Organic Electronic Device Comprising an Organic Semiconductor Layer

Abstract

The present invention relates to compounds comprising a TAE structure, for use as a layer material for electronic devices, and to an organic electronic device comprising the layer material, and a method of manufacturing the same.

##STR00001##

Claims

1. A compound according to formula 1: ##STR00082## wherein X.sup.1 to X.sup.20 are independently selected from CH, CZ, and/or at least two of X.sup.1 to X.sup.5, X.sup.6 to X.sup.10, X.sup.11 to X.sup.15, X.sup.16 to X.sup.20, which are connected to each other by a chemical bond, are bridged to form an annelated non-hetero aromatic ring, and wherein at least one X.sup.1 to X.sup.2 is selected from CZ; Z is a substituent of formula II: ##STR00083## wherein Ar.sup.1 is a substituted or unsubstituted phenylene, substituted or unsubstituted biphenylene, substituted or unsubstituted triphenylene, substituted or unsubstituted anthracene or substituted or unsubstituted C.sub.14 to C.sub.18 fused non-hetero aryl, wherein the substituents of the substituted phenylene, biphenylene, triphenylene, anthracene or C.sub.14 to C.sub.18 fused non-hetero aryl are independently selected from nitrile, linear C.sub.1-20 alkyl, branched C.sub.3-20 alkyl or C.sub.3-20 cyclic alkyl, linear C.sub.1-12 fluorinated alkyl, linear C.sub.1-12 fluorinated alkoxy, branched C.sub.3-12 fluorinated alkyl, branched C.sub.3-12 fluorinated alkoxy, C.sub.3-12 cyclic fluorinated alkyl, C.sub.3-12 cyclic fluorinated alkoxy, OR, SR, (PO)R.sub.2, NR.sup.2R.sup.3 or BR.sup.2R.sup.3; Ar.sup.2 is independently selected from substituted or unsubstituted Cao non-hetero aryl, wherein the substituents of the C.sub.6-60 non-hetero aryl are independently selected from C.sub.1-C.sub.20 linear alkyl, C.sub.3-C.sub.20 branched alkyl or C.sub.3-C.sub.20 cyclic alkyl; C.sub.1-C.sub.20 linear alkoxy, C.sub.3-C.sub.20 branched alkoxy; linear fluorinated C.sub.1-C.sub.12 alkyl, or linear fluorinated C.sub.1-C.sub.2 alkoxy; C.sub.3-C.sub.2 branched cyclic fluorinated alkyl, C.sub.3-C.sub.12 cyclic fluorinated alkyl, C.sub.3-C.sub.2 cyclic fluorinated alkoxy, nitrile, OR, SR, (CO)R, (CO)NR.sub.2, SiR.sub.3, (SO)R, (SO).sub.2R, (PO)R.sub.2; or Ar.sup.2 is formula 1, with the exception that X.sup.1 to X.sup.20 are not CZ; R, R.sup.2 and R.sup.3 is independently selected from H, C.sub.1-C.sub.20 linear alkyl, C.sub.1-C.sub.20 alkoxy, C.sub.1-C.sub.20 thioalkyl, C.sub.3-C.sub.20 branched alkyl, C.sub.3-C.sub.20 cyclic alkyl, C.sub.3-C.sub.20 branched alkoxy, C.sub.3-C.sub.20 cyclic alkoxy, C.sub.6-C.sub.20 branched thioalkyl, C.sub.3-C.sub.20 cyclic thioalkyl, C.sub.6-C.sub.20 non-hetero aryl; n is 1 or 2; m is selected from 1, 2 or 3; wherein none of the non-hetero aromatic rings A, B, C and D are connected via a single bond to a triazine ring; wherein the compound of formula I comprises at least 8 to 14 non-hetero aromatic rings; wherein a non-hetero 6 member aromatic ring of Ar.sup.2 bonds direct via a single bond to Ar.sup.1; wherein only one tetra aryl ethylene group (TAE) bonds direct via a single bond to Ar.sup.1; and optional excluding compounds of formula 1 that are superimposable on its mirror image.

2. The compound according to claim 1, wherein the compound of formula I comprises at least 8 to 14 non-hetero aromatic rings.

3. The compound according to claim 1, wherein the compound of formula 1 comprises at least 8 to 14 non-hetero 6-member aromatic rings and is free of a hetero atom.

4. The compound according to claim 1, wherein the Ar.sup.1 group comprises at least 1 to 3 non-hetero aromatic 6 membered rings.

5. The compound according to claim 1, wherein in formula I: X.sup.1 to X.sup.20 are independently selected from CH, CZ, wherein one X.sup.1 to X.sup.20 is selected from CZ; Z is a substituent of formula II: ##STR00084## wherein Ar.sup.1 is independently selected from substituted or unsubstituted phenylene, biphenylene, triphenylene or anthracene, wherein the substituents are independently selected from nitrile, fluorinated C.sub.1-C.sub.6 alkyl or fluorinated C.sub.1-C.sub.6 alkoxy, OR, SR, (CO)R, (CO)NR.sub.2, SiR.sub.3, (SO)R, (SO).sub.2R, (PO)R.sub.2; Ar.sup.2 are independently selected from substituted or unsubstituted C.sub.12-60 aryl, wherein the substituents are independently selected from nitrile, di-alkyl phosphine oxide, di-aryl phosphine oxide, fluorinated C.sub.1-C.sub.6 alkyl or fluorinated C.sub.1-C.sub.6 alkoxy, OR, SR, (CO)R, (CO)NR.sub.2, SiR.sub.3, (S)R, (SO).sub.2R, (PO)R.sub.2; R is independently selected from a linear C.sub.1-C.sub.20 alkyl, linear C.sub.1-C.sub.20 alkoxy, linear C.sub.1-C.sub.20 thioalkyl, a branched C.sub.3-C.sub.20 alkyl, branched C.sub.3-C.sub.20 alkoxy, branched C.sub.3-C.sub.20 thioalkyl, C.sub.6-20 aryl; n is selected from 1 or 2; m is selected from 1, 2 or 3.

6. The compound according to claim 1, wherein in formula I: X.sup.1 to X.sup.20 are independently selected from CH and CZ, wherein one X.sup.1 to X.sup.20 is selected from CZ; Z is a substituent of formula II: ##STR00085## wherein Ar.sup.1 is independently selected from substituted or unsubstituted phenylene, biphenylene, triphenylene or anthracen, wherein the substituents are independently selected from nitrile, fluorinated C.sub.1-C.sub.6 alkyl or fluorinated C.sub.1-C.sub.6 alkoxy, OR, SR, (CO)R, (CO)NR.sub.2, SiR.sub.3, (SO)R, (SO).sub.2R (PO)R.sub.2; Ar.sup.2 is independently selected from substituted or unsubstituted C.sub.12-52 aryl, wherein the substituents are independently selected from nitrile, fluorinated C.sub.1-C.sub.6 alkyl or fluorinated C.sub.1-C.sub.6 alkoxy, OR, SR, (CO)R, (CO)NR.sub.2, SiR.sub.3, (SO)R, (SO).sub.2R, (PO)R.sub.2; R is independently selected from a linear C.sub.1-C.sub.10 alkyl, linear C.sub.1-C.sub.10 alkoxy, linear C.sub.1-C.sub.10 thioalkyl, a branched C.sub.3-C.sub.10 alkyl, branched C.sub.3-C.sub.10 alkoxy, branched C.sub.3-C.sub.10 thioalkyl, C.sub.6-12 aryl; n is selected from 1; m is selected from 1 or 2.

7. The compound according to claim 1, wherein Z is selected from formula E1 to E9: ##STR00086## ##STR00087## wherein Z.sup.1 to Z.sup.15 are independently selected from CH, CR.sup.1, and/or at least two of Z.sup.1 to Z.sup.5, Z.sup.6 to Z.sup.10, Z.sup.11 to Z.sup.15, which are connected to each other by a chemical bond, are bridged to form an annelated non-hetero aromatic ring; R.sup.1 is selected from nitrile, (PO)R.sub.2, NR.sup.2R.sup.3 or BR.sup.2R.sup.3; R.sup.2 and R.sup.3 are independently selected selected from H, linear C.sub.1-C.sub.20 alkyl, linear C.sub.1-C.sub.20 alkoxy, linear C.sub.1-C.sub.20 thioalkyl, a branched C.sub.3-C.sub.20 alkyl, branched C.sub.3-C.sub.20 alkoxy, branched C.sub.3-C.sub.20 thioalkyl, or C.sub.6-20 non-hetero aryl; Ar.sup.2 is independently selected from substituted or unsubstituted non-hetero C.sub.6-60 aryl; wherein the substituents are independently selected from nitrile, di-alkyl phosphine oxide, di-aryl phosphine oxide, fluorinated C.sub.1-C.sub.6 alkyl or fluorinated C.sub.1-C.sub.6 alkoxy, OR, SR, (CO)R, (CO)NR.sub.2, SiR.sub.3, (SO)R, (SO).sub.2R, (PO)R.sub.2; R is independently selected from a linear C.sub.1-C.sub.20 alkyl, linear C.sub.1-C.sub.20 alkoxy, linear C.sub.1-C.sub.20 thioalkyl, a branched C.sub.3-C.sub.20 alkyl, branched C.sub.3-C.sub.20 alkoxy, branched C.sub.3-C.sub.20 thioalkyl, C.sub.6-20 non-hetero aryl; m is selected from 1, 2 or 3.

8. The compound according to claim 1, wherein Ar.sup.2 is selected from formula F1 to F4: ##STR00088## wherein Y.sup.1 to Y.sup.5 are independently selected from CH, CR.sup.3, and/or at least two of Y.sup.1 to Y.sup.5, which are connected to each other by a chemical bond, are bridged to form an annelated non-hetero aromatic ring, wherein R.sup.3 is independently selected from a linear C.sub.1-C.sub.20 alkyl, linear C.sub.1-C.sub.20 alkoxy, linear C.sub.1-C.sub.20 thioalkyl, a branched C.sub.3-C.sub.20 alkyl, branched C.sub.3-C.sub.20 alkoxy, branched C.sub.3-C.sub.20 thioalkyl, substituted or unsubstituted C.sub.6-20 non-hetero aryl, wherein the substituents are independently selected from nitrile, fluorinated C.sub.1-C.sub.6 alkyl or fluorinated C.sub.1-C.sub.6 alkoxy, OR, SR, (CO)R, (CO)NR.sub.2, SiR.sub.3, (SO)R, (SO).sub.2R, (PO)R.sub.2; ##STR00089##

9. The compound according to claim 1, wherein Ar.sup.2 comprises at least one substituted or unsubstituted 1,1,2,2-Tetraphenylethylene group.

10. The compound according to claim 1, wherein the compounds of formula I are selected from G1 to G34: ##STR00090## ##STR00091## ##STR00092## ##STR00093## ##STR00094## ##STR00095## ##STR00096## ##STR00097## ##STR00098## ##STR00099## ##STR00100## ##STR00101## ##STR00102##

11. An organic electronic device comprising an organic semiconductor layer, wherein at least one organic semiconductor layer comprises a compound of formula I according to claim 1.

12. The organic electronic device according to claim 11, wherein the organic semiconductor layer is arranged between a photoactive layer and a cathode layer.

13. The organic electronic device according to claim 11, wherein the at least one organic semiconductor layer further comprises at least one alkali halide or alkali organic complex.

14. The organic electronic device according to claim 11, wherein the electronic device comprises at least one organic semiconductor layer, at least one anode layer, at least one cathode layer and at least one emission layer.

15. The organic electronic device according to claim 11, wherein the electronic device is a light emitting device, thin film transistor, a battery, a display device or a photovoltaic cell.

16. The compound according to claim 1, wherein the compound of formula I comprises at least 8 to 14 non-hetero aromatic 6-member rings.

17. The compound according to claim 1, wherein the compound of formula I comprises at least one of the non-hetero aromatic rings A, B, C and D, wherein at least one aromatic ring thereof is different substituted.

18. The compound according to claim 1, wherein the compound of formula I comprises at least one substituent comprising a hetero atom selected from the group consisting of N, O, S, (PO)R.sub.2, and CN.

19. The compound according to claim 1, wherein the compound of formula I comprises one non-hetero tetraarylethylene group (TAE) only.

20. The compound according to claim 1, wherein the Ar.sup.2 group comprises 1 to 9 non-hetero aromatic 6 membered rings.

21. The compound according to claim 1, wherein at least one non-hetero C.sub.6 to C.sub.18 arylene is annelated to at least one non-hetero aromatic ring A, B, C and D of formula (1).

Description

DESCRIPTION OF THE DRAWINGS

[0516] These and/or other aspects and advantages of the present invention will become apparent and more readily appreciated from the following description of the exemplary embodiments, taken in conjunction with the accompanying drawings, of which:

[0517] FIG. 1 is a schematic sectional view of an organic light-emitting diode (OLED), according to an exemplary embodiment of the present invention with an emission layer, one electron transport layer and an electron injection layer;

[0518] FIG. 2 is a schematic sectional view of an organic light-emitting diode (OLED), according to an exemplary embodiment of the present invention with an emission layer and two electron transport layers;

[0519] FIG. 3 is a schematic sectional view of an OLED, according to an exemplary embodiment of the present invention with an emission layer and three electron transport layers;

[0520] FIG. 4 is a schematic sectional view of an organic light-emitting diode (OLED), according to an exemplary embodiment of the present invention with an emission layer and one electron transport layer;

[0521] FIG. 5 is a schematic sectional view of an organic light-emitting diode (OLED), according to an exemplary embodiment of the present invention with an emission layer and two electron transport layers;

[0522] FIG. 6 is a schematic sectional view of an OLED, according to an exemplary embodiment of the present invention with an emission layer and three electron transport layers.

[0523] Reference will now be made in detail to the exemplary aspects, examples of which are illustrated in the accompanying drawings, wherein like reference numerals refer to the like elements throughout. The exemplary embodiments are described below, in order to explain the aspects, by referring to the figures.

[0524] Herein, when a first element is referred to as being formed or disposed on 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 a second element, no other elements are disposed there between.

[0525] The term contacting sandwiched refers to an arrangement of three layers whereby the layer in the middle is in direct contact with the two adjacent layers.

[0526] The organic light emitting diodes according to an embodiment of the present invention may include a hole transport region; an emission layer; and a first electron transport layer comprising a compound according to formula I.

[0527] FIG. 1 is a schematic sectional view of an organic light-emitting diode 100, according to an exemplary embodiment of the present invention. The OLED 100 comprises an emission layer 150, an electron transport layer (ETL) 161 comprising a compound of formula I and an electron injection layer 180, whereby the first electron transport layer 161 is disposed directly on the emission layer 150 and the electron injection layer 180 is disposed directly on the first electron transport layer 161.

[0528] FIG. 2 is a schematic sectional view of an organic light-emitting diode 100, according to an exemplary embodiment of the present invention. The OLED 100 comprises an emission layer 150 and an electron transport layer stack (ETL) 160 comprising a first electron transport layer 161 comprising a compound of formula I and a second electron transport layer 162, whereby the second electron transport layer 162 is disposed directly on the first electron transport layer 161.

[0529] FIG. 3 is a schematic sectional view of an organic light-emitting diode 100, according to an exemplary embodiment of the present invention. The OLED 100 comprises an emission layer 150 and an electron transport layer stack (ETL) 160 comprising a first electron transport layer 161 that comprises a compound of formula I, a second electron transport layer 162 that comprises a compound of formula I but different to the compound of the first electron transport layer, and a third electron transport layer 163, whereby the second electron transport layer 162 is disposed directly on the first electron transport layer 161 and the third electron transport layer 163 is disposed directly on the first electron transport layer 162.

[0530] FIG. 4 is a schematic sectional view of an organic light-emitting diode 100, according to an exemplary embodiment of the present invention. The OLED 100 comprises a substrate 110, a first anode electrode 120, a hole injection layer (HIE) 130, a hole transport layer (HTL) 140, an emission layer (EML) 150, one first electron transport layer (ETL) 161, an electron injection layer (EIL) 180, and a cathode electrode 190. The first electron transport layer (ETL) 161 comprises a compound of formula I and optionally an alkali halide or alkali organic complex. The electron transport layer (ETL) 161 is formed directly on the EML 150.

[0531] FIG. 5 is a schematic sectional view of an organic light-emitting diode 100, according to an exemplary embodiment of the present invention. The OLED 100 comprises a substrate 110, a first anode electrode 120, a hole injection layer (HIE) 130, a hole transport layer (HTL) 140, an emission layer (EML) 150, an electron transport layer stack (ETL) 160, an electron injection layer (EIL) 180, and a cathode electrode 190. The electron transport layer (ETL) 160 comprises a first electron transport layer 161 and a second electron transport layer 162, wherein the first electron transport layer is arranged near to the anode (120) and the second electron transport layer is arranged near to the cathode (190). The first and/or the second electron transport layer comprise a compound of formula I and optionally an alkali halide or alkali organic complex.

[0532] FIG. 6 is a schematic sectional view of an organic light-emitting diode 100, according to an exemplary embodiment of the present invention. The OLED 100 comprises a substrate 110, a first anode electrode 120, a hole injection layer (HIE) 130, a hole transport layer (HTL) 140, an emission layer (EML) 150, an electron transport layer stack (ETL) 160, an electron injection layer (EIL) 180, and a second cathode electrode 190. The electron transport layer stack (ETL) 160 comprises a first electron transport layer 161, a second electron transport layer 162 and a third electron transport layer 163. The first electron transport layer 161 is formed directly on the emission layer (EML) 150. The first, second and/or third electron transport layer comprise a compound of formula I that is different for each layer, and optionally an alkali halide or alkali organic complex.

[0533] A substrate may be further disposed under the anode 120 or on the cathode 190. The substrate may be a substrate that is used in a general organic light emitting diode and may be a glass substrate or a transparent plastic substrate with strong mechanical strength, thermal stability, transparency, surface smoothness, ease of handling, and water resistance.

[0534] The hole injection layer 130 may improve interface properties between ITO as an anode and an organic material used for the hole transport layer 140, and may be applied on a non-planarized ITO and thus may planarize the surface of the ITO. For example, the hole injection layer 130 may include a material having particularly desirable conductivity between a work function of ITO and HOMO of the hole transport layer 140, in order to adjust a difference a work function of ITO as an anode and HOMO of the hole transport layer 140.

[0535] When the hole transport region comprises a hole injection layer 130, the hole injection layer may be formed on the anode 120 by any of a variety of methods, for example, vacuum deposition, spin coating, casting, Langmuir-Blodgett (LB) method, or the like.

[0536] When hole injection layer is formed using vacuum deposition, vacuum deposition conditions may vary depending on the material that is used to form the hole injection layer, and the desired structure and thermal properties of the hole injection layer to be formed and for example, vacuum deposition may be performed at a temperature of about 100 C. to about 500 C., a pressure of about 10.sup.8 torr to about 10.sup.3 torr, and a deposition rate of about 0.01 to about 100 /sec, but the deposition conditions are not limited thereto.

[0537] When the hole injection layer is formed using spin coating, the coating conditions may vary depending on the material that is used to form the hole injection layer, and the desired structure and thermal properties of the hole injection layer to be formed. For example, the coating rate may be in the range of about 2000 rpm to about 5000 rpm, and a temperature at which heat treatment is performed to remove a solvent after coating may be in a range of about 80 C. to about 200 C., but the coating conditions are not limited thereto.

[0538] Conditions for forming the hole transport layer and the electron blocking layer may be defined based on the above-described formation conditions for the hole injection layer.

[0539] A thickness of the hole transport region may be from about 100 to about 10000 , for example, about 100 to about 1000 . When the hole transport region comprises the hole injection layer and the hole transport layer, a thickness of the hole injection layer may be from about 100 to about 10,000 , for example about 100 to about 1000 and a thickness of the hole transport layer may be from about 50 to about 2,000 , for example about 100 to about 1500 . When the thicknesses of the hole transport region, the HIT, and the HTL are within these ranges, satisfactory hole transport characteristics may be obtained without a substantial increase in operating voltage.

[0540] A thickness of the emission layer may be about 100 to about 1000 , for example about 200 to about 600 . When the thickness of the emission layer is within these ranges, the emission layer may have improved emission characteristics without a substantial increase in a operating voltage.

[0541] Next, an electron transport region is disposed on the emission layer.

[0542] The electron transport region may include at least one of a second electron transport layer, a first electron transport layer comprising a compound of formula I, and an electron injection layer.

[0543] The thickness of the electron transport layer may be from about 20 to about 1000 , for example about 30 to about 300 . When the thickness of the electron transport layer is within these ranges, the electron transport layer may have improved electron transport auxiliary ability without a substantial increase in operating voltage.

[0544] A thickness of the electron transport layer may be about 100 to about 1000 , for example about 150 to about 500 . When the thickness of the electron transport layer is within these ranges, the electron transport layer may have satisfactory electron transporting ability without a substantial increase in operating voltage.

[0545] In addition, the electron transport region may include an electron injection layer (EIL) that may facilitate injection of electrons from the anode.

[0546] The electron injection layer is disposed on an electron transport layer and may play a role of facilitating an electron injection from a cathode and ultimately improving power efficiency and be formed by using any material used in a related art without a particular limit, for example, LiF, Liq, NaCl, CsF, Li.sub.2O, BaO, Yb and the like.

[0547] The electron injection layer may include at least one selected from LiF, NaCl, CsF, Li.sub.2O, and BaO.

[0548] A thickness of the EIF may be from about 1 to about 100 , or about 3 to about 90 . When the thickness of the electron injection layer is within these ranges, the electron injection layer may have satisfactory electron injection ability without a substantial increase in operating voltage.

[0549] The anode can be disposed on the organic layer. A material for the anode may be a metal, an alloy, or an electrically conductive compound that have a low work function, or a combination thereof. Specific examples of the material for the anode 120 may be lithium (Li, magnesium (Mg), aluminum (Al), aluminum-lithium (AlLi, calcium (Ca), magnesium-indium (MgIn), magnesium-silver (MgAg), silver (Ag) etc. In order to manufacture a top-emission light-emitting device, the anode 120 may be formed as a light-transmissive electrode from, for example, indium tin oxide ITO) or indium zinc oxide IZO).

[0550] According to another aspect of the invention, a method of manufacturing an organic electroluminescent device is provided, wherein [0551] on an anode electrode (120) the other layers of hole injection layer (130), hole transport layer (140), optional an electron blocking layer, an emission layer (130), first electron transport layer (161) comprising a compound of formula I, second electron transport layer (162), electron injection layer (180), and a cathode (190), are deposited in that order; or [0552] the layers are deposited the other way around, starting with the cathode (190).

Organic Semiconductor Layer

[0553] The organic electronic device according to the present invention may comprise an organic semiconductor layer, wherein at least one organic semiconductor layer comprises a compound of formula I.

[0554] The organic semiconductor layer of the organic electronic device according to the invention is essentially non-emissive or non-emitting.

[0555] The organic semiconductor layer can be an electron transport layer, a hole injection layer, a hole transport layer, an emission layer, an electron blocking layer, a hole blocking layer or an electron injection layer, preferably an electron transport layer or an emission layer, more preferred an electron transport layer.

[0556] According to one embodiment, the organic semiconductor layer can be arranged between a photoactive layer and a cathode layer, preferably between an emission layer or light-absorbing layer and the cathode layer, preferably the organic semiconductor layer is an electron transport layer.

[0557] According to one embodiment, the organic semiconductor layer may comprise at least one alkali halide or alkali organic complex.

Organic Electronic Device

[0558] An organic electronic device according to the invention comprises an organic semiconductor layer comprising a compound according to formula I.

[0559] An organic electronic device according to one embodiment may include a substrate, an anode layer, an organic semiconductor layer comprising a compound of formula 1 and a cathode layer.

[0560] An organic electronic device according to one embodiment comprises at least one organic semiconductor layer comprising at least one compound of formula I, at least one anode layer, at least one cathode layer and at least one emission layer, wherein the organic semiconductor layer is preferably arranged between the emission layer and the cathode layer.

[0561] An organic light-emitting diode (OLED) according to the invention may include an anode, a hole transport layer (HTL), an emission layer (EML), an electron transport layer (ETL) comprising at least one compound of formula 1, and a cathode, which are sequentially stacked on a substrate. In this regard, the HTL, the EML, and the ETL are thin films formed from organic compounds.

[0562] An organic electronic device according to one embodiment can be a light emitting device, thin film transistor, a battery, a display device or a photovoltaic cell, and preferably a light emitting device.

[0563] According to one embodiment the OLED may have the following layer structure, wherein the layers having the following order:

an anode layer, a hole injection layer, optional a first hole transport layer, optional a second hole transport layer, an emission layer, an electron transport layer comprising a compound of formula 1 according to the invention, an electron injection layer, and a cathode layer.

[0564] According to another aspect of the present invention, there is provided a method of manufacturing an organic electronic device, the method using: [0565] at least one deposition source, preferably two deposition sources and more preferred at least three deposition sources.

[0566] The methods for deposition that can be suitable comprise: [0567] deposition via vacuum thermal evaporation; [0568] deposition via solution processing, preferably the processing is selected from spin-coating, printing, casting; and/or [0569] slot-die coating.

[0570] According to various embodiments of the present invention, there is provided a method using: [0571] a first deposition source to release the compound of formula 1 according to the invention, and [0572] a second deposition source to release the alkali halide or alkali organic complex, preferably a lithium halide or lithium organic complex;
the method comprising the steps of forming the electron transport layer stack; whereby for an organic light-emitting diode (OLED): [0573] the first electron transport layer is formed by releasing the compound of formula 1 according to the invention from the first deposition source and the alkali halide or alkali organic complex, preferably a lithium halide or lithium organic complex from the second deposition source.

[0574] According to various embodiments of the present invention, the method may further include forming on the anode electrode an emission layer and at least one layer selected from the group consisting of forming a hole injection layer, forming a hole transport layer, or forming a hole blocking layer, between the anode electrode and the first electron transport layer.

[0575] According to various embodiments of the present invention, the method may further include the steps for forming an organic light-emitting diode (OLED), wherein [0576] on a substrate a first anode electrode is formed, [0577] on the first anode electrode an emission layer is formed, [0578] on the emission layer an electron transport layer stack is formed, preferably a first electron transport layer is formed on the emission layer and optional a second electron transport layer is formed, [0579] and finally a cathode electrode is formed, [0580] optional a hole injection layer, a hole transport layer, and a hole blocking layer, formed in that order between the first anode electrode and the emission layer, [0581] optional an electron injection layer is formed between the electron transport layer and the cathode electrode.

[0582] According to various embodiments of the present invention, the method may further include forming an electron injection layer on a first electron transport layer. However, according to various embodiments of the OLED of the present invention, the OLED may not comprise an electron injection layer.

[0583] According to various embodiments, the OLED may have the following layer structure, wherein the layers having the following order:

an anode, first hole transport layer, second hole transport layer, emission layer, optional second electron transport layer, first electron transport layer comprising a compound of formula 1 according to the invention, optional an electron injection layer, and a cathode.

[0584] According to another aspect of the invention, it is provided an electronic device comprising at least one organic light emitting device according to any embodiment described throughout this application, preferably, the electronic device comprises the organic light emitting diode in one of embodiments described throughout this application. More preferably, the electronic device is a display device.

[0585] Hereinafter, the embodiments are illustrated in more detail with reference to examples. However, the present disclosure is not limited to the following examples. Reference will now be made in detail to the exemplary aspects.

Preparation of Compounds of Formula 1

[0586] Compound of formula 1 may be prepared as described below and disclosed by Huang et al

Chemical Communications (Cambridge, United Kingdom) (2012), 48(77), 9586-9588.

General Procedure for Suzuki Coupling:

[0587] ##STR00055##

[0588] Setup is brought under inert atmosphere. Flask is charged with A, B, C, and D in a counter flow of nitrogen. Water (dist.) is degassed for 30 min with N.sub.2 (under stirring). Solvent mixture is added and the mixture is heated with stirring. (TLC control.).

Synthesis of Compounds of Formula 1: Synthesis of dimethyl(3-(10-(3-(1,2,2-triphenylvinyl)phenyl)anthracen-9-yl)phenyl)phosphine oxide (G1)

[0589] ##STR00056##

[0590] Reagents and reaction conditions: 9-bromo-10-(3-(1,2,2-triphenylvinyl)phenyl)anthracene (1.0 eq.), dimethyl(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)phosphine oxide (1.2 eq.), chloro(crotyl)(2-dicyclohexylphosphino-2,6-dimethoxybiphenyl)palladium(II) (Pd-172) (0.02 eq.), potassium phosphate (3.0 eq.). 17 h at 90 C. (450 mL, toluene/ethanol/H.sub.2O 6/2/1).

[0591] When the reaction was completed according TLC, the reaction was cooled down to room temperature and the aqueous phase was separated. A mixture of water and brine (1/1) was added to the organic phase and the precipitated was then filtered. The solid was dissolved in chloroform and filtered over a pad of florisil (as eluent chloroform was initially used and the polarity was gradually increased to ethylacetate/methanol 24/1). Solvent was partially evaporated and the precipated was filtered. Compound was recrystallized first in DMF and then in acethylacetate. 8.6 g (38% yield). MS (ESI): 661 (M+H).

Synthesis of Intermediates

[0592] Synthesis of 4,4,5,5-tetramethyl-2-(3-(1,2,2-triphenylvinyl)phenyl)-1,3,2-dioxaborolane, 4,4,5,5-tetramethyl-2-(4-(1,2,2-triphenylvinyl)phenyl)-1,3,2-dioxaborolane, (2-(3-bromophenyl)-ethene-1,1,2-triyl)tribenzene and (2-(4-bromophenyl)ethene-1,1,2-triyl)tribenzene according to Chemical Communications, 48(77), 9586-9588; 2012.

##STR00057##

Synthesis of 9-bromo-10-(3-(1,2,2-triphenylvinyl)phenyl)anthracene

[0593] ##STR00058##

[0594] 9-(3-(1,2,2-triphenylvinyl)phenyl)anthracene (1.0 eq.) and NBS (1.2 eq.) were placed in a flask, and dissolved in CHCl.sub.3 (600 mL). The resulting solution was heated to 40 C. for 4 days, and then cooled down to room temperature. The precipitate was filtered and triturated in chloroform. 31.3 g, (76% yield). The compound was directly used in the next step.

Synthesis of 9-(3-(1,2,2-triphenylvinyl)phenyl)anthracene

[0595] ##STR00059##

[0596] Reagents and reaction conditions: (2-(3-bromophenyl)ethene-1,1,2-triyl)tribenzene (1.0 eq.), anthracen-9-ylboronic acid (1.7 eq.), tetrakistriphenylphosphine palladium (0) (Pd(PPh.sub.3).sub.4) (0.02 eq.)+[1,1-Bis(diphenylphosphino)ferrocene]dichloropalladium(II) (Pd(dppf)Cl2) (0.02 eq.), potassium carbonate (3.0 eq.), 2-Dicyclohexylphosphino-2,4,6-triisopropylbiphenyl (0.05 eq.). 7 days at 90 C. (525 mL, glyme/water 2.5/1.0).

[0597] When the reaction was completed according TLC, the reaction was cooled down to room temperature. The precipitate was filtered and washed with water. Solid was dissolved in hot toluene, filtered hot over a pad of silicagel and then solvent was partially evaporated. Solid was filtered, triturated in dichloromethane (filtered hot), and recrystallized in toluene 36.1 g, (71% yield). ESI-MS: 508 (M).

Preparation of 3,3-bis(1,2,2-triphenylvinyl)-1,1:3,1:3,1-quaterphenyl (G4)

[0598] ##STR00060##

[0599] A flask was flushed with nitrogen and charged with 4,4,5,5-tetramethyl-2-(3-(1,2,2-triphenylvinyl)phenyl)-1,3,2-dioxaborolane (20.0 g, 43.6 mmol) and 3,3-dibromo-1,1-biphenyl (6.5 g, 20.8 mmol), Pd(dppf)Cl.sub.2 (76 mg, 0.1 mmol). A mixture of deaerated toluene/ethanol (3:1, 200 mL) and a deaerated solution of K.sub.2CO.sub.3 (5.7 g, 42.0 mmol) in water (21 mL) were added consecutively and the reaction mixture was heated to 105 C. under a nitrogen atmosphere for 3 hours. After cooling down to 0 C., the resulting precipitate was isolated by suction filtration and washed with toluene and hexane. The crude product was then dissolved in dichloromethane (1.2 L) and the organic phase was washed with water (4500 mL). After drying over MgSO.sub.4, the organic phase was filtered through a silica gel pad. After rinsing with additional dichloromethane (1.5 L), the solvent was completely removed under vacuum. The crude solid was then recrystallized in toluene (170 mL). The precipitate was collected by suction filtration to yield 14.3 g (84%) of a white solid after drying. Final purification was achieved by sublimation. HPLC: 100%.

Preparation of 3,3-bis(1,2,2-triphenylvinyl)-1,1:4,1-terphenyl (G2)

[0600] ##STR00061##

[0601] A flask was flushed with nitrogen and charged with 4,4,5,5-tetramethyl-2-(3-(1,2,2-triphenylvinyl)phenyl)-1,3,2-dioxaborolane (13.8 g, 30.3 mmol) and 1,4-dibromobenzene (3.4 g, 14.4 mmol), Pd(dppf)Cl.sub.2 (53 mg, 0.07 mmol). A mixture of deaerated toluene/ethanol (3:1, 140 mL) and a deaerated solution of K.sub.2CO.sub.3 (4.0 g, 28.8 mmol) in water (14.4 mL) were added consecutively and the reaction mixture was heated to 105 C. under a nitrogen atmosphere for 3 hours. After cooling down to room temperature, the resulting precipitate was isolated by suction filtration and washed with toluene and hexane. The crude product was then dissolved in dichloromethane (600 mL) and the organic phase was washed with water (3300 mL). After drying over MgSO.sub.4, the organic phase was filtered through a florisil pad. The solvent was completely removed under vacuum and the crude solid was then recrystallized in toluene (80 mL). The precipitate was collected by suction filtration to yield 7.7 g (72%) of a white solid after drying. Final purification was achieved by sublimation. HPLC: 99.70%.

Preparation of 3,3-bis(1,2,2-triphenylvinyl)-5-(3-(1,2,2-triphenylvinyl)phenyl)-1,1:3,1-terphenyl (G5)

[0602] ##STR00062##

[0603] A flask was flushed with nitrogen and charged with 4,4,5,5-tetramethyl-2-(3-(1,2,2-triphenylvinyl)phenyl)-1,3,2-dioxaborolane (25.0 g, 54.5 mmol) and 1,3,5-tribromobenzene (5.5 g, 17.3 mmol), Pd(dppf)Cl.sub.2 (63 mg, 0.09 mmol). A mixture of deaerated toluene/ethanol (3:1, 240 mL) and a deaerated solution of K.sub.2CO.sub.3 (4.8 g, 34.6 mmol) in water (17 mL) were added consecutively and the reaction mixture was heated to 105 C. under a nitrogen atmosphere for 21 hours. After cooling down to room temperature, additional toluene was added (250 mL) and the crude reaction was washed with water (4300 mL). After drying over MgSO.sub.4, the organic phase was filtered through a florisil pad. After rinsing with additional toluene (1.0 L), the solvent was completely removed under vacuum and the crude mixture was stirred in ethanol (150 mL) at room temperature. The solid was collected by suction filtration and recrystallized in acetonitrile (300 mL). Pure solid was collected by suction filtration at 70 C. to yield 16.3 g (88%) of a white solid after drying. Final purification was achieved by sublimation. HPLC: 99.0%.

Preparation of 4,5, 6-triphenyl-3-(1,2,2-triphenylvinyl)-1,1:2,1:3,1-quaterphenyl (G6)

[0604] ##STR00063##

[0605] A flask was flushed with nitrogen and charged with 4,4,5,5-tetramethyl-2-(3,4,5-triphenyl-[1,1:2,1-terphenyl]-3-yl)-1,3,2-dioxaborolane (20.0 g, 34.2 mmol) and (2-(3-bromophenyl)ethene-1,1,2-triyl)tribenzene (12.8 g, 31.1 mmol), Pd(dppf)Cl.sub.2 (113 mg, 0.16 mmol). A mixture of deaerated toluene/ethanol (3:1, 240 mL) and a deaerated solution of K.sub.2CO3 (4.8 g, 34.6 mmol) in water (17 mL) were added consecutively and the reaction mixture was heated to 105 C. under a nitrogen atmosphere for 5 hours. After cooling down to room temperature, additional toluene was added (250 mL) and the crude reaction was washed with water (4300 mL). After drying over MgSO.sub.4, the organic phase was filtered through a florisil pad. After rinsing with additional toluene (2.0 L), the solvent was partially removed under vacuum and hexane (300 mL) was added to induce precipitation. The crude mixture was collected by suction filtration and recrystallized in ethylacetate (150 mL) to yield 16.9 g (69%) of a white solid after drying. Final purification was achieved by sublimation. HPLC: 99.9%.

Preparation of 3,3-bis(1,2,2-triphenylvinyl)-1,1:3,1-terphenyl (G3)

[0606] ##STR00064##

[0607] A flask was flushed with nitrogen and charged with 4,4,5,5-tetramethyl-2-(3-(1,2,2-triphenylvinyl)phenyl)-1,3,2-dioxaborolane (20.0 g, 44.0 mmol) and 1,3-dibromobenzene (4.9 g, 20.8 mmol), Pd(dppf)Cl.sub.2 (76 mg, 0.10 mmol). A mixture of deaerated toluene/ethanol (3:1, 200 mL) and a deaerated solution of K.sub.2CO.sub.3 (5.7 g, 42.0 mmol) in water (21 mL) were added consecutively and the reaction mixture was heated to 105 C. under a nitrogen atmosphere for 21 hours. After cooling down to room temperature, additional toluene was added (300 mL) and the crude reaction was washed with water (4300 mL). After drying over MgSO.sub.4, the organic phase was filtered through a florisil pad. After rinsing with additional toluene (1.0 L), the solvent was completely removed. The crude mixture was recrystallized in acetonitrile. The precipitate was collected by suction filtration at 60 C. Finally, it was stirred in ethanol (180 mL). The precipitate was collected by suction filtration to yield 14.1 g (92%) of a white solid after drying. Final purification was achieved by sublimation. HPLC: 99.9%.

General Procedure for Fabrication of Organic Electronic Devices

[0608] In general organic electronic devices may be organic light-emitting diodes (OLEDs), organic photovoltaic cells (OSCs), organic field-effect transistors (OFETs) or organic light emitting transistors (OLETs).

Any functional layer in the organic electronic device may comprise a compound of formula 1 or may consist of a compound of formula 1.

[0609] An OLED may be composed of individual functional layers to form a top-emission OLED which emits light through the top electrode. Herein, the sequence of the individual functional layers may be as follows wherein contact interfaces between the individual layers are shown as /: non-transparent anode layer (bottom electrode)/hole injection layer/hole transport layer/electron blocking layer/emission layer/hole blocking layer/electron transport layer/electron injection layer/transparent cathode layer (top electrode). Each layer may in itself be constituted by several sub-layers.

[0610] An OLED may be composed of individual functional layers to form a bottom-emission OLED which emits light through the bottom electrode. Herein, the sequence of the individual functional layers may be as follows wherein contact interfaces between the individual layers are shown as /: transparent anode layer (bottom electrode)/hole injection layer/hole transport layer/electron blocking layer/emission layer/hole blocking layer/electron transport layer/electron injection layer/non-transparent cathode layer (top electrode). Each layer may in itself be constituted by several sub-layers.

[0611] Top-emission OLED devices were prepared to demonstrate the technical benefit utilizing the compounds of formula 1 in an organic electronic device.

Fabrication of Top Emission Devices

[0612] For top emission devices in Table 3 and 4, a glass substrate was cut to a size of 50 mm50 mm0.7 mm, ultrasonically cleaned with isopropyl alcohol for 5 minutes and then with pure water for 5 minutes, and cleaned again with UV ozone for 30 minutes, to prepare a first electrode. 100 nm Ag were deposited at a pressure of 10.sup.5 to 10.sup.7 mbar to form the anode. Then, 92 vol.-% Biphenyl-4-yl(9,9-diphenyl-9H-fluoren-2-yl)-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]-amine (CAS 1242056-42-3) with 8 vol.-% 4,4,4-((1E,1E,1E)-cyclopropane-1,2,3-triylidenetris(cyanomethanylylidene))tris(2,3,5,6-tetrafluorobenzonitrile) was vacuum deposited on the Ag electrode, to form a HIL having a thickness of 10 nm. Then, Biphenyl-4-yl(9,9-diphenyl-9H-fluoren-2-yl)-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]-amine (CAS 1242056-42-3) was vacuum deposited on the HIL, to form a HTL having a thickness of 118 nm. Then, N,N-bis(4-(dibenzo[b,d]furan-4-yl)phenyl)-[1,1:4,1-terphenyl]-4-amine (CAS 1198399-61-9) was vacuum deposited on the HTL, to form an electron blocking layer (EBL) having a thickness of 5 nm.

[0613] 97 vol.-% H09 (Sun Fine Chemicals) as EML host and 3 vol.-% BD200 (Sun Fine Chemicals) as fluorescent blue dopant were co-deposited on the EBL, to form a blue-emitting EML with a thickness of 20 nm.

[0614] Then, the hole blocking layer is formed with a thickness of 5 nm by depositing a mixture 2,4-diphenyl-6-(3-(triphenylen-2-yl)-[1,1-biphenyl]-3-yl)-1,3,5-triazine (CAS 1638271-85-8) and 9-([1,1-biphenyl]-3-yl)-9-([1,1-biphenyl]-4-yl)-9H,9H-3,3-bicarbazole (CAS 1643479-47-3) in a volume ratio of 30:70 on the emission layer for inventive example 7. For inventive example 10 to 12, the hole blocking layer is formed with a thickness of 5 nm by co-depositing compound ET-1 (diphenyl(3-(10-phenylanthracen-9-yl)-[1,1-biphenyl]-4-yl)phosphine oxide (WO2017178392A1)) and compound of formula I in a volume ratio of 40:60 on the emission layer, see Table 4.

[0615] Then, the electron transporting layer is formed on the hole blocking layer. The electron transport layer of inventive example 7 comprises 70 wt.-% of compound of formula 1 (or of the comparative compound) and 30 wt.-% of Lithium tetra(1H-pyrazol-1-yl)borate (CAS 14728-62-2). The electron transport layer of inventive example 10 to 12 comprises 75 wt.-% of compound ET-1 and 25 wt.-% of Lithium tetra(1H-pyrazol-1-yl)borate (CAS 14728-62-2).

[0616] Then, for top emission devices the electron injection layer is formed on the electron transporting layer by deposing Yb with a thickness of 2 nm. Ag is evaporated at a rate of 0.01 to 1 /s at 10.sup.7 mbar to form a cathode with a thickness of 11 nm. A cap layer of Biphenyl-4-yl(9,9-diphenyl-9H-fluoren-2-yl)-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]-amine is formed on the cathode with a thickness of 75 nm.

[0617] 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.

[0618] To assess the performance of the inventive examples compared to the existing art, the light output of the top emission OLEDs is measured under ambient conditions (20 C.). Current voltage measurements are performed using a Keithley 2400 sourcemeter, and recorded in V. At 10 mA/cm.sup.2 for top emission devices, a spectrometer CAS140 CT from Instrument Systems, which has been calibrated by Deutsche Akkreditierungsstelle (DAkkS), is used for measurement of CIE coordinates and brightness in Candela. The current efficiency Ceff is determined at 10 mA/cm.sup.2 in cd/A.

[0619] In top emission devices, the emission is forward directed, non-Lambertian and also highly dependent on the micro-cavity. Therefore, the external quantum efficiency (EQE) and power efficiency in lm/W will be higher compared to bottom emission devices.

Compounds Used

[0620]

TABLE-US-00001 IUPAC name Formula Reference Biphenyl-4-yl(9,9-diphenyl- 9H-fluoren-2-yl)-[4-(9-phenyl- 9H-carbazol-3-yl)phenyl]- amine (CAS 1242056-42-3) [00065] US2016322581 4,4,4-((1E,1E,1E)- cyclopropane-1,2,3- triylidenetris(cyanomethanylyl- idene))tris(2,3,5,6- tetrafluorobenzonitrile) [00066] US2008265216 N,N-bis(4-(dibenzo[b,d]furan- 4-yl)phenyl)-[1,1:4,1- terphenyl]-4-amine (CAS 1198399-61-9) [00067] JP2014096418 H09 Fluorescent-blue host material Commecially available from Sun Fine Chemicals, Inc, S. Korea H06 Fluorescent-blue host material - Commercially available from Sun Fine Chemicals, Inc, S. Korea BD200 - Fluorescent-blue emitter material Commercially available from Sun Fine Chemicals, Inc, S. Korea 2,4-diphenyl-6-(4,5,6- triphenyl- [1,1:2,1:3,1:3,1- quinquephenyl]-3-yl)-1,3,5- triazine [00068] 8-Hydroxyquinolinolato- lithium (850918-68-2) Alkali organic complex 1 = AOC-1 [00069] WO2013079217 Lithium tetra(1H-pyrazol-1- yl)borate (CAS 14728-62-2) Alkali organic complex 2 = AOC-2 [00070] WO2013079676 2,4-diphenyl-6-(3- (triphenylen-2-yl)-[1,1- biphenyl]-3-yl)-1,3,5-triazine (1638271-85-8) [00071] 9-([1,1-biphenyl]-3-yl)-9- ([1,1-biphenyl]-4-yl)-9H,9H- 3,3-bicarbazole (1643479-47- 3) [00072]

Melting Point

[0621] The melting point (Tm) is determined as peak temperatures from the DSC curves of the above TGA-DSC measurement or from separate DSC measurements (Mettler Toledo DSC822e, heating of samples from room temperature to completeness of melting with heating rate 10 K/min under a stream of pure nitrogen. Sample amounts of 4 to 6 mg are placed in a 40 L Mettler Toledo aluminum pan with lid, a<1 mm hole is pierced into the lid).

Glass Transition Temperature

[0622] The glass transition temperature (Tg) is measured under nitrogen and using a heating rate of 10 K per min in a Mettler Toledo DSC 822e differential scanning calorimeter as described in DIN EN ISO 11357, published in March 2010.

Rate Onset Temperature

[0623] The rate onset temperature (T.sub.RO) for transfer into the gas phase is determined by loading 100 mg compound into a VTE source. As VTE source a point source for organic materials is used as supplied by Kurt J. Lesker Company (www.lesker.com) or CreaPhys GmbH (http://www.creaphys.com). The VTE (vacuum thermal evaporation) source temperature is determined through a thermocouple in direct contact with the compound in the VTE source.

[0624] The VTE source is heated at a constant rate of 15 K/min at a pressure of 10.sup.7 to 10.sup.8 mbar in the vacuum chamber 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 ngstrom per second. To determine the rate onset temperature, the deposition rate on a logarithmic scale is plotted against the VIE source temperature. The rate onset is the temperature at which noticeable deposition on the QCM detector occurs (defined as a rate of 0.02 /s. 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. The rate onset temperature is an indirect measure of the volatility of compound. The higher the rate onset temperature the lower is the volatility of a compound.

Technical Effect of the Invention

[0625] In summary, organic electronic devices comprising compounds with formula 1 inherent to their molecular structure have higher current efficiency. The glass transition temperature and rate onset temperature are within the range acceptable for mass production of organic semiconductor layers.

[0626] Table 1: Structural formulae, glass transition temperature, melting temperature, rate onset temperature of comparative compounds.

TABLE-US-00002 TABLE 1 Tg Tm T.sub.RO Name Formula [ C.] [ C.] [ C.] Comparative Compound 1 Comparative- 1 [00073] 120 276 Comparative compound 2 Comparative- 2 [00074] 385 243 Comparative compound 3 Comparative- 3 [00075] 115 308 198

[0627] Table 2: Structural formulae, glass transition temperature, melting temperature, rate onset temperature of inventive compounds.

TABLE-US-00003 TABLE 2 Tg Tm T.sub.RO Name Formula [ C.] [ C.] [ C.] Inventive Example 7 G1 [00076] 132 304 243 Inventive Example 8 G4 [00077] 263 112 243 Inventive Example 9 G3 [00078] 192 105 216 Inventive Example 10 G2 [00079] 283 112 242 Inventive Example 11 G5 [00080] 258 137 n/a Inventive Example 12 G6 [00081] 201 127 221

[0628] In Table 1 are shown glass transition temperatures, melting temperatures, rate onset temperatures of comparative compounds.

[0629] In Table 2 are shown glass transition temperatures, melting temperatures, rate onset temperatures of compounds of formula 1.

TABLE-US-00004 TABLE 3 Performance data of top emission OLED devices comprising an electron transport layer, which comprises the compounds of formula I and comparative compounds and an alkali organic complex. The inventive examples show increased cd/A efficiencies Comparative Alkali vol.-% cd/A compounds and vol.-% organic alkali Operating efficiency at compounds of compound complex organic Thickness CIE voltage at 10 10 mA/cm.sup.2 formula 1 of formula 1 (AOC) complex ETL/nm 1931 y mA/cm.sup.2 (V) (cd/A) Comparative example 1 Comparative-1 50 AOC-1 50 31 0.042 3.64 7.04 Comparative example 1 Comparative-2 50 AOC-1 50 31 0.044 3.61 6.40 Comparative example 1 Comparative-3 70 AOC-2 30 36 0.044 3.41 6.92 Inventive example 7 G1 70 AOC-2 30 36 0.045 3.78 7.18

TABLE-US-00005 TABLE 4 Performance data of top emission OLED devices comprising a hole blocking layer, which comprises the compounds of formula I. The inventive example show increased cd/A efficiencies vol.-% vol.-% cd/A Compound compound Electron Electron Operating efficiency at of of transport transport Thickness CIE voltage at 10 10 mA/cm.sup.2 formula 1 formula 1 material material ETL/nm 1931 y mA/cm.sup.2 (V) (cd/A) Inventive example 10 G2 60 ET-1 40 31 0.045 3.77 7.20 Inventive example 11 G5 60 ET-1 40 31 0.042 3.59 7.9 Inventive example 12 G6 60 ET-1 40 31 0.045 3.76 7.5

[0630] While this invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims. Therefore, the aforementioned embodiments should be understood to be exemplary but not limiting the present invention in any way.