Organic Electronic Device Comprising a Substrate, an Anode Layer, a Cathode Layer, at Least One First Emission Layer, and a Hole Injection Layer That Comprises a Metal Complex

Abstract

The present invention relates to an organic electronic device comprising a substrate (110), an anode layer (120), a cathode layer (190), at least one first emission layer (150), and a hole injection layer (130), wherein • - the hole injection layer comprises a metal complex, wherein • - the metal complex comprises at least one electropositive metal atom having an electro-negativity value according to Allen of less than 2.4, and • - the metal complex comprises at least one anionic ligand comprising at least 4 covalently bound atoms; • - the anode layer comprises a first anode sub-layer (121) and a second anode sub-layer (122), wherein • - the first anode sub-layer comprises a first metal having a work function in the range of > 4 and < 6 eV, and • - the second anode sub-layer comprises a transparent conductive oxide; wherein • - the hole injection layer is arranged between the first emission layer and the anode layer, • - the first anode sub-layer is arranged closer to the substrate, and the second anode sub-layer is arranged closer to the hole injection layer.

Claims

1. An organic electronic device comprising a substrate, an anode layer, a cathode layer, at least one first emission layer, and a hole injection layer, wherein the hole injection layer comprises a metal complex, wherein the metal complex comprises at least one electropositive metal atom having an electro-negativity value according to Allen of less than 2.4, and the metal complex comprises at least one anionic ligand comprising at least 4 covalently bound atoms; the anode layer comprises a first anode sub-layer and a second anode sub-layer, wherein the first anode sub-layer comprises a first metal having a work function in the range of > 4 and ≤ 6 eV, and the second anode sub-layer comprises a transparent conductive oxide; wherein the hole injection layer is arranged between the first emission layer and the anode layer, the first anode sub-layer is arranged closer to the substrate, and the second anode sub-layer is arranged closer to the hole injection layer.

2. An organic electronic device comprising a substrate, an anode layer, a cathode layer, at least one first emission layer, and a hole injection layer in accordance with claim 1, wherein the hole injection layer comprises a metal complex, wherein the metal complex has the formula (I): ##STR00150## wherein M is a metal ion, n is the valency of M, L is a ligand comprising at least 4 covalently bound atoms, wherein at least two atoms are selected from carbon atoms, n is an integer from 1 to 4, and wherein the charge neutral form of M has an electro-negativity value according to Allen of less than 2.4; the anode layer comprises a first anode sub-layer and a second anode sub-layer, wherein the first anode sub-layer comprises a first metal having a work function in the range of ≥ 4 and ≤ 6 eV, the second anode sub-layer comprises a transparent conductive oxide; wherein the hole injection layer is arranged between the first emission layer and the anode layer, the first anode sub-layer is arranged closer to the substrate, and the second anode sub-layer is arranged closer to the hole injection layer.

3. The organic electronic device according to claim 1, wherein the hole injection layer is free of ionic liquids, metal phthalocyanine, CuPc, HAT-CN, Pyrazino[2,3-f][1,10]phenanthroline-2,3-dicarbonitrile, F.sub.4TCNQ, metal fluoride and/or metal oxides, wherein the metal in the metal oxide is selected from Re and/or Mo.

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

5. The organic electronic device according to claim 2, wherein the metal complex of formula (I) has a molecular weight Mw of ≥ 287 and ≤ 2000 g/mol.

6. The organic electronic device according to claim 2, wherein the anode layer of the organic electronic device comprises in addition a third anode sub-layer.

7. The organic electronic device according to claim 2 , wherein the transparent conductive oxide is selected from the group comprising indium tin oxide or indium zinc oxide.

8. The organic electronic device according to claim 2 wherein the first metal of the first anode sub-layer is selected from the group comprising Ag, Mg, Al, Cr, Pt, Au, Pd, Ni, Nd, or Ir.

9. The organic electronic device according to claim 2 wherein the hole injection layer further comprises a matrix compound.

10. The organic electronic device according to claim 9, wherein the matrix compound of the hole injection layer has a molecular weight Mw of ≥ 400 and ≤ 2000 g/mol.

11. The organic electronic device according to claim 9 , wherein the HOMO level of the matrix compound of the hole injection layer is further away from vacuum level than the HOMO level of N2,N2,N2′,N2′,N7,N7,N7′,N7′-octakis(4-methoxyphenyl)-9,9′-spirobi[fluorene]-2,2′,7,7′-tetraamine when determined under the same conditions.

12. The organic electronic device according to claim 9, wherein the matrix compound of the hole injection layer comprises at least one arylamine compound, diarylamine compound, triarylamine compound, a compound of formula (II) or a compound of formula (III) : ##STR00151## ##STR00152## wherein: T.sup.1, T.sup.2, T.sup.3, T.sup.4 and T.sup.5 are independently selected from a single bond, phenylene, biphenylene, terphenylene or naphthenylene; T.sup.6 is phenylene, biphenylene, terphenylene or naphthenylene; Ar.sup.1, Ar.sup.2, Ar.sup.3, Ar.sup.4 and Ar.sup.5 are independently selected from substituted or unsubstituted C.sub.6 to C.sub.20 aryl, or substituted or unsubstituted C.sub.3 to C.sub.20 heteroarylene, substituted or unsubstituted biphenylene, substituted or unsubstituted fluorene, substituted 9-fluorene, substituted 9,9-fluorene, substituted or unsubstituted naphthalene, substituted or unsubstituted anthracene, substituted or unsubstituted phenanthrene, substituted or unsubstituted pyrene, substituted or unsubstituted perylene, substituted or unsubstituted triphenylene, substituted or unsubstituted tetracene, substituted or unsubstituted tetraphene, substituted or unsubstituted dibenzofurane, substituted or unsubstituted dibenzothiophene, substituted or unsubstituted xanthene, substituted or unsubstituted carbazole, substituted 9-phenylcarbazole, substituted or unsubstituted azepine, substituted or unsubstituted dibenzo[b,f]azepine, substituted or unsubstituted 9,9′-spirobi[fluorene], substituted or unsubstituted spiro[fluorene-9,9′-xanthene], or a substituted or unsubstituted aromatic fused ring system comprising at least three substituted or unsubstituted aromatic rings selected from the group comprising substituted or unsubstituted non-hetero, substituted or unsubstituted hetero 5-member rings, substituted or unsubstituted 6-member rings and/or substituted or unsubstituted 7-member rings, substituted or unsubstituted fluorene, or a fused ring system comprising 2 to 6 substituted or unsubstituted 5- to 7-member rings and the rings are selected from the group comprising (i) unsaturated 5- to 7-member ring of a heterocycle, (ii) 5- to 6-member of an aromatic heterocycle, (iii) unsaturated 5- to 7-member ring of a non-heterocycle, (iv) 6-member ring of an aromatic non-heterocycle; wherein the substituents of Ar.sup.1, Ar.sup.2, Ar.sup.3, Ar.sup.4 and Ar.sup.5 are selected the same or different from the group comprising H, D, F, C(—O)R.sup.2, CN, Si(R.sup.2).sub.3, P(—O)(R.sup.2).sub.2, OR.sup.2, S(—O)R.sup.2, S(—O).sub.2R.sup.2, substituted or unsubstituted straight-chain alkyl having 1 to 20 carbon atoms, substituted or unsubstituted branched alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cyclic alkyl having 3 to 20 carbon atoms, substituted or unsubstituted alkenyl or alkynyl groups having 2 to 20 carbon atoms, substituted or unsubstituted alkoxy groups having 1 to 20 carbon atoms, substituted or unsubstituted aromatic ring systems having 6 to 40 aromatic ring atoms, and substituted or unsubstituted heteroaromatic ring systems having 5 to 40 aromatic ring atoms, unsubstituted C.sub.6 to C.sub.18 aryl, unsubstituted C.sub.3 to C.sub.18 heteroaryl, a fused ring system comprising 2 to 6 unsubstituted 5- to 7-member rings and the rings are selected from the group comprising unsaturated 5- to 7-member ring of a heterocycle, 5- to 6-member of an aromatic heterocycle, unsaturated 5- to 7-member ring of a non-heterocycle, and 6-member ring of an aromatic non-heterocycle, wherein R.sup.2 is selected from H, D, straight-chain alkyl having 1 to 6 carbon atoms, branched alkyl having 1 to 6 carbon atoms, cyclic alkyl having 3 to 6 carbon atoms, alkenyl or alkynyl groups having 2 to 6 carbon atoms, C.sub.6 to C.sub.18 aryl or C.sub.3 to C.sub.18 heteroaryl.

13. The organic electronic device according to claim 12, wherein T.sup.1, T.sup.2, T.sup.3, T.sup.4 and T.sup.5 are independently selected from a single bond, phenylene, biphenylene, terphenylene or naphthenylene; T.sup.6 is phenylene, biphenylene, terphenylene or naphthenylene; Ar.sup.1, Ar.sup.2, Ar.sup.3, Ar.sup.4 and Ar.sup.5 are independently selected from substituted or unsubstituted C.sub.6 to C.sub.20 aryl, or substituted or unsubstituted C.sub.3 to C.sub.20 heteroarylene, substituted or unsubstituted biphenylene, substituted or unsubstituted fluorene, substituted 9-fluorene, substituted 9,9-fluorene, substituted or unsubstituted naphthalene, substituted or unsubstituted anthracene, substituted or unsubstituted phenanthrene, substituted or unsubstituted pyrene, substituted or unsubstituted perylene, substituted or unsubstituted triphenylene, substituted or unsubstituted tetracene, substituted or unsubstituted tetraphene, substituted or unsubstituted dibenzofurane, substituted or unsubstituted dibenzothiophene, substituted or unsubstituted xanthene, substituted or unsubstituted carbazole, substituted 9-phenylcarbazole, substituted or unsubstituted azepine, substituted or unsubstituted dibenzo[b,f]azepine, substituted or unsubstituted 9,9′-spirobi[fluorene], substituted or unsubstituted spiro[fluorene-9,9′-xanthene], or a substituted or unsubstituted aromatic fused ring system comprising at least three substituted or unsubstituted aromatic rings selected from the group comprising substituted or unsubstituted non-hetero, substituted or unsubstituted hetero 5-member rings, substituted or unsubstituted 6-member rings and/or substituted or unsubstituted 7-member rings, substituted or unsubstituted fluorene, or a fused ring system comprising 2 to 6 substituted or unsubstituted 5- to 7-member rings and the rings are selected from the group comprising (i) unsaturated 5- to 7-member ring of a heterocycle, (ii) 5- to 6-member of an aromatic heterocycle, (iii) unsaturated 5- to 7-member ring of a non-heterocycle, (iv) 6-member ring of an aromatic non-heterocycle; wherein the substituents of Ar.sup.1, Ar.sup.2, Ar.sup.3, Ar.sup.4 and Ar.sup.5 are selected the same or different from the group comprising H, straight-chain alkyl having 1 to 20 carbon atoms, branched alkyl having 1 to 20 carbon atoms, cyclic alkyl having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, C.sub.6 to C.sub.18 aryl, C.sub.3 to C.sub.18 heteroaryl, a fused ring system comprising 2 to 6 unsubstituted 5- to 7-member rings and the rings are selected from the group comprising unsaturated 5- to 7-member ring of a heterocycle, 5- to 6-member of an aromatic heterocycle, unsaturated 5- to 7-member ring of a non-heterocycle, and 6-member ring of an aromatic non-heterocycle.

14. The organic electronic device according to claim 12, wherein Ar.sup.1, Ar.sup.2, Ar.sup.3, Ar.sup.4 and Ar.sup.5 are independently selected from D1 to D16: ##STR00153## ##STR00154## ##STR00155## ##STR00156## ##STR00157## ##STR00158## ##STR00159## ##STR00160## ##STR00161## ##STR00162## ##STR00163## ##STR00164## ##STR00165## ##STR00166## ##STR00167## ##STR00168## wherein the asterix “*” denotes the binding position.

15. The organic electronic device according to claim 12, wherein the matrix compound of formula (II) or formula (III) are selected from F1 to F18: ##STR00169## ##STR00170## ##STR00171## ##STR00172## ##STR00173## ##STR00174## ##STR00175## ##STR00176## ##STR00177## ##STR00178## ##STR00179## ##STR00180## ##STR00181## ##STR00182## ##STR00183## ##STR00184## ##STR00185## ##STR00186## .

16. The organic electronic device according to claim 2, wherein the ligand L in compound of formula (I) is selected from a group comprising at least three carbon atoms, at least four carbon atoms, at least two oxygen atoms or one oxygen and one nitrogen atom, two to four oxygen atoms, two to four oxygen atoms and zero to two nitrogen atoms, at least one or more groups selected from halogen, F, CN, substituted or unsubstituted C.sub.1 to C.sub.6 alkyl, substituted or unsubstituted C.sub.1 to C.sub.6 alkoxy, two or more groups selected from halogen, F, CN, substituted or unsubstituted C.sub.1 to C.sub.6 alkyl, substituted or unsubstituted C.sub.1 to C.sub.6 alkoxy, at least one or more groups selected from halogen, F, CN, substituted C.sub.1 to C.sub.6 alkyl, substituted C.sub.1 to C.sub.6 alkoxy, two or more groups selected from halogen, F, CN, perfluorinated C.sub.1 to C.sub.6 alkyl, perfluorinated C.sub.1 to C.sub.6 alkoxy, one or more groups selected from substituted or unsubstituted C.sub.1 to C.sub.6 alkyl, substituted or unsubstituted C.sub.6 to C.sub.12 aryl, substituted or unsubstituted C.sub.3 to C.sub.12 heteroaryl, wherein the substituents are selected from D, C.sub.6 aryl, C.sub.3 to C.sub.9 heteroaryl, C.sub.1 to C.sub.6 alkyl, C.sub.1 to C.sub.6 alkoxy, C.sub.3 to C.sub.6 branched alkyl, C.sub.3 to C.sub.6 cyclic alkyl, C.sub.3 to C.sub.6 branched alkoxy, C.sub.3 to C.sub.6 cyclic alkoxy, partially or perfluorinated C.sub.1 to C.sub.16 alkyl, partially or perfluorinated C.sub.1 to C.sub.16 alkoxy, partially or perdeuterated C.sub.1 to C.sub.6 alkyl, partially or perdeuterated C.sub.1 to C.sub.6 alkoxy, COR.sup.3, COOR.sup.3, halogen, F or CN; wherein R.sup.3 is selected from C.sub.6 aryl, C.sub.3 to C.sub.9 heteroaryl, C.sub.1 to C.sub.6 alkyl, C.sub.1 to C.sub.6 alkoxy, C.sub.3 to C.sub.6 branched alkyl, C.sub.3 to C.sub.6 cyclic alkyl, C.sub.3 to C.sub.6 branched alkoxy, C.sub.3 to C.sub.6 cyclic alkoxy, partially or perfluorinated C.sub.1 to C.sub.16 alkyl, partially or perfluorinated C.sub.1 to C.sub.16 alkoxy, partially or perdeuterated C.sub.1 to C.sub.6 alkyl, partially or perdeuterated C.sub.1 to C.sub.6 alkoxy.

17. The organic electronic device according to claim 2, wherein n in formula (I) is an integer from 1 to 4.

18. The organic electronic device according to claim 2, wherein the metal complex is selected from the following formulas (Ia) to (Id): ##STR00187## ##STR00188## ##STR00189## ##STR00190## wherein M is a metal ion; n is the valency of M; A.sup.1 and A.sup.2 are independently selected from substituted or unsubstituted C.sub.1 to C.sub.12 alkyl, substituted or unsubstituted C.sub.6 to C.sub.12 aryl, substituted or unsubstituted C.sub.3 to C.sub.12 heteroaryl; wherein the substituents of A.sup.1 and A.sup.2 are independently selected from D, C.sub.6 aryl, C.sub.3 to C.sub.9 heteroaryl, C.sub.1 to C.sub.6 alkyl, C.sub.1 to C.sub.6 alkoxy, C.sub.3 to C.sub.6 branched alkyl, C.sub.3 to C.sub.6 cyclic alkyl, C.sub.3 to C.sub.6 branched alkoxy, C.sub.3 to C.sub.6 cyclic alkoxy, partially or perfluorinated C.sub.1 to C.sub.16 alkyl, partially or perfluorinated C.sub.1 to C.sub.16 alkoxy, partially or perdeuterated C.sub.1 to C.sub.6 alkyl, partially or perdeuterated C.sub.1 to C.sub.6 alkoxy, COR.sup.1, COOR.sup.1, halogen, F or CN, wherein R.sup.1 is selected from C.sub.6 aryl, C.sub.3 to C.sub.9 heteroaryl, C.sub.1 to C.sub.6 alkyl, C.sub.1 to C.sub.6 alkoxy, C.sub.3 to C.sub.6 branched alkyl, C.sub.3 to C.sub.6 cyclic alkyl, C.sub.3 to C.sub.6 branched alkoxy, C.sub.3 to C.sub.6 cyclic alkoxy, partially or perfluorinated C.sub.1 to C.sub.16 alkyl, partially or perfluorinated C.sub.1 to C.sub.16 alkoxy, partially or perdeuterated C.sub.1 to C.sub.6 alkyl, partially or perdeuterated C.sub.1 to C.sub.6 alkoxy.

19. The organic electronic device according to claim 18 wherein at least one of A.sup.1 and A.sup.2 comprises a substituent, wherein at least one of the substituents of A.sup.1 and A.sup.2 is independently selected from C.sub.3 to C.sub.9 heteroaryl, C.sub.1 to C.sub.6 alkoxy, C.sub.3 to C.sub.6 branched alkoxy, C.sub.3 to C.sub.6 cyclic alkoxy, partially or perfluorinated C.sub.1 to C.sub.16 alkyl, partially or perfluorinated C.sub.1 to C.sub.16 alkoxy, partially or perdeuterated C.sub.1 to C.sub.6 alkoxy, COR.sup.1, COOR.sup.1, halogen, F or CN.

20. The organic electronic device according to claim 2, wherein the ligand L is independently selected from G1 to G66: ##STR00191## ##STR00192## ##STR00193## ##STR00194## ##STR00195## ##STR00196## ##STR00197## ##STR00198## ##STR00199## ##STR00200## ##STR00201## ##STR00202## ##STR00203## ##STR00204## ##STR00205## ##STR00206## ##STR00207## ##STR00208## ##STR00209## ##STR00210## ##STR00211## ##STR00212## ##STR00213## ##STR00214## ##STR00215## ##STR00216## ##STR00217## ##STR00218## ##STR00219## ##STR00220## ##STR00221## ##STR00222## ##STR00223## ##STR00224## ##STR00225## ##STR00226## ##STR00227## ##STR00228## ##STR00229## ##STR00230## ##STR00231## ##STR00232## ##STR00233## ##STR00234## ##STR00235## ##STR00236## ##STR00237## ##STR00238## ##STR00239## ##STR00240## ##STR00241## ##STR00242## ##STR00243## ##STR00244## ##STR00245## ##STR00246## ##STR00247## ##STR00248## ##STR00249## ##STR00250## ##STR00251## ##STR00252## ##STR00253## ##STR00254## ##STR00255## ##STR00256## .

21. The organic electronic device according to claim 2, wherein metal complex is selected from: Li TFSI, K TFSI, Cs TFSI, Ag TFSI, Mg(TFSI).sub.2, Mn(TFSI).sub.2, Sc(TFSI).sub.3, Mg[N(SO.sub.2.sup.iC.sub.3F.sub.7).sub.2].sub.2, Zn[N(SO.sub.2.sup.iC.sub.3F.sub.7).sub.2].sub.2, Ag[N(SO.sub.2.sup.iC.sub.3F.sub.7).sub.2], Ag[N(SO.sub.2C.sub.3F.sub.7).sub.2], Ag[N(SO.sub.2C.sub.4F.sub.9).sub.2], Ag[N(SO.sub.2CF.sub.3)(SO.sub.2C.sub.4F.sub.9)], Cs[N(SO.sub.2C.sub.4F.sub.9).sub.2], Mg[N(SO.sub.2C.sub.4F.sub.9).sub.2].sub.2, Ca[N(SO.sub.2C.sub.4F.sub.9).sub.2].sub.2, Ag[N(SO.sub.2C.sub.4F.sub.9).sub.2], Cu[N(SO.sub.2.sup.iC.sub.3F.sub.7).sub.2].sub.2, Cu[N(SO.sub.2C.sub.3F.sub.7).sub.2].sub.2, Cu[N(SO.sub.2CF.sub.3) (SO.sub.2C.sub.4F.sub.9)].sub.2, Mg[N(SO.sub.2CF.sub.3) (SO.sub.2C.sub.4F.sub.9)].sub.2, Mn[N(SO.sub.2CF.sub.3) (SO.sub.2C.sub.4F.sub.9)].sub.2, Cu[N(SO.sub.2CH.sub.3) (SO.sub.2C.sub.4F.sub.9)].sub.2, Ag[N(SO.sub.2CH.sub.3) (SO.sub.2C.sub.4F.sub.9)], ##STR00257## ##STR00258## ##STR00259## ##STR00260## ##STR00261## ##STR00262## ##STR00263## ##STR00264## ##STR00265## ##STR00266## ##STR00267## ##STR00268## Cu [N(SO.sub.2C.sub.2H.sub.5) (SO.sub.2C.sub.4F.sub.9)].sub.2, Cu [N(SO.sub.2.sup.iC.sub.3H.sub.7) (SO.sub.2C.sub.4F.sub.9)].sub.2, Cu [N(SO.sub.2.sup.iC.sub.3F.sub.7) (SO.sub.2C.sub.4F.sub.9)].sub.2, ##STR00269## ##STR00270## wherein “i” denotes “iso”.

22. The organic electronic device according to claim 2, wherein the hole injection layer comprises a first hole injection sub-layer comprising the metal complex of formula (I) and a second hole injection sub-layer comprising a matrix compound , wherein the first hole injection sub-layer is arranged closer to the anode layer and the second hole injection sub-layer is arranged closer to the at least one emission layer.

23. The organic electronic device according to claim 2, wherein the hole injection layer comprises a first hole injection sub-layer consists of the metal complex of formula (I) and a second hole injection sub-layer comprising a matrix compound, wherein the first hole injection sub-layer is arranged closer to the anode layer and the second hole injection sub-layer is arranged closer to the at least one emission layer.

24. The organic electronic device according to claim 2, wherein the organic electronic device further comprises a hole transport layer, wherein the hole transport layer is arranged between the hole injection layer and the at least one emission layer.

25. The organic electronic device according to claim 24, wherein the hole transport layer comprises a matrix compound, or a matrix compound that is in the hole injection layer and hole transport layer are the same.

26. The organic electronic device according to claim 2, wherein the organic electronic device is a light emitting device or a display device.

Description

DESCRIPTION OF THE DRAWINGS

[0355] The aforementioned components, as well as the claimed components and the components to be used in accordance with the invention in the described embodiments, are not subject to any special exceptions with respect to their size, shape, material selection and technical concept such that the selection criteria known in the pertinent field can be applied without limitations.

[0356] Additional details, characteristics and advantages of the object are disclosed in the dependent claims and the following description of the respective figures which in an exemplary fashion show preferred embodiments according to the invention. Any embodiment does not necessarily represent the full scope, however, and reference is made therefore to the claims and herein for interpreting the scope. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are intended to provide further explanation of the present invention as claimed.

FIGS. 1 to 9

[0357] FIG. 1 is a schematic sectional view of an organic electronic device, according to an exemplary embodiment of the present invention;

[0358] FIG. 2 is a schematic sectional view of an organic electronic device, according to an exemplary embodiment of the present invention;

[0359] FIG. 3 is a schematic sectional view of an organic electronic device, according to an exemplary embodiment of the present invention.

[0360] FIG. 4 is a schematic sectional view of an organic electronic device, according to an exemplary embodiment of the present invention;

[0361] FIG. 5 is a schematic sectional view of an organic electronic device, according to an exemplary embodiment of the present invention;

[0362] FIG. 6 is a schematic sectional view of an organic electronic device, according to an exemplary embodiment of the present invention;

[0363] FIG. 7 is a schematic sectional view of an organic electronic device, according to an exemplary embodiment of the present invention;

[0364] FIG. 8 is a schematic sectional view of an organic electronic device, according to an exemplary embodiment of the present invention;

[0365] FIG. 9 is a schematic sectional view of an organic electronic device, according to an exemplary embodiment of the present invention.

[0366] Hereinafter, the FIGS. 1 to 9 are illustrated in more detail with reference to examples. However, the present disclosure is not limited to the following figures.

[0367] Herein, when a first element is referred to as being formed or disposed “on” or “onto” a second element, the first element can be disposed directly on the second element, or one or more other elements may be disposed there between. When a first element is referred to as being formed or disposed “directly on” or “directly onto” a second element, no other elements are disposed there between.

[0368] FIG. 1 is a schematic 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) that comprises a first anode sub-layer (121) and a second anode sub-layer (122) and a hole injection layer (HIL) (130). The HIL (130) is disposed on the anode layer (120). Onto the HIL (130), a first emission layer (EML) (150), and a cathode layer (190) are disposed.

[0369] FIG. 2 is a schematic 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) that comprises a first anode sub-layer (121), a second anode sub-layer (122) and a third anode sub-layer (123), and a hole injection layer (HIL) (130). The HIL (130) is disposed on the anode layer (120) comprising a first anode sub-layer (121), a second anode sub-layer (122) and a third anode sub-layer (123). Onto the HIL (130), a first emission layer (EML) (150), and a cathode layer (190) are disposed.

[0370] FIG. 3 is a schematic 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) that comprises a first anode sub-layer (121) and a second anode sub-layer (122), and a hole injection layer (HIL) (130) comprising a first hole injection sub-layer (131) and a second hole injection sub-layer (132). The HIL (130) comprising a first hole injection sub-layer (131) and a second hole injection sub-layer (132) is disposed on the anode layer (120). Onto the HIL (130), a first emission layer (EML) (150), and a cathode layer (190) are disposed.

[0371] FIG. 4 is a schematic 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) that comprises a first anode sub-layer (121) a second anode sub-layer (122) and a third anode sub-layer (123), and a hole injection layer (HIL) (130) comprising a first hole injection sub-layer (131) and a second hole injection sub-layer (132). The HIL (130) comprising a first hole injection sub-layer (131) and a second hole injection sub-layer (132) is disposed on the anode layer (120). Onto the HIL (130), a first emission layer (EML) (150), and a cathode layer (190) are disposed.

[0372] FIG. 5 is a schematic 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) that comprises a first anode sub-layer (121) and a second anode sub-layer (122), and a hole injection layer (HIL) (130). The HIL (130) is disposed on the anode layer (120). Onto the HIL (130), an hole transport layer (HTL) (140), a first emission layer (EML) (150), a hole blocking layer (BL) (155), an electron transport layer (ETL) (160), and a cathode layer (190) are disposed.

[0373] FIG. 6 is a schematic 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) that comprises a first anode sub-layer (121), a second anode sub-layer (122) and a third anode sub-layer (123), and a hole injection layer (HIL) (130). The HIL (130) is disposed on the anode layer (120). Onto the HIL (130), an hole transport layer (HTL) (140), a first emission layer (EML) (150), a hole blocking layer (HBL) (155), an electron transport layer (ETL) (160), and a cathode layer (190) are disposed.

[0374] FIG. 7 is a schematic 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) that comprises a first anode sub-layer (121) and a second anode sub-layer (122) and a hole injection layer (HIL) (130). The HIL (130) is disposed on the anode layer (120). Onto the HIL (130), a hole transport layer (HTL) (140), an electron blocking layer (EBL) (145), a first emission layer (EML) (150), a hole blocking layer (HBL) (155), an electron transport layer (ETL) (160), and a cathode layer (190) are disposed.

[0375] FIG. 8 is a schematic 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) that comprises a first anode sub-layer (121) and a second anode sub-layer (122) and a hole injection layer (HIL) (130). The HIL (130) comprises a first hole injection sub-layer (131) and a second hole injection sub-layer (132), wherein the first hole injection sub-layer (131) is disposed on the second anode sub-layer (122) and the second hole injection sub-layer (132) is disposed on the first hole injection sub-layer (131). Onto the HIL (130), a hole transport layer (HTL) (140), an electron blocking layer (EBL) (145), a first emission layer (EML) (150), a hole blocking layer (HBL) (155), an electron transport layer (ETL) (160), and a cathode layer (190) are disposed.

[0376] FIG. 9 is a schematic 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) that comprises a first anode sub-layer (121), a second anode sub-layer (122) and a third anode sub-layer (123), and a hole injection layer (HIL) (130). The HIL (130) is disposed on the anode layer (120). Onto the HIL (130), a hole transport layer (HTL) (140), an electron blocking layer (EBL) (145), a first emission 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) are disposed.

[0377] While not shown in FIG. 1 to FIG. 9, a capping and/or a sealing layer may further be formed on the cathode layer 190, in order to seal the organic electronic device 100. In addition, various other modifications may be applied thereto.

[0378] Hereinafter, the embodiments are illustrated in more detail with reference to examples. However, the present disclosure is not limited to the following examples.

DETAILED DESCRIPTION

[0379] The invention is furthermore illustrated by the following examples which are illustrative only and non-binding.

[0380] The compound of formulae (II) and (III) and metal complexes of formula (I) or formulae (Ia) to (Id) may be prepared as described in the literature.

Rate Onset Temperature

[0381] The rate onset temperature (T.sub.RO) is determined by loading 100 mg compound into a VTE source. As VTE source a point source for organic materials may be used as supplied by Kurt J. Lesker Company (www.lesker.com) or CreaPhys GmbH (http://www.creaphys.com). The VTE source is heated at a constant rate of 15 K/min at a pressure of less than 10.sup.-5 mbar and the temperature inside the source measured with a thermocouple. Evaporation of the compound is detected with a QCM detector which detects deposition of the compound on the quartz crystal of the detector. The deposition rate on the quartz crystal is measured in Ǻngstrom per second. To determine the rate onset temperature, the deposition rate is plotted against the VTE source temperature. The rate onset is the temperature at which noticeable deposition on the QCM detector occurs. For accurate results, the VTE source is heated and cooled three time and only results from the second and third run are used to determine the rate onset temperature.

[0382] To achieve good control over the evaporation rate of an organic compound, the rate onset temperature may be in the range of 200 to 255° C. If the rate onset temperature is below 200° C. the evaporation may be too rapid and therefore difficult to control. If the rate onset temperature is above 255° C. the evaporation rate may be too low which may result in low tact time and decomposition of the organic compound in VTE source may occur due to prolonged exposure to elevated temperatures.

[0383] The rate onset temperature is an indirect measure of the volatility of a compound. The higher the rate onset temperature the lower is the volatility of a compound.

[0384] In Table 1 are shown rate onset temperatures T.sub.RO for metal complexes of formula (I) and formulae (Ia) to (Id).

TABLE-US-00001 Metal complexes of formula (I) and formulae (Ia) to (Id) Name Chemical formula T.sub.RO (°C) MC-1 Li TFSI 222 MC-2 K TFSI 236 MC-3 Cs TFSI 224 MC-4 Ag TFSI 258 MC-5 Mg (TFSI).sub.2 243 MC-6 Mn (TFSI).sub.2 229 MC-7 Sc (TFSI).sub.3 258 MC-8 Mg [N(SO.sub.2.sup.iC.sub.3F.sub.7).sub.2].sub.2 166 MC-9 Zn [N(SO.sub.2.sup.iC.sub.3F.sub.7).sub.2].sub.2 118 MC-10 Ag [N(SO.sub.2.sup.1C.sub.3F.sub.7).sub.2] 232 MC-11 Ag [N(SO.sub.2C.sub.3F.sub.7).sub.2] 254 MC-12 Ag [N(SO.sub.2C.sub.4F.sub.9).sub.2] 262 MC-13 Ag [N(SO.sub.2CF.sub.3)(SO.sub.2C.sub.4F.sub.9)] 230 MC-14 Cs [N(SO.sub.2C.sub.4F.sub.9).sub.2] 245 MC-15 Mg [N(SO.sub.2C.sub.4F.sub.9).sub.2].sub.2 219 MC-16 Ca [N(SO.sub.2C.sub.4F.sub.9).sub.2].sub.2 278 MC-17 Ag [N(SO.sub.2C.sub.4F.sub.9).sub.2] 232 MC-18 Cu [N(SO.sub.2.sup.iC.sub.3F.sub.7).sub.2].sub.2 101 MC-19 Cu [N(SO.sub.2C.sub.3F.sub.7).sub.2].sub.2 118 MC-20 Cu [N(SO.sub.2CF.sub.3) (SO.sub.2C.sub.4F.sub.9)].sub.2 113 MC-21 Mg [N(SO.sub.2CF.sub.3) (SO.sub.2C.sub.4F.sub.9)].sub.2 124 MC-22 Mn [N(SO.sub.2CF.sub.3) (SO.sub.2C.sub.4F.sub.9)].sub.2 202 MC-21 Cu [N(SO.sub.2CH.sub.3) (SO.sub.2C.sub.4F.sub.9)].sub.2 179 MC-22 Ag [N(SO.sub.2CH.sub.3) (SO.sub.2C.sub.4F.sub.9)] - MC-23 [00129] 254 MC-24 [00130] 238 MC-25 [00131] 262 MC-23 [00132] 254 MC-26 [00133] 180 MC-27 [00134] - MC-28 [00135] 167 MC-29 [00136] 282 MC-24 [00137] 238 MC-30 [00138] 263 MC-31 [00139] 194 MC-32 [00140] 190 MC-33 Cu [N(SO.sub.2C.sub.2H.sub.5) (SO.sub.2C.sub.4F.sub.9)].sub.2 156 MC-34 Cu [N(SO.sub.2.sup.iC.sub.3H.sub.7) (SO.sub.2C.sub.4F.sub.9)].sub.2 153 MC-35 Cu [N(SO.sub.2.sup.iC.sub.3F.sub.7) (SO.sub.2C.sub.4F.sub.9)].sub.2 229 MC-36 [00141] 168 MC-37 [00142] 160

[0385] As can be seen in Table 1, the metal complexes of formula (I) and formulae (Ia) to (Id) have rate onset temperatures suitable for mass production of organic electronic devices.

HOMO and LUMO

[0386] The HOMO and LUMO are calculated with the program package TURBOMOLE V6.5 (TURBOMOLE GmbH, Litzenhardtstrasse 19, 76135 Karlsruhe, Germany). The optimized geometries and the HOMO and LUMO energy levels of the molecular structures are determined by applying the hybrid functional B3LYP with a 6-31G* basis set in the gas phase. If more than one conformation is viable, the conformation with the lowest total energy is selected.

[0387] If calculated by this method, the HOMO level of N2,N2,N2′,N2′,N7,N7,N7′,N7′-octakis(4-methoxyphenyl)-9,9′-spirobi[fluorene]-2,2′,7,7′-tetraamine is -4.27 eV.

Matrix Compounds in the Hole Injection Layer And/or Hole Transport Layer

[0388] In Table 1 are shown the HOMO levels and rate onset temperatures T.sub.RO for matrix compounds of formula (I). HOMO levels were calculated using TURBOMOLE V6.5 (TURBOMOLE GmbH, Litzenhardtstrasse 19, 76135 Karlsruhe, Germany) by applying the hybrid functional B3LYP with a 6-31G* basis set in the gas phase.

TABLE-US-00002 Matrix compounds for hole injection layers Name Structure HOMO level (eV) T.sub.RO (°C) Biphenyl-4-yl(9,9-diphenyl-9H-fluoren-2-yl)-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]-amine F3 [00143] -4.69 265 N,N′-Bis(naphthalen-1-yl)-N,N′-bis(phenyl)-benzidine F1 [00144] -4.72 272 N4,N4″-di(naphthalen-1-yl)-N4,N4″-diphenyl-[1,1′:4′,1″-terphenyl]-4,4″-diamine (CAS 139255-16-6) F2 [00145] -4.81 260 N-(9,9-dimethyl-9H-fluoren-2-yl)-N-(9,9-diphenyl-9H-fluoren-2-yl)dibenzo [b,d] fura n-1-amine F4 [00146] -4.82 219 9,9-dimethyl-N,N-bis(4-(naphthalen-1-yl)phenyl)-9H-fluoren-2-amine F8 [00147] -4.84 232 N-([1,1′-biphenyl]-4-yl)-N-(2-(9,9-diphenyl-9H-fluoren-4-yl)phenyl)-9,9-dimethyl-9H-fluoren-2-amine F9 [00148] -4.84 218 N-(9,9-diphenyl-9H-fluoren-2-yl)-N,9-diphenyl-9H-carbazol-2-amine F18 [00149] -4.73 216

[0389] As can be seen in Table 2, the matrix compound of formula (II) or (III) have rate onset temperatures suitable for mass production of organic electronic devices.

General Procedure for Fabrication of Organic Electronic Devices Comprising a Hole Injection Layer Comprising a Metal Complex and a Matrix Compound

[0390] For Examples 1 to 25 and Examples 36 to 79 in Table 3, 4 and 5, a glass substrate with an anode layer comprising a first anode sub-layer of 120 nm Ag, a second anode sub-layer of 8 nm ITO and a third anode sub-layer of 10 nm ITO was cut to a size of 50 mm x 50 mm x 0.7 mm, ultrasonically washed with water for 60 minutes and then with isopropanol for 20 minutes. The liquid film was removed in a nitrogen stream, followed by plasma treatment, see Table 3, 4 and 5, to prepare the anode layer. The plasma treatment was performed in nitrogen atmosphere or in an atmosphere comprising 97.6 vol.-% nitrogen and 2.4 vol.-% oxygen, see Table 3, 4 and 5.

[0391] Then, the matrix compound and the metal complex were co-deposited in vacuum on the anode layer, to form a hole injection layer (HIL) having a thickness of 10 nm. The composition of the hole injection layer can be seen in Table 3, 4 and 5.

[0392] Then, the matrix compound was vacuum deposited on the HIL, to form a HTL having a thickness of 123 nm. The matrix compound in the HTL is selected the same as the matrix compound in the HIL. The matrix compound can be seen in Table 3, 4 and 5.

[0393] Then N-(dibenzo[b,d]furan-4-yl)phenyl)-N-(9-phenyl-9H-fluoren-9-yl)phenyl)-[1,1′-biphenyl]-4-amine (CAS 1824678-59-2) was vacuum deposited on the HTL, to form an electron blocking layer (EBL) having a thickness of 5 nm.

[0394] Then 97 vol.-% H09 as EML host and 3 vol.-% BD200 (Sun Fine Chemicals, Korea) as fluorescent blue emitter dopant were deposited on the EBL, to form a blue-emitting first emission layer (EML) with a thickness of 20 nm.

[0395] Then a hole blocking layer was formed with a thickness of 5 nm by depositing 2-(3′-(9,9-dimethyl-9H-fluoren-2-yl)-[1,1′-biphenyl]-3-yl)-4,6-diphenyl-1,3,5-triazine on the emission layer EML.

[0396] Then the electron transporting layer having a thickness of 31 nm was formed on the hole blocking layer by depositing 50 wt.-% 4′-(4-(4-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)naphthalen-1-yl)-[1,1′-biphenyl]-4-carbonitrile and 50 wt.-% of LiQ.

[0397] Then Ag:Mg (90:10 vol.-%) was evaporated at a rate of 0.01 to 1 Å/s at 10.sup.-7 mbar to form a cathode layer with a thickness of 13 nm on the electron transporting layer.

[0398] Then, F3 was deposited on the cathode layer to form a capping layer with a thickness of 75 nm.

Comparative Example 1

[0399] For comparative example 1 in Table 3, a 15 Ω /cm.sup.2 glass substrate with 90 nm ITO (available from Corning Co.) was cut to a size of 50 mm × 50 mm × 0.7 mm, ultrasonically washed with water for 60 minutes and then with isopropanol for 20 minutes. The liquid film was removed in a nitrogen stream, followed by plasma treatment in nitrogen atmosphere at a power of 100 W for 75 seconds to prepare the anode layer.

[0400] Then, 99 wt.-% F3 and 1 wt.-% MC-11 were co-deposited in vacuum on the anode layer, to form a hole injection layer (HIL) having a thickness of 10 nm.

[0401] Then, F3 was vacuum deposited on the HIL, to form a HTL having a thickness of 123 nm.

[0402] Then, the EBL, EML, HBL and ETL are deposited in this order on the HTL, as described for example 1 above.

[0403] Then Al was evaporated at a rate of 0.01 to 1 Å/s at 10.sup.-7 mbar to form a cathode layer with a thickness of 100 nm on the electron transporting layer.

Comparative Example 2

[0404] For comparative example 2 in Table 3, a glass substrate was cut to a size of 50 mm × 50 mm × 0.7 mm, ultrasonically washed with water for 60 minutes and then with isopropanol for 20 minutes. The liquid film was removed in a nitrogen stream, followed by plasma treatment in nitrogen atmosphere at a power of 100 W for 75 seconds, to prepare the substrate.

[0405] Then, 100 nm Ag was deposited in vacuum on the substrate to form the anode layer.

[0406] Then, 99 wt.-% F3 and 1 wt.-% MC-11 were co-deposited in vacuum on the anode layer, to form a hole injection layer (HIL) having a thickness of 10 nm.

[0407] Then, F3 was vacuum deposited on the HIL, to form a HTL having a thickness of 123 nm.

[0408] Then, the EBL, EML, HBL and ETL, cathode layer and capping layer are deposited in this order on the HTL, as described for example 1 above.

Comparative Example 3

[0409] Comparative example 3 in Table 4 was prepared as example 12 but without the hole injection layer (HIL). In comparative example 3, the hole transport layer (HTL) was deposited directly on the anode layer.

Comparative Example 4

[0410] Comparative example 4 in Table 3 was prepared as Example 40. In comparative example 4, the hole injection layer comprises metal complex CuPc. CuPc may also be named copper(II) phthalocyanine.

Comparative Example 5

[0411] Comparative example 5 in Table 3 was prepared as in Example 40 but without the metal complex MC-26. In comparative example 5, the hole injection layer consisting of F3 was deposited directly on the anode layer. Then, the hole transport layer was deposited directly on the hole injection layer, as described for Example 40 above.

Comparative Example 6

[0412] Comparative example 6 in Table 5 was prepared as Example 79. In comparative example 4, the hole injection layer comprises metal complex CuPc.

Comparative Example 7

[0413] Comparative example 7 in Table 5 was prepared as Example 79 but without the metal complex MC-26. In comparative example 7, the hole injection layer consisting of F1 was deposited directly on the anode layer. Then, the hole transport layer was deposited directly on the hole injection layer, as described for Example 79 above.

General Procedure for Fabrication of Organic Electronic Devices Comprising a Hole Injection Layer Comprising a First Sub-Layer and a Second Sub-Layer

[0414] For Examples 26 to 35 and Examples 80 and 81 in Table 6, a glass substrate with an anode layer comprising a first anode sub-layer of 120 nm Ag, a second anode sub-layer of 8 nm ITO and a third anode sub-layer of 10 nm ITO was cut to a size of 50 mm × 50 mm × 0.7 mm, ultrasonically washed with water for 60 minutes and then with isopropanol for 20 minutes. The liquid film was removed in a nitrogen stream, followed by plasma treatment in an atmosphere comprising 97.6 vol.-% nitrogen and 2.4 vol.-% oxygen at a power of 75 W for 35 seconds, to prepare the anode layer.

[0415] Then, the metal complex was deposited in vacuum on the anode layer to form a first hole injection sub-layer. The composition and thickness of the first hole injection sub-layer can be seen in Table 6.

[0416] Then, the matrix compound was deposited in vacuum on the first hole injection sub-layer to form a second hole-injection sub-layer. The composition and thickness of the second hole injection sub-layer can be seen in Table 6.

[0417] Then, the matrix compound was vacuum deposited on the second hole injection sub-layer to form a HTL with a thickness of 123 nm. The matrix compound in the HTL is selected the same as the matrix compound in the second hole injection sub-layer. The matrix compound can be seen in Table 6.

[0418] Then, the EBL, EML, HBL and ETL, cathode layer and capping layer are deposited in this order on the HTL, as described for examples 1 to 25 above.

Comparative Example 8

[0419] Comparative example 8 in Table 6 was prepared as Example 81. In comparative example 8, the first hole injection sub-layer comprises metal complex CuPc.

Comparative Example 9

[0420] Comparative example 9 in Table 6 was prepared as Example 81 but without the metal complex MC-26. In comparative example 9, the first hole injection sub-layer consisting of F1 was deposited directly on the anode layer. Then, the second hole injection sub-layer was deposited directly on the hole injection layer, as described for Example 81 above.

Comparative Example 10

[0421] Comparative example 10 in Table 6 was prepared as Example 80 but without the metal complex MC-26. In comparative example 8, the first hole injection sub-layer consisting of F3 was deposited directly on the anode layer. Then, the second hole injection sub-layer was deposited directly on the hole injection layer, as described for Example 80 above.

[0422] The organic electronic device was protected from ambient conditions by encapsulation of the device with a glass slide. Thereby, a cavity is formed, which includes a getter material for further protection.

[0423] To assess the performance of the inventive examples compared to the prior art, the current efficiency is measured at 20° C. The current-voltage characteristic is determined using a Keithley 2635 source measure unit, by sourcing an operating voltage U in V and measuring the current in mA flowing through the device under test. The voltage applied to the device is varied in steps of 0.1V in the range between 0 V and 10 V.

Technical Effect

[0424] In Table 3 are shown data for organic electronic devices comprising a hole injection layer comprising F3 as matrix compound and a variety of metal complexes of formula (I) and formulae (Ia) to (Id). F3 has a HOMO level of -4.69 eV.

[0425] In comparative example 1, the anode layer consists of ITO. The anode layer is treated with nitrogen plasma for 75 s at a power of 100 W. The hole injection layer comprises 1 wt.-% metal complex MC-11. The operating voltage is 4.89 V.

[0426] In comparative example 2, the anode layer consists of Ag. The same plasma treatment was applied to the substrate as above. The hole injection layer has the same composition as in comparative example 1. The operating voltage is > 10 V.

[0427] In example 1, the anode layer consists of a first anode sub-layer consisting of Ag and a second and third anode sub-layer consisting of ITO. The same plasma treatment was applied as above. The hole injection layer has the same composition as in comparative examples 1 and 2. The operating voltage is improved to 4.65 V.

[0428] In example 2, the anode layer is the same as in example 1. The anode layer is treated with a nitrogen oxygen plasma (97.6 vol.-% nitrogen and 2.4 vol.-% oxygen) for 60 s at a power of 100 W. The hole injection layer has the same composition as in comparative examples 1 and 2 and example 1. The operating voltage is further improved to 4.52 V.

[0429] In example 3, the anode layer and the hole injection layer are the same as in example 2. The anode layer is treated with a nitrogen oxygen plasma (97.6 vol.-% nitrogen and 2.4 vol.-% oxygen) for 30 s at a power of 75 W. The operating voltage is comparable to example 2. In summary, the plasma treatment does not have a substantial impact on operating voltage.

[0430] In example 4, the anode layer and plasma treatment are the same as in example 3. The hole injection layer comprises 1 wt.-% metal complex MC-10. The operating voltage is in a similar range to example 3.

[0431] In example 5, the anode layer and plasma treatment are the same as in example 4. The hole injection layer comprises 1 wt.-% metal complex MC-13. The operating voltage is in a similar range to example 4.

[0432] In example 6, the anode layer is the same as in example 5. The anode layer is treated with a nitrogen oxygen plasma (97.6 vol.-% nitrogen and 2.4 vol.-% oxygen) for 35 s at a power of 75 W. The hole injection layer comprises 1 wt.-% metal complex MC-14. MC-14 comprises Cs cation instead of Ag cation. The operating voltage is improved to 4.17 V.

[0433] In example 7, the anode layer and plasma treatment are the same as in example 6. The hole injection layer comprises 1 wt.-% metal complex MC-15. MC-15 comprises a Mg cation instead of a Cs cation. The operating voltage is in a similar range to example 6.

[0434] In example 8, the anode layer and plasma treatment are the same as in example 4. The hole injection layer comprises 1 wt.-% metal complex MC-16. MC-16 comprises a Ca cation instead of a Mg cation. The operating voltage is 4.58 V, and thereby still substantially improved over comparative examples 1 and 2.

[0435] In example 9 and 10, the hole injection layer comprises two further metal complexes, namely Li TFSI and Cu (TFSI).sub.2. Again the operating voltage is improved over comparative examples 1 and 2.

[0436] In example 11, the anode layer and plasma treatment are the same as in example 5. The hole injection layer comprises 1 wt.-% MC-32. MC-32 comprises a Bi cation and a ligand of formula (Ic). The operating voltage is improved over comparative examples 1 and 2.

[0437] In examples 36 to 69, the anode layer and plasma treatment are the same as in example 3. The hole injection layer comprises a range of metal complexes at a range of concentrations. The operating voltage is improved over comparative examples 1 2, 3 and 4.

[0438] In comparative example 4, the hole injection layer comprises metal complex CuPc. CuPc comprises a Cu(II) cation and a phthalocyanine ligand. The phthalocyanine ligand has two negative charges. Compared to Example 40, the operating voltage is increased from 4.47 to 5.06 V.

[0439] In comparative example 5, the hole injection layer is free of metal complex. Compared to example 40, the operating voltage is increased from 4.47 to 4.83 V.

[0440] In Table 4 are shown data for organic electronic devices comprising an anode layer consisting of a first anode sub-layer consisting of Ag and a second and third anode sub-layer consisting of ITO. The anode layer was treated with a nitrogen oxygen plasma (97.6 vol.-% nitrogen and 2.4 vol.-% oxygen) for 35 s at a power of 75 W. In comparative example 3, the organic electronic device is free of a hole injection layer. The operating voltage is very high at 7.17 V.

[0441] In examples 12 to 21, the hole injection layer comprises matrix compound F2. F2 has a HOMO level of -4.81 eV.

[0442] In example 12, the hole injection layer further comprises 2 wt.-% metal complex MC-10. The operating voltage is improved to 4.45 V.

[0443] In examples 13 and 14, the concentration of metal complex is increased to 3 and 5 wt.-% respectively. The operating voltage is further improved to 4.32 and 4.12 V, respectively.

[0444] In examples 15 to 18, the hole injection layer further comprises 2 to 10 wt.-% metal complex MC-17. The operating voltage is improved to 4.3 to 4.14 V.

[0445] In examples 19 to 21, the hole injection layer further comprises 2 to 5 wt.-% metal complex MC-26. MC-26 comprises a Cu cation instead of a Ag cation. The operating voltage is further improved to 4.18 to 4.1 V.

[0446] In summary, a substantial improvement in performance can be obtained, in particular if the concentration of metal complex is 3 wt.-% or higher.

[0447] In Table 5, data are shown for organic electronic devices comprising an anode layer consisting of a first anode sub-layer consisting of Ag and a second and third anode sub-layer consisting of ITO. The anode layer was treated with a nitrogen oxygen plasma (97.6 vol.-% nitrogen and 2.4 vol.-% oxygen) for 35 s at a power of 75 W.

[0448] In example 22, the hole injection layer comprises 97 wt.-% matrix compound F4 and 3 wt.-% metal complex MC-5. F4 has a HOMO level of -4.82 eV. The operating voltage is improved for 4.17 V.

[0449] In example 23, the hole injection layer comprises 97 wt.-% matrix compound F9 and 3 wt.-% metal complex MC-5. F9 has a HOMO level of -4.84 eV. The operating voltage is still within an acceptable range at 4.42 V.

[0450] In example 24, the hole injection layer comprises 97 wt.-% matrix compound F4 and 3 wt.- % metal complex MC-32. MC-32 comprises a Bi cation and a ligand of formula (Ic). The operating voltage is improved to 4.27 V.

[0451] In example 25, the hole injection layer comprises 97 wt.-% matrix compound F4 and 3 wt.-% metal complex MC-31. MC-31 comprises a Zn cation and a ligand of formula (Ib). The operating voltage is improved to 4.41 V.

[0452] In example 70 to 79, the hole injection layer comprises a range of matrix compounds and a range of metal complexes. The operating voltage is improved compared to comparative examples 6 and 7.

[0453] In comparative example 6, the hole injection layer comprises metal complex CuPc. Compared to example 79, the operating voltage is increased from 4.82 to 6.08 V.

[0454] In comparative example 7, the hole injection layer consists of matrix compound F1. Compared to example 79, the operating voltage is increased from 4.82 to 5.57 V.

[0455] In summary, even if the HOMO level of the matrix compound further away vacuum level the performance of organic electronic devices is improved.

[0456] In Table 6 are shown data for an organic electronic device comprising an anode layer consisting of a first anode sub-layer consisting of Ag and a second and third anode sub-layer consisting of ITO. The anode layer was treated with a nitrogen oxygen plasma (97.6 vol.-% nitrogen and 2.4 vol.-% oxygen) for 35 s at a power of 75 W. The hole injection layer comprises of a first hole injection sub-layer comprising a metal complex of formula (I) and formulae (Ia) to (Id) and a second hole injection sub-layer comprising of matrix compound.

[0457] In example 26, the first hole injection sub-layer comprises of metal complex MC-14 and the second hole injection sub-layer comprises of matrix compound F3. The first hole injection sub-layer has a thickness of 2 nm. The operating voltage is 4.5 V, and thereby substantially improved over comparative examples 1 and 2, see Table 3.

[0458] In examples 27 and 28, the thickness of the first hole injection sub-layer is increased to 3 and 5 nm, respectively. The operating voltage is comparable to example 26.

[0459] In examples 29 to 31, the first hole injection sub-layer comprises of metal complex MC-32 with a thickness of 2 to 5 nm. The second hole injection sub-layer comprises matrix compound F3. The operating voltage is substantially improved to comparative examples 1 and 2.

[0460] In example 32, the second hole injection sub-layer comprises matrix compound F4. F4 has a HOMO level of -4.82 eV. The HOMO level is further away from vacuum level than the HOMO level of F3, see Table 6. The operating voltage is improved to 4.12 V.

[0461] In example 33, the second hole injection sub-layer comprises matrix compound F9. F9 has a HOMO level of -4.84 eV. Thereby the HOMO level is even further away from vacuum level compared to F3. The operating voltage is improved to 4.25 V.

[0462] In example 34, the first hole injection sub-layer comprises metal complex MC-31. The second hole injection sub-layer comprises matrix compound F4. F4 has a HOMO level of -4.82 eV. The operating voltage is improved to 4.14 V.

[0463] In example 35, the second hole injection sub-layer comprises matrix compound F9. F9 has a HOMO level of -4.84 eV. The operating voltage is improved to 4.32 V.

[0464] In examples 80 and 81, the first hole injection sub-layer comprises metal complex MC-26. The second hole injection sub-layer comprises matrix compounds F3 and F1, respectively. The HOMO level of F3 and F1 can be seen in Table 6. The operating voltage is in a range comparable to Examples 29 and 30.

[0465] In comparative example 8, the first hole-injection sub-layer comprises metal complex CuPc. The second hole injection sub-layer comprises matrix compound F1. Compared to Example 81, the operating voltage is increased from 4.62 V to > 10 V.

[0466] In comparative examples 9 and 10, the first hole injection sub-layer and the second hole injection sub-layer consist of matrix compounds F1 (comparative example 9) and F3 (comparative example 10), respectively. The HOMO level of F1 and F3 can be seen in Table 6. The operating voltage is substantially increased compared to Examples 26 to 35 and Examples 80 and 81.

[0467] In summary, a substantial improvement in performance, in particular operating voltage, may be achieved in organic electronic devices according to invention.

[0468] A reduction in operating voltage is beneficial for reduced power consumption and improved battery life, in particular in mobile devices.

TABLE-US-00003 Organic electronic devices comprising a hole injection layer comprising a metal complex and a matrix compound Anode Gas P [W] t [s] Matrix compound Concentration matrix compound [wt.-%] Metal complex Concentration of metal complex [wt%] U At 50 mA/cm.sup.2 [V] Comparative example 1 ITO N.sub.2 100 75 F3 99 MC-11 1 4.89 Comparative example 2 Ag N.sub.2 100 75 F3 99 MC-11 1 > 10 Example 1 ITO/Ag/ITO N.sub.2 100 75 F3 99 MC-11 1 4.65 Example 2 ITO/Ag/ITO N.sub.2: O.sub.2 100 60 F3 99 MC-11 1 4.52 Example 3 ITO/Ag/ITO N.sub.2: O.sub.2 75 30 F3 99 MC-11 1 4.56 Example 4 ITO/Ag/ITO N.sub.2: O.sub.2 75 30 F3 99 MC-10 1 4.64 Example 5 ITO/Ag/ITO N.sub.2: O.sub.2 75 30 F3 99 MC-13 1 4.60 Example 6 ITO/Ag/ITO N.sub.2: O.sub.2 75 35 F3 99 MC-14 1 4.17 Example 7 ITO/Ag/ITO N.sub.2: O.sub.2 75 35 F3 99 MC-15 1 4.16 Example 8 ITO/Ag/ITO N.sub.2: O.sub.2 75 35 F3 99 MC-16 1 4.58 Example 9 ITO/Ag/ITO N.sub.2: O.sub.2 75 35 F3 99 Li TFSI 1 4.58 Example 10 ITO/Ag/ITO N.sub.2: O.sub.2 75 35 F3 99 Cu (TFSI).sub.2 1 3.91 Example 11 ITO/Ag/ITO N.sub.2: O.sub.2 75 30 F3 99 MC-32 1 4.53 Example 36 ITO/Ag/ITO N.sub.2: O.sub.2 75 30 F3 99 MC-25 1 4.54 Example 37 ITO/Ag/ITO N.sub.2: O.sub.2 75 30 F3 97 MC-25 3 4.5 Example 38 ITO/Ag/ITO N.sub.2: O.sub.2 75 30 F3 95 MC-25 5 4.49 Example 39 ITO/Ag/ITO N.sub.2: O.sub.2 75 30 F3 92 MC-25 8 4.48 Example 40 ITO/Ag/ITO N.sub.2: O.sub.2 75 30 F3 99 MC-26 1 4.47 Example 41 ITO/Ag/ITO N.sub.2: O.sub.2 75 30 F3 99 MC-30 1 4.56 Example 42 ITO/Ag/ITO N.sub.2: O.sub.2 75 30 F3 97 MC-30 3 4.48 Example 43 ITO/Ag/ITO N.sub.2: O.sub.2 75 30 F3 95 MC-30 5 4.51 Example 44 ITO/Ag/ITO N.sub.2: O.sub.2 75 30 F3 90 MC-30 10 4.50 Example 45 ITO/Ag/ITO N.sub.2: O.sub.2 75 30 F3 99 MC-33 1 4.48 Example 46 ITO/Ag/ITO N.sub.2: O.sub.2 75 30 F3 98 MC-33 2 4.43 Example 47 ITO/Ag/ITO N.sub.2: O.sub.2 75 30 F3 97 MC-33 3 4.42 Example 48 ITO/Ag/ITO N.sub.2: O.sub.2 75 30 F3 95 MC-33 5 4.41 Example 49 ITO/Ag/ITO N.sub.2: O.sub.2 75 30 F3 93 MC-33 7 4.41 Example 50 ITO/Ag/ITO N.sub.2: O.sub.2 75 30 F3 90 MC-33 10 4.41 Example 51 ITO/Ag/ITO N.sub.2: O.sub.2 75 30 F3 99 MC-34 1 4.52 Example 52 ITO/Ag/ITO N.sub.2: O.sub.2 75 30 F3 98 MC-34 2 4.44 Example 53 ITO/Ag/ITO N.sub.2: O.sub.2 75 30 F3 97 MC-34 3 4.45 Example 54 ITO/Ag/ITO N.sub.2: O.sub.2 75 30 F3 95 MC-34 5 4.42 Example 55 ITO/Ag/ITO N.sub.2: O.sub.2 75 30 F3 93 MC-34 7 4.45 Example 56 ITO/Ag/ITO N.sub.2: O.sub.2 75 30 F3 90 MC-34 10 4.47 Example 57 ITO/Ag/ITO N.sub.2: O.sub.2 75 30 F3 99 MC-35 1 4.6 Example 58 ITO/Ag/ITO N.sub.2: O.sub.2 75 30 F3 98 MC-35 2 4.51 Example 59 ITO/Ag/ITO N.sub.2: O.sub.2 75 30 F3 96 MC-35 4 4.48 Example 60 ITO/Ag/ITO N.sub.2: O.sub.2 75 30 F3 99 MC-36 1 4.57 Example 61 ITO/Ag/ITO N.sub.2: O.sub.2 75 30 F3 95 MC-36 5 4.48 Example 62 ITO/Ag/ITO N.sub.2: O.sub.2 75 30 F3 92 MC-36 8 4.48 Example 63 ITO/Ag/ITO N.sub.2: O.sub.2 75 30 F3 90 MC-36 10 4.50 Example 64 ITO/Ag/ITO N.sub.2: O.sub.2 75 30 F3 99 MC-37 1 4.45 Example 65 ITO/Ag/ITO N.sub.2: O.sub.2 75 30 F3 98 MC-37 2 4.41 Example 66 ITO/Ag/ITO N.sub.2: O.sub.2 75 30 F3 97 MC-37 3 4.40 Example 67 ITO/Ag/ITO N.sub.2: O.sub.2 75 30 F3 95 MC-37 5 4.40 Example 68 ITO/Ag/ITO N.sub.2: O.sub.2 75 30 F3 93 MC-37 7 4.40 Example 69 ITO/Ag/ITO N.sub.2: O.sub.2 75 30 F3 90 MC-37 10 4.41 Comparative example 4 ITO/Ag/ITO N.sub.2: O.sub.2 75 30 F3 99 CuPc 1 5.06 Comparative example 5 ITO/Ag/ITO N.sub.2: O.sub.2 75 30 F3 100 - 0 4.83

TABLE-US-00004 Organic electronic devices comprising a hole injection layer comprising a metal complex and a matrix compound Anode Gas P [W] t [s] Matrix compound Concentration matrix compound [wt.-%] Metal complex Concentration of metal complex [wt%] U At 50 mA/cm.sup.2 [V] Comparative example 3 ITO/Ag/ITO N.sub.2: O.sub.2 75 35 - 7.17 Example 12 ITO/Ag/ITO N.sub.2: O.sub.2 75 35 F2 98 MC-10 2 4.45 Example 13 ITO/Ag/ITO N.sub.2: O.sub.2 75 35 F2 97 MC-10 3 4.32 Example 14 ITO/Ag/ITO N.sub.2: O.sub.2 75 35 F2 95 MC-10 5 4.12 Example 15 ITO/Ag/ITO N.sub.2: O.sub.2 75 35 F2 97 MC-17 3 4.30 Example 16 ITO/Ag/ITO N.sub.2: O.sub.2 75 35 F2 95 MC-17 5 4.21 Example 17 ITO/Ag/ITO N.sub.2: O.sub.2 75 35 F2 93 MC-17 7 4.17 Example 18 ITO/Ag/ITO N.sub.2: O.sub.2 75 35 F2 90 MC-17 10 4.14 Example 19 ITO/Ag/ITO N.sub.2: O.sub.2 75 35 F2 98 MC-26 2 4.18 Example 20 ITO/Ag/ITO N.sub.2: O.sub.2 75 35 F2 97 MC-26 3 4.13 Example 21 ITO/Ag/ITO N.sub.2: O.sub.2 75 35 F2 95 MC-26 5 4.10

TABLE-US-00005 Organic electronic devices comprising a hole injection layer comprising a metal complex and a matrix compound Anode Gas P [W] t [s] Matrix compound HOMO level of matrix compound [eV] Concentration matrix compound [wt.-%] Metal complex Concentration of metal complex [wt%] U At 50 mA/cm.sup.2 [V] Example 22 ITO/Ag/ITO N.sub.2: O.sub.2 75 35 F4 -4.82 97 MC-5 3 4.17 Example 23 ITO/Ag/ITO N.sub.2: O.sub.2 75 35 F9 -4.84 97 MC-5 3 4.42 Example 24 ITO/Ag/ITO N.sub.2: O.sub.2 75 35 F4 -4.82 97 MC-32 3 4.27 Example 25 ITO/Ag/ITO N.sub.2: O.sub.2 75 35 F4 -4.82 97 MC-31 3 4.41 Example 70 ITO/Ag/ITO N.sub.2: O.sub.2 75 30 F4 -4.82 95 MC-25 5 4.31 Example 71 ITO/Ag/ITO N.sub.2: O.sub.2 75 30 F4 -4.82 90 MC-25 10 4.28 Example 72 ITO/Ag/ITO N.sub.2: O.sub.2 75 30 F4 -4.82 85 MC-25 15 4.29 Example 73 ITO/Ag/ITO N.sub.2: O.sub.2 75 30 F2 -4.81 95 MC-25 5 4.17 Example 74 ITO/Ag/ITO N.sub.2: O.sub.2 75 30 F2 -4.81 90 MC-25 10 4.16 Example 75 ITO/Ag/ITO N.sub.2: O.sub.2 75 30 F2 -4.81 85 MC-25 15 4.15 Example 76 ITO/Ag/ITO N.sub.2: O.sub.2 75 30 F18 -4.73 98 MC-35 2 4.58 Example 77 ITO/Ag/ITO N.sub.2: O.sub.2 75 30 F18 -4.73 94 MC-35 6 4.44 Example 78 ITO/Ag/ITO N.sub.2: O.sub.2 75 30 F18 -4.73 90 MC-35 10 4.42 Example 79 ITO/Ag/ITO N.sub.2: O.sub.2 75 30 F1 -4.72 99 MC-26 1 4.82 Comparative example 6 ITO/Ag/ITO N.sub.2: O.sub.2 75 30 F1 -4.72 99 CuPc 1 6.08 Comparative example 7 ITO/Ag/ITO N.sub.2: O.sub.2 75 30 F1 -4.72 100 - 0 5.57

TABLE-US-00006 Organic electronic device comprising a hole injection layer comprising a first hole injection sub-layer (“first sub-layer”) and a second hole injection sub-layer (“second sub-layer”) Anode Gas P [W] t [s] Composition of first sub-layer Thickness of first sub-layer [nm] Composition of second sub-layer Thickness of second sub-layer [nm] HOMO level of compound in second sub-layer [eV] U At 50 mA/cm.sup.2 [V] Example 26 ITO/Ag/ITO N.sub.2: O.sub.2 75 35 MC-14 2 F3 8 -4.69 4.50 Example 27 ITO/Ag/ITO N.sub.2: O.sub.2 75 35 MC-14 3 F3 7 -4.69 4.54 Example 28 ITO/Ag/ITO N.sub.2: O.sub.2 75 35 MC-14 5 F3 5 -4.69 4.55 Example 29 ITO/Ag/ITO N.sub.2: O.sub.2 75 35 MC-32 2 F3 8 -4.69 4.68 Example 30 ITO/Ag/ITO N.sub.2: O.sub.2 75 35 MC-32 3 F3 7 -4.69 4.63 Example 31 ITO/Ag/ITO N.sub.2: O.sub.2 75 35 MC-32 5 F3 5 -4.69 4.55 Example 32 ITO/Ag/ITO N.sub.2: O.sub.2 75 35 MC-32 3 F4 7 -4.82 4.12 Example 33 ITO/Ag/ITO N.sub.2: O.sub.2 75 35 MC-32 3 F9 7 -4.84 4.25 Example 34 ITO/Ag/ITO N.sub.2: O.sub.2 75 35 MC-31 3 F4 7 -4.82 4.14 Example 35 ITO/Ag/ITO N.sub.2: O.sub.2 75 35 MC-31 3 F9 7 -4.84 4.32 Example 80 ITO/Ag/ITO N.sub.2: O.sub.2 75 35 MC-26 5 F3 3 -4.69 4.66 Example 81 ITO/Ag/ITO N.sub.2: O.sub.2 75 35 MC-26 5 F1 4 -4.72 4.62 Comparative example 8 ITO/Ag/ITO N.sub.2: O.sub.2 75 35 CuPc 5 F1 4 -4.72 > 10 Comparative example 9 ITO/Ag/ITO N.sub.2: O.sub.2 75 35 F3 5 F1 3 -4.72 6.08 Comparative example 10 ITO/Ag/ITO N.sub.2: O.sub.2 75 35 F3 5 F3 3 -4.69 5.11

[0469] Comparative examples 4, 6 and 8 are examples of the invention with increased operating voltage.

[0470] The particular combinations of elements and features in the above detailed embodiments are exemplary only; the interchanging and substitution of these teachings with other teachings in this and the patents/applications incorporated by reference are also expressly contemplated. As those skilled in the art will recognize, variations, modifications, and other implementations of what is described herein can occur to those of ordinary skill in the art without departing from the spirit and the scope of the invention as claimed. Accordingly, the foregoing description is by way of example only and is not intended as limiting. In the claims, the word “comprising” does not exclude other elements or steps, and the indefinite article “a” or “an” does not exclude a plurality. The mere fact that certain measures are recited in mutually different dependent claims does not indicate that a combination of these measured cannot be used to advantage. The invention’s scope is defined in the following claims and the equivalents thereto. Furthermore, reference signs used in the description and claims do not limit the scope of the invention as claimed.