A Ce(IV) Metal Complex, an Organic Electronic Device Comprising an Anode Layer, a Cathode Layer and a Charge Generation Layer, Wherein the Charge Generation Layer Comprises a P-Type Charge Generation Layer That Comprises the Ce(IV) Metal Complex and a N-Type Charge Generation Layer

Abstract

The present invention is directed to an organic electronic device comprising an anode layer, a cathode layer and a charge generation layer, wherein the charge generation layer comprises a p-type charge generation layer and a n-type charge generation layer, wherein the n-type charge generation layer comprising an organic electron transport compound and a metal dopant, wherein the metal dopant is selected from a metal with an electronegativity of 1.4 eV by Pauling scale; the p-type charge generation layer comprising an organic hole transport compound and a Ce(IV) metal complex, and wherein the Ce(IV) metal complex comprises at least one anionic ligand L.

Claims

1.-15. (canceled)

16. An organic electronic device comprising an anode layer, a cathode layer and a charge generation layer, wherein the charge generation layer comprises a p-type charge generation layer and a n-type charge generation layer, wherein the n-type charge generation layer comprising an organic electron transport compound and a metal dopant, wherein the metal dopant is selected from a metal with an electronegativity of 1.4 eV by Pauling scale; the p-type charge generation layer comprising an organic hole transport compound and a Ce(IV) metal complex, wherein the Ce(IV) metal complex comprises at least one anionic ligand L, wherein the anionic ligand comprising per ligand L at least 16 covalently bound atoms; wherein the n-type charge generation layer is arranged closer to the anode layer and the p-type charge generation layer is arranged closer to the cathode layer.

17. An organic electronic device comprising an anode layer, a cathode layer and a charge generation layer, wherein the charge generation layer comprises a p-type charge generation layer and a n-type charge generation layer, wherein the n-type charge generation layer comprises an organic electron transport compound and a metal dopant; and the p-type charge generation layer comprises: an organic hole transport compound, and a Ce(IV) metal complex, wherein the Ce(IV) metal complex has the formula (I):
Ce.sup.4(L.sup.).sub.4(AL).sub.n(I), wherein L is an anionic ligand comprising at least 16 covalently bound atoms, wherein at least two atoms are selected from carbon atoms; AL is an ancillary ligand which coordinates to the metal M; n is an integer selected from 0 to 2; wherein the n-type charge generation layer is arranged closer to the anode layer and the p-type charge generation layer is arranged closer to the cathode layer.

18. The organic electronic device according to claim 17, wherein the Ce(IV) metal complex has the formula (Ia): ##STR00077## wherein 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; A.sup.3 is selected from H or D; 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 the substituents on A.sup.1 and A.sup.2 are independently selected from halogen, F, C.sub.1 to C.sub.3 perhalogenated, perfluorinated alkyl, perfluorinated alkoxy, perfluorinated C.sub.1 to C.sub.3 alkyl or perfluorinated C.sub.1 to C.sub.3 alkoxy, or (O).sub.lC.sub.mH.sub.2m-C.sub.nHalo.sub.n2n+1 with l=0 or 1, m=1 or 2, n=1 to 3 and Halo=halogen or F.

20. The organic electronic device according to claim 18, wherein at least one of A.sup.1 and A.sup.2 is substituted alkyl and the substituents of the alkyl are fluorine with the number n.sub.F (of fluorine substituents) and n.sub.H (of hydrogens) follow the equation: n.sub.F>n.sub.H+2.

21. The organic electronic device according to claim 18, wherein at least one of A.sup.1 and A.sup.2 is selected from perfluorinated C.sub.1 to C.sub.6 alkyl, phenyl substituted with F or CF.sub.3.

22. The organic electronic device according to claim 18, wherein at least one of A.sup.1 and A.sup.2 is selected from perfluorinated alkyl or aryl.

23. 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 are 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, CN, or 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.

24. The organic electronic device according to claim 18, wherein at least one of A.sup.1 and A.sup.2 comprises at least two substituents, wherein the substituents on A.sup.1 and A.sup.2 are 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, CN, CF.sub.3, C.sub.2F.sub.5, C.sub.3F.sub.7, C.sub.4F.sub.9, OCF.sub.3, OC.sub.2F.sub.5, 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.

25. The organic electronic device according to claim 18, wherein the sum of A.sup.1 and A.sup.2 comprise 3 carbon atoms and 30 carbon atoms.

26. The organic electronic device according to claim 16, wherein the organic hole transport compound is selected from the group comprising of at least one arylamine compound, diarylamine compound, triarylamine compound, a compound of formula (IIIa) or a compound of formula (IIIb): ##STR00078## 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 may be 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.

27. The organic electronic device according to claim 16, wherein the metal dopant is selected from a metal with an electronegativity of 1.35 eV by Pauling scale.

28. The organic electronic device according to claim 16, wherein the metal dopant is a metal selected from the group comprising Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Sm, Eu or Yb.

29. The organic electronic device according to claim 17, wherein the AL is selected from the group comprising H.sub.2O, C.sub.2 to C.sub.40 mono- or multi-dentate ethers and C.sub.2 to C.sub.40 thioethers, C.sub.2 to C.sub.40 amines, C.sub.2 to C.sub.40 phosphine, C.sub.2 to C.sub.20 alkyl nitrile or C.sub.2 to C.sub.40 aryl nitrile, or a compound according to Formula (II); ##STR00079## wherein R.sup.6 and R.sup.7 are independently selected from C.sub.1 to C.sub.20 alkyl, C.sub.1 to C.sub.20 heteroalkyl, C.sub.6 to C.sub.20 aryl, heteroaryl with 5 to 20 ring-forming atoms, halogenated or perhalogenated C.sub.1 to C.sub.20 alkyl, halogenated or perhalogenated C.sub.1 to C.sub.20 heteroalkyl, halogenated or perhalogenated C.sub.6 to C.sub.20 aryl, halogenated or perhalogenated heteroaryl with 5 to 20 ring-forming atoms, or at least one R.sup.6 and R.sup.7 are bridged and form a 5 to 20 member ring, or the two R.sup.6 and/or the two R.sup.7 are bridged and form a 5 to 40 member ring or form a 5 to 40 member ring comprising an unsubstituted or C.sub.1 to C.sub.12 substituted phenanthroline.

30. The organic electronic device according to claim 17, wherein the ligand L of formula (I) comprising per ligand L at least 14 covalently bound atoms; or the ligand L of formula (I) comprising: at least three carbon atoms, alternatively at least four carbon atoms, and/or 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, and/or 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, alternatively 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, alternatively 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, and/or 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 may be 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.

31. The organic electronic device according to claim 17, wherein the ligand L of formula (I) are selected from G1 to G60: ##STR00080## ##STR00081## ##STR00082## ##STR00083## ##STR00084## ##STR00085## ##STR00086## ##STR00087## ##STR00088##

32. The organic electronic device according to claim 18, wherein the substituents selected from A.sup.1 and A.sup.2 are selected the same or independently from the following Formulas D1 to D68: ##STR00089## ##STR00090## ##STR00091## ##STR00092## ##STR00093## ##STR00094## ##STR00095## ##STR00096## ##STR00097## wherein the * denotes the binding position.

33. The organic electronic device according to claim 17, wherein the Ce(IV) metal complex of formula (I) are selected from Ce(IV) metal complexes E1 to E17: ##STR00098## ##STR00099## ##STR00100## ##STR00101##

34. The organic electronic device according to claim 16, wherein the organic electronic device is a light emitting device or a display device.

35. A Ce(IV) metal complex of formula (Ia): ##STR00102##

Description

DESCRIPTION OF THE DRAWINGS

[0481] 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.

[0482] 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 5

[0483] FIG. 1 is a schematic sectional view of an OLED comprising a charge generation layer, according to an exemplary embodiment of the present invention.

[0484] FIG. 2 is a schematic sectional view of an OLED comprising a charge generation layer, according to an exemplary embodiment of the present invention.

[0485] FIG. 3 is a schematic sectional view of a stacked OLED comprising a charge generation layer, according to an exemplary embodiment of the present invention.

[0486] FIG. 4 is a schematic sectional view of a stacked OLED comprising a charge generation layer, according to an exemplary embodiment of the present invention.

[0487] FIG. 5 is a schematic sectional view of a stacked OLED comprising a charge generation layer, according to an exemplary embodiment of the present invention.

[0488] Hereinafter, the figures are illustrated in more detail with reference to examples. However, the present disclosure is not limited to the following figures.

[0489] 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.

[0490] FIG. 1 is a schematic sectional view of an OLED 100, according to one exemplary embodiment of the present invention.

[0491] Referring to FIG. 1 the OLED 100 includes an anode layer 120, an n-type charge generation layer (n-CGL) 185, wherein the n-type charge generation layer (n-CGL) 185 comprises an electron transport compound and a metal dopant, a p-type charge generation layer (p-GCL) 135, wherein the p-type charge generation layer (p-GCL) 135 may comprise a Ce(IV) metal complex or a Ce(IV) metal complex of formula (I) and an organic hole transport compound, and a cathode layer 190.

[0492] FIG. 2 is a schematic sectional view of an OLED 100, according to one exemplary embodiment of the present invention.

[0493] Referring to FIG. 2 the OLED 100 includes a substrate 110, an anode layer 120, an n-type charge generation layer (n-CGL) 185, wherein the n-type charge generation layer (n-CGL) 185 comprises an electron transport compound and a metal dopant, a p-type charge generation layer (p-GCL) 135, wherein the p-type charge generation layer (p-GCL) 135 may comprise a Ce(IV) metal complex or a Ce(IV) metal complex of formula (I) and an organic hole transport compound, and a cathode layer 190.

[0494] FIG. 3 is a schematic sectional view of an OLED 100, according to one exemplary embodiment of the present invention.

[0495] Referring to FIG. 3 the OLED 100 includes a substrate 110, an anode layer 120, a hole injection layer (HIL) 130, a first hole transport layer (HTL1) 140, an electron blocking layer (EBL) 145, an emission layer (EML) 150, a hole blocking layer (HBL) 155, an electron transport layer (ETL) 160, an n-type charge generation layer (n-CGL) 185, a p-type charge generation layer (p-GCL) 135, a second hole transport layer (HTL2) 141, and electron injection layer (EIL) 180 and a cathode layer 190. The HIL may comprise a Ce(IV) metal complex or a Ce(IV) metal complex of formula (I).

[0496] FIG. 4 is a schematic sectional view of a stacked OLED 100, according to another exemplary embodiment of the present invention. FIG. 4 differs from FIG. 3 in that the OLED 100 of FIG. 4 further comprises a second emission layer.

[0497] Referring to FIG. 4 the OLED 100 includes a substrate 110, an anode layer 120, a hole injection layer (HIL) 130, a first hole transport layer (HTL) 140, a first electron blocking layer (EBL) 145, a first emission layer (EML) 150, an optional first hole blocking layer (HBL) 155, a first electron transport layer (ETL) 160, an n-type charge generation layer (n-CGL) 185, a p-type charge generation layer (p-GCL) 135, a second hole transport layer (HTL) 141, a second electron blocking layer (EBL) 146, a second emission layer (EML) 151, an optional second hole blocking layer (HBL) 156, a second electron transport layer (ETL) 161, an electron injection layer (EIL) 181 and a cathode layer 190. The HIL may comprise a Ce(IV) metal complex or a Ce(IV) metal complex of formula (I).

[0498] FIG. 5 is a schematic sectional view of a stacked OLED 100, according to another exemplary embodiment of the present invention. FIG. 5 differs from FIG. 4 in that the OLED 100 of FIG. 5 further comprises a charge generation connecting layer.

[0499] Referring to FIG. 5 the OLED 100 includes a substrate 110, an anode layer 120, a hole injection layer (HIL) 130, a first hole transport layer (HTL) 140, a first electron blocking layer (EBL) 145, a first emission layer (EML) 150, an optional first hole blocking layer (HBL) 155, a first electron transport layer (ETL) 160, an n-type charge generation layer (n-CGL) 185, a charge generation connecting layer 125 (c-CGL), a p-type charge generation layer (p-GCL) 135, a second hole transport layer (HTL) 141, a second electron blocking layer (EBL) 146, a second emission layer (EML) 151, an optional second hole blocking layer (HBL) 156, a second electron transport layer (ETL) 161, an electron injection layer (EIL) 181 and a cathode layer 190. The HIL may comprise a Ce(IV) metal complex or a Ce(IV) metal complex of formula (I).

[0500] While not shown in FIG. 1, FIG. 2, FIG. 3, FIG. 4 and FIG. 5, 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.

[0501] 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

[0502] The invention is furthermore illustrated by the following examples which are illustrative only and non-binding.

[0503] The compound of formulae (IIIa) and (IIIb) and Ce(IV) metal complex, Ce(IV) metal complexes of formula (I) or formula (Ia) may be prepared by methods known in the art.

Decomposition Temperature T.SUB.dec

[0504] The decomposition temperature T.sub.dec is measured by loading a sample of 9 to 11 mg into a Mettler Toledo 100 L aluminum pan without lid under nitrogen in a Mettler Toledo TGA-DSC 1 machine. The following heating program was used: 25 C. isothermal for 3 min; 25 C. to 600 C. with 10 K/min.

[0505] The decomposition temperature was determined based on the onset of the decomposition in TGA.

[0506] The decomposition temperature indicates the temperature at which the compound decomposes. The higher the decomposition temperature the higher the thermal stability of a compound.

Rate Onset Temperature

[0507] 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 Angstrom 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.

[0508] To achieve good control over the evaporation rate of an organic compound, the rate onset temperature may be in the range of 100 to 300 C. If the rate onset temperature is below 100 C. the evaporation may be too rapid and therefore difficult to control. If the rate onset temperature is above 300 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.

[0509] 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.

HOMO

[0510] The HOMO energy is calculated with the program package TURBOMOLE V6.5 (TURBOMOLE GmbH, Litzenhardtstrasse 19, 76135 Karlsruhe, Germany) from the optimized geometry by applying the hybrid functional B3LYP with a Def-TZVP basis set in the gas phase and inclusion of dispersion forces as D3BJ. Geometry is optimized by applying the hybrid functional B3LYP with a Def-SVP basis set in the gas phase and inclusion of dispersion forces as D3BJ. If more than one conformation is viable, the conformation with the lowest total energy is selected. If calculated by this method, the HOMO 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.

LUMO

[0511] The LUMO energy is calculated as single point energy calculation with the program package TURBOMOLE V6.5 (TURBOMOLE GmbH, Litzenhardtstrasse 19, 76135 Karlsruhe, Germany) from the optimized geometry by applying the hybrid functional B3LYP with a Def-TZVP basis set in the gas phase and inclusion of dispersion forces as D3BJ. Geometry is optimized by applying the hybrid functional B3LYP with a Def-SVP basis set in the gas phase and inclusion of dispersion forces as D3BJ. If more than one conformation is viable, the conformation with the lowest total energy is selected.

General Procedure for Fabrication of OLEDs Comprising a n-CGL and a p-CGL

[0512] For bottom-emission OLEDs, see Table 3, a 15 /cm.sup.2 glass substrate with 90 nm ITO (available from Corning Co.) was cut to a size of 50 mm50 mm0.7 mm, ultrasonically washed with isopropyl alcohol for 5 minutes and then with pure water for 5 minutes, and washed again with UV ozone for 30 minutes, to prepare the anode.

[0513] Then 95 wt.-% organic hole transport compound F3 and 5 wt.-% 4,4,4-((1E,1E,1E)-cyclopropane-1,2,3-triylidenetris(cyanomethanylylidene))tris(2,3,5,6-tetrafluorobenzonitrile) was vacuum co-deposited on the anode, to form a HIL having a thickness of 10 nm.

[0514] Then the same organic hole transport compound was vacuum deposited on the HIL, to form a first HTL having a thickness of 125 nm.

[0515] Then N,N-bis(4-(dibenzo[b,d]furan-4-yl)phenyl)-[1,1:4,1-terphenyl]-4-amine was vacuum deposited on the first HTL, to form a first electron blocking layer (EBL1) having a thickness of 5 nm.

[0516] Then 97 vol.-% H09 (Sun Fine Chemicals, Korea) as EML host and 3 vol.-% BD200 (Sun Fine Chemicals, Korea) as fluorescent blue dopant were deposited on the EBL, to form a first emission layer (EML1) with a thickness of 20 nm.

[0517] Then a first electron transport layer (ETL1) is formed on the first emission layer by depositing 2-(3-(9,9-dimethyl-9H-fluoren-2-yl)-[1,1-biphenyl]-3-yl)-4,6-diphenyl-1,3,5-triazine having a thickness of 25 nm.

[0518] Then, the n-type charge generation layer (n-CGL) having a thickness of 15 nm is formed on the ETL1 by co-depositing an organic electron transport compound ETM and a metal dopant. The composition of the n-CGL can be seen in Table 3.

[0519] Then, the p-type charge generation layer (p-CGL) having a thickness of 10 nm is formed on the n-CGL by co-depositing an organic hole transport compound HTM and a metal complex. The composition of the p-CGL can be seen in Table 3.

[0520] Then, a second hole transport layer (HTL2) having a thickness of 20 nm is formed on the p-CGL by depositing an organic hole transport compound as in the first hole transport layer. The composition of the second hole transport layer is the same as of the first hole transport layer.

[0521] Then N,N-bis(4-(dibenzo[b,d]furan-4-yl)phenyl)-[1,1:4,1-terphenyl]-4-amine was vacuum deposited on the second HTL, to form a second electron blocking layer (EBL2) having a thickness of 5 nm.

[0522] Then 97 vol.-% H09 (Sun Fine Chemicals, Korea) as EML host and 3 vol.-% BD200 (Sun Fine Chemicals, Korea) as fluorescent blue dopant were deposited on the EBL, to form a second emission layer (EML2) with a thickness of 20 nm.

[0523] Then a second electron transport layer (ETL2) is formed on the second emission layer by depositing 2-(3-(9,9-dimethyl-9H-fluoren-2-yl)-[1,1-biphenyl]-3-yl)-4,6-diphenyl-1,3,5-triazine having a thickness of 10 nm.

[0524] Then, the electron injection layer (EIL) having a thickness of 25 nm is formed on the second electron transport layer by co-depositing 99 vol.-% 3-Phenyl-3H-benzo[b]dinaphtho[2,1-d:1,2-f]phosphepine-3-oxide and 1 vol.-% Yb.

[0525] Then Al is vacuum deposited on the electron injection layer at a rate of 0.01 to 1 /s at 10.sup.7 mbar to form a cathode layer with a thickness of 100 nm.

[0526] The OLED stack is 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.

General Procedure for Fabrication of OLEDs Comprising a n-CGL, a p-CGL and a c-CGL

[0527] For bottom-emission OLEDs, see Table 4, a 15 /cm.sup.2 glass substrate with 90 nm ITO (available from Corning Co.) was cut to a size of 50 mm50 mm0.7 mm, ultrasonically washed with isopropyl alcohol for 5 minutes and then with pure water for 5 minutes, and washed again with UV ozone for 30 minutes, to prepare the anode.

[0528] Then 95 wt.-% organic hole transport compound F3 and 5 wt.-% 4,4,4-((1E,1E,1E)-cyclopropane-1,2,3-triylidenetris(cyanomethanylylidene))tris(2,3,5,6-tetrafluorobenzonitrile) was vacuum co-deposited on the anode, to form a HIL having a thickness of 10 nm.

[0529] Then the same organic hole transport compound was vacuum deposited on the HIL, to form a first HTL having a thickness of 125 nm.

[0530] Then N,N-bis(4-(dibenzo[b,d]furan-4-yl)phenyl)-[1,1:4,1-terphenyl]-4-amine was vacuum deposited on the first HTL, to form a first electron blocking layer (EBL1) having a thickness of 5 nm.

[0531] Then 97 vol.-% H09 (Sun Fine Chemicals, Korea) as EML host and 3 vol.-% BD200 (Sun Fine Chemicals, Korea) as fluorescent blue dopant were deposited on the EBL, to form a first emission layer (EML1) with a thickness of 20 nm.

[0532] Then a first electron transport layer (ETL1) is formed on the first emission layer by depositing 2-(3-(9,9-dimethyl-9H-fluoren-2-yl)-[1,1-biphenyl]-3-yl)-4,6-diphenyl-1,3,5-triazine having a thickness of 25 nm.

[0533] Then, the n-type charge generation layer (n-CGL) having a thickness of 15 nm is formed on the ETL1 by co-depositing an organic electron transport compound ETM and a metal dopant. The composition of the n-CGL can be seen in Table 4.

[0534] Then, the charge generation connecting layer (c-CGL) having a thickness of 2 nm is formed on the n-CGL by co-depositing a conducting compound. The composition of the c-CGL can be seen in Table 4.

[0535] Then, the p-type charge generation layer (p-CGL) having a thickness of 10 nm is formed on the c-CGL by co-depositing an organic hole transport compound HTM and a metal complex.

[0536] The composition of the p-CGL can be seen in Table 4.

[0537] Then, a second hole transport layer (HTL2) having a thickness of 20 nm is formed on the p-CGL by depositing an organic hole transport compound as in the first hole transport layer. The composition of the second hole transport layer is the same as of the first hole transport layer.

[0538] Then N,N-bis(4-(dibenzo[b,d]furan-4-yl)phenyl)-[1,1:4,1-terphenyl]-4-amine was vacuum deposited on the second HTL, to form a second electron blocking layer (EBL2) having a thickness of 5 nm.

[0539] Then 97 vol.-% H09 (Sun Fine Chemicals, Korea) as EML host and 3 vol.-% BD200 (Sun Fine Chemicals, Korea) as fluorescent blue dopant were deposited on the EBL, to form a second emission layer (EML2) with a thickness of 20 nm.

[0540] Then a second electron transport layer (ETL2) is formed on the second emission layer by depositing 2-(3-(9,9-dimethyl-9H-fluoren-2-yl)-[1,1-biphenyl]-3-yl)-4,6-diphenyl-1,3,5-triazine having a thickness of 10 nm.

[0541] Then, the electron injection layer (EIL) having a thickness of 25 nm is formed on the second electron transport layer by co-depositing 99 vol.-% 3-Phenyl-3H-benzo[b]dinaphtho[2,1-d:1,2-f]phosphepine-3-oxide and 1 vol.-% Yb.

[0542] Then Al is vacuum deposited on the electron injection layer at a rate of 0.01 to 1 /s at 10.sup.7 mbar to form a cathode layer with a thickness of 100 nm.

[0543] The OLED stack is 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.

[0544] 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 a voltage 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. Likewise, the luminance-voltage characteristics and CIE coordinates are determined by measuring the luminance in cd/m.sup.2 using an Instrument Systems CAS-140CT array spectrometer (calibrated by Deutsche Akkreditierungsstelle (DAkkS)) for each of the voltage values. The cd/A efficiency at 10 mA/cm.sup.2 is determined by interpolating the luminance-voltage and current-voltage characteristics, respectively.

[0545] Lifetime LT of the device is measured at ambient conditions (20 C.) and 30 mA/cm.sup.2, using a Keithley 2400 source meter, and recorded in hours.

[0546] The brightness of the device is measured using a calibrated photo diode. The lifetime LT is defined as the time till the brightness of the device is reduced to 97% of its initial value.

Technical Effect of the Invention

[0547] In Table 1 are shown the LUMO energy, decomposition temperatures T.sub.dec and rate onset temperatures TRO for Ce(IV) metal complexes of formula (I) and formula (Ia).

TABLE-US-00003 TABLE 1 Ce(IV) metal complexes of formula (I) and formula (Ia) LUMO T.sub.dec T.sub.RO Name Chemical formula (eV) ( C.) ( C.) MC-1 [00053] 4.6 >440 270 MC-2 [00054] 4.8 n.d. .sup.1) n.d. MC-3 [00055] 4.7 n.d. n.d. MC-4 [00056] 4.9 >270 122 MC-5 [00057] 4.9 n.d. 120 MC-6 [00058] 4.9 n.d n.d MC-7 [00059] 5.1 n.d. n.d. MC-8 [00060] 5.5 n.d. n.d. MC-9 [00061] 5.5 n.d n.d MC-10 [00062] 5.2 n.d. n.d. MC-11 [00063] 5.5 n.d n.d MC-12 [00064] 5.3 n.d. n.d. MC-13 [00065] 5.0 n.d. n.d. MC-14 [00066] 5.4 >280 146 MC-16 [00067] 5.4 n.d. n.d. .sup.1) n.d. = not determined

[0548] As can be seen in Table 1, the Ce(IV) metal complexes of formula (I) or formula (Ta) have LUMO energies, decomposition temperatures and/or rate onset temperatures suitable for mass production of organic electronic devices.

[0549] In particular, the LUMO of Ce(IV) metal complexes of formula (I) or formula (Ta) are in the range suitable for doping of organic hole transport compounds of formula (IIIa) or (IIIb).

Organic Hole Transport Compound

[0550] In Table 2 are shown the HOMO energies and rate onset temperatures T.sub.RO for hole transport compounds of formula (IIIa) or (IIIb). HOMO energies were calculated using TURBOMOLE V6.5 (TURBOMOLE GmbH, Litzenhardtstrasse 19, 76135 Karlsruhe, Germany) by applying the hybrid functional B3LYP with a Def-TZVP basis set in the gas phase with inclusion of dispersion as D3BJ.

TABLE-US-00004 TABLE 2 Organic hole transport compounds of formula (IIIa) or (IIIb) Name Chemical formula HOMO (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 [00068] 4.89 265 N,N- Bis(naphthalen-1- yl)-N,N- bis(phenyl)- benzidine F1 [00069] 4.90 272 N4,N4- di(naphthalen-1- yl)-N4,N4- diphenyl- [1,1:4,1- terphenyl]-4,4- diamine F2 [00070] 4.99 260 N-(9,9-dimethyl- 9H-fluoren-2-yl)- N-(9,9-diphenyl- 9H-fluoren-2- yl)dibenzo[b,d] furan-1-amine F4 [00071] 5.03 219 9,9-dimethyl-N,N- bis(4-(naphthalen- 1-yl)phenyl)-9H- fluoren-2-amine F8 [00072] 5.02 232 N-([1,1-biphenyl]- 4-yl)-N-(2-(9,9- diphenyl-9H- fluoren-4- yl)phenyl)-9,9- dimethyl-9H- fluoren-2-amine F9 [00073] 5.03 218 N-(9,9-diphenyl- 9H-fluoren-2-yl)- N,9-diphenyl-9H- carbazol-2-amine F18 [00074] 4.95 216

[0551] As can be seen in Table 2, the organic hole transport compounds of formula (IIIa) or (IIIb) have rate onset temperatures suitable for mass production of organic electronic devices.

[0552] In Table 3 are shown data for organic electronic devices comprising a p-type charge generation layer comprising a Ce(IV) metal complex of formula (I) or formula (Ia) or comparative compound CC1, and an organic hole transport compound HTM; and a n-type charge generation layer comprising an organic electron transport compound ETM and a metal dopant.

[0553] In comparative example 1-1 and examples 1-1, 1-2 and 1-3, the n-type charge generation layer comprises phosphine oxide compound ETM-1 as organic electron transport compound

##STR00075##

[0554] In comparative example 1-1, the p-type charge generation layer comprises comparative compound CC-1 as metal complex

##STR00076##

[0555] The operating voltage is 8.57 V, the cd/A efficiency is 3.08 cd/A and the lifetime is 12 hours.

[0556] In examples 1-1, 1-2 and 1-3, the p-type charge generation layer comprises a Ce(IV) metal complex according to invention. As can be seen in Table 3, in examples 1-1, 1-2 and 1-3, the operating voltage is reduced and the cd/A efficiency and/or lifetime are improved.

[0557] In examples 2-1, 2-2, 2-3 and 2-4, the OLED further comprises a connecting layer (c-CGL) between the n-CGL and the p-CGL. In examples 2-1, 2-2, 2-3 and 2-4, the connecting layer consists of ZnPc. As can be seen in Table 4, the operating voltage is reduced compared to comparative example 1-1. The cd/A efficiency and lifetime are improved further compared to Examples 1-1 and 1-2.

[0558] In summary, an improvement in operating voltage, cd/A efficiency and/or lifetime has been obtained.

[0559] A lower operating voltage and improved cd/A efficiency may be important for the battery life of organic electronic devices, in particular mobile devices.

[0560] An improvement in lifetime may be important for the long-term stability of organic electronic devices.

TABLE-US-00005 TABLE 3 Performance of an organic electroluminescent device comprising a charge generation layer (CGL) n-type CGL p-type CGL Concen- Concen- Operating cd/A Concen- tration Concen- tration voltage efficien LT97 tration metal Thick- tration metal Thick- at 10 cy at 10 at 30 ETM Metal dopant ness HTM Metal complex ness mA/cm.sup.2 mA/cm.sup.2 mA/cm.sup.2 ETM (vol.-%) dopant (vol. %) (nm) HTM (wt.-%) complex (wt.-%) (nm) (V) (cd/A) (h) Compar- ETM- 99 Yb 1 15 F3 80 CC-1 20 10 8.6 3.1 12 ative 1 example 1-1 Example ETM- 99 Yb 1 15 F3 80 MC-4 20 10 7.5 12 74 1-1 1 Example ETM- 99 Yb 1 15 F3 80 MC-1 20 10 8.1 11.9 79 1-2 1 Example ETM- 99 Yb 1 15 F3 80 MC-14 20 10 7.5 12.2 78 1-3 1

TABLE-US-00006 TABLE 4 Performance of an organic electroluminescent device comprising a charge generation layer (CGL) n-type CGL p-type CGL Concen- c-CGL Concen- Operating cd/A Concen- tration Con- Concen- tration voltage efficiency LT97 tration metal Thick- ducting Thick- tration metal Thick- at 10 at 10 at 30 ETM Metal dopant ness com- ness HTM Metal complex ness mA/cm.sup.2 mA/cm.sup.2 mA/cm.sup.2 ETM (vol.-%) dopant (vol. %) (nm) pound (nm) HTM (wt.-%) complex (wt.-%) (nm) (V) (cd/A) (h) Ex- ETM- 99 Yb 1 15 ZnPc 2 F3 90 MC-4 10 10 7.7 12.8 90 ample 1 2-1 Ex- ETM- 99 Yb 1 15 ZnPc 2 F3 80 MC-4 20 10 7.3 12.75 87 ample 1 2-2 Ex- ETM- 99 Yb 1 15 ZnPc 2 F3 80 MC-14 10 10 7.8 12.9 87 ample 1 2-3 Ex- ETM- 99 Yb 1 15 ZnPc 2 F3 80 MC-14 20 10 7.3 12.85 88 ample 1 2-4

[0561] 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.