection characteristics without substantially damaging the driving voltage.

[0428] According to one embodiment of the present invention, the hole injection layer may include:

[0429] - 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), and

[0430] - 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 metal complexes of formulas (II), (IIa), (IIb), (IIc), (IId) and (IIe), and preferably (II), (IIa) to (IId); preferably the weight % of the metal complexes of formulas (II), (IIa), (IIb), (IIc), (IId) and (IIe), and preferably (II), (IIa) to (IId) is less than the weight % of the hole transport compound or the hole transport compound according to formula (I); wherein the weight % of the components is based on the total weight of the hole injection layer.

[0431] According to one embodiment of the present invention, the hole injection layer may include:

[0432] - At least about ≥5 vol% to about ≤90 vol%, preferably about ≥30 vol% to about ≤80 vol%, more preferably about ≥40 vol% to about ≤80 vol%, and even more preferably about ≥50 vol% to about ≤80 vol% of a hole transport compound or a hole transport compound of formula (I), and

[0433] - At least about ≥10 vol% to about ≤95 vol%, preferably about ≥20 vol% to about ≤70 vol%, more preferably about ≥20 vol% to about ≤60 vol%, and even more preferably about ≥20 vol% to about ≤50 vol% of metal complexes of formulas (II), (IIa), (IIb), (IIc), (IId) and (IIe), and preferably (II), (IIa) to (IId); preferably the volume % of the metal complexes of formulas (II), (IIa), (IIb), (IIc), (IId) and (IIe), and preferably (II), (IIa) to (IId) is less than the volume % of the hole transport compound or the hole transport compound according to formula (I); wherein the weight % of the component is based on the total weight of the hole injection layer.

[0434] Other layers

[0435] According to the present invention, in addition to the layers already mentioned above, the organic electronic device may also include other layers. Exemplary embodiments of each layer are described below:

[0436] base

[0437] The substrate can be any substrate commonly used in the manufacture of electronic devices, such as organic light-emitting diodes (OLEDs). If light is to be emitted through the substrate, the substrate should be a transparent or translucent material, such as a glass substrate or a transparent plastic substrate. If light is to be emitted through the top surface, the substrate can be a transparent or opaque material, such as a glass substrate, a plastic substrate, a metal substrate, or a silicon substrate.

[0438] Anode layer

[0439] The anode layer can be formed by deposition or sputtering of the material used to form the anode layer. The material used to form the anode layer can be a high work function material to facilitate hole injection. The anode material can also be selected from low work function materials (i.e., aluminum). The anode layer can be a transparent or reflective electrode. Transparent conductive oxides, such as indium tin oxide (ITO), indium zinc oxide (IZO), tin dioxide (SnO2), aluminum zinc oxide (AlZO), and zinc oxide (ZnO), can be used to form the anode layer. Metals, typically silver (Ag), gold (Au), or metal alloys, can also be used to form the anode layer.

[0440] Hole transport layer

[0441] According to one embodiment, the organic electronic device may further include a hole transport layer, wherein the hole transport layer may be disposed between the hole injection layer and the cathode layer, and optionally the 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.

[0442] According to one embodiment, the organic electronic device may include a hole transport layer, wherein the hole transport layer contains a hole transport compound according to the invention or a hole transport compound of formula (I), preferably the hole transport compound or the hole transport compound of formula (I) in the hole injection layer and the hole transport layer may be the same.

[0443] According to another embodiment, the organic electronic device may include a hole transport layer, wherein the hole transport layer may include the hole transport compound or the hole transport compound of formula (I); wherein the hole transport compound or the hole transport compound of formula (I) is selected in both the hole injection layer and the hole transport layer.

[0444] According to one embodiment, the hole transport layer may contain the hole transport compound or the hole transport compound of formula (I); wherein the hole transport compound or the hole transport compound of formula (I) is selected in both the hole injection layer and the hole transport layer, and the hole transport compound or the hole transport compound of formula (I) may not contain heteroatoms that are not part of an aromatic ring and / or an unsaturated 7-membered ring, preferably the hole transport compound or the hole transport compound of formula (I) may not contain N atoms except for N atoms that are part of an aromatic ring or an unsaturated 7-membered ring.

[0445] According to one embodiment, the hole transport layer may comprise the hole transport compound or the hole transport compound of formula (I); wherein the hole transport compound or the hole transport compound of formula (I) is selected in both the hole injection layer and the hole transport layer, 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.

[0446] According to one embodiment, the hole transport layer may comprise the hole transport compound or the hole transport compound of formula (I); wherein the hole transport compound or the hole transport compound of formula (I) is selected in both the hole injection layer and the hole transport layer, 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.

[0447] According to one embodiment, the hole transport layer may comprise the hole transport compound or the hole transport compound of formula (I); wherein the selection of the hole transport compound or the hole transport compound of formula (I) is the same in the hole injection layer and in the hole transport layer, and wherein for the hole transport compound according to formula (I):

[0448] -Ar 3 Options are available from D1 to D15, with D1 to D6 being preferred:

[0449]

[0450] According to one implementation, Ar 1 Selectable from D7 to D13. Ar 2 You can choose from D1 to D6, or D7 to D13. Ar 4 You can choose from D1 to D6, or D7 to D13. Ar 5 You can choose from D1 to D6, or D7 to D13. Ar 6 Selectable from D7 to D13.

[0451] According to one embodiment, the hole transport layer may comprise the hole transport compound or the hole transport compound of formula (I); wherein the selection of the hole transport compound or the hole transport compound of formula (I) is the same in the hole injection layer and in the hole transport layer, and wherein for the hole transport compound according to formula (I):

[0452] Ar 3 Options are available from D1 to D15, with D1 to D6 being preferred:

[0453]

[0454] If m>0 and k>0, then Ar 1 Ar can be selected from D7 to D15, or if k > 0 and m = 0, then Ar 1 The options are from D7 to D15, or if k > 1, then Ar. 1 Selectable from D1 to D6;

[0455] If m>0 and k>0, then Ar 2 The options are from D1 to D6; or if m > 0 and k = 0, then Ar 2 Selectable from D7 to D15;

[0456] If q > 0, then Ar 4 Ar can be selected from D1 to D6, or if q = 0 and r > 0, then Ar 4 The options are from D1 to D6; or if q and r = 0, then Ar 4 Selectable from D7 to D15;

[0457] If q > 0 and r > 0, then Ar 5 Ar can be selected from D1 to D6, or if q>0 and r=0, then Ar 5 Selectable from D7 to D15;

[0458] If r>0, q>0, then Ar 6 The options are from D7 to D15, or if r > 0 and q = 0, then Ar 6 The options are from D7 to D15, or if r > 1, then Ar. 6 You can choose from D1 to D6.

[0459] According to one embodiment, the hole transport layer may comprise the hole transport compound or the hole transport compound of formula (I); wherein the hole transport compound or the hole transport compound of formula (I) is selected in both the hole injection layer and the hole transport layer, and wherein the hole transport compound or the hole transport compound of formula (I) may be selected from F1 to F13:

[0460]

[0461]

[0462] 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, such as Merck or Lumtec.

[0463] The hole transport layer may not contain: N,N'-bis(naphthyl-1-yl)-N,N'-bis(phenyl)-9,9-dimethylfluorene, N,N'-bis(3-methylphenyl)-N,N'-bis(phenyl)-9,9-dimethylfluorene, N,N'-bis(naphthyl-1-yl)-N,N'-bis(phenyl)-9,9-dimethylfluorene, N,N'-bis(naphthyl-1-yl)-N,N'-bis(phenyl)-2,2-dimethylbenzidine, N,N'-bis(3-methylphenyl)-N,N'-bis(phenyl)-9,9-spirodifluorene, 2,2',7,7'-tetra(N,N-diphenylamino)-9,9'-spirodifluorene, N,N'-bis(naphthyl-1-yl)-N,N'-bis(phenyl)-9,9 ...dimethylfluorene, N,N'-bis(naphthyl-1-yl)-N,N'-bis(phenyl)-9,9-dimethylfluorene, N,N'-bis(naphthyl-1-yl)-N,N'-bis(phenyl)-9,9-dimethylfluorene, N,N'-bis(naphthyl-1-yl)-N,N'-bis(phenyl)-9,9-dimethylfluorene, N,N'-bis(naphthyl-1-yl)-N,N'-bis(phenyl)-9,9-dimethylfluorene, N,N' -N,N'-bis(phenyl)-benzidine, N,N'-bis(naphthyl-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-dimethylfluorene, N,N'-bis(naphthyl-1-yl)-N,N'-bis(phenyl)-9,9-spirodifluorene, di-[4-(N,N-dimethylamino)-phenyl]cyclohexane, 2,2',7,7'-tetra(N,N-dimethylamino)spirodifluorene, 9,9-bis[4-(N,N-bis-biphenyl-4-yl-amino)phenyl]-9 H-fluorene, 2,2',7,7'-tetratetra(N,N-naphthyl(phenyl)-amino]-9,9'-spirodifluorene, 2,7-bis(N,N-bis(9,9-spirodifluorene-2-yl)-amino]-9,9'-spirodifluorene, 2,2'-bis(N,N-bis(biphenyl-4-yl)amino]-9,9'-spirodifluorene, N,N'-bis(phenanthrene-9-yl)-N,N'-bis(phenyl)benzidine, N,N,N',N'-tetratetra(naphthyl-2-yl)benzidine, 2,2'-bis(N,N-di-phenyl-amino)-9,9-spirodifluorene, 9,9-bis[4-(N,N-bis-naphthyl-2-yl-amino)phenyl]-9H-fluorene, 9,9-bis [4-(N,N'-bis-naphthyl-2-yl-N,N'-bis-phenyl-amino)-phenyl]-9H-fluorene, titanium phthalocyanine oxide, copper phthalocyanine, 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinone dimethyl ether, 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, 4,4',4”-tris(N,N-diphenyl-amino)triphenylamine, pyrazino[2,3-f][1,10]phenanthroline-2,3-dicarboxynitrile, N,N,N',N'-Tetra(4-methoxyphenyl)benzidine, HTM014, HTM081, HTM163, HTM222, EL-301, HTM226, HTM355, HTM133, HTM334, HTM604, and EL-22T. The abbreviations indicate the manufacturer's name, such as Merck or Lumtec.

[0464] 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 the HTL is formed by vacuum deposition or spin coating, the deposition and coating conditions can be similar to those for forming the HIL. However, the conditions for vacuum or solution deposition can vary depending on the compound used to form the HTL.

[0465] The thickness of the HTL can be in the range of about 5nm to about 250nm, preferably about 10nm to about 200nm, more preferably about 20nm to about 190nm, more preferably about 40nm to about 180nm, more preferably about 60nm to about 170nm, more preferably about 80nm to about 200nm, more preferably about 100nm to about 180nm, and more preferably about 120nm to about 170nm.

[0466] When the thickness of the HTL is within this range, the HTL can have excellent hole transport characteristics without substantially damaging the driving voltage.

[0467] Electron blocking layer

[0468] The function of an electron blocking layer (EBL) is to prevent electrons from transferring from the light-emitting layer to the hole transport layer, thereby confining electrons within the light-emitting layer. This improves efficiency, operating voltage, and / or lifetime. Typically, the electron blocking layer contains a triarylamine compound.

[0469] If the triplet energy level of the electron blocking layer is high, it can also be called a triplet control layer.

[0470] If a phosphorescent green or blue emitting layer is used, the function of the triplet control layer is to reduce triplet quenching. This allows for higher luminous efficiency of the phosphorescent emitting layer. The triplet control layer can be selected from triarylamine compounds whose triplet energy levels are higher than those of the phosphorescent emitters in adjacent emitting layers.

[0471] The thickness of the electron blocking layer can be selected between 2 and 20 nm.

[0472] Photoactive Alpha Layer (PAL)

[0473] The photoactive layer converts electric current into photons or photons into electric current.

[0474] PAL can be formed on HTL by vacuum deposition, spin coating, slot die coating, printing, casting, LB deposition, etc. When PAL is formed using vacuum deposition or spin coating, the deposition and coating conditions can be similar to those for HIL formation. However, the deposition and coating conditions can vary depending on the compound used to form PAL.

[0475] It can be specified that the photoactive layer does not contain the compound of formula (I).

[0476] The photoactive layer can be a light-emitting layer or a light-absorbing layer.

[0477] Emissive Layer (EML)

[0478] EML can be formed on HTL or EBL by vacuum deposition, spin coating, slot die coating, printing, casting, LB deposition, etc. When forming EML using vacuum deposition or spin coating, the deposition and coating conditions can be similar to those for forming HIL. However, the deposition and coating conditions can vary depending on the compound used to form the EML.

[0479] It can be specified that the luminescent layer does not contain the compound of formula (I).

[0480] The luminescent layer (EML) can be formed by a combination of a host and a luminescent dopant. Examples of hosts are: Alq3,4,4'-N,N'-dicarbazole biphenyl (HTC-10), poly(n-vinylcarbazole) (PVK), 9,10-bis(naphthyl-2-yl)anthracene (ADN), 4,4',4”-tris(carbazole-9-yl)triphenylamine (TCTA), 1,3,5-tris(N-phenylbenzimidazol-2-yl)benzene (TPBI), 3-tert-butyl-9,10-bis-2-naphthylanthracene (TBADN), stilbene aryl (DSA), and bis(2-(2-hydroxyphenyl)benzothiazole)zinc (Zn(BTZ)2).

[0481] The luminescent dopant can be a phosphorescent or fluorescent luminescent material. Phosphorescent luminescent materials and those emitting light via thermally activated delayed fluorescence (TADF) are preferred due to their high efficiency. The luminescent material can be a small molecule or a polymer.

[0482] Examples of red-emitting dopants include PtOEP, Ir(piq)3, and Btp2lr(acac), but are not limited to these. These compounds are phosphorescent; however, fluorescent red-emitting dopants can also be used.

[0483] Examples of phosphorescent green luminescent dopants are Ir(ppy)3 (ppy = phenylpyridine), Ir(ppy)2 (acac), and Ir(mpyp)3.

[0484] Examples of phosphorescent blue emitting electron dopants are F₂Irpic, (F₂ppy)₂Ir(tmd), Ir(dfppz)₃, and terfluorene. Examples of fluorescent blue emitting electron dopants are 4,4'-bis(4-diphenylaminostyryl)biphenyl (DPAVBi) and 2,5,8,11-tetratert-butylperylene (TBPe).

[0485] Based on 100 parts by weight of the host, the amount of luminescent dopant can range from about 0.01 to about 50 parts by weight. Alternatively, the luminescent layer can be composed of a luminescent polymer. The thickness of the EML can be from about 10 nm to about 100 nm, for example, from about 20 nm to about 60 nm. When the thickness of the EML is within this range, the EML can exhibit excellent luminescence without substantially impairing the driving voltage.

[0486] Hole blocking layer (HBL)

[0487] Hole blocking layers (HBLs) can be formed on EMLs using methods such as vacuum deposition, spin coating, slot die coating, printing, casting, and LB deposition to prevent holes from diffusing into ETLs. When the EML contains phosphorescent dopants, the HBL can also have triplet exciton blocking functionality.

[0488] HBL can also be called auxiliary ETL or a-ETL.

[0489] When forming HBLs using vacuum deposition or spin coating, the deposition and coating conditions can be similar to those for forming HILs. However, the deposition and coating conditions can vary depending on the compound used to form the HBL. Generally, any compound used to form HBLs can be used. Examples of compounds used to form HBLs include... Diazole derivatives, triazole derivatives, phenanthrene-rhein derivatives, and triazine derivatives.

[0490] The thickness of the HBL can range from about 5 nm to about 100 nm, for example, from about 10 nm to about 30 nm. When the thickness of the HBL is within this range, the HBL can have excellent hole blocking properties without substantially impairing the driving voltage.

[0491] Electron Transport Layer (ETL)

[0492] The organic electronic device according to the present invention may further include an electron transport layer (ETL).

[0493] According to another embodiment of the invention, the electron transport layer may further comprise an azazine compound, preferably a triazine compound.

[0494] In one embodiment, the electron transport layer may further comprise a dopant selected from alkali metal organic complexes, preferably LiQ.

[0495] The thickness of the ETL can range from about 15 nm to about 50 nm, for example, from about 20 nm to about 40 nm. When the thickness of the ETL is within this range, the ETL can have satisfactory electron injection properties without substantially impairing the driving voltage.

[0496] According to another embodiment of the present invention, the organic electronic device may further include a hole-blocking layer and an electron transport layer, wherein the hole-blocking layer and the electron transport layer comprise an azazine compound. Preferably, the azazine compound is a triazine compound.

[0497] Electron Injection Layer (EIL)

[0498] Optional electron transport layers (EILs) that facilitate electron injection from the cathode can be formed on the electron transport layer (ETL), preferably directly on it. Examples of materials for forming EILs include lithium 8-hydroxyquinoline (LiQ), LiF, NaCl, CsF, Li₂O, BaO, Ca, Ba, Yb, and Mg, which are known in the art. The deposition and coating conditions for forming EILs are similar to those for forming HILs, but the deposition and coating conditions may vary depending on the material used to form the EIL.

[0499] The thickness of the EIL can range from about 0.1 nm to about 10 nm, for example, from about 0.5 nm to about 9 nm. When the thickness of the EIL is within this range, the EIL can have satisfactory electron injection properties without substantially impairing the driving voltage.

[0500] cathode layer

[0501] The cathode layer is formed on an ETL or optionally an EIL. The cathode layer can be formed of a metal, alloy, 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 such as ITO or IZO.

[0502] The thickness of the cathode layer can range from about 5 nm to about 1000 nm, for example, from about 10 nm to about 100 nm. When the thickness of the cathode layer is in the range of about 5 nm to about 50 nm, the cathode layer may be transparent or translucent, even if it is formed of metal or metal alloy.

[0503] It should be understood that the cathode layer is not part of the electron injection layer or the electron transport layer.

[0504] Organic light-emitting diode (OLED)

[0505] The organic electronic device according to the present invention can be an organic light-emitting device.

[0506] According to one aspect of the present invention, an organic light-emitting diode (OLED) is provided, comprising: a substrate; an anode layer formed on the substrate; a 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; a light-emitting layer; an electron transport layer; and a cathode layer.

[0507] According to another aspect of the present invention, an OLED is provided, comprising: a substrate; an anode layer formed on the substrate, a hole injection layer comprising first and second sublayers, a hole transport layer, a light-emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, and a cathode layer.

[0508] The first sub-layer is arranged adjacent to the anode layer and the second sub-layer is arranged adjacent to the hole transport layer.

[0509] The first sublayer comprises a metal complex of formula (II) or is composed of a metal complex of formula (II), and the second sublayer comprises a hole transport compound or a hole transport compound of formula (I) or is composed of a hole transport compound of formula (I).

[0510] According to another aspect of the present invention, an OLED is provided, 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 electron blocking layer; a light-emitting layer; a hole blocking layer; an electron transport layer; and a cathode layer.

[0511] According to another aspect of the present invention, an OLED is provided, comprising: a substrate; an anode layer formed on the substrate, including a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, and a cathode layer, comprising first and second sublayers of the present invention.

[0512] The first sub-layer is arranged adjacent to the anode layer and the second sub-layer is arranged adjacent to the hole transport layer.

[0513] The first sublayer comprises a metal complex of formula (II) or is composed of a metal complex of formula (II), and the second sublayer comprises a hole transport compound or a hole transport compound of formula (I) or is composed of a hole transport compound of formula (I).

[0514] According to another aspect of the present invention, an OLED is provided, 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 electron blocking layer; a light-emitting layer; a hole blocking layer; an electron transport layer; an electron injection layer; and a cathode layer.

[0515] According to another aspect of the present invention, an OLED is provided, comprising: a substrate; an anode layer formed on the substrate, including a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, and a cathode layer, comprising first and second sublayers of the present invention.

[0516] The first sub-layer is arranged adjacent to the anode layer and the second sub-layer is arranged adjacent to the hole transport layer.

[0517] The first sublayer comprises a metal complex of formula (II) or is composed of a metal complex of formula (II), and the second sublayer comprises a hole transport compound or a hole transport compound of formula (I) or is composed of a hole transport compound of formula (I).

[0518] According to various embodiments of the present invention, OLED layers can be provided arranged between the aforementioned layers, on a substrate, or on a top electrode.

[0519] For example, according to Figure 2 The OLED can be formed by the following method, wherein on a substrate (110), an anode layer (120), a hole injection layer (130) containing 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), a light-emitting layer (150), a hole blocking layer (155), an electron transport layer (160), an electron injection layer (180), and a cathode layer (190) are successively formed.

[0520] Manufacturing method

[0521] According to another aspect of the present invention, a method for manufacturing an organic electronic device, the method using:

[0522] - At least one sedimentary source, preferably two sedimentary sources, more preferably at least three sedimentary sources.

[0523] Suitable deposition methods include:

[0524] - Deposition is performed via vacuum thermal evaporation;

[0525] - Deposition is performed via solution processing, preferably spin coating, printing, casting; and / or

[0526] - Slit-type die coating.

[0527] According to various embodiments of the present invention, a method is provided, the method using:

[0528] - The first deposition source releases a hole transport compound according to formula (I) of the invention, and

[0529] - The second sedimentary source releases metal complexes of type (II).

[0530] The method includes the step of forming a hole injection layer; thus, for organic light-emitting diodes (OLEDs):

[0531] - The hole injection layer is formed by releasing a hole transport compound of formula (I) according to the invention from the first deposition source and a metal complex of formula (II) from the second deposition source.

[0532] According to various embodiments of the present invention, the method may further include forming at least one layer selected from the following on the hole injection layer: forming a hole transport layer, forming a hole blocking layer, forming a light-emitting layer, forming a hole blocking layer, forming an electron transport layer, and / or forming an electron injection layer, and / or forming a cathode layer.

[0533] According to various embodiments of the present invention, the method may further include the step of forming an organic light-emitting diode (OLED), wherein

[0534] - Form an anode layer on the substrate.

[0535] - A hole injection layer is formed on the anode layer, the hole injection layer comprising a hole transport compound of formula (I) and a metal complex of formula (II).

[0536] - A hole transport layer is formed on the hole injection layer, the hole injection layer comprising a hole transport compound of formula (I) and a metal complex of formula (II).

[0537] - A light-emitting layer is formed on the hole transport layer.

[0538] - An electron transport layer is formed on the light-emitting layer, and optionally a hole blocking layer is formed on the light-emitting layer.

[0539] -and finally, the cathode layer is formed.

[0540] -Optionally, a hole blocking layer is formed sequentially between the hole injection layer and the light-emitting layer.

[0541] -Optionally, an electron injection layer is formed between the electron transport layer and the cathode layer.

[0542] According to various embodiments, the OLED may have the following layer structure, wherein the layers have the following order:

[0543] An anode layer comprising a hole-transporting compound or a hole-transporting compound of formula (I) and a metal complex of formula (II), a hole-transporting layer, an optional electron-blocking layer, a light-emitting layer, an optional hole-blocking layer, an electron-transporting layer, an optional electron-injecting layer, and a cathode layer.

[0544] According to one embodiment, the organic electronic device of the present invention is formed by vacuum deposition of the hole injection layer and the cathode layer.

[0545] According to another aspect of the present invention, an electronic device is provided that includes at least one organic light-emitting device according to any embodiment described throughout this application, preferably, the electronic device includes an organic light-emitting diode as described in one of the embodiments described throughout this application. More preferably, the electronic device is a display device.

[0546] The embodiments described below will be described in more detail with reference to examples. However, this disclosure is not limited to the following embodiments. Exemplary aspects will now be referred to in detail. Attached Figure Description

[0547] The aforementioned components in the described embodiments, as well as the claimed components and components used according to the invention, are not subject to any special exceptions in terms of their size, shape, material selection, and technical concept, and therefore selection criteria known in the relevant field can be applied without restriction.

[0548] Additional details, features, and advantages of the invention are disclosed in the dependent claims and the following description of the various drawings, which illustrate preferred embodiments of the invention in an exemplary manner. However, any embodiment is not necessarily representative of the full scope, and therefore the scope should be interpreted with reference to the claims and this document. It should be understood that the foregoing general description and the following detailed description are merely exemplary and explanatory, and are intended to provide further explanation of the claimed invention.

[0549] Figure 1 This is a schematic cross-sectional view of an organic electronic device according to an exemplary embodiment of the present invention;

[0550] Figure 2 This is a schematic cross-sectional view of an organic light-emitting diode (OLED) according to an exemplary embodiment of the present invention;

[0551] Figure 3 This is a schematic cross-sectional view of an OLED according to an exemplary embodiment of the present invention.

[0552] The accompanying drawings are described in more detail below with reference to the embodiments. However, this disclosure is not limited to the following drawings.

[0553] In this document, when a first element is referred to as being formed or disposed "on" or "to" a second element, the first element may be directly disposed on the second element, or one or more other elements may be disposed therebetween. When a first element is referred to as being formed or disposed "directly" on or "to" a second element, there are no other elements in between.

[0554] Figure 1 This is a schematic cross-sectional view of an organic electronic device 100 according to an exemplary embodiment of the present invention. The organic electronic device 100 includes a substrate 110, an anode layer 120, and a hole injection layer (HIL) (130). The HIL 130 is disposed on the anode layer 120. A photoactive layer (PAL) 170 and a cathode layer 190 are disposed on the HIL 130.

[0555] Hole injection layer (HIL) 130 may include first and second sublayers, wherein the first sublayer is disposed on the anode and the second sublayer is disposed on the first sublayer. Photoactive layer (PAL) 170 is disposed on the second sublayer.

[0556] Figure 2 This 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 disposed on the anode layer 120. On the HIL 130, 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 are disposed. Optionally, an electron transport layer stack (ETL) can be used instead of a single electron transport layer 160.

[0557] Hole injection layer (HIL) 130 may include first and second sublayers, wherein the first sublayer is disposed on the anode and the second sublayer is disposed on the first sublayer. Hole transport layer (HTL) 140 is disposed on the second sublayer.

[0558] Figure 3 This is a schematic cross-sectional view of OLED 100 according to another exemplary embodiment of the present invention. Figure 3 and Figure 2 The difference is Figure 3 The OLED 100 includes an electron blocking layer (EBL) 145 and a hole blocking layer (HBL) 155.

[0559] refer to Figure 3The 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.

[0560] Although Figure 1 , Figure 2 and Figure 3 Not shown, but a sealing layer can also be formed on the cathode layer 190 to seal the organic electronic device 100. Additionally, various other modifications can be made to it.

[0561] The embodiments described below will be described in more detail with reference to the examples. However, this disclosure is not limited to the following examples. Detailed Implementation

[0562] The present invention is further illustrated by the following embodiments, which are merely illustrative and not restrictive.

[0563] Hole transport compounds and hole transport compounds of formula (I) and metal complexes of formula (II) can be prepared as described in the literature.

[0564] Standard starting temperature

[0565] Standard starting temperature (T) RO The determination was made by loading 100 mg of the hole-transfer compound into a VTE source. As the VTE source, a point source of organic material supplied by companies such as Kurt J. Lesker Company (www.lesker.com) or CreaPhys GmbH (http: / / www.creaphys.com) was used. In quantities less than 10... -5 The VTE source was heated at a constant rate of 15 K / min under a pressure of millibars, and the internal temperature of the VTE source was measured using thermocouples. Evaporation of the hole transport compound was detected using a QCM detector, which also detected the deposition of the hole transport compound on a quartz crystal of the detector. The deposition rate on the quartz crystal was... Measurements were taken in units of 1. To determine the standard onset temperature, the deposition rate was plotted against the VTE source temperature. The standard onset is the temperature at which significant deposition appears on the QCM detector. For accurate results, the VTE source was heated and cooled three times, and only the results from the second and third runs were used to determine the standard onset temperature.

[0566] To achieve good control over the evaporation rate of the metal complex of formula (II), the standard starting temperature can be in the range of ≥110°C to ≤300°C, preferably ≥115°C to ≤290°C. If the standard starting temperature is too low, evaporation may be too rapid and therefore difficult to control. If the standard starting temperature is too high, the evaporation rate may be too low, which can lead to a low cycle time, and the metal complex of formula (II) in the VTE source may decompose due to prolonged exposure to high temperatures.

[0567] To achieve good control over the evaporation rate of the hole-transporting compound of this invention, a standard onset temperature can be in the range of 120°C to 300°C. If the standard onset temperature is too low, evaporation may be too rapid and therefore difficult to control. If the standard onset temperature is too high, the evaporation rate may be too low, which can result in a low cycle time.

[0568] The standard onset temperature is an indirect measure of a compound's volatility. The higher the standard onset temperature, the lower the compound's volatility.

[0569] HOMO and LUMO

[0570] HOMO and LUMO levels were calculated using the package TURBOMOLE V6.5 (TURBOMOLE GmbH, Litzenhardtstrasse 19, 76135 Karlsruhe, Germany). The optimized geometry of the molecular structure, along with the HOMO and LUMO levels, was determined by applying the hybrid functional B3LYP with a 6-31G* basis set in the gas phase. If more than one conformation was feasible, the conformation with the lowest total energy was selected. HOMO and LUMO levels are recorded in electron volts (eV).

[0571] General procedure for fabricating an OLED that includes a hole injection layer and a light-emitting layer containing a fluorescent blue light emitter.

[0572] For OLEDs, see Examples 1 to 11 and Comparative Examples 1 to 3 in Tables 3 and 4, using 15Ω / cm ITO with 90nm. 2 A glass substrate (available from Corning Co.) was cut to a size of 50 mm × 50 mm × 0.7 mm, ultrasonically washed with isopropanol for 5 minutes, ultrasonically washed with pure water for 5 minutes, and then washed with UV ozone for 30 minutes to prepare the anode layer.

[0573] Then, 70 vol% of the hole transport compound and 30 vol% of the metal complex were vacuum co-deposited on the anode layer to form a hole injection layer (HIL) with 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 vol% of the hole transport compound and 30 vol% of HAT-CN were vacuum co-deposited on the anode layer to form an HIL with a thickness of 10 nm.

[0574] Then, the hole transport compound is vacuum deposited onto the HIL to form an HTL with a thickness of 128 nm. The hole transport compound selected in the HTL is the same as that in the HIL. The hole transport compounds are shown in Tables 3 and 4.

[0575] Then, N,N-bis(4-(dibenzo[b,d]furan-4-yl)phenyl)-[1,1':4',1”-terphenyl]-4-amine (CAS1198399-61-9) was vacuum deposited on the HTL to form an electron blocking layer (EBL) with a thickness of 5 nm.

[0576] Then, 97 vol% HTC-6 as the EML host and 3 vol% BD200 (Sun Fine Chemicals, Korea) as the fluorescent blue emitting dopant were deposited on the EBL to form a blue emitting EML with a thickness of 20 nm.

[0577] Then, a hole-blocking layer with a thickness of 5 nm is formed by depositing 2-(3'-(9,9-dimethyl-9H-fluorene-2-yl)-[1,1'-biphenyl]-3-yl)-4,6-diphenyl-1,3,5-triazine on the light-emitting layer EML.

[0578] Then, an electron transport layer with a thickness of 31 nm is formed on the hole blocking layer by depositing 50 wt% 4'-(4-(4-(4,6-diphenyl-1,3,5-triazine-2-yl)phenyl)naphth-1-yl)-[1,1'-biphenyl]-4-carboxynitrile and 50 wt% LiQ.

[0579] Then, in 10 -7 0.01 to millibars Al evaporates at a rate that forms a cathode layer with a thickness of 100 nm on the electron transport layer.

[0580] By encapsulating the device with a glass substrate, the OLED stack is protected against environmental conditions. This creates a cavity containing a getter material for further protection.

[0581] General procedure for fabricating an OLED that includes a hole injection layer and an emissive layer containing a phosphorescent green emitting element.

[0582] For OLEDs, see Examples 12 and 13 and Comparative Examples 4 and 5 in Table 5, using 15Ω / cm ITO with 90nm. 2 A glass substrate (available from Corning Co.) was cut into 50mm × 50mm × 0.7mm dimensions, ultrasonically washed with isopropanol for 5 minutes, ultrasonically washed with pure water for 5 minutes, and then washed with UV ozone for 30 minutes to prepare the anode layer.

[0583] Then, 70 vol% of the hole transport compound and 30 vol% of the metal complex were vacuum co-deposited on the anode layer to form a hole injection layer (HIL) with a thickness of 10 nm. The composition of the hole injection layer is shown in Table 5. In Comparative Examples 4 and 5, 70 vol% of the hole transport compound and 30 vol% of HAT-CN were deposited on the anode layer to form an HIL with a thickness of 10 nm.

[0584] Then, the hole transport compound is vacuum deposited on the HIL to form an HTL with a thickness of 165 nm. The hole transport compound selected in the HTL is the same as that in the HIL. The hole transport compounds are shown in Table 5.

[0585] Then, 90 vol% GH-1 as the EML host and 10 vol% GD-1 as the phosphorescent green emitting dopant were vacuum co-deposited onto the HTL to form a green emitting EML with a thickness of 40 nm. The chemical formulas of GH-1 and GD-1 are shown below:

[0586]

[0587] Then, a hole-blocking layer with a thickness of 25 nm is formed by depositing 2,4-diphenyl-6-(3'-(triphenylide-2-yl)-[1,1'-biphenyl]-3-yl)-1,3,5-triazine on the light-emitting layer EML.

[0588] Then, an electron transport layer with a thickness of 10 nm is formed on the hole blocking layer by depositing 99 vol% 3-phenyl-3H-benzo[b]dinaphtho[2,1-d:1′,2′-f]phosphatane-3-oxide and 1 vol% Yb.

[0589] Then, in 10 -7 0.01 to millibars Al evaporates at a rate that forms a cathode layer with a thickness of 100 nm on the electron transport layer.

[0590] By encapsulating the device with a glass substrate, the OLED stack is protected against environmental conditions. This creates a cavity containing a getter material for further protection.

[0591] General procedure for fabricating an OLED including a hole injection layer containing first and second sublayers.

[0592] For OLEDs, see Examples 14 to 28 and Comparative Examples 6 to 11 in Table 6, using 15Ω / cm ITO with 90nm. 2A glass substrate (available from Corning Co.) was cut into 50mm × 50mm × 0.7mm dimensions, ultrasonically washed with isopropanol for 5 minutes, ultrasonically washed with pure water for 5 minutes, and then washed with UV ozone for 30 minutes to prepare the anode layer.

[0593] Then, a hole injection layer comprising the first and second sublayers is vacuum-deposited onto the anode layer. First, a metal complex is vacuum-deposited onto the anode layer to form a first sublayer with a thickness of 3 or 5 nm, as shown in Table 6. In Comparative Examples 6 to 11, HAT-CN is deposited onto the anode layer to form a first sublayer with a thickness of 3 or 5 nm, as shown in Table 6.

[0594] Then, the hole transport compound is vacuum deposited on the first sublayer to form a second sublayer with a thickness of 7 or 5 nm, as shown in Table 6.

[0595] Then, a hole transport compound is vacuum deposited onto the hole injection layer to form an HTL. The hole transport compound in the HTL is selected the same as that in the HIL, as shown in Table 6. The selection is such that the combined thickness of the second sublayer and the HTL reaches a total thickness of 128 nm.

[0596] Then, N,N-bis(4-(dibenzo[b,d]furan-4-yl)phenyl)-[1,1':4',1”-terphenyl]-4-amine (CAS1198399-61-9) was vacuum deposited on the HTL to form an electron blocking layer (EBL) with a thickness of 5 nm.

[0597] Then, 97 vol% HTC-6 as the EML host and 3 vol% BD200 (Sun Fine Chemicals, Korea) as the fluorescent blue emitting dopant were deposited on the EBL to form a blue emitting EML with a thickness of 20 nm.

[0598] Then, a hole-blocking layer with a thickness of 5 nm is formed by depositing 2-(3'-(9,9-dimethyl-9H-fluorene-2-yl)-[1,1'-biphenyl]-3-yl)-4,6-diphenyl-1,3,5-triazine on the light-emitting layer EML.

[0599] Then, an electron transport layer with a thickness of 31 nm is formed on the hole blocking layer by depositing 50 wt% 4'-(4-(4-(4,6-diphenyl-1,3,5-triazine-2-yl)phenyl)naphth-1-yl)-[1,1'-biphenyl]-4-carboxynitrile and 50 wt% LiQ.

[0600] Then, in 10 -7 0.01 to millibars Al evaporates at a rate that forms a cathode layer with a thickness of 100 nm on the electron transport layer.

[0601] By encapsulating the device with a glass substrate, the OLED stack is protected against environmental conditions. This creates a cavity containing a getter material for further protection.

[0602] To evaluate the performance of embodiments of the present invention compared to the prior art, current efficiency was measured at 20°C. Using a Keithley 2635 source measurement unit, the current-voltage characteristics were determined by providing an operating voltage in V and measuring the current flowing through the device under test in mA. The voltage applied to the device varied in 0.1V steps between 0V and 10V. To protect the instrument from damage, measurements were stopped at 10V.

[0603] Technical effect

[0604] To investigate the usefulness of the hole injection layer of the present invention, preferred materials were tested in light of their thermal properties, as shown in Tables 1 and 2.

[0605] Table 1 shows the HOMO levels and standard onset temperatures T0 of the hole transport compounds of the present invention, calculated using the program TURBOMOLE V6.5 (TURBOMOLE GmbH, Litzenhardtstrasse 19, 76135 Karlsruhe, Germany). RO .

[0606] Table 1: Chemical formulas and physical properties of the hole transport compounds of the present invention

[0607]

[0608]

[0609]

[0610] As can be seen from Table 1, the hole transport compound has a standard onset temperature suitable for large-scale production of organic electronic devices.

[0611] Table 2 shows the standard onset temperature T of the metal complex of formula (II). RO .

[0612] Table 2: Metal complexes of formula (II)

[0613]

[0614]

[0615]

[0616]

[0617] As can be seen from Table 2, the metal complex of formula (II) has a standard onset temperature suitable for the large-scale production of organic electronic devices.

[0618] Table 3 shows the performance of OLEDs containing a fluorescent blue emitter and a hole injection layer at 10 mA / cm². 2 The hole injection layer contains 70 vol% HTC-10 and 30 vol% of a metal complex of formula (II) at the operating voltage. The HOMO level of HTC-10 is -5.30 eV.

[0619] Table 3: Performance of OLEDs Containing Fluorescent Blue Emitters

[0620] Hole transport compounds Metal complexes <![CDATA[10mA / cm 2 The following is a list of U[V]]]> Comparative Example 1 HTC-10 HAT-CN >10 Example 1 HTC-10 <![CDATA[Cu(TFSI)2]]> 6.9 Example 2 HTC-10 MC-24 6.3 Example 3 HTC-10 MC-6 5.3 Example 4 HTC-10 MC-27 5.4 Example 5 HTC-10 MC-29 5.2

[0621] In Comparative Example 1, the prior art material HAT-CN was used at a concentration of 30% by volume. HAT-CN has the following formula:

[0622]

[0623] The HOMO of the HAT-CN is -8.83eV. The operating voltage exceeds 10V.

[0624] In Example 1, the hole injection layer contains Cu(TFSI)₂ as a metal complex. The operating voltage is significantly improved to 6.9V.

[0625] In Example 2, the hole injection layer comprised a different Cu(II) complex, namely MC-24. Compared to Example 1, the TFSI ligand was replaced with an amide ligand comprising a trifluoromethyl group and a substituted aryl group. The operating voltage was further improved to 6.3V.

[0626] In Example 3, the hole injection layer comprises MC-6. Compared to Example 1, Cu(II) cations are replaced by Mn(II) cations. Compared to Example 1, the operating voltage is improved from 6.9V to 5.3V.

[0627] In Example 4, the hole injection layer comprises a Mg complex. Compared to Example 2, Cu(II) cations were replaced by Mn(II) cations. The operating voltage was improved from 6.3V to 5.4V.

[0628] In Example 5, the hole injection layer comprises 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 remains within the range acceptable for large-scale production.

[0629] Table 4 shows the performance of OLEDs containing a fluorescent blue emitting element and a hole injection layer at 10 mA / cm². 2 The hole injection layer contains 70 vol% hole transport compound and 30 vol% metal complex of formula (II) at the operating voltage.

[0630] Table 4: Performance of OLEDs Containing Fluorescent Blue Emitters

[0631] Hole transport compounds HOMO level [eV] Metal complexes <![CDATA[10mA / cm 2 The following is a list of U[V]]]> Comparative Example 2 HTC-5 -5.10 HAT-CN >10 Comparative Example 3 HTC-13 -5.67 HAT-CN >10 Example 6 HTC-5 -5.10 MC-29 4.1 Example 7 HTC-6 -5.13 MC-29 4.1 Example 8 HTC-7 -5.13 MC-29 5.1 Example 9 HTC-9 -5.28 MC-29 5.7 Example 10 HTC-10 -5.30 MC-29 5.9 Example 11 HTC-13 -5.67 MC-29 7.0

[0632] In Comparative Example 2, the hole injection layer comprises the hole transport compound HTC-5 and 30 vol% HAT-CN. HAT-CN is free of metal complexes. HTC-5 contains anthracene groups. The HOMO level of HTC-5 is -5.10 eV. The operating voltage exceeds 10 V.

[0633] In Comparative Example 3, the hole injection layer comprises the hole transport compound HTC-13 and 30 vol% HAT-CN. HTC-13 contains three dibenzofuranyl groups. The HOMO level is -5.67 eV, thus further from the vacuum level than in Comparative Example 2. The operating voltage exceeds 10 V.

[0634] In Example 6, the hole injection layer comprises HTC-5 and the metal complex MC-29. The operating voltage is significantly reduced to 4.1V.

[0635] In Example 7, the hole injection layer comprises HTC-6 and the metal complex MC-29. HTC-6 comprises anthracene and dibenzofuranyl groups. The HOMO level is -5.13 eV, thus further from the vacuum level than in Comparative Example 2. The operating voltage remains constant at 4.1 V.

[0636] In Example 8, the hole injection layer comprises HTC-7 and the metal complex MC-29. HTC-7 comprises anthracene and dibenzofuranyl groups. The HOMO level is -5.13 eV, thus further from the vacuum level than in Example 6. The operating voltage is slightly higher than in Example 7. However, the operating voltage is significantly lower than in Comparative Example 2.

[0637] In Example 9, the hole injection layer comprises HTC-9 and the metal complex MC-29. HTC-9 comprises dibenzo-acrylidine and carbazole groups. The HOMO level is -5.28 eV, thus further from the vacuum level than in Example 6. The operating voltage is slightly higher than in Example 8. However, the operating voltage is significantly lower than in Comparative Example 2.

[0638] In Example 10, the hole injection layer comprises HTC-10 and a metal complex MC-29. HTC-10 contains two carbazole groups. The HOMO level is -5.30 eV, thus further from the vacuum level compared to Example 9. However, the operating voltage is significantly lower than that of Comparative Example 2.

[0639] In Example 11, the hole injection layer comprised HTC-13 and the metal complex MC-29. HTC-13 contained three dibenzofuranyl groups. The HOMO level was -5.67 eV, thus further from the vacuum level compared to Example 6. The operating voltage was slightly higher than in Example 10. However, the operating voltage was significantly lower than in Comparative Example 2.

[0640] Table 5 shows the performance of OLEDs containing phosphorescent green emitters and hole injection layers at 10 mA / cm². 2 The hole injection layer contains a hole transport compound and a 30 vol% metal complex of formula (II) at the operating voltage.

[0641] Table 5: Performance of OLEDs Containing Phosphorescent Green Emitters

[0642] Hole transport compounds HOMO level [eV] Metal complexes <![CDATA[10mA / cm 2 The following is a list of U[V]]]> Comparative Example 4 HTC-5 -5.10 HAT-CN >10 Example 12 HTC-5 -5.10 MC-29 4.5 Comparative Example 5 HTC-10 -5.30 HAT-CN >10 Example 13 HTC-10 -5.30 MC-29 6.3

[0643] In Comparative Example 4, the hole injection layer comprises the hole transport compound HTC-5 and 30 vol% HAT-CN. HTC-5 contains anthracene groups. The HOMO level of HTC-5 is -5.10 eV. The operating voltage exceeds 10 V.

[0644] In Example 12, the hole injection layer comprises HTC-5 and the metal complex MC-29. The operating voltage is significantly reduced to 4.1V.

[0645] In Comparative Example 5, the hole injection layer comprises the hole transport compound HTC-10 and 30 vol% HAT-CN. HTC-10 contains two carbazole groups. The HOMO level of HTC-10 is -5.30 eV. The operating voltage exceeds 10 V.

[0646] In Example 13, the hole injection layer comprises HTC-10 and the metal complex MC-29. The operating voltage is significantly reduced to 6.3V.

[0647] Table 6 shows the performance of OLEDs containing a fluorescent blue emitter and a hole injection layer at 10 mA / cm². 2 The operating voltage is specified below, wherein the hole injection layer comprises a first sublayer composed of a metal complex of formula (II) and a second sublayer composed of a hole transport compound.

[0648] In Comparative Example 6, the first sublayer comprises HAT-CN, a prior art hole injection material, with a thickness of 3 nm. The second sublayer comprises the hole transport compound HTC-6. The operating voltage exceeds 10 V.

[0649] In Comparative Example 7, the first sublayer contains HAT-CN, and the second sublayer contains the hole transport compound HTC-7. The operating voltage exceeds 10V.

[0650] In Comparative Example 8, the first sublayer contains HAT-CN, and the second sublayer contains the hole transport compound HTC-10. The operating voltage exceeds 10V.

[0651] In Example 14, the first sublayer comprised a metal complex MC-29 with a thickness of 3 nm. The second sublayer comprised a hole transport compound HTC-6. The operating voltage was 4.0 V, thus showing a significant improvement compared to Comparative Example 6.

[0652] In Examples 15 through 17, the first sublayer was identical to that of Example 14. The second sublayer contained a series of hole transport compounds whose HOMO levels were further away from the vacuum level than those of HTC-6. In all examples, the operating voltage was significantly improved compared to Comparative Examples 6, 7, and 8.

[0653] In Examples 18 to 20, the first sublayer comprised the metal complex MC-27. MC-27 differs from MC-29 in the metal cation and ligand, as shown in Table 2. The second sublayer comprised a series of hole transport compounds. In all examples, the operating voltage was significantly improved compared to Comparative Examples 6, 7, and 8.

[0654] In Example 21, the first sublayer comprises the metal complex MC-30. MC-30 differs from MC-29 in the metal cation and ligand, as shown in Table 2. The second sublayer comprises HTC-7. The operating voltage is 6.6V, thus representing an improvement over Comparative Example 7.

[0655] In Comparative Examples 9 to 11, the first sublayer comprises HAT-CN, a hole injection material according to the prior art, with a thickness of 5 nm. The second sublayer comprises a series of hole transport compounds. The operating voltage exceeds 10 V.

[0656] In Example 22, the first sublayer comprised a metal complex MC-29 with a thickness of 3 nm. The second sublayer comprised a hole transport compound HTC-6. The operating voltage was 4.0 V, thus showing a significant improvement compared to Comparative Example 9. Performance was comparable to that of Example 14.

[0657] In Examples 23 to 25, the first sublayer was the same as in Example 22. The second sublayer contained various hole transport compounds whose HOMO energy levels were further away from the vacuum energy level than those of HTC-6. In all examples, the operating voltage was significantly improved compared to Comparative Examples 9, 10, and 11.

[0658] In Examples 26 and 27, the first sublayer comprises the metal complex MC-27. MC-27 differs from MC-29 in the metal cation and ligand, as shown in Table 2. The second sublayer comprises a series of hole transport compounds. In all examples, the operating voltage was significantly improved compared to Comparative Examples 9, 10, and 11.

[0659] In Example 28, the first sublayer comprises the metal complex MC-30. MC-30 differs from MC-29 in the metal cation and ligand, as shown in Table 2. The second sublayer comprises HTC-7. The operating voltage is 5.4V, thus representing an improvement over Comparative Example 10.

[0660] In summary, a significant improvement in operating voltage was achieved for OLEDs incorporating the hole injection layer according to the present invention.

[0661] Lowering the operating voltage can help reduce power consumption and improve battery life, especially in mobile devices.

[0662]

[0663] The specific combinations of elements and features in the detailed embodiments described above are merely exemplary; these teachings are also explicitly considered to be interchangeable and superseded by other teachings herein and in patents / applications incorporated by reference. As will be appreciated by those skilled in the art, variations, modifications, and other implementations of the description herein are conceived by those of ordinary skill in the art without departing from the spirit and scope of the claimed invention. Therefore, the foregoing description is by way of example only and not intended to be limiting. In the claims, the word “comprising” does not exclude other elements or steps, and the singular forms “a” or “an” do not exclude plural references. The fact that specific measures are enumerated in dissimilar dependent claims does not imply that combinations of these measures cannot be advantageously used. The scope of the invention is defined by the claims and their equivalents. Furthermore, the reference numerals used in the specification and claims do not limit the scope of the claimed invention.

Claims

1. 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 wherein the hole injection layer comprises a hole transport compound and a metal complex, wherein... -The hole transport compound has formula (I): (Ar 1 ) k ─(Ar 2 ) m ─On 3 ─(Ar 4 ) p ─(Ar 5 ) q ─(Ar 6 ) r (I), in k, m, q, r are each independently selected from 0, 1, or 2. p is 1, 2, or 3. Where 2≤k+m+q+r+p≤11, Ar 1 To Ar 6 Independently selected from: heterocycles with substituted or unsubstituted unsaturated 5- to 7-membered rings, substituted or unsubstituted C6 to C6 rings. 30 Aryl, substituted or unsubstituted C3 to C4 30 The rings are selected from: (i) heterocyclic rings with unsaturated 5 to 7-membered rings, (ii) aromatic heterocyclic rings with 5 to 6 members, (iii) non-heterocyclic rings with unsaturated 5 to 7-membered rings, and (iv) aromatic non-heterocyclic rings with 6-membered rings. Among them, Ar 1 To Ar 6 The substituents are selected from: H, D, C1 to C1. 12 Alkyl, unsubstituted C6 to C6 18 Aryl, unsubstituted C3 to C 18 Heteroaryl groups, comprising fused ring systems of 2 to 6 unsubstituted 5- to 7-membered rings, wherein the rings are selected from unsaturated 5- to 7-membered heterocycles, 5- to 6-membered aromatic heterocycles, unsaturated 5- to 7-membered non-heterocycles, and 6-membered aromatic non-heterocycles; and in The hole transport compound of formula (I) has a molecular weight Mw of ≥400 and ≤2000 g / mol. - When determined under the same conditions, the HOMO level of the hole-transporting compound of formula (I) is further from the vacuum level than the HOMO level of N4,N4”'-di(naphthyl-1-yl)-N4,N4”'-diphenyl-[1,1':4',1”:4”,1”'-tetraphenyl]-4,4”'-diamine; and -The metal complex has formula (II): in M is a metal ion. n is the valence of M, where n is an integer from 1 to 4. L is a ligand containing at least two carbon atoms; The molecular weight (Mw) of the metal complex is ≥400 g / mol and ≤1500 g / mol, and The hole injection layer is arranged adjacent to the anode layer.

2. The organic electronic device according to claim 1, wherein the hole injection layer does not emit light.

3. The organic electronic device according to claim 1, wherein in formula (I): Ar 1 To Ar 6 Independently selected from: substituted or unsubstituted biphenylide, 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 biphenylide, substituted or unsubstituted tetraphenyl, substituted or unsubstituted benzo[a]anthracene, substituted or unsubstituted dibenzofuran, substituted or unsubstituted dibenzothiophene, substituted or unsubstituted xanthan, substituted or unsubstituted carbazole, substituted or unsubstituted azaheptan, substituted or unsubstituted dibenzo[b] [f]-Azaheptanyl, 9,9'-spirobis[fluorene], substituted or unsubstituted spiro[fluorene-9,9'-xanton], substituted or unsubstituted 9,14-dihydrodibenzo[2,3:6,7]azaheptanyl[4,5-b]indole, or substituted or unsubstituted aromatic fused ring systems comprising at least three substituted or unsubstituted aromatic rings selected from substituted or unsubstituted non-heterocyclic rings, substituted or unsubstituted heterocyclic 5-membered rings, substituted or unsubstituted 6-membered rings, and / or substituted or unsubstituted 7-membered rings. Among them, Ar 1 To Ar 6 The substituents are selected from: H, D, C1 to C1. 12 Alkyl, unsubstituted C6 to C6 18 aryl, or unsubstituted C3 to C 18 Heteroaryl groups comprise fused ring systems of 2 to 6 unsubstituted 5- to 7-membered rings, wherein the rings are selected from unsaturated 5- to 7-membered heterocycles, 5- to 6-membered aromatic heterocycles, unsaturated 5- to 7-membered non-heterocycles, and 6-membered aromatic non-heterocycles.

4. The organic electronic device according to claim 1, wherein the molecular weight Mw of the hole transport compound according to formula (I) is ≥550 g / mol and ≤900 g / mol.

5. The organic electronic device according to claim 1, wherein M is selected from: metal ions, wherein the electronegativity of the corresponding metal according to Allen is less than 2.4, alkali metals, alkaline earth metals, rare earth metals or transition metals, metals with an atomic mass ≥ 24 Da, and metals with an atomic mass ≥ 24 Da and an oxidation number ≥ 2.

6. The organic electronic device according to claim 1, wherein the molecular weight Mw of the metal complex is ≥580 g / mol and ≤1500 g / mol.

7. The organic electronic device according to claim 1, wherein L is a group selected from substances comprising: - At least three carbon atoms, or at least four carbon atoms, and / or - at least two oxygen atoms or one oxygen atom and one nitrogen atom, two to four oxygen atoms, two to four oxygen atoms and zero to two nitrogen atoms, and / or - At least one or more groups selected from halogens, F, CN, substituted or unsubstituted C1 to C6 alkyl, substituted or unsubstituted C1 to C6 alkoxy groups; or two or more groups selected from halogens, F, CN, substituted or unsubstituted C1 to C6 alkyl, substituted or unsubstituted C1 to C6 alkoxy groups; at least one or more groups selected from halogens, F, CN, substituted C1 to C6 alkyl, substituted C1 to C6 alkoxy groups; or two or more groups selected from halogens, F, CN, perfluorinated C1 to C6 alkyl, perfluorinated C1 to C6 alkoxy groups; or one or more groups selected from substituted or unsubstituted C1 to C6 alkyl, substituted or unsubstituted C6 to C6 alkoxy groups. 12 aryl, and / or substituted or unsubstituted C3 to C4 12 heteroaryl groups, The substituents are selected from: D, C6 aryl, C3 to C9 heteroaryl, C1 to C6 alkyl, C1 to C6 alkoxy, C3 to C6 branched alkyl, C3 to C6 cyclic alkyl, C3 to C6 branched alkoxy, C3 to C6 cyclic alkoxy, partially or perfluorinated C1 to C6 alkyl groups. 16 Alkyl, partially or perfluorinated C1 to C2 16 Alkoxy, partially or fully deuterated C1 to C6 alkyl, partially or fully deuterated C1 to C6 alkoxy, COR 6 COOR 6 ,halogen, F, or CN; Where R 6 Selected from: C6 aryl, C3 to C9 heteroaryl, C1 to C6 alkyl, C1 to C6 alkoxy, C3 to C6 branched alkyl, C3 to C6 cyclic alkyl, C3 to C6 branched alkoxy, C3 to C6 cyclic alkoxy, partially or perfluorinated C1 to C 16 Alkyl, partially or perfluorinated C1 to C2 16 Alkoxy, partially or fully deuterated C1 to C6 alkyl, partially or fully deuterated C1 to C6 alkoxy.

8. The organic electronic device according to claim 1, wherein the metal complex according to formula (II) is non-luminescent.

9. The organic electronic device of claim 1, wherein the hole injection layer comprises a hole transport compound and a metal complex: -The hole transport compound described herein has formula (I): (Ar 1 ) k ─(Ar 2 ) m ─On 3 ─(Ar 4 ) p ─(Ar 5 ) q ─(Ar 6 ) r (I), in k, m, q, r are each independently selected from 0, 1, or 2. p is 1, 2, or 3. Where 2≤k+m+q+r+p≤11, Ar 1 To Ar 6 Independently selected from: heterocycles with substituted or unsubstituted unsaturated 5- to 7-membered rings, substituted or unsubstituted C6 to C6 rings. 30 Aryl, substituted or unsubstituted C3 to C4 30 The rings are selected from: (i) heterocyclic rings with unsaturated 5 to 7-membered rings, (ii) aromatic heterocyclic rings with 5 to 6 members, (iii) non-heterocyclic rings with unsaturated 5 to 7-membered rings, and (iv) aromatic non-heterocyclic rings with 6-membered rings. Ar when k=1 2 Ar 3 Ar when q=1 4 Ar when r=1 5 Selected independently from: Substituted or unsubstituted unsaturated 5- to 7-membered heterocycles, substituted or unsubstituted C6 to C6 rings. 30 Aranediols, substituted or unsubstituted C3 to C4 30 Heteroarylene compounds, substituted or unsubstituted biphenylidene compounds, substituted or unsubstituted fluorene compounds, substituted or unsubstituted naphthalene compounds, substituted or unsubstituted anthracene compounds, substituted or unsubstituted phenanthrene compounds, substituted or unsubstituted pyrene compounds, substituted or unsubstituted perylene compounds, substituted or unsubstituted triphenylidene compounds, substituted or unsubstituted tetraphenylbenzene compounds, substituted or unsubstituted benzo[a]anthracene compounds, substituted or unsubstituted dibenzofuran compounds, substituted or unsubstituted dibenzothiophene compounds, substituted or unsubstituted xanthanene compounds, substituted or unsubstituted carbazole compounds, substituted or unsubstituted azaheptanyl compounds, substituted or unsubstituted diphenylene oxides, etc. Benzo[b,f]azacycloheptanyl, 9,9'-spirobis[fluorene], substituted or unsubstituted spiro[fluorene-9,9'-xanton], substituted or unsubstituted 9,14-dihydrodibenzo[2,3:6,7]azacycloheptanyl[4,5-b]indole, or a substituted or unsubstituted aromatic fused ring system comprising at least three substituted or unsubstituted aromatic rings selected from substituted or unsubstituted non-heterocyclic rings, substituted or unsubstituted heterocyclic 5-membered rings, substituted or unsubstituted 6-membered rings and / or substituted or unsubstituted 7-membered rings; Ar when k=0 2 Ar when m=0 and k=0 3 Ar when q and r = 0 4 Ar when r=0 5 Selected independently from: Substituted or unsubstituted unsaturated 5- to 7-membered heterocycles, substituted or unsubstituted C6 to C6 rings. 30 Aryl, substituted or unsubstituted C3 to C4 30 Heteroaryl, substituted or unsubstituted biphenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthrayl, substituted or unsubstituted phenanthyl, substituted or unsubstituted pyrene, substituted or unsubstituted peryl, substituted or unsubstituted triphenylimide, substituted or unsubstituted tetraphenyl, substituted or unsubstituted benzoanthrayl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophene, substituted or unsubstituted xanthonyl, substituted or unsubstituted carbazole, substituted or unsubstituted azaheptanyl, substituted or unsubstituted Substituted dibenzo[b,f]azacycloheptanyl, 9,9'-spirobis[fluorenyl], substituted or unsubstituted spiro[fluorenyl-9,9'-xanton], substituted or unsubstituted 9,14-dihydrodibenzo[2,3:6,7]azacycloheptanyl[4,5-b]indole, or substituted or unsubstituted aromatic fused ring systems comprising at least three substituted or unsubstituted aromatic rings selected from substituted or unsubstituted non-heterocyclic rings, substituted or unsubstituted heterocyclic 5-membered rings, substituted or unsubstituted 6-membered rings and / or substituted or unsubstituted 7-membered rings; The substituents are selected from: H, D, C1 to C1. 12 Alkyl, unsubstituted C6 to C6 18 aryl, or unsubstituted C3 to C 18 heteroaryl; and -The metal complex therein has formula (II).

10. The organic electronic device according to claim 1, wherein the hole transport compound according to formula (I) is selected from compounds comprising at least 1 to 6 substituted or unsubstituted aromatic fused ring systems containing heteroaromatic rings, heterocycles comprising at least 1 to 3 substituted or unsubstituted unsaturated 5 to 7-membered rings, aromatic fused ring systems comprising at least 2 to 5 substituted or unsubstituted aromatic fused ring systems containing heteroaromatic rings, heterocycles comprising at least 1 to 3 substituted or unsubstituted unsaturated 5 to 7-membered rings, aromatic fused ring systems comprising 3 or 4 substituted or unsubstituted aromatic fused ring systems containing heteroaromatic rings, heterocycles comprising at least 1 to 3 substituted or unsubstituted unsaturated 5 to 7-membered rings, the aromatic fused ring system containing heteroaromatic rings being unsubstituted, or heterocycles comprising at least 1 to 3 unsubstituted unsaturated 5 to 7-membered rings.

11. The organic electronic device according to claim 1, wherein... - The hole transport compound according to formula (I) is selected from the following compounds: substituted or unsubstituted aromatic fused ring systems having at least 2 to ≤6 fused aromatic rings, said fused aromatic rings being selected from substituted or unsubstituted non-heteroaromatic rings, substituted or unsubstituted heterocyclic 5-membered rings, substituted or unsubstituted 6-membered rings, and / or substituted or unsubstituted unsaturated 5- to 7-membered rings; and unsubstituted aromatic fused ring systems having at least 2 to ≤6 fused aromatic rings, said fused aromatic rings being selected from unsubstituted non-heteroaromatic rings, unsubstituted heterocyclic 5-membered rings, unsubstituted 6-membered rings, and unsubstituted unsaturated 5- to 7-membered rings.

12. The organic electronic device according to claim 1, wherein the hole transport compound according to formula (I) is selected from compounds comprising 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, wherein the at least one unsaturated 5-membered ring or the at least one unsaturated 7-membered ring comprises at least 1 to 3 heteroatoms.

13. The organic electronic device according to claim 1, wherein the hole transport compound according to formula (I) is selected from compounds that are free of heteroatoms not part of an aromatic ring, free of heteroatoms part of an unsaturated 7-membered ring, or free of N atoms except for N atoms that are part of an aromatic ring or part of an unsaturated 7-membered ring.

14. The organic electronic device according to claim 1, wherein the hole transport compound according to formula (I) is selected from the group consisting of: -Has at least 6 to 12 aromatic rings; -Having at least ≥4 to ≤11 non-heteroaromatic rings, -Having at least 1 to ≤4 aromatic 5-membered rings - Heterocyclic rings having at least one or two unsaturated 5- to 7-membered rings -Having at least 6 to 12 aromatic rings, wherein... At least 4 to 11 of them are non-heteroaromatic rings, and At least 1 to 4 aromatic rings are heterocyclic aromatic rings, and the total number of non-heterocyclic and heterocyclic aromatic rings does not exceed 12 aromatic rings. -Having at least 6 to 12 aromatic rings, wherein... At least 4 to 11 of them are non-heteroaromatic rings, and At least 1 to 4 aromatic rings are heterocyclic aromatic rings, and the total number of non-heterocyclic and heterocyclic aromatic rings does not exceed 12 aromatic rings; and The hole transport compound contains at least 1 to 4 aromatic 5-membered rings.

15. The organic electronic device according to claim 1 or 2, wherein for formula (I): -Ar 3 Selected from D1 to D17: If m>0 and k>0, then Ar 1 Selected from D7 to D15 and D17, or if k>0 and m=0, then Ar 1 Selected from D7 to D15 and D17, or if k>1, then Ar 1 Selected from D1 to D6; If m>0 and k>0, then Ar 2 Selected from D1 to D6; or if m>0 and k=0, then Ar 2 Selected from D7 to D15 and D17; If q > 0, then Ar 4 Selected from D1 to D6, or if q = 0 and r > 0, then Ar 4 Selected from D1 to D6; or if q and r = 0, then Ar 4 Selected from D7 to D15 and D17; If q > 0 and r > 0, then Ar 5 Selected from D1 to D6, or if q>0 and r=0, then Ar 5 Selected from D7 to D15 and D17; If r>0, q>0, then Ar 6 Selected from D7 to D15 and D17, or if r > 0, q = 0, then Ar 6 Selected from D7 to D15 and D17, or if r>1, then Ar 6 Selected from D1 to D6.

16. The organic electronic device according to claim 1, wherein the hole transport compound according to formula (I) is selected from F1 to F13:

17. The organic electronic device according to claim 1, wherein n is an integer from 1 to 4.

18. The organic electronic device according to claim 1, wherein the metal complex is selected from formulas (IIa) to (IIe): in M is a metal ion; n is the valence of M, where n is an integer from 1 to 4; A 1 and A 2 Independently selected from substituted or unsubstituted C1 to C1 12 Alkyl, substituted or unsubstituted C6 to C 12 Aryl, substituted or unsubstituted C3 to C 12 Mixed aromatics; A 3 Selected from H, D, substituted or unsubstituted C1 to C2 12 Alkyl, substituted or unsubstituted C6 to C 12 Aryl, substituted or unsubstituted C3 to C 12 Mixed aromatics; Where A 1 and A 2 and / or A 3 The substituents are independently selected from: D, C6 aryl, C3 to C9 heteroaryl, C1 to C6 alkyl, C1 to C6 alkoxy, C3 to C6 branched alkyl. C3 to C6 cyclic alkyl groups, C3 to C6 branched alkoxy groups, C3 to C6 cyclic alkoxy groups, partially or perfluorinated C1 to C6 cyclic alkoxy groups. 16 Alkyl, partially or perfluorinated C1 to C2 16 Alkoxy groups, partially or fully deuterated C1 to C6 alkyl groups, partially or fully deuterated C1 to C6 alkoxy groups, COR 1 COOR 1 Halogen, F, or CN Where R 1 Selected from: C6 aryl, C3 to C9 heteroaryl, C1 to C6 alkyl, C1 to C6 alkoxy, C3 to C6 branched alkyl, C3 to C6 cyclic alkyl, C3 to C6 branched alkoxy, C3 to C6 cyclic alkoxy, partially or perfluorinated C1 to C 16 Alkyl, partially or perfluorinated C1 to C2 16 Alkoxy, partially or fully deuterated C1 to C6 alkyl, partially or fully deuterated C1 to C6 alkoxy.

19. The organic electronic device according to claim 18, wherein A 1 and A 2 and / or A 3 It is selected from the following groups: where A 1 and A 2 and / or A 3 At least one of them contains a substituent, wherein A 1 and A 2 and / or A 3 At least one of the substituents is independently selected from: C3 to C9 heteroaryl, C1 to C6 alkoxy, C3 to C6 branched alkoxy, C3 to C6 cyclic alkoxy, partially or perfluorinated C1 to C 16 Alkyl, partially or perfluorinated C1 to C2 16 Alkoxy groups, partially or fully deuterated C1 to C6 alkoxy groups, COR 1 COOR 1 Halogen, F, or CN, A 1 and A 2 and / or A 3 At least one of them contains at least two substituents, wherein A 1 and A 2 and / or A 3 The substituents on the [chain] are independently selected from: C3 to C9 heteroaryl, C1 to C6 alkoxy, C3 to C6 branched alkoxy, C3 to C6 cyclic alkoxy, partially or perfluorinated C1 to C [chain] ... 16 Alkyl, partially or perfluorinated C1 to C2 16 Alkoxy groups, partially or fully deuterated C1 to C6 alkoxy groups, COR 1 COOR 1 Halogen, F, or CN.

20. The organic electronic device according to claim 1 or 19, wherein L is independently selected from G1 to G64:

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

22. The organic electronic device according to claim 21, wherein the at least one photoactive layer is a light-emitting layer.

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

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

26. The organic electronic device of claim 1, wherein the organic electronic device further comprises a hole transport layer, 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 at least one photoactive layer or at least one light-emitting layer.

27. The organic electronic device of claim 26, wherein the hole transport layer comprises a hole transport compound according to formula (I).

28. The organic electronic device according to claim 27, wherein the hole transport compound of formula (I) in the hole injection layer and the hole transport layer are selected to be the same.

29. The organic electronic device according to 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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