An Organic Electronic Device Comprising an Anode Layer, a Cathode Layer, at Least One Photoactive Layer, and a Semiconductor Layer That Comprises a Metal Complex

Abstract

The present invention relates to an organic electronic device comprising an anode layer, a cathode layer, at least one photoactive layer, and a semiconductor layer, wherein the photoactive layer and the semiconductor layer are arranged between the anode layer and the cathode layer, wherein the semiconductor layer is arranged between the photoactive layer and the anode layer; wherein 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 (TCO); wherein the second anode sub-layer is arranged closer to the semiconductor layer than the first anode sub layer; wherein the semiconductor layer comprises at least one metal complex, wherein the metal complex comprises a metal cation and at least one anionic ligand, wherein the anionic ligand comprises at least four covalently bound atoms, and wherein the semiconductor layer comprises the metal complex in a range of 31 percent by weight to 100 percent by weight, based on the total weight of the semiconductor layer.

Claims

1. An organic electronic device comprising an anode layer, a cathode layer, at least one photoactive layer, and a semiconductor layer, wherein the photoactive layer and the semiconductor layer are arranged between the anode layer and the cathode layer, wherein the semiconductor layer is arranged between the photoactive layer and the anode layer; wherein 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 (TCO); wherein the second anode sub-layer is arranged closer to the semiconductor layer than the first anode sub layer; wherein the semiconductor layer comprises at least one metal complex, wherein the metal complex comprises a metal cation and at least one anionic ligand, wherein the anionic ligand comprises at least four covalently bound atoms, and wherein the semiconductor layer comprises the metal complex in a range of 31 percent by weight to 100 percent by weight, based on the total weight of the semiconductor layer.

2. The organic electronic device according to claim 1, wherein the semiconductor layer is free of copper-phthalocyanine (CuPc).

3. The organic electronic device according to claim 1, wherein the semiconductor layer is free of metal phthalocyanine (Pc) or CuPc.

4. The organic electronic device according to claim 1, 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, Ir.

5. The organic electronic device according to claim 1, wherein the semiconductor layer comprises the metal complex in a range of 31 percent by weight to 90 percent by weight, based on the total weight of the semiconductor layer.

6. The organic electronic device according to claim 1, wherein the metal complex is represented by formula (I)
Q.sub.rM.sup.s(L.sup.).sub.s(I) wherein M is a metal cation, s is the valency of M; L is an anionic ligand comprising at least 4 covalently bound atoms, wherein the anionic ligand comprises at least two atoms selected from carbon atoms, s is an integer from 1 to 4; Q is a charge-neutral ligand which coordinates to the metal cation M, r is an integer selected from 0 to 2.

7. The organic electronic device according to claim 6, wherein the metal cation M is selected from alkali, alkaline earth, transition, rare earth metal or group III to V metal

8. The organic electronic device according to claim 6, wherein the charge neutral ligand Q 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); ##STR00136## 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.

9. The organic electronic device according to claim 6, wherein the anionic ligand L is selected from formula (III) ##STR00137## wherein m, and n are independently selected from 0, 1; m+n1; a, and b are independently selected from 0, 1; a+b1; Z is selected from CR.sup.3, N, or O; if Z is O then a is 0 when m is 0 or b is o when n is 0; A.sup.1 and A.sup.2 are independently selected from CO, CO, SO, or SO.sub.2; A.sup.1 and A.sup.2 together can form a cycle with Z; R.sup.1 and R.sup.2 are independently selected from substituted or unsubstituted C.sub.6 to C.sub.24 aryl, substituted or unsubstituted C.sub.2 to C.sub.24 heteroaryl, substituted or unsubstituted C.sub.1 to C.sub.12 alkyl, substituted or unsubstituted C.sub.3 to C.sub.24 carbocyclyl, or C.sub.2 to C.sub.24 heterocyclyl, wherein for the case that A.sup.1 and A.sup.2 are selected from CO or CO, R.sup.1 and R.sup.2 may also be selected from D or H, wherein the substituents on R.sup.1 or R.sup.2 are independently selected from halogen, F, Cl, CN, substituted or unsubstituted C.sub.1 to C.sub.12 alkyl, partially or fully fluorinated C.sub.1 to C.sub.12 alkyl, substituted or unsubstituted C.sub.1 to C.sub.12 alkoxy, partially or fully fluorinated C.sub.1 to C.sub.12 alkoxy, substituted or unsubstituted C.sub.6 to C.sub.18 aryl, and substituted or unsubstituted C.sub.2 to C.sub.18 heteroaryl, and wherein the substituents of the substituted or unsubstituted C.sub.1 to C.sub.12 alkyl, substituted or unsubstituted C.sub.1 to C.sub.12 alkoxy, substituted or unsubstituted C.sub.6 to C.sub.18 aryl, and substituted or unsubstituted C.sub.2 to C.sub.18 heteroaryl are selected from halogen, F, Cl, CN, C.sub.1 to C.sub.6 alkyl, partially or fully fluorinated C.sub.1 to C.sub.6 alkyl, CF.sub.3, OCH.sub.3, fully fluorinated C.sub.1 to C.sub.6 alkoxy, or OCF.sub.3; and R.sup.3 is selected from H, D, CN, substituted or unsubstituted C.sub.6 to C.sub.24 aryl, substituted or unsubstituted C.sub.2 to C.sub.24 heteroaryl, substituted or unsubstituted C.sub.1 to C.sub.12 alkyl, substituted or unsubstituted C.sub.3 to C.sub.24 carbocyclyl, or substituted or unsubstituted C.sub.2 to C.sub.24 heterocyclyl; wherein the substituents on R.sup.3 is selected from halogen, F, Cl, CN, substituted or unsubstituted C.sub.1 to C.sub.12 alkyl, partially or fully fluorinated C.sub.1 to C.sub.12 alkyl, substituted or unsubstituted C.sub.1 to C.sub.12 alkoxy, partially or fully fluorinated C.sub.1 to C.sub.12 alkoxy, substituted or unsubstituted C.sub.6 to C.sub.18 aryl, and substituted or unsubstituted C.sub.2 to C.sub.18 heteroaryl, and wherein the substituents of the substituted or unsubstituted C.sub.1 to C.sub.12 alkyl, substituted or unsubstituted C.sub.1 to C.sub.12 alkoxy, substituted or unsubstituted C.sub.6 to C.sub.18 aryl, and substituted or unsubstituted C.sub.2 to C.sub.18 heteroaryl are selected from halogen, F, Cl, CN, C.sub.1 to C.sub.6 alkyl, partially or fully fluorinated C.sub.1 to C.sub.6 alkyl, CF.sub.3, OCH.sub.3, fully fluorinated C.sub.1 to C.sub.6 alkoxy, or OCF.sub.3.

10. The organic electronic device according to claim 6, wherein the metal complex according to formula (I) is selected from one of the formulae (IVa) to (IVd): ##STR00138## wherein R.sup.1 and R.sup.2 are independently selected from substituted or unsubstituted C.sub.6 to C.sub.24 aryl, substituted or unsubstituted C.sub.2 to C.sub.24 heteroaryl, substituted or unsubstituted C.sub.1 to C.sub.12 alkyl, substituted or unsubstituted C.sub.3 to C.sub.24 carbocyclyl, or C.sub.2 to C.sub.24 heterocyclyl, wherein for formula (IVa) R.sup.1 and R.sup.2 may also be selected from D or H, wherein the substituents on R.sup.1 or R.sup.2 are independently selected from halogen, F, Cl, CN, substituted or unsubstituted C.sub.1 to C.sub.12 alkyl, partially or fully fluorinated C.sub.1 to C.sub.12 alkyl, substituted or unsubstituted C.sub.1 to C.sub.12 alkoxy, partially or fully fluorinated C.sub.1 to C.sub.12 alkoxy, substituted or unsubstituted C.sub.6 to C.sub.18 aryl, and substituted or unsubstituted C.sub.2 to C.sub.18 heteroaryl, and wherein the substituents of the substituted or unsubstituted C.sub.1 to C.sub.12 alkyl, substituted or unsubstituted C.sub.1 to C.sub.12 alkoxy, substituted or unsubstituted C.sub.6 to C.sub.18 aryl, and substituted or unsubstituted C.sub.2 to C.sub.18 heteroaryl are selected from halogen, F, Cl, CN, C.sub.1 to C.sub.6 alkyl, partially or fully fluorinated C.sub.1 to C.sub.6 alkyl, CF.sub.3, OCH.sub.3, fully fluorinated C.sub.1 to C.sub.6 alkoxy, or OCF.sub.3; and R.sup.3 is selected from H, D, CN, substituted or unsubstituted C.sub.6 to C.sub.24 aryl, substituted or unsubstituted C.sub.2 to C.sub.24 heteroaryl, substituted or unsubstituted C.sub.1 to C.sub.12 alkyl, substituted or unsubstituted C.sub.3 to C.sub.24 carbocyclyl, or substituted or unsubstituted C.sub.2 to C.sub.24 heterocyclyl, wherein the substituents on R.sup.3 are selected from halogen, F, Cl, CN, substituted or unsubstituted C.sub.1 to C.sub.12 alkyl, partially or fully fluorinated C.sub.1 to C.sub.12 alkyl, substituted or unsubstituted C.sub.1 to C.sub.12 alkoxy, partially or fully fluorinated C.sub.1 to C.sub.12 alkoxy, substituted or unsubstituted C.sub.6 to C.sub.18 aryl, and substituted or unsubstituted C.sub.2 to C.sub.18 heteroaryl, and wherein the substituents of the substituted or unsubstituted C.sub.1 to C.sub.12 alkyl, substituted or unsubstituted C.sub.1 to C.sub.12 alkoxy, substituted or unsubstituted C.sub.6 to C.sub.18 aryl, and substituted or unsubstituted C.sub.2 to C.sub.18 heteroaryl are selected from halogen, F, Cl, CN, C.sub.1 to C.sub.6 alkyl, partially or fully fluorinated C.sub.1 to C.sub.6 alkyl, CF.sub.3, OCH.sub.3, fully fluorinated C.sub.1 to C.sub.6 alkoxy, or OCF.sub.3.

11. The organic electronic device according to claim 6, wherein the anionic ligand L is selected from formula (VIa) or VIb): ##STR00139## wherein R.sup.1 and R.sup.2 are independently selected from substituted or unsubstituted C.sub.6 to C.sub.24 aryl, substituted or unsubstituted C.sub.2 to C.sub.24 heteroaryl, substituted or unsubstituted C.sub.1 to C.sub.12 alkyl, substituted or unsubstituted C.sub.3 to C.sub.24 carbocyclyl, or C.sub.2 to C.sub.24 heterocyclyl, wherein for formula (VIa) R.sup.1 and R.sup.2 may also be selected from D or H, wherein the substituents on R.sup.1 or R.sup.2 are independently selected from halogen, F, Cl, CN, substituted or unsubstituted C.sub.1 to C.sub.12 alkyl, partially or fully fluorinated C.sub.1 to C.sub.12 alkyl, substituted or unsubstituted C.sub.1 to C.sub.12 alkoxy, partially or fully fluorinated C.sub.1 to C.sub.12 alkoxy, substituted or unsubstituted C.sub.6 to C.sub.18 aryl, and substituted or unsubstituted C.sub.2 to C.sub.18 heteroaryl, and wherein the substituents of the substituted or unsubstituted C.sub.1 to C.sub.12 alkyl, substituted or unsubstituted C.sub.1 to C.sub.12 alkoxy, substituted or unsubstituted C.sub.6 to C.sub.18 aryl, and substituted or unsubstituted C.sub.2 to C.sub.18 heteroaryl are selected from halogen, F, Cl, CN, C.sub.1 to C.sub.6 alkyl, partially or fully fluorinated C.sub.1 to C.sub.6 alkyl, CF.sub.3, OCH.sub.3, fully fluorinated C.sub.1 to C.sub.6 alkoxy, or OCF.sub.3; and R.sup.3 is selected from H, D, CN, substituted or unsubstituted C.sub.6 to C.sub.24 aryl, substituted or unsubstituted C.sub.2 to C.sub.24 heteroaryl, substituted or unsubstituted C.sub.1 to C.sub.12 alkyl, substituted or unsubstituted C.sub.3 to C.sub.24 carbocyclyl, or substituted or unsubstituted C.sub.2 to C.sub.24 heterocyclyl, wherein the substituents on R.sup.3 are selected from halogen, F, Cl, CN, substituted or unsubstituted C.sub.1 to C.sub.12 alkyl, partially or fully fluorinated C.sub.1 to C.sub.12 alkyl, substituted or unsubstituted C.sub.1 to C.sub.12 alkoxy, partially or fully fluorinated C.sub.1 to C.sub.12 alkoxy, substituted or unsubstituted C.sub.6 to C.sub.18 aryl, and substituted or unsubstituted C.sub.2 to C.sub.18 heteroaryl, and wherein the substituents of the substituted or unsubstituted C.sub.1 to C.sub.12 alkyl, substituted or unsubstituted C.sub.1 to C.sub.12 alkoxy, substituted or unsubstituted C.sub.6 to C.sub.18 aryl, and substituted or unsubstituted C.sub.2 to C.sub.18 heteroaryl are selected from halogen, F, Cl, CN, C.sub.1 to C.sub.6 alkyl, partially or fully fluorinated C.sub.1 to C.sub.6 alkyl, CF.sub.3, OCH.sub.3, fully fluorinated C.sub.1 to C.sub.6 alkoxy, or OCF.sub.3.

12. The organic electronic device according to claim 1, wherein the anionic ligand L is selected from one of the following formulae G1 to G140: ##STR00140## ##STR00141## ##STR00142## ##STR00143## ##STR00144## ##STR00145## ##STR00146## ##STR00147## ##STR00148## ##STR00149## ##STR00150## ##STR00151## ##STR00152## ##STR00153##

13. The organic electronic device according to claim 1, wherein the semiconductor layer comprises a substantially covalent matrix compound.

14. The organic electronic device according to claim 1, wherein the semiconductor layer is in direct contact to the anode layer.

15. The organic electronic device according to claim 1, wherein the semiconductor layer is a hole injection layer.

16. The organic electronic device according to claim 1, wherein the anode layer of the organic electronic device comprises in addition a third anode sub-layer; wherein the first anode sub-layer is arranged between the third anode sub-layer and the second anode sub-layer.

17. The organic electronic device according to claim 1, wherein the organic electronic device further comprises a hole transport layer, wherein the hole transport layer is arranged between the semiconductor layer and the at least one emission layer.

18. The organic electronic device according to claim 1, wherein the organic electronic device is a light emitting device or a display device.

Description

DESCRIPTION OF THE DRAWINGS

[0409] 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.

[0410] 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

[0411] FIG. 1 is a schematic sectional view of an organic electronic device, according to an exemplary embodiment of the present invention;

[0412] FIG. 2 is a schematic sectional view of an organic electronic device, according to an exemplary embodiment of the present invention;

[0413] FIG. 3 is a schematic sectional view of an organic electronic device, according to an exemplary embodiment of the present invention.

[0414] FIG. 4 is a schematic sectional view of an organic electronic device, according to an exemplary embodiment of the present invention;

[0415] FIG. 5 is a schematic sectional view of an organic electronic device, according to an exemplary embodiment of the present invention;

[0416] FIG. 6 is a schematic sectional view of an organic electronic device, according to an exemplary embodiment of the present invention;

[0417] FIG. 7 is a schematic sectional view of an organic electronic device, according to an exemplary embodiment of the present invention;

[0418] FIG. 8 is a schematic sectional view of an organic electronic device, according to an exemplary embodiment of the present invention;

[0419] FIG. 9 is a schematic sectional view of an organic electronic device, according to an exemplary embodiment of the present invention.

[0420] 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.

[0421] 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.

[0422] 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.

[0423] 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.

[0424] 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 (EIL) (150), and a cathode layer (190) are disposed.

[0425] 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 (EIL) (150), and a cathode layer (190) are disposed.

[0426] 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 (EIL) (150), a hole blocking layer (BL) (155), an electron transport layer (ETL) (160), and a cathode layer (190) are disposed.

[0427] 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 (EIL) (150), a hole blocking layer (HBL) (155), an electron transport layer (ETL) (160), and a cathode layer (190) are disposed.

[0428] 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.

[0429] 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.

[0430] 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.

[0431] 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.

[0432] 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

[0433] The invention is furthermore illustrated by the following examples which are illustrative only and non-binding.

[0434] Metal complexes in particular compounds of formula (I) may be prepared as described below or are commercially available:

Synthesis of tris(((Z)-4-oxo-3-(2,3,5-trifluoro-6-(trifluoromethyl)pyridin-4-yl)pent-2-en-2-yl)oxy)iron (E1)

Synthesis of 3-(2,3,5-trifluoro-6-(trifluoromethyl)pyridin-4-yl)pentane-2,4-dione (ligand)

##STR00123##

[0435] To 2.41 g (100.43 mmol) sodium hydride in a flame-dried Schleck flask 200 mL dry glyme was added via a double-needle cannula. The suspension was cooled with an ice-bath and 10.3 mL (100.43 mmol) of acetylacetone was added dropwise. During the addition the temperature should not rise above 10 C. 20 g (91.30 mmol) of 2,3,4,5-tetrafluoro-6-(trifluormethyl)pyridine was added with a syringe. The mixture was stirred at room temperature for 5 days and then added to 0.5 L water, and acidified with conc. HCl to pH 1. The product was extracted with ethyl acetate. The combined organic layers were washed with water, dried over sodium sulfate, filtered and the solvent was removed under reduced pressure. The crude product was dissolved in hot methanol/water (3:1) and after cooling the precipitate was filtered off and dried in high vacuum. Yield: 10.5 g (38%)

Synthesis of tris(((Z)-4-oxo-3-(2,3,5-trifluoro-6-(trifluoromethyl)pyridin-4-yl)pent-2-en-2-yl)oxy)iron (E1)

##STR00124##

[0436] 7.0 g (23.4 mmol) of substituted acetylacetone was dissolved in 70 mL of methanol. 1.90 g (23.4 mmol) of sodium bicarbonate was dissolved in 20 mL of water and added to the solution. The resulting suspension was heated to reflux and to the cloudy solution a solution of 1.27 g (7.8 mmol) iron(III)chloride in 5 mL water was added drop wise. The mixture was stirred for 30 min under reflux. After cooling the residue was filtered off and washed with water. The crude product was dissolved in THF and precipitated from methanol/water, filtered off and dried in high vacuum. Yield: 5.17 g (70%)

Synthesis of tris(((Z)-3-(2,6-bis(trifluoromethyl)pyridin-4-yl)-4-oxopent-2-en-2-yl)oxy)iron (E2)

Synthesis of 3-(2,6-bis(trifluoromethyl)pyridin-4-yl)pentane-2,4-dione (ligand)

[0437] 83.20 g (252.3 mmol) caesium carbonate were suspended in 250 mL dry DMF under inert conditions and cooled using an ice bath. 13 mL (43.9 mmol) acetylacetone were added drop wise to the cold suspension and 26.23 g (105.1 mmol) of 4-chloro-2,6-bis(trifluoromethyl)pyridine were added with nitrogen counterflow. The mixture was heated to 60 C. for 20 h. The solid was filtered off and washed with ethyl acetate. The mother liquor was added to 400 mL 2N hydrochloric acid. After phase separation, the aqueous layer was extracted with ethyl acetate and the combined organic layers were washed with brine, dried over magnesium sulphate and the solvent removed under reduced pressure. The crude product was slurry washed with methanol/water, dissolved in dichloromethane and hexane (1:10), filtered over silica gel and sublimed in high vacuum at 100 C. 17.8 g (54%) product was obtained as a yellow-white solid.

Synthesis of tris(((Z)-3-(2,6-bis(trifluoromethyl)pyridin-4-yl)-4-oxopent-2-en-2-yl)oxy)iron (E2)

[0438] 17.05 g (54.44 mmol) of 3-(2,6-bis(trifluoromethyl)pyridin-4-yl)pentane-2,4-dione were suspended in 160 mL methanol and 4.57 g (54.44 mmol) sodium bicarbonate were added. 2.94 g (18.15 mmol) iron trichloride were dissolved cautiously in 20 ml water and added drop wise to the suspension. The mixture was stirred at room temperature overnight. The solid was filtered off, washed carefully with water and dried in high vacuum. 13.4 g crude product was recrystallized from 120 ml chlorobenzene to obtain 9.56 g (53%) as an orange solid. A 2.sup.nd fraction (2.03 g, 11%) was obtained from crystallisation of the mother liquor in 40 mL chlorobenzene.

Synthesis of 4-(2,4-dioxopentan-3-yl)-2,6-bis(trifluoromethyl)benzonitrile (ligand)

[0439] 28.6 g (87.7 mmol) caesium carbonate were suspended in 100 mL dry DMF under inert conditions. 4.5 mL (43.9 mmol) acetylacetone and 10 g (36.6 mmol) of 4-chloro-2,6-bis(trifluoromethyl)benzonitrile were added at room temperature. The mixture was heated to 60 C. for 20 h. The solid was filtered off and washed with ethyl acetate. The mother liquor was added to 250 mL 2N hydrochloric acid. After phase separation, the aqueous layer was extracted with ethyl acetate and the combined organic layers were washed with brine, dried over magnesium sulphate and the solvent removed under reduced pressure. The crude product was slurry washed with methanol/water and ethyl acetate/hexane to obtain 8.7 g (71% yield) product as an off-white, crystalline solid.

##STR00125##

4-(2,4-dioxopentan-3-yl)-2,6-bis(trifluoromethyl)benzonitrile

Synthesis of bis(((Z)-3-(4-cyano-3,5-bis(trifluoromethyl)phenyl)-4-oxopent-2-en-2-yl)oxy)copper (E3)

[0440] 3.0 g (8.9 mmol) of 4-(2,4-dioxopentan-3-yl)-2,6-bis(trifluoromethyl)benzonitrile were dissolved in 20 ml acetonitrile and 0.89 g (4.45 mmol) copper(II) acetate monohydrate were added. The mixture was stirred at room temperature for one hour. 30 ml water were added and the precipitate filtered off, washed with water and hexane and dried in high vacuum. 3.15 g (96%) product was obtained as a greyish-violet powder.

##STR00126##

bis(((Z)-3-(4-cyano-3,5-bis(trifluoromethyl)phenyl)-4-oxopent-2-en-2-yl)oxy)copper

Magnesium bis(trifluoromethylsulfonyl)imide (E4)

[0441] Magnesium bis(trifluoromethylsulfonyl)imide (E4) [[133395-16-1]) is commercially available from Alfa Aesar or ABCR.

Synthesis of sodium bis((perfluoropropan-2-yl)sulfonyl)amide (E5)

[0442] 5.0 g (10.39 mmol) bis((perfluoropropan-2-yl)sulfonyl)amide was dissolved in 40 mL water and 0.55 g (5.20 mmol) sodium carbonate dissolved in 10 mL water and added drop wise. The mixture was stirred for 1 hour and the solvent cautiously removed under reduced pressure. 30 ml toluene were added to the residue and removed under reduced pressure. After repeating the last step the product was dried overnight in high vacuum. 4.80 g (92%) product was obtained as a white solid.

Synthesis of magnesium bis((perfluorobutyl)sulfonyl)amide (E6)

[0443] 5.1 g (8.77 mmol) bis((perfluorobutyl)sulfonyl)amide was dissolved in 20 mL dry methyl tert-butyl ether and 0.2 g (8.77 mmol) magnesium turnings were added. The mixture was heated to 50 C. for one hour. The solvent was removed under reduced pressure and 40 ml dry toluene was added. Half the solvent was removed under reduced pressure and the mixture was stirred in an ice bath for 30 min. The precipitate was filtered off using a Schlenk frit and was washed toluene. The residue was treated again with 0.1 g magnesium in 10 mL methyl tert-butyl ether at 50 C. for one hour, the excess magnesium was filtered off and the solvent removed under reduced pressure and the residue dried in high vacuum overnight. 3.23 g (65%) product was obtained as white solid.

(Bismuthanetriyltris(oxy))tris((3,5-bis(trifluoromethyl)phenyl)methanone) (E7)

[0444] A mixture of 3.84 g (14.9 mmol, 3.1 eq.) of 3,5-bis-trifluoromethyl benzoic acid and 2.31 g (4.8 mmol) of tri-o-tolyl bismuthine in 80 ml of toluene was stirred and heated at 80 C. for 2 h under dry conditions. After cooling to room temperature, the suspension was filtered and the obtained solid washed with toluene (210 ml), then dried over night at 50 C. in a high vacuum. Yield: 4.5 g (98%) of a creamy-white fluffy solid.

Synthesis of sodium sodium bis((perfluorobutyl)sulfonyl)amide (E8)

[0445] 10.2 g (17.55 mmol) bis((perfluorobutyl)sulfonyl)amide was dissolved in 50 mL water and 0.93 g (8.77 mmol) sodium carbonate dissolved in 10 mL water and added drop wise. The product was dried overnight in high vacuum. 10.6 g (100%) product was obtained as a white solid.

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

[0446] For Examples 1-28 in Table 2, 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 mm50 mm0.7 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 2, 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 2.

[0447] Then, the matrix compound (F4) N-(9,9-dimethyl-9H-fluoren-2-yl)-N-(9,9-diphenyl-9H-fluoren-2yl)dibenzo[b,d]furan-1-amine and the metal complex given in Table 2 were co-deposited in vacuum on the anode layer, to form a hole injection layer (HIL) having a thickness as given in Table 2.

[0448] Then, the matrix compound (F4) N-(9,9-dimethyl-9H-fluoren-2-yl)-N-(9,9-diphenyl-9H-fluoren-2yl)dibenzo[b,d]furan-1-amine was vacuum deposited on the HIL, to form a HTL having a thickness of 128 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 2.

[0449] Then N,N-di([1,1-biphenyl]-4-yl)-3-(9H-carbazol-9-yl)-[1,1-biphenyl]-4-amine was vacuum deposited on the HTL, to form an electron blocking layer (EBL) having a thickness of 5 nm.

[0450] 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.

[0451] 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.

[0452] Then the electron transporting layer having a thickness of 31 nm was formed on the hole blocking layer by depositing 50 wt.-%

[0453] 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.

[0454] Then electron injection layer having a thickness of 2 nm was formed on the electron transporting layer by depositing Yb.

[0455] Then Ag:Mg (90:10-wt %) was evaporated at a rate of 0.01 to 1 /s at 10-7 mbar to form a cathode layer with a thickness of 13 nm on the electron injection layer.

[0456] Then, F3 was deposited on the cathode layer to form a capping layer with a thickness of 75 nm.

Comparative Examples 1 to 3Bottom Emission on ITO

[0457] For comparative examples 1 to 3 in Table 2, 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 water for 60 minutes and then with isopropanol for 20 minutes. The liquid film was removed in a nitrogen stream.

[0458] Then, 69 wt.-% F4 and 31 wt.-% E1 were co-deposited in vacuum on the anode layer, to form a hole injection layer (HIL) having a thickness as given in Table 2.

[0459] Then, F4 was vacuum deposited on the HIL, to form a HTL having a thickness of 135 nm.

[0460] Then, the EBL, EML, HBL and ETL are deposited in this order on the HTL, as described in the general procedure of manufacture above.

[0461] Then Al was evaporated 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 on the electron transporting layer.

Comparative Examples 4 to 6Top Emission on Ag

[0462] In comparative examples 4 to 6 (Table 2), the anode layer consists of Ag. The anode layer was either treated with plasma in nitrogen atmosphere or in an atmosphere comprising 97.6 vol.-% nitrogen and 2.4 vol.-% oxygen, or not treated with plasma.

[0463] Then, 69 wt.-% F4 and 31 wt.-% E1 were co-deposited in vacuum on the anode layer, to form a hole injection layer (HIL) having a thickness as given in Table 2.

[0464] Then, F4 was vacuum deposited on the HIL, to form a HTL having a thickness of 135 nm.

[0465] Then, the EBL, EML, HBL and ETL are deposited in this order on the HTL, as described in the general procedure for manufacture above.

[0466] 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 0V and 10V. 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.

[0467] In bottom emission devices, the emission is predominately Lambertian and quantified in percent external quantum efficiency (EQE). To determine the efficiency EQE in % the light output of the device is measured using a calibrated photodiode at 10 mA/cm.sup.2.

[0468] In top emission devices, the emission is forward directed, non-Lambertian and also highly dependent on the micro-cavity. Therefore, the efficiency EQE will be higher compared to bottom emission devices. To determine the efficiency EQE in % the light output of the device is measured using a calibrated photodiode at 10 mA/cm.sup.2.

[0469] Lifetime LT of the device is measured at ambient conditions (20 C.) and 30 mA/cm.sup.2, using a Keithley 2400 sourcemeter, and recorded in hours.

[0470] 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.

[0471] The increase in operating voltage AU is used as a measure of the operational voltage stability of the device. This increase is determined during the LT measurement and by subtracting the operating voltage after 1 hour after the start of operation of the device from the operating voltage after 100 hours.

[00001]$U=[U100h)-U\left(1h\right)]$ [0472] or the operating voltage after 1 hour after the start of operation of the device from the operating voltage after 100 hours.

[00002]$U=[U100h)-U\left(1h\right)]$

[0473] The smaller the value of AU the better is the operating voltage stability.

Technical Effect of the Invention

TABLE-US-00001 TABLE 1 Structures of metal complexes used in the examples. Structure Name [00127] C1 [00128] E1 [00129] E2 [00130] E3 [00131] E4 [00132] E5 [00133] E6 [00134] E7 [00135] E8

TABLE-US-00002 TABLE 2 Results Ceff EQE Layer Concentration at 10 At 10 thickness p-HIL metal compex Voltage mA/cm.sup.2 mA/cm2 Anode Plasma [nm] complex host [wt %] [V] [cd/A] [%] Comp. Ex 1 ITO N.sub.2 3 E1 F4 31 10.05 4.92 5.59 Comp. Ex 2 ITO N.sub.2 5 E1 F4 31 10.01 4.98 5.65 Comp. Ex 3 ITO N.sub.2 10 E1 F4 31 10.60 4.89 Comp. Ex 4 Ag N.sub.2; N.sub.2:O.sub.2; 3 E1 F4 31 >10 or without Comp. Ex 5 Ag N.sub.2; N.sub.2:O.sub.2; 5 E1 F4 31 >10 or without Comp. Ex 6 Ag N.sub.2; N.sub.2:O.sub.2; 10 E1 F4 31 >10 or without Comp. Ex 7 ITO/Ag/ITO N.sub.2:O.sub.2 3 C1 F4 31 >10 Comp. Ex. 8 ITO/Ag/ITO N.sub.2:O.sub.2 5 C1 F4 31 >10 Comp. Ex. 9 ITO/Ag/ITO N.sub.2:O.sub.2 10 C1 F4 31 >10 Comp. Ex. 10 ITO/Ag/ITO N.sub.2:O.sub.2 3 C1 F4 75 >10 Comp. Ex. 11 ITO/Ag/ITO N.sub.2:O.sub.2 5 C1 F4 75 >10 Comp. Ex. 12 ITO/Ag/ITO N.sub.2:O.sub.2 10 C1 F4 75 >10 Comp. Ex. 13 ITO/Ag/ITO N.sub.2:O.sub.2 3 C1 100 >10 Comp. Ex. 14 ITO/Ag/ITO N.sub.2:O.sub.2 5 C1 100 >10 Comp. Ex. 15 ITO/Ag/ITO N.sub.2:O.sub.2 10 C1 100 >10 Inv. Ex 1 ITO/Ag/ITO N.sub.2 5 E1 F4 31 4.43 6.09 12.19 Inv. Ex 2 ITO/Ag/ITO N.sub.2:O.sub.2 3 E1 F4 31 3.73 6.88 13.96 Inv. Ex 3 ITO/Ag/ITO N.sub.2:O.sub.2 5 E1 F4 31 3.71 6.91 13.96 Inv. Ex 4 ITO/Ag/ITO N.sub.2:O.sub.2 10 E1 F4 31 3.70 6.94 13.88 Inv. Ex 5 ITO/Ag/ITO N.sub.2:O.sub.2 3 E1 F4 50 3.72 6.97 13.88 Inv. Ex 6 ITO/Ag/ITO N.sub.2:O.sub.2 5 E1 F4 50 3.71 6.89 13.87 Inv. Ex 7 ITO/Ag/ITO N.sub.2:O.sub.2 3 E1 F4 75 3.72 6.87 13.93 Inv. Ex 8 ITO/Ag/ITO N.sub.2:O.sub.2 5 E1 F4 75 3.72 6.86 13.91 Inv. Ex 9 ITO/Ag/ITO N.sub.2:O.sub.2 3 E3 F4 31 3.71 6.78 13.83 Inv. Ex 10 ITO/Ag/ITO N.sub.2:O.sub.2 5 E3 F4 31 3.70 6.98 13.99 Inv. Ex 11 ITO/Ag/ITO N.sub.2:O.sub.2 10 E3 F4 31 3.69 6.93 13.94 Inv. Ex 12 ITO/Ag/ITO N.sub.2:O.sub.2 3 E2 F4 31 3.71 6.74 13.93 Inv. Ex 13 ITO/Ag/ITO N.sub.2:O.sub.2 5 E2 F4 31 3.69 6.76 13.96 Inv. Ex 14 ITO/Ag/ITO N.sub.2:O.sub.2 10 E2 F4 31 3.68 6.67 13.82 Inv. Ex 15 ITO/Ag/ITO N.sub.2:O.sub.2 3 E2 F4 40 3.69 7.04 13.96 Inv. Ex 16 ITO/Ag/ITO N.sub.2:O.sub.2 5 E2 F4 40 3.67 6.91 13.83 Inv. Ex 17 ITO/Ag/ITO N.sub.2:O.sub.2 10 E2 F4 40 3.68 6.83 13.70 Inv. Ex 18 ITO/Ag/ITO N.sub.2:O.sub.2 3 E2 F4 50 3.72 6.87 13.93 Inv. Ex 19 ITO/Ag/ITO N.sub.2:O.sub.2 5 E2 F4 50 3.68 6.64 13.82 Inv. Ex 20 ITO/Ag/ITO N.sub.2:O.sub.2 7 E2 F4 50 3.69 6.65 13.73 Inv. Ex 21 ITO/Ag/ITO N.sub.2:O.sub.2 10 E2 F4 50 3.72 6.46 13.48 Inv. Ex 22 ITO/Ag/ITO N.sub.2:O.sub.2 3 E2 F4 75 3.70 6.89 14.03 Inv. Ex 23 ITO/Ag/ITO N.sub.2:O.sub.2 5 E2 F4 75 3.71 6.85 13.90 Inv. Ex 24 ITO/Ag/ITO N.sub.2:O.sub.2 10 E5 F4 31 3.68 6.89 14.03 Inv. Ex 25 ITO/Ag/ITO N.sub.2:O.sub.2 10 E4 F4 31 3.68 6.92 14.02 Inv. Ex 26 ITO/Ag/ITO N.sub.2:O.sub.2 10 E6 F4 31 3.72 7.07 14.27 Inv. Ex 27 ITO/Ag/ITO N.sub.2:O.sub.2 10 E7 F4 31 3.71 6.96 14.04 Inv. Ex 28 ITO/Ag/ITO N.sub.2:O.sub.2 10 E8 F4 31 3.67 6.94 14.08

[0474] As can be seen from Table 2, the operating voltage of the inventive example may be lower than the comparative example.

[0475] A lower operating voltage may be beneficial for improved battery life, in particular in mobile devices.

[0476] As can be seen from Table 2, the external quantum efficiency EQE may be substantially reduced in comparison to the comparative examples.

[0477] A high external quantum efficiency EQE may be beneficial for reduced power consumption and improved battery life, in particular in mobile devices.

[0478] As can be seen from Table 2, the current efficiency (CEff) may be higher than for the comparative example. A high efficiency may be beneficial for reduced power consumption and improved battery life, in particular in mobile devices.

[0479] 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.