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 I: ##STR00140## wherein X.sup.1 to X.sup.20 are independently selected from N, CH, CR.sup.1, 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 aromatic ring or annelated heteroaromatic ring, and wherein at least one X.sup.1 to X.sup.20 is selected from CZ; R.sup.1 is selected from NR.sup.2R.sup.3 or BR.sup.2R.sup.3; R.sup.2 and R.sup.3 are independently selected C.sub.6-24 aryl and C.sub.2-20 heteroaryl; Z is a substituent of formula II: ##STR00141## wherein Ar.sup.1 is independently selected from substituted or unsubstituted C.sub.6-C.sub.60 aryl and substituted or unsubstituted C.sub.2-C.sub.60 heteroaryl, wherein the substituents of C.sub.6-C.sub.60 aryl or C.sub.2-C.sub.60 heteroaryl are independently selected from 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; Ar.sup.2 is independently selected from: formula I, with the exception that X.sup.1 to X.sup.20 are not CZ, substituted or unsubstituted C.sub.2-C.sub.60 heteroaryl; wherein the substituents of the C.sub.2-C.sub.60 heteroaryl 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.12 alkoxy; C.sub.3-C.sub.12 branched cyclic fluorinated alkyl, C.sub.3-C.sub.12 cyclic fluorinated alkyl, C.sub.3-C.sub.12 cyclic fluorinated alkoxy, nitrile, OR, SR, (CO)R, (CO)NR.sub.2, SiR.sub.3, (SO)R, (SO).sub.2R, (PO)R.sub.2; with the provision that the Ar.sup.2 group comprises 3 to 8 non-hetero aromatic 6 membered rings; R is independently selected from a 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.3-C.sub.20 branched thioalkyl, C.sub.3-C.sub.20 cyclic thioalkyl, C.sub.6-C.sub.20 aryl and C.sub.3-C.sub.20 heteroaryl; n is 1 or 2; m is selected from 1, 2 or 3; wherein none of the aromatic rings A, B, C and D are connected via a single bond to a triazine ring; and the compound of formula I comprises at least one hetero atom, wherein the hetero atom is selected from N, O, (PO)R.sub.2, CN; and the compound of formula I comprises at least 8 to 14 aromatic rings; and the heteroatom of a heteroarylene of Ar.sup.1 is selected from N, O, B, Si, P, Se; and optional excluding compounds of formula I that are superimposable on its mirror image.

2. The compound according to claim 1, wherein the compound of formula I comprises at least 1 to 5 hetero aromatic rings.

3. The compound according to claim 1, wherein the Ar.sup.1 group comprises 1 to 3 aromatic 6 membered rings.

4. The compound according to claim 1, wherein Ar.sup.1 is independently selected from substituted or unsubstituted C.sub.6-18 aryl and substituted or unsubstituted C.sub.4-C.sub.17 heteroaryl, wherein the substituents are independently selected from the group consisting of nitrile, di-alkyl phosphine oxide, di-aryl phosphine oxide, C.sub.2-C.sub.16 heteroaryl, fluorinated C.sub.1-C.sub.6 alkyl, fluorinated C.sub.1-C.sub.6 alkoxy, OR, SR, (CO)R, (CO)NR.sub.2, SiR.sub.3, (SO)R, (SO).sub.2R, and (PO)R.sub.2.

5. The compound according to claim 1, wherein the compound of formula I exclude two tetraarylethylene (TAE) groups connected direct via a single bond.

6. The compound according to claim 1, wherein in formula I: X.sup.1 to X.sup.20 are independently selected from CH, CR.sup.1, CZ, wherein at least one X.sup.1 to X.sup.20 is selected from CZ; R.sup.1 is independently selected from NR.sup.2R.sup.3 and BR.sup.2R.sup.3; R.sup.2 and R.sup.3 are independently selected C.sub.6-16 aryl and C.sub.2-12 heteroaryl; Z is a substituent of formula II: ##STR00142## wherein Ar.sup.1 is independently selected from substituted or unsubstituted C.sub.6-C.sub.18 aryl and substituted or unsubstituted C.sub.4-C.sub.14 heteroaryl, wherein the substituents are independently selected from the group consisting of nitrile, di-alkyl phosphine oxide, di-aryl phosphine oxide, C.sub.2-C.sub.16 heteroaryl, fluorinated C.sub.1-C.sub.6 alkyl, fluorinated C.sub.1-C.sub.6 alkoxy, OR, SR, (CO)R, (CO)NR.sub.2, SiR.sub.3, (SO)R, (SO).sub.2R, and (PO)R.sub.2; Ar.sup.2 are independently selected from substituted or unsubstituted C.sub.10-C.sub.59 heteroaryl; wherein the substituents are independently selected from the group consisting of nitrile, di-alkyl phosphine oxide, di-aryl phosphine oxide, C.sub.2-C.sub.16 heteroaryl, fluorinated C.sub.1-C.sub.6 alkyl, fluorinated C.sub.1-C.sub.6 alkoxy, OR, SR, (CO)R, (CO)NR.sub.2, SiR.sub.3, (SO)R, (SO).sub.2R, and (PO)R.sub.2; R is independently selected from a C.sub.1-C.sub.20 linear alkyl, 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-C.sub.20 aryl and C.sub.3-C.sub.20 heteroaryl; n is 1 or 2; m is selected from 1, 2 or 3.

7. 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: ##STR00143## wherein Ar.sup.1 is independently selected from unsubstituted C.sub.6-18 aryl and unsubstituted C.sub.4-C.sub.17 heteroaryl, Ar.sup.2 is independently selected from substituted or unsubstituted C.sub.3-C.sub.51 heteroaryl, wherein the substituents are independently selected from the group consisting of nitrile, di-alkyl phosphine oxide, di-aryl phosphine oxide, C.sub.2-C.sub.16 heteroaryl, fluorinated C.sub.1-C.sub.6 alkyl, fluorinated C.sub.1-C.sub.6 alkoxy, OR, SR, (CO)R, (CO)NR.sub.2, SiR.sub.3, (SO)R, (SO).sub.2R, and (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.20 alkoxy, branched C.sub.3-C.sub.10 thioalkyl, C.sub.6-C.sub.12 aryl and C.sub.3-C.sub.11 heteroaryl; n is selected from 1; m is selected from 1 or 2.

8. The compound according to claim 1, wherein Z is selected from formula E1 to E9: ##STR00144## Z.sup.1 to Z.sup.15 are independently selected from N, 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 aromatic ring or heteroaromatic ring; R.sup.1 is selected from NR.sup.2R.sup.3 or BR.sup.2R.sup.3; R.sup.2 and R.sup.3 are independently selected C.sub.6-16 aryl and C.sub.2-12 heteroaryl; Ar.sup.2 is independently selected from substituted or unsubstituted C.sub.2-C.sub.60 heteroaryl, wherein the substituents are independently selected from nitrile, di-alkyl phosphine oxide, di-aryl phosphine oxide, c.sub.2-c.sub.36 heteroaryl, fluorinated C.sub.1-C.sub.6 alkyl or fluorinated C.sub.1-C.sub.6 alkoxy, wherein the substituents are independently selected from the group consisting of nitrile, di-alkyl phosphine oxide, di-aryl phosphine oxide C.sub.2-C.sub.16 heteroaryl, fluorinated C.sub.1-C.sub.6 alkyl, fluorinated C.sub.1-C.sub.6 alkoxy, OR, SR, (CO)R, (CO)NR.sub.2, SiR.sub.3, (SO)R, (SO).sub.2R, and (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 and C.sub.3-C.sub.20 heteroaryl; m is selected from 1, 2 or 3.

9. The compound according to claim 1, wherein Ar.sup.2 is selected from formula F1 to F25: ##STR00145## wherein Y.sup.1 to Y.sup.5 are independently selected from N, 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 aromatic ring or heteroaromatic ring, with the provision that F1 comprises at least one hetero atom, wherein R.sup.3 is independently selected from a linear C.sub.1-C.sub.20 alkyl, linear C.sub.1C.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 aryl and substituted or unsubstituted C.sub.3-C.sub.20 heteroaryl, wherein the substituents are independently selected from the group consisting of nitrile, di-alkyl phosphine oxide, di-aryl phosphine oxide, C.sub.2-C.sub.16 heteroaryl, fluorinated C.sub.1-C.sub.6 alkyl, fluorinated C.sub.1-C.sub.6 alkoxy, OR, SR, (CO)R, (CO)NR.sub.2, SiR.sub.3, (SO)R, (SO).sub.2R, and (PO)R.sub.2; ##STR00146## wherein R=naphthyl, p-biphenyl or o-biphenyl; ##STR00147## ##STR00148## ##STR00149## ##STR00150##

10. The compound according to claim 1, wherein Z is selected from formula E1 to E9.

11. The compound according to claim 1, wherein Ar.sup.2 comprises at least one pyridine, at least one pyrimidine, at least one triazine ring, or a combination thereof.

12. The compound according to claim 1, wherein Ar.sup.2 comprises at least one substituted or unsubstituted 1,1,2,2-Tetraphenylethylene group, which is bonded via a single bond to a pyridine, a pyrimidine, a triazine ring, or a phenyl group.

13. The compound according to claim 1, wherein the compounds of formula I are selected from G1 to G49: ##STR00151## ##STR00152## ##STR00153## wherein R=napthyl, p-biphenyl or o-biphenyl; ##STR00154## ##STR00155## ##STR00156## ##STR00157## ##STR00158## ##STR00159## ##STR00160## ##STR00161## ##STR00162## ##STR00163## ##STR00164## ##STR00165## ##STR00166## ##STR00167## ##STR00168## ##STR00169## ##STR00170## ##STR00171## ##STR00172## ##STR00173##

14. 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.

15. The organic electronic device according to claim 14, wherein the organic semiconductor layer is arranged between a photoactive layer and a cathode layer.

16. The organic electronic device according to claim 14, wherein the at least one organic semiconductor layer further comprises at least one alkali halide or alkali organic complex.

17. The organic electronic device according to claim 14, 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.

18. The organic electronic device according to claim 14, wherein the electronic device is selected from the group consisting of a light emitting device, a thin film transistor, a battery, a display device, and a photovoltaic cell.

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

20. The compound according to claim 1, wherein the compound of formula I comprises at least one hetero atom N.

21. The compound according to claim 1, wherein the compound of formula I comprises at least one hetero N and at least one substituent selected from (PO)R.sub.2 or CN.

22. The compound according to claim 1, wherein the compound of formula I comprises at least one triazine ring.

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

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

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

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

27. The compound according to claim 1, wherein Z is selected from formula E1 to E9 and bonded via a single bond to a triazine ring of Ar.sup.2.

28. The compound according to claim 1, wherein Z is selected from formula E1 or E5 and bonded via a single bond to a triazine ring of Ar.sup.2.

29. The compound according to claim 1, wherein Ar.sup.2 comprises at least one nitril substituent, at least one phosphine oxide substituent, or a combination thereof.

Description

DESCRIPTION OF THE DRAWINGS

[0582] 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:

[0583] 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;

[0584] 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;

[0585] 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;

[0586] 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;

[0587] 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;

[0588] 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.

[0589] 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.

[0590] 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.

[0591] 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.

[0592] 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.

[0593] 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.

[0594] 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.

[0595] 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.

[0596] 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 (HIL) 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.

[0597] 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 (HIL) 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.

[0598] 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 (HIL) 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.

[0599] 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.

[0600] 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.

[0601] 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.

[0602] 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.

[0603] 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.

[0604] 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.

[0605] 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 HIL, and the HTL are within these ranges, satisfactory hole transport characteristics may be obtained without a substantial increase in operating voltage.

[0606] 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.

[0607] Next, an electron transport region is disposed on the emission layer.

[0608] 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.

[0609] 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.

[0610] 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.

[0611] In addition, the electron transport region may include an electron injection layer (EIL) that may facilitate injection of electrons from the anode.

[0612] 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.

[0613] The electron injection layer may include at least one selected from LiF, NaCl, CsF, Li.sub.2O, and BaO.

[0614] A thickness of the EIL 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.

[0615] 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).

[0616] According to another aspect of the invention, a method of manufacturing an organic electroluminescent device is provided, wherein [0617] 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 [0618] the layers are deposited the other way around, starting with the cathode (190).

Organic Semiconductor Layer

[0619] 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.

[0620] The organic semiconductor layer of the organic electronic device according to the invention is essentially non-emissive or non-emitting.

[0621] 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.

[0622] 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.

[0623] According to one embodiment, the organic semiconductor layer may comprise at least one alkali halide or alkali organic complex.

Organic Electronic Device

[0624] An organic electronic device according to the invention comprises an organic semiconductor layer comprising a compound according to formula I.

[0625] 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.

[0626] 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.

[0627] 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.

[0628] 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.

[0629] 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.

[0630] According to another aspect of the present invention, there is provided a method of manufacturing an organic electronic device, the method using: [0631] at least one deposition source, preferably two deposition sources and more preferred at least three deposition sources.

[0632] The methods for deposition that can be suitable comprise: [0633] deposition via vacuum thermal evaporation; [0634] deposition via solution processing, preferably the processing is selected from spin-coating, printing, casting; and/or [0635] slot-die coating.

[0636] According to various embodiments of the present invention, there is provided a method using: [0637] a first deposition source to release the compound of formula 1 according to the invention, and [0638] 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): [0639] 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.

[0640] 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.

[0641] According to various embodiments of the present invention, the method may further include the steps for forming an organic light-emitting diode (OLED), wherein [0642] on a substrate a first anode electrode is formed, [0643] on the first anode electrode an emission layer is formed, [0644] 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, [0645] and finally a cathode electrode is formed, [0646] 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, [0647] optional an electron injection layer is formed between the electron transport layer and the cathode electrode.

[0648] 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.

[0649] 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.

[0650] 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.

[0651] 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

[0652] 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:

[0653] ##STR00087##

[0654] 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 N2 (under stirring). Solvent mixture is added and the mixture is heated with stirring. (TLC control.).

Synthesis of Compounds of Formula 1

Synthesis of 7-(3-(1,2,2-triphenylvinyl)-[1,1-biphenyl]-3-yl)dibenzo[c,h]acridine

[0655] ##STR00088##

[0656] Reagents and reaction conditions: (2-(3-bromophenyl)ethene-1,1,2-triyl)tribenzene (1.0 eq.), 7-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)dibenzo[c,h]acridine (1.2 eq.), tetrakistriphenylphosphine palladium (0) (Pd(PPh.sub.3).sub.4) (0.02 eq.), potassium carbonate (3.0 eq.). 18 h at 95 C. (112 mL, glyme/H.sub.2O 2.5/1).

[0657] When the reaction was completed according TLC, precipitate was filtered and washed with water. Then it was dissolved in dichloromethane and filtered over a pad of florisil, then concentrated. Upon addition of hexane, precipitation took place. Crude was dissolved in toluene and filtered over a pad of florisil. Solvent was evaporated and the residue was dissolved in dichloromethane and precipitated upon addition of hexane. 5.2 g (37% yield). MS (ESI): 686 (M+H).

Synthesis of 2-(5-(4,6-diphenyl-1,3,5-triazin-2-yl)-3-(1,2,2-triphenylvinyl)-[1,1-biphenyl]-3-yl)benzo[d]thiazole

[0658] ##STR00089##

[0659] Reagents and reaction conditions: 2-chloro-4,6-diphenyl-1,3,5-triazine (1.0 eq.), 2-(5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-3-(1,2,2-triphenylvinyl)-[1,1-biphenyl]-3-yl)benzo[d]thiazole (1.2 eq.), tetrakistriphenylphosphine palladium (0) (Pd(PPh.sub.3).sub.4) (0.02 eq.), potassium carbonate (2.0 eq.). (130 mL, dioxane/H.sub.2O 3/1).

[0660] When the reaction was completed according TLC, precipitate was filtered, washed with water and methanol, dissolved in hot toluene and filtered over a pad of silicagel. Solvent was evaporated and the solid was then recrystallized in chlorobenzene. 8.6 g (60% yield). MS (ESI): 773 (M+H).

Synthesis of 2-([1,1-biphenyl]-3-yl)-4-phenyl-6-(3-(1,2,2-triphenylvinyl)-[1,1-biphenyl]-4-yl)-1,3,5-triazine

[0661] ##STR00090##

[0662] Reagents and reaction conditions: 2-([1,1-biphenyl]-3-yl)-4-(4-chlorophenyl)-6-phenyl-1,3,5-triazine (1.0 eq.), 4,4,5,5-tetramethyl-2-(3-(1,2,2-triphenylvinyl)phenyl)-1,3,2-dioxaborolane (1.2 eq.), chloro(crotyl)(2-dicyclohexylphosphino-2,6-dimethoxybiphenyl)palladium(II) (Pd-172) (0.02 eq.), potassium phosphate (2.0 eq.). 20h at 50 C. (250 mL, THF/H.sub.2O 4/1).

[0663] When the reaction was completed according TLC, precipitate was filtered, dissolved in dichloromethane and washed with water. Organic phase was filtered over a pad of florisil, then concentrated to induce precipitation. The solid was then triturated in dichloromethane. 11.0 g (67% yield). MS (ESI): 716 (M+H).

Synthesis of 2-(dibenzo[b,d]furan-3-yl)-4-phenyl-6-(3-(1,2,2-triphenylvinyl)-[1,1-biphenyl]-4-yl)-1,3,5-triazine

[0664] ##STR00091##

[0665] Reagents and reaction conditions: 2-(4-chlorophenyl)-4-(dibenzo[b,d]furan-2-yl)-6-phenyl-1,3,5-triazine (1.0 eq.), 4,4,5,5-tetramethyl-2-(3-(1,2,2-triphenylvinyl)phenyl)-1,3,2-dioxaborolane (1.2 eq.), chloro(crotyl)(2-dicyclohexylphosphino-2,6-dimethoxybiphenyl)palladium(II) (Pd-172) (0.02 eq.), potassium phosphate (2.0 eq.). 17 h at 45 C. (250 mL, THF/H.sub.2O 4/1).

[0666] When the reaction was completed according TLC, it was cooled down to 5 C. Precipitate was filtered, dissolved in chloroform and washed with water. Organic phase was filtered over a pad of florisil and then concentrated. With the addition of hexane, some precipitate was formed, filtered and further recrystallized in toluene. 15.7 g (93% yield). MS (ESI): 730 (M+H).

Synthesis of 2-(dibenzo[b,d]thiophen-3-yl)-4-phenyl-6-(3-(1,2,2-triphenylvinyl)-[1,1-biphenyl]-3-yl)-1,3,5-triazine

[0667] ##STR00092##

Reagents and reaction conditions: 2-(3-chlorophenyl)-4-(dibenzo[b,d]thiophen-3-yl)-6-phenyl-1,3,5-triazine (1.0 eq.), 4,4,5,5-tetramethyl-2-(3-(1,2,2-triphenylvinyl)phenyl)-1,3,2-dioxaborolane (1.2 eq.), chloro(crotyl)(2-dicyclohexylphosphino-2,6-dimethoxybiphenyl)palladium(II) (Pd-172) (0.02 eq.), potassium phosphate (2.0 eq.). 1 h at 100 C. (222 mL, THF/H.sub.2O 4/1).

[0668] When the reaction was completed according TLC, the precipitate was filtered, dissolved in chloroform and washed with water. Organic phase was filtered over a pad of silicagel and then solvent was evaporated. Solid was triturated in methanol. 14.8 g (89% yield). MS (ESI): 746 (M+H).

Synthesis of 2-(dibenzo[b,d]furan-3-yl)-4-phenyl-6-(3-(1,2,2-triphenylvinyl)-[1,1-biphenyl]-3-yl)-1,3,5-triazine

[0669] ##STR00093##

[0670] Reagents and reaction conditions: 2-(3-chlorophenyl)-4-(dibenzo[b,d]furan-3-yl)-6-phenyl-1,3,5-triazine (1.0 eq.), 2-(3-chlorophenyl)-4-(dibenzo[b,d]furan-3-yl)-6-phenyl-1,3,5-triazine (1.0 eq.), 4,4,5,5-tetramethyl-2-(3-(1,2,2-triphenylvinyl)phenyl)-1,3,2-dioxaborolane (1.2 eq.), chloro(crotyl)(2-dicyclohexylphosphino-2,6-dimethoxybiphenyl)palladium(II) (Pd-172) (0.05 eq.), potassium phosphate (5.0 eq.): 138 h at 75 C. (160 mL, THF/H.sub.2O 4/1).

[0671] When the reaction was completed according TLC, the precipitate was filtered, dissolved in dichloromethane and washed with water. Organic phase was filtered over a pad of Florisil and then solvent was evaporated. Crude solid was triturated in toluene. 8.2 g (70% yield). MS (ESI): 730 (M+H), 752 (M+Na).

Synthesis of 2-(dibenzo[b,d]furan-3-yl)-4-phenyl-6-(4-(1,2,2-triphenylvinyl)-[1,1-biphenyl]-4-yl)-1,3,5-triazine

[0672] ##STR00094##

[0673] Reagents and reaction conditions: 2-(4-chlorophenyl)-4-(dibenzo[b,d]furan-3-yl)-6-phenyl-1,3,5-triazine (1.0 eq.), 4,4,5,5-tetramethyl-2-(4-(1,2,2-triphenylvinyl)phenyl)-1,3,2-dioxaborolane (1.2 eq.), chloro(crotyl)(2-dicyclohexylphosphino-2,6-dimethoxybiphenyl)palladium(II) (Pd-172) (0.02 eq.), potassium phosphate (2.0 eq.). 65 h at 50 C. (250 mL, THF/H.sub.2O 4/1).

[0674] When the reaction was completed according TLC, the precipitate was filtered, dissolved in chloroform and washed with water. Organic phase was filtered over a pad of silicagel and then solvent was evaporated. Crude solid was triturated in hexane. 14.8 g (88% yield). MS (ESI): 730.

Synthesis of 2-(dibenzo[b,d]furan-3-yl)-4-phenyl-6-(4-(1,2,2-triphenylvinyl)-[1,1-biphenyl]-3-yl)-1,3,5-triazine

[0675] ##STR00095##

[0676] Reagents and reaction conditions: 2-(3-chlorophenyl)-4-(dibenzo[b,d]furan-3-yl)-6-phenyl-1,3,5-triazine (1.0 eq.), 4,4,5,5-tetramethyl-2-(4-(1,2,2-triphenylvinyl)phenyl)-1,3,2-dioxaborolane (1.2 eq.), chloro(crotyl)(2-dicyclohexylphosphino-2,6-dimethoxybiphenyl)palladium(II) (Pd-172) (0.05 eq.), potassium phosphate (5.0 eq.). 2 h at 100 C. and 1 h at 45 C. (300 mL, THF/H.sub.2O 4/1).

[0677] When the reaction was completed according TLC, reaction was cooled down to room temperature and precipitate was filtered, dissolved in chloroform and washed with water. Organic phase was filtered over a pad of silicagel and solvent was then evaporated. Crude solid was then dissolved in dichloromethane and precipitation occurred upon addition of hexane. Precipitate was filtered. 7.8 g (81% yield). MS (ESI): 730 (M+H).

Synthesis of 2-phenyl-4,6-bis(3-(1,2,2-triphenylvinyl)-[1,1-biphenyl]-4-yl)-1,3,5-triazine

[0678] ##STR00096##

[0679] Reagents and reaction conditions: 2,4-bis(4-chlorophenyl)-6-phenyl-1,3,5-triazine (1.0 eq.), 4,4,5,5-tetramethyl-2-(3-(1,2,2-triphenylvinyl)phenyl)-1,3,2-dioxaborolane (1.2 eq.), chloro(crotyl)(2-dicyclohexylphosphino-2,6-dimethoxybiphenyl)palladium(II) (Pd-172) (0.02 eq.), potassium phosphate (2.0 eq.). 18 h at 50 C. (100 mL, THF/H.sub.2O 4/1).

[0680] When the reaction was completed according TLC, the reaction was cooled down to 5 C. The precipitate was filtered and washed with water. Solid was dissolved in chlorobenzene and filtered over a pad of florisil and then solvent was evaporated. Sticky solid was stirred in hexane and filtered. 5.8 g (57% yield). MS (ESI): 970 (M+H).

Synthesis of Intermediates

[0681] 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.

##STR00097##

[0682] Synthesis of 2-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)pyridine according to Angewandte Chemie International Edition, 54(50), 15284-15288; 2015.

##STR00098##

[0683] Synthesis of 2-chloro-4,6-di(naphthalen-2-yl)-1,3,5-triazine according to U.S. Pat. Appl. Publ., 20130248830, 26 Sep. 2013

##STR00099##

[0684] Synthesis of 2,4-dichloro-6-(naphthalen-2-yl)-1,3,5-triazine according to Repub. Korean Kongkae Taeho Kongbo, 2014094408, 30 Jul. 2014

##STR00100##

[0685] Synthesis of 2-([1,1-biphenyl]-4-yl)-4,6-dichloro-1,3,5-triazine according to PCT Int. Appl., 2016204375, 22 Dec. 2016

##STR00101##

[0686] Synthesis of 2,4-dichloro-6-(dibenzo[b,d]furan-3-yl)-1,3,5-triazine was synthesized by Grignard reaction following the same procedure than the one reported for the naphtyl analogue (2,4-dichloro-6-(naphthalen-2-yl)-1,3,5-triazine)

##STR00102##

[0687] Synthesis of 2-(3-bromo-5-chlorophenyl)benzo[d]thiazole was synthesized starting from 3-bromo-5-chlorobenzoic acid following the same procedure as for the synthesis of 2-(4-bromophenyl)benzo[d]thiazole (From Eur. Pat. Appl., 1746096, 24 Jan. 2007)

##STR00103##

[0688] Synthesis of 7-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)dibenzo[c,h]acridine was carried out according PCT Int. Appl., 2013079217, 6 Jun. 2013

##STR00104##

[0689] Synthesis of 2-(dibenzo[b,d]thiophen-3-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was carried out according PCT Int. Appl., 2015165826, 5 Nov. 2015

##STR00105##

Synthesis of 2-chloro-4-(dibenzo[b,d]thiophen-3-yl)-6-phenyl-1,3,5-triazine

[0690] ##STR00106##

[0691] Reagents and reaction conditions: 2,4-dichloro-6-phenyl-1,3,5-triazine (1.0 eq.), 2-(dibenzo[b,d]thiophen-3-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (0.8 eq.), tetrakistriphenylphosphine palladium (0) (Pd(PPh.sub.3).sub.4) (0.02 eq.), potassium carbonate (2.0 eq.). 4 h at 65 C. (270 mL THF/toluene/H.sub.2O 1/1/1).

[0692] When the reaction was completed according TLC, the solvent was evaporated. The crude mixture was dissolved in toluene and washed with water. Organic phase was filtered over a pad of florisil, and the solvent was partially evaporated. Upon addition of hexane, precipitation was observed. Solid was then filtered, and recrystallized in toluene. 12.6 g (37% yield). GC-MS: 373.

Synthesis of 2-chloro-4-(dibenzo[b,d]furan-3-yl)-6-phenyl-1,3,5-triazine

[0693] ##STR00107##

[0694] Reagents and reaction conditions: 2,4-dichloro-6-phenyl-1,3,5-triazine (1.0 eq.), dibenzo[b,d]furan-3-ylboronic acid (0.8 eq.), tetrakistriphenylphosphine palladium (0) (Pd(PPh.sub.3).sub.4) (0.02 eq.), potassium carbonate (2.0 eq.). 1 h at 100 C. (1110 mL THF/toluene/H.sub.2O 1/1/1).

[0695] When the reaction was completed according TLC, the reaction was cooled down to 5 C. The precipitate was filtered and washed with water. Solid was dissolved in chloroform at 60 C., filtered over a pad of silicagel and then solvent is partially evaporated. Upon addition of hexane a precipitate was formed. The solid was filtered and further purified by sublimation 63 g (41% yield). GC-MS: 357.

Synthesis of 2-chloro-4-(9,9-diphenyl-9H-fluoren-2-yl)-6-phenyl-1,3,5-triazine

[0696] ##STR00108##

[0697] Reagents and reaction conditions: 2,4-dichloro-6-phenyl-1,3,5-triazine (1.0 eq.), 2-(9,9-diphenyl-9H-fluoren-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (0.8 eq.), tetrakistriphenylphosphine palladium (0) (Pd(PPh.sub.3).sub.4) (0.02 eq.), potassium carbonate (2.0 eq.). 7 h at 95 C. (900 mL THF/toluene/H.sub.2O 1/1/1).

[0698] When the reaction was completed according TLC, aqueous phase was separated and organic phase was washed with water. Organic solvent was partially evaporated and upon addition of acetonitrile, precipitation was observed. Solid was then filtered, and further purified through column chromatography (toluene/hexane 1/2). 14.5 g (42% yield). ESI-MS: 508 (M+H).

Synthesis of 2-chloro-4-(dibenzo[b,d]furan-3-yl)-6-(naphthalen-2-yl)-1,3,5-triazine

[0699] ##STR00109##

[0700] Reagents and reaction conditions: 2,4-dichloro-6-(naphthalen-2-yl)-1,3,5-triazine (1.0 eq.), dibenzo[b,d]furan-3-ylboronic acid (0.8 eq.), tetrakistriphenylphosphine palladium (0) (Pd(PPh.sub.3).sub.4) (0.02 eq.), potassium carbonate (2.0 eq.). 2 h at 90 C. (2550 mL, THF/toluene/H.sub.2O 1/1/1).

[0701] 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 chlorobenzene, filtered over a pad of silicagel and then solvent was partially evaporated. Solid was filtered, triturated in ethylacetate and further purified by sublimation. 130.8 g, (41% yield). ESI-MS: 408 (M+H).

Synthesis of 2-([1,1-biphenyl]-4-yl)-4-chloro-6-(dibenzo[b,d]furan-3-yl)-1,3,5-triazine

[0702] ##STR00110##

[0703] Reagents and reaction conditions: 2-([1,1-biphenyl]-4-yl)-4,6-dichloro-1,3,5-triazine (1.0 eq.), dibenzo[b,d]furan-3-ylboronic acid (0.8 eq.), tetrakistriphenylphosphine palladium (0) (Pd(PPh.sub.3).sub.4) (0.02 eq.), potassium carbonate (2.0 eq.). 4 h at 65 C. (2400 mL THF/toluene/H.sub.2O 1/1/1).

[0704] 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. 60 g, (27% yield). ESI-MS: 434 (M+H).

Synthesis of 2-([1,1-biphenyl]-2-yl)-4-chloro-6-(dibenzo[b,d]furan-3-yl)-1,3,5-triazine

[0705] ##STR00111##

[0706] Reagents and reaction conditions: 2,4-dichloro-6-(dibenzo[b,d]furan-3-yl)-1,3,5-triazine (1.0 eq.), [1,1-biphenyl]-2-ylboronic acid (0.8 eq.), tetrakistriphenylphosphine palladium (0) (Pd(PPh.sub.3).sub.4) (0.05 eq.), potassium carbonate (2.5 eq.). 11 h at 65 C. (570 mL THF/toluene/H.sub.2O 1/1/1).

[0707] When the reaction was completed according TLC, the solvent was evaporated. The crude mixture was dissolved in chloroform and washed with water. Organic phase was filtered over a pad of silicagel and the solvent was partially evaporated. Upon addition of hexane, precipitation was observed. Solid was then filtered, stirred in dichloromethane and filtered again. 12.8 g (39% yield). GC-MS: 433.

Synthesis of 2-([1,1-biphenyl]-3-yl)-4-(4-chlorophenyl)-6-phenyl-1,3,5-triazine

[0708] ##STR00112##

[0709] Reagents and reaction conditions: 2-([1,1-biphenyl]-3-yl)-4-chloro-6-phenyl-1,3,5-triazine (1.0 eq.), (3-chlorophenyl)boronic acid (1.1 eq.), tetrakistriphenylphosphine palladium (0) (Pd(PPh.sub.3).sub.4) (0.02 eq.), potassium carbonate (2.0 eq.). 17 h at 75 C. (220 mL THF/H.sub.2O 1/1).

[0710] When the reaction was completed according TLC, the reaction was cooled down to room temperature. The precipitate was filtered and washed with water and methanol. Solid was dissolved in dichloromethane, filtered over a pad of silicagel and then solvent was partially evaporated. Upon addition of hexane precipitation took place. Solid was filtered. 19.6 g, (53% yield). GC-MS: 419.

Synthesis of 2-(4-chlorophenyl)-4-(dibenzo[b,d]furan-3-yl)-6-phenyl-1,3,5-triazine

[0711] ##STR00113##

[0712] Reagents and reaction conditions: 2-chloro-4-(4-chlorophenyl)-6-phenyl-1,3,5-triazine (1.0 eq.), dibenzo[b,d]furan-3-ylboronic acid (1.1 eq.), tetrakistriphenylphosphine palladium (0) (Pd(PPh.sub.3).sub.4) (0.02 eq.), potassium carbonate (2.0 eq.). 5 h at 75 C. (405 mL, THF/H.sub.2O 2/1). When the reaction was completed according TLC, the reaction was cooled down to 5 C. The precipitate was filtered and washed with water. Solid was triturated in toluene. 34.3 g (92% yield). GC-MS: 433

Synthesis of 2-(3-chlorophenyl)-4-(dibenzo[b,d]thiophen-3-yl)-6-phenyl-1,3,5-triazine

[0713] ##STR00114##

[0714] Reagents and reaction conditions: 2-chloro-4-(3-chlorophenyl)-6-phenyl-1,3,5-triazine (1.0 eq.), 2-(dibenzo[b,d]thiophen-3-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (1.1 eq.), tetrakistriphenylphosphine palladium (0) (Pd(PPh.sub.3).sub.4) (0.02 eq.), potassium carbonate (2.0 eq.). 15 h at 90 C. (450 mL THF/H.sub.2O 2/1).

[0715] When the reaction was completed according TLC, the reaction was cooled down to room temperature. The precipitate was filtered and washed with water and methanol. Solid was dissolved in dichloromethane, filtered over a pad of silicagel and then solvent was partially evaporated to induce precipitation. Solid was filtered. 31.4 g, (70% yield). ESI-MS: 449 (M+H).

Synthesis of 2-(3-chlorophenyl)-4-(dibenzo[b,d]furan-3-yl)-6-phenyl-1,3,5-triazine

[0716] ##STR00115##

[0717] Reagents and reaction conditions: 2-chloro-4-(3-chlorophenyl)-6-phenyl-1,3,5-triazine (1.0 eq.), dibenzo[b,d]furan-3-ylboronic acid (1.1 eq.), tetrakistriphenylphosphine palladium (0) (Pd(PPh.sub.3).sub.4) (0.02 eq.), potassium carbonate (2.0 eq.). 19 h at 90 C. (150 mL THF/H.sub.2O 2/1). When the reaction was completed according TLC, the reaction was cooled down to room temperature. The precipitate was filtered and washed with water and methanol. Solid was triturated in toluene and filtered. 12.2 g, (85% yield). ESI-MS: 434 (M+H).

Synthesis of 2-(4-chlorophenyl)-4-(dibenzo[b,d]furan-3-yl)-6-phenyl-1,3,5-triazine

[0718] ##STR00116##

[0719] Reagents and reaction conditions: 2-chloro-4-(4-chlorophenyl)-6-phenyl-1,3,5-triazine (1.0 eq.), dibenzo[b,d]furan-3-ylboronic acid (1.1 eq.), tetrakistriphenylphosphine palladium (0) (Pd(PPh.sub.3).sub.4) (0.02 eq.), potassium carbonate (2.0 eq.). 5 h at 75 C. (400 mL THF/H.sub.2O 2/1).

[0720] When the reaction was completed according TLC, the reaction was cooled down to 5 C. The precipitate was filtered and washed with water. The solid was triturated in toluene, and filtered. 34.3 g, (92% yield). ESI-MS: 434 (M+H).

Synthesis of 2,4-bis(4-chlorophenyl)-6-phenyl-1,3,5-triazine BV18158

[0721] ##STR00117##

[0722] Reagents and reaction conditions: 2,4-dichloro-6-phenyl-1,3,5-triazine (1.0 eq.), (4-chlorophenyl)boronic acid (1.1 eq.), tetrakistriphenylphosphine palladium (0) (Pd(PPh.sub.3).sub.4) (0.02 eq.), potassium carbonate (2.0 eq.). 13 h at 90 C. (800 mL THF/H.sub.2O 2/1).

[0723] When the reaction was completed according TLC, the reaction was cooled down to 5 C. The precipitate was filtered and washed with water and methanol. Solid was dissolved in hot chloroform, filtered hot over a pad of silicagel and then solvent was partially evaporated to induce precipitation. Solid was filtered. 4.0 g (12.2% yield). GC-MS: 377.

Synthesis of 2-(5-chloro-3-(1,2,2-triphenylvinyl)-[1,1-biphenyl]-3-yl)benzo[d]thiazole

[0724] ##STR00118##

[0725] Reagents and reaction conditions: 2-(3-bromo-5-chlorophenyl)benzo[d]thiazole (1.0 eq.), 4,4,5,5-tetramethyl-2-(3-(1,2,2-triphenylvinyl)phenyl)-1,3,2-dioxaborolane (1.2 eq.), tetrakistriphenylphosphine palladium (0) (Pd(PPh.sub.3).sub.4) (0.02 eq.), potassium carbonate (2.0 eq.). 11 h at 65 C. (175 mL, dioxane/H.sub.2O 4/1).

[0726] When the reaction was completed according TLC, the solvent was evaporated. The crude mixture was dissolved in chloroform and washed with water. Solvent was evaporated and the residue was dissolved in MTBE and upon addition of isopropanol, precipitation was observed. Solid was then filtered. 15.5 g (87% yield). The compound was directly used in the next step.

Synthesis of 2-(5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-3-(1,2,2-triphenylvinyl)-[1,1-biphenyl]-3-yl)benzo[d]thiazole

[0727] ##STR00119##

[0728] A flask was dried under vacuum and flushed with nitrogen. In the counterflow of nitrogen, the flask was charged with 2-(5-chloro-3-(1,2,2-triphenylvinyl)-[1,1-biphenyl]-3-yl)benzo[d]thiazole (1.0 eq.), 4,4,4,4,5,5,5,5-octamethyl-2,2-bi(1,3,2-dioxaborolane) (1.3 eq.), tris(dibenzylideneacetone)dipalladium(O) (Pd.sub.2(dba).sub.3) (0.025 eq.), potassium acetate (3.0 eq.), 2-Dicyclohexylphosphino-2,4,6-triisopropylbiphenyl (0.05 eq.), and dioxane (265 mL, anhydrous). The reaction was stirred for 12 h at room temperature. When the reaction was completed according TLC, the reaction was cooled down to room temperature and the precipitate was filtered off. Solvent from the reaction was evaporated and the resulting oil was dissolved in hexane. The precipitate formed was filtered, and dissolved in dichloromethane. Upon addition of hexane and acetonitrile, precipitation was observed. Solid was filtered. 15.5 g, (88% yield). ESI-MS: 668 (M+H).

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

[0729] ##STR00120##

[0730] 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

[0731] ##STR00121##

[0732] 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)Cl.sub.2) (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).

[0733] 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).

[0734] General Procedure for Fabrication of Organic Electronic Devices

[0735] 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.

[0736] 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.

[0737] 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.

[0738] 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

[0739] For all top emission devices, Examples 1 to 7 and comparative examples 1 to 3, 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- 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.

[0740] For top emission devices 97 vol.-% H09 (Sun Fine Chemicals) as EML host and 3 vol.-% BD200 (Sun Fine Chemicals) as fluorescent blue dopant were deposited on the EBL, to form a blue-emitting EML with a thickness of 20 nm. Then, the hole blocking layer is formed with a thickness of 5 nm by depositing 2,4-diphenyl-6-(4,5, 6-triphenyl-[1,1: 2,1: 3,1:3,1-quinquephenyl]-3-yl)-1,3,5-triazine on the emission layer. Then, the electron transporting layer is formed on the hole blocking layer according to Examples 1 to 7 and comparative examples 1 to 3 with a the thickness of 31 nm. The electron transport layer comprises 50 wt.-% of compound of formula 1 (or of the comparative compound) and 50 wt.-% of 8-Hydroxyquinolinolato-lithium (LiQ).

[0741] Then 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.

[0742] 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.

[0743] 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.

[0744] 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 1 m/W will be higher compared to bottom emission devices.

Compounds Used

[0745]

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) [00122] US2016322581 4,4,4-((1E,1E,1E)- cyclopropane-1,2,3- triylidenetris(cyanomethanyl- ylidene))tris(2,3,5,6- tetrafluorobenzonitrile) [00123] US2008265216 N,N-bis(4-(dibenzo[b,d]furan- 4-yl)phenyl)-[1,1:4,1- terphenyl]-4-amine (CAS 1198399-61-9) [00124] JP2014096418 H09 Fluorescent-blue host material Commercially 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 [00125] 8-Hydroxyquinolinolato- lithium (850918-68-2) Alkali organic complex 1 = AOC-1 [00126] WO2013079217 Lithium tetra(1H-pyrazol-1- yl)borate (CAS 14728-62-2) Alkali organic complex 2 = AOC-2 [00127] WO2013079676 2,4-diphenyl-6-(3- (triphenylen-2-yl)-[1,1- biphenyl]-3-yl)-1,3,5-triazine (1638271-85-8) [00128] 9-([1,1-biphenyl]-3-yl)-9- ([1,1-biphenyl]-4-yl)-9H,9H- 3,3-bicarbazole (1643479-47- 3) [00129]

Melting Point

[0746] 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

[0747] 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

[0748] 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.

[0749] 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 {acute over ()}ngstrom per second. To determine the rate onset temperature, the deposition rate on a logarithmic scale is plotted against the VTE source temperature. The rate onset is the temperature at which noticeable deposition on the QCM detector occurs (defined as a rate of 0.02{acute over ()}/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 a compound. The higher the rate onset temperature the lower is the volatility of a compound.

Technical Effect of the Invention

[0750] 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.

[0751] 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 [00130] 120 276 Comparative compound 2 Comparative- 2 [00131] 385 243 Comparative compound 3 Comparative- 3 [00132] 115 308 198

[0752] 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 Compound 1 G1 [00133] 129 285 280 Inventive compound 2 G2 [00134] 132 274 277 Inventive Compound 3 G3 [00135] 129 287 262 Inventive Compound 4 G7 [00136] 110 248 Inventive Compound 5 G8 [00137] 145 165 Inventive Compound 6 G9 [00138] 261 Inventive Compound 7 G11 [00139] 128 261 229

[0753] In Table 1 are shown glass transition temperatures, melting temperatures, rate onset temperatures of comparative compounds.

[0754] In Table 2 are shown glass transition temperatures, melting temperatures, rate onset temperatures of compounds of formula 1.

[0755] Table 3: Performance data of top emission OLED devices comprising an electron transport layer, which comprises the compounds of formula 1 and comparative compounds and an alkali organic complex. The inventive examples show increased cd/A efficiencies

TABLE-US-00004 TABLE 3 Comparative Alkali vol.-% Operating cd/A compounds and vol.-% organic alkali voltage at 10 efficiency at compounds of compound of complex organic Thickness CIE mA/cm.sup.2 10 mA/cm.sup.2 formula 1 formula 1 (AOC) complex ETL/nm 1931 y (V) (cd/A) Comparative Comparative-1 50 AOC-1 50 31 0.042 3.64 7.04 example 1 Comparative Comparative-2 50 AOC-1 50 31 0.044 3.61 6.40 example 2 Comparative Comparative-3 70 AOC-2 30 36 0.044 3.41 6.92 example 3 Inventive G1 50 AOC-1 50 31 0.045 3.54 7.92 example 1 Inventive G2 50 AOC-1 50 31 0.052 3.45 8.22 example 2 Inventive G3 50 AOC-1 50 31 0.046 3.63 8.12 example 3 Inventive G7 50 AOC-1 50 31 0.048 3.71 8.00 example 4 Inventive G8 50 AOC-1 50 31 0.046 3.71 8.02 example 5 Inventive G9 50 AOC-1 50 31 0.049 3.70 8.08 example 6 Inventive G11 50 AOC-1 50 31 0.043 3.65 7.62 example 7

[0756] 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.