Compound and Organic Semiconducting Layer, Organic Electronic Device, Display Device and Lighting Device Comprising the Same

Abstract

The present invention relates to an organic compound of formula (1), suitable for use as a layer material for electronic devices, and it relates to an organic semiconductor layer comprising at least one compound thereof, as well as to an organic electronic device comprising at least one organic semiconductor layer, and a method of manufacturing the same.

##STR00001##

Claims

1. A compound according to formula 1: ##STR00090## wherein R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are independently selected from hydrogen, substituted or unsubstituted C.sub.6 to C.sub.38 aryl, substituted or unsubstituted C.sub.3 to C.sub.36 heteroaryl or C.sub.1 to C.sub.16 alkyl group, —PO(R′).sub.2, D, F, CN, or formula 2; ##STR00091##  wherein the substituents are selected from C.sub.6 to C.sub.18 aryl, C.sub.3 to C.sub.25 heteroaryl, —PO(R′).sub.2, D, F or CN, C.sub.1 to C.sub.16 alkyl, partially or perfluorinated C.sub.1 to C.sub.16 alkyl, partially or perdeuterated C.sub.1 to C.sub.16 alkyl, C.sub.1 to C.sub.16 alkoxy, partially or perfluorinated C.sub.1 to C.sub.16 alkoxy, partially or perdeuterated C.sub.1 to C.sub.16 alkoxy; R′ is independently selected from alkyl, aryl or heteroaryl; a, b, c, d and e are independently 0, 1 or 2, wherein at least one of a, b, c or d is 1 or 2; wherein at least one of R.sup.1, R.sup.2, R.sup.3 or R.sup.4 is formula 2 Ar.sup.1 is selected from substituted or unsubstituted C.sub.6 to C.sub.38 arylene, substituted or unsubstituted C.sub.3 to C.sub.36 heteroarylene or C.sub.1 to C.sub.16 alkylene group, wherein the substituents are selected from C.sub.6 to C.sub.18 aryl, C.sub.3 to C.sub.25 heteroaryl, —PO(R′).sub.2, D, F or CN, C.sub.1 to C.sub.16 alkyl, partially or perfluorinated C.sub.1 to C.sub.16 alkyl, partially or perdeuterated C.sub.1 to C.sub.16 alkyl, C.sub.1 to C.sub.16 alkoxy, partially or perfluorinated C.sub.1 to C.sub.16 alkoxy, partially or perdeuterated C.sub.1 to C.sub.16 alkoxy; Ar.sup.2 is selected from substituted or unsubstituted C.sub.6 to C.sub.38 aryl, substituted or unsubstituted C.sub.3 to C.sub.36 heteroaryl or C.sub.1 to C.sub.16 alkyl group, wherein the substituents are selected from C.sub.6 to C.sub.18 aryl, C.sub.3 to C.sub.25 heteroaryl, —PO(R′).sub.2, D, F or CN, C.sub.1 to C.sub.16 alkyl, partially or perfluorinated C.sub.1 to C.sub.16 alkyl, partially or perdeuterated C.sub.1 to C.sub.16 alkyl, C.sub.1 to C.sub.16 alkoxy, partially or perfluorinated C.sub.1 to C.sub.16 alkoxy, partially or perdeuterated C.sub.1 to C.sub.16 alkoxy; wherein Ar.sup.1 does not contain one or more CN substituents when Ar.sup.2 is substituted or unsubstituted C.sub.6 to C.sub.38 aryl; wherein the following compound 3 is excluded: ##STR00092##

2. The compound of formula 1 according to claim 1, wherein at least two of a, b, c or d are 0, 1 or 2; or a and b are 0 and c or d is independently selected from 1 or 2; or c and d are 0 and a or b is independently selected from 1 or 2; or a and c are 0 and b or d is independently selected from 1 or 2; or b and d are 0 and a or c is independently selected from 1 or 2; or at least three selected from a, b, c and d are 0 and one selected from a, b, c or d is 1; or at least three selected from a, b, c and d are 1 or 2.

3. The compound of formula 1 according to claim 1, wherein e is selected from 0, 1 or 2.

4. The compound of formula 1 according to claim 1, wherein at least two of R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are selected same when a+b+c+d≥2,

5. The compound of formula 1 according to claim 1, wherein at least one of R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are independently selected from H, nitrile, phenyl, naphthyl, biphenyl, pyridinyl, dibenzofuran, dibenzothiophene or carbazole.

6. The compound of formula 1 according to claim 1, wherein at most one two or three of R.sup.1, R.sup.2, R.sup.3 or R.sup.4 is H.

7. The compound of formula 1 according to claim 1, wherein one or two of R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are formula 2.

8. The compound of formula 1 according to claim 1, wherein Ar.sup.1 is selected from substituted or unsubstituted phenylene, biphenylene, terphenylene, naphthylene, phenanthrylene, triphenylene, anthracenylene, wherein the substituents are selected from C.sub.6 to C.sub.18 aryl, C.sub.3 to C.sub.25 heteroaryl, —PO(R′).sub.2, D, F or CN, C.sub.1 to C.sub.16 alkyl, partially or perfluorinated C.sub.1 to C.sub.16 alkyl, partially or perdeuterated C.sub.1 to C.sub.16 alkyl, C.sub.1 to C.sub.16 alkoxy, partially or perfluorinated C.sub.1 to C.sub.16 alkoxy, partially or perdeuterated C.sub.1 to C.sub.16 alkoxy.

9. The compound of formula 1 according to claim 1, wherein Ar.sup.2 is selected from substituted or unsubstituted aryl selected from a group consisting of anthracenyl, fluoranthenyl, pyrenyl, substituted or unsubstituted heteroaryl selected from a group consisting of pyridine, pyrimidine, triazine, quinoline, quinoxaline, benzoacridine, dibenzoacridine, phenanthroline, carbazole, dibenzofurane, dibenzothiophene, wherein the substituents are selected from C.sub.6 to C.sub.18 aryl, C.sub.3 to C.sub.25 heteroaryl, —PO(R′).sub.2, D, F or CN, C.sub.1 to C.sub.16 alkyl, partially or perfluorinated C.sub.1 to C.sub.16 alkyl, partially or perdeuterated C.sub.1 to C.sub.16 alkyl, C.sub.1 to C.sub.16 alkoxy, partially or perfluorinated C.sub.1 to C.sub.16 alkoxy, partially or perdeuterated C.sub.1 to C.sub.16 alkoxy.

10. The compound of formula 1 according to claim 1, wherein R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are independently selected from hydrogen, CN, or D1 to D54: ##STR00093## ##STR00094## ##STR00095## ##STR00096## ##STR00097## ##STR00098## ##STR00099## ##STR00100##

11. The compound of formula 1 according to claim 1, wherein Ar.sup.1 is selected from E1 to E14: ##STR00101## ##STR00102##

12. The compound of formula 1 according to claim 1, wherein Ar.sup.2 is selected from F1 to F13: ##STR00103## ##STR00104## wherein R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10, R.sup.11, R.sup.12, R.sup.13, R.sup.14 are independently selected from single bond, hydrogen, substituted or unsubstituted phenyl, naphthyl, biphenyl, pyridinyl, dibenzofuryl, benzofuranyl, dibenzothienyl, benzothiophenyl, anthracenyl, phenanthryl, carbazolyl, wherein the substituents are selected from C.sub.6 to C.sub.18 aryl, C.sub.3 to C.sub.25 heteroaryl, —PO(R′).sub.2, D, F or CN, C.sub.1 to C.sub.16 alkyl, partially or perfluorinated C.sub.1 to C.sub.16 alkyl, partially or perdeuterated C.sub.1 to C.sub.16 alkyl, C.sub.1 to C.sub.16 alkoxy, partially or perfluorinated C.sub.1 to C.sub.16 alkoxy, partially or perdeuterated C.sub.1 to C.sub.16 alkoxy; and wherein one of R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10, R.sup.11, R.sup.12, R.sup.13, R.sup.14 represents a single bond only, and the single bond is the single bond that bonds Ar.sup.2 to Ar.sup.1.

13. The compound of formula 1 according to claim 1, wherein R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10, R.sup.11, R.sup.12, R.sup.13, R.sup.14 are independently selected from G1 to G72: ##STR00105## ##STR00106## ##STR00107## ##STR00108## ##STR00109## ##STR00110## ##STR00111## ##STR00112## ##STR00113## ##STR00114## ##STR00115##

14. The compound of formula 1 according to claim 1, wherein Ar.sup.2 is selected from H1 to H92: ##STR00116## ##STR00117## ##STR00118## ##STR00119## ##STR00120## ##STR00121## ##STR00122## ##STR00123## ##STR00124## ##STR00125## ##STR00126## ##STR00127## ##STR00128## ##STR00129## ##STR00130## ##STR00131## ##STR00132## ##STR00133##

15. The compound of formula 1 according to claim 1, wherein the compound of formula 1 is selected from J1 to J53: ##STR00134## ##STR00135## ##STR00136## ##STR00137## ##STR00138## ##STR00139## ##STR00140## ##STR00141## ##STR00142## ##STR00143## ##STR00144## ##STR00145## ##STR00146## ##STR00147## ##STR00148## ##STR00149## ##STR00150## ##STR00151##

16. An organic semiconductor layer comprising at least one compound of formula 1 according to claim 1.

17. The organic semiconductor layer according to claim 16, wherein the organic semiconductor layer further comprises a metal, metal salt or organic metal complex.

18. An organic electronic device comprising an anode layer, a cathode layer and at least one organic semiconductor layer according to claim 16, wherein the at least one organic semiconductor layer comprises a compound of formula 1 according to claim 1.

19. An organic electronic device according to claim 18 further comprising at least one emission layer, wherein the organic semiconductor layer is arranged between the at least one emission layer and the cathode layer.

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

21. The compound of formula 1 according to claim 1, wherein R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are independently selected from hydrogen, substituted or unsubstituted C.sub.6 to C.sub.38 aryl, substituted or unsubstituted C.sub.3 to C.sub.36 heteroaryl or C.sub.1 to C.sub.16 alkyl group, —PO(R′).sub.2, D, F, CN, or formula 2; ##STR00152##  wherein the substituents are selected from C.sub.6 to C.sub.18 aryl, C.sub.3 to C.sub.25 heteroaryl, —PO(R′).sub.2, D, F or CN, C.sub.1 to C.sub.6 alkyl, partially or perfluorinated C.sub.1 to C.sub.16 alkyl, partially or perdeuterated C.sub.1 to C.sub.16 alkyl, C.sub.1 to C.sub.16 alkoxy, partially or perfluorinated C.sub.1 to C.sub.16 alkoxy, partially or perdeuterated C.sub.1 to C.sub.16 alkoxy; R′ is independently selected from alkyl, aryl or heteroaryl; a, b, c, d and e are independently 0, 1 or 2, wherein at least one of a, b, c or d is 1 or 2; wherein at least one of R.sup.1, R.sup.2, R.sup.3 or R.sup.4 is formula 2; Ar.sup.1 is selected from substituted or unsubstituted C.sub.6 to C.sub.38 arylene, substituted or unsubstituted C.sub.3 to C.sub.36 heteroarylene or C.sub.1 to C.sub.16 alkylene group, wherein the substituents are selected from C.sub.6 to C.sub.18 aryl, C.sub.3 to C.sub.25 heteroaryl, —PO(R′).sub.2, D, F or CN, C.sub.1 to C.sub.6 alkyl, partially or perfluorinated C.sub.1 to C.sub.16 alkyl, partially or perdeuterated C.sub.1 to C.sub.16 alkyl, C.sub.1 to C.sub.16 alkoxy, partially or perfluorinated C.sub.1 to C.sub.16 alkoxy, partially or perdeuterated C.sub.1 to C.sub.16 alkoxy; Ar.sup.2 is selected from substituted or unsubstituted C.sub.6 to C.sub.38 aryl, substituted or unsubstituted C.sub.3 to C.sub.36 heteroaryl or C.sub.1 to C.sub.6 alkyl group, wherein the substituents are selected from C.sub.6 to C.sub.18 aryl, C.sub.3 to C.sub.25 heteroaryl, —PO(R′).sub.2, D, F or CN, C.sub.1 to C.sub.16 alkyl, partially or perfluorinated C.sub.1 to C.sub.16 alkyl, partially or perdeuterated C.sub.1 to C.sub.16 alkyl, C.sub.1 to C.sub.16 alkoxy, partially or perfluorinated C.sub.1 to C.sub.16 alkoxy, partially or perdeuterated C.sub.1 to C.sub.16 alkoxy.

22. The compound of formula 1 according to claim 1, wherein the substituents on R.sup.1, R.sup.2, R.sup.3, R.sup.4, Ar.sup.1 and Ar.sup.2 are independently selected from C.sub.6 to C.sub.18 aryl, C.sub.3 to C.sub.25 heteroaryl, —PO(R′).sub.2, D, F or CN, C.sub.1 to C.sub.6 alkyl, partially or perfluorinated C.sub.1 to C.sub.16 alkyl, partially or perdeuterated C.sub.1 to C.sub.16 alkyl, C.sub.1 to C.sub.16 alkoxy, partially or perfluorinated C.sub.1 to C.sub.16 alkoxy, partially or perdeuterated C.sub.1 to C.sub.16 alkoxy.

23. The compound of formula 1 according to claim 1, wherein at least two of a, b, c or d are 0 or 1; or a and bare 0 and c or d is 1; or c and d are 0 and a or b is 1; or a and c are 0 and b or d is 1; or band dare 0 and a or c is 1; or at least two of a, b, c and d is 1.

24. The compound of formula 1 according to claim 1, wherein e is selected from 0 or 1.

25. The compound of formula 1 according to claim 1, wherein R1 and R2 or R3 and R4 are selected same when a+b+c+d≥2.

26. The compound of formula 1 according to claim 1, wherein R1 and R3 or R2 and R4 are selected same when a+b+c+d≥2.

27. The organic semiconductor layer according to claim 16, wherein the organic semiconductor layer further comprises LiQ or alkali borate.

Description

DESCRIPTION OF THE DRAWINGS

[0333] 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:

[0334] 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;

[0335] 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;

[0336] 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;

[0337] 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;

[0338] 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;

[0339] 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.

[0340] 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.

[0341] 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.

[0342] 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.

[0343] 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 1.

[0344] 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 compound of formula 1 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.

[0345] 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 (ETL1) 161 comprising compound of formula 1 and a second electron transport layer (ETL2) 162, whereby the second electron transport layer 162 is disposed directly on the first electron transport layer 161. Alternatively, the electron transport layer stack (ETL) 160 comprises a first electron transport layer 161 and a second electron transport layer 162 comprising a compound of formula 1, whereby the second electron transport layer 162 is disposed directly on the first electron transport layer 161.

[0346] 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 (ETL1) 161 that comprises compound of formula 1, a second electron transport layer (ETL2) 162 that comprises compound of formula 1 but different to the compound of the first electron transport layer, and a third electron transport layer (ETL3) 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.

[0347] 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 (ETL1) 161, an electron injection layer (EIL) 180, and a cathode electrode 190. The first electron transport layer (ETL1) 161 comprises compound of formula 1 and optionally an alkali halide or alkali organic complex. The electron transport layer (ETL1) 161 is formed directly on the EML 150.

[0348] 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 compound of formula 1 and optionally an alkali halide or alkali organic complex.

[0349] 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 (ETL1) 161, a second electron transport layer (ETL2) 162 and a third electron transport layer (ETL3) 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 compound of formula 1 that is different for each layer, and optionally an alkali halide or alkali organic complex.

Organic Semiconductor Layer

[0350] According to another aspect an organic semiconductor layer may comprise at least one compound of formula 1.

[0351] According to one embodiment the organic semiconductor layer may comprises at least one compound of formula 1 and further comprises a metal, metal salt or organic alkali metal complex, preferably alkali metal complex, more preferably LiQ or alkali borate.

[0352] According to one embodiment the organic semiconductor layer may comprises at least one compound of formula 1 and further comprises a metal, metal salt or organic metal complex, preferably an organic monovalent or divalent metal complex, more preferably LiQ or alkali borate.

[0353] According to one embodiment the organic semiconductor layer may comprises at least one compound of formula 1 and LiQ.

[0354] According to one embodiment the organic semiconductor layer may comprises at least one compound of formula 1 and alkali borate.

[0355] According to one embodiment, wherein at least one organic semiconductor layer is arranged between the emission layer and the cathode, preferably between the electron injection layer and the cathode.

[0356] In another embodiment, the organic semiconductor layer is a first electron transport layer and it is arranged between the emission layer and the second electron transport layer.

[0357] According to one embodiment, the organic semiconductor layer is arranged between the first and second emission layer. The organic semiconductor layer can be an electron transport layer, an emission layer, a hole blocking layer, a charge generation layer and/or an electron injection layer, preferably an electron transport layer or a charge generation layer, and more preferred an electron transport layer.

[0358] 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.

[0359] According to one embodiment, the organic semiconductor layer may comprise at least one alkali halide or alkali organic complex.

[0360] An organic semiconductor layer comprises a compound according to formula 1, 1a or 1b is essentially non-emissive or non-emitting.

Organic Electronic Device

[0361] An organic electronic device comprising an anode layer, a cathode layer and at least one organic semiconductor layer according, wherein the at least one organic semiconductor layer comprises a compound of formula 1.

[0362] An organic electronic device according to one embodiment, which comprises at least one organic semiconductor layer that comprises a compound according to formula 1, wherein this layer is essentially non-emissive or non-emitting.

[0363] According to one embodiment, the organic electronic device may comprises at least one organic semiconductor layer comprising compound of formula 1 that is an electron transport layer, an emission layer, a hole blocking layer, a charge generation layer and/or an electron injection layer, preferably an electron transport layer or a charge generation layer, more preferred an electron transport layer.

[0364] The organic electronic device according to according to one embodiment may comprises at least one organic semiconductor layer, wherein the organic semiconductor layer comprising compound of formula 1 is 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

[0365] The organic electronic device according to one embodiment may comprises at least one organic semiconductor layer comprising compound of formula 1, wherein the at least one organic semiconductor layer further comprises at least one alkali halide or alkali organic complex.

[0366] An organic electronic device according to one embodiment comprises at least one organic semiconductor layer comprising at least one compound of formula 1, at least one anode layer, at least one cathode layer and at least one emission layer, wherein the organic semiconductor layer comprising at least one compound of formula 1 is preferably arranged between the emission layer and the cathode layer.

[0367] An organic electronic device according to one embodiment comprises at least one organic semiconductor layer comprising at least one compound of formula 1, at least one anode layer, at least one cathode layer, at least one emission layer and at least one auxiliary electron transport layer, wherein the organic semiconductor layer comprising at least one compound of formula 1 is preferably arranged between the auxiliary electron transport layer and the cathode layer.

[0368] An organic electronic device according to one embodiment comprises at least one organic semiconductor layer comprising at least one compound of formula 1 and further comprises at least one alkali halide or alkali organic complex.

[0369] 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.

[0370] 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. A light emitting device can be an OLED.

[0371] 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 compound of formula 1 according to the invention, an electron injection layer, and a cathode layer.

[0372] According to another aspect of the present invention, there is provided a method of manufacturing an organic electronic device, the method using: [0373] at least one deposition source, preferably two deposition sources and more preferred at least three deposition sources.

[0374] The methods for deposition that can be suitable comprise: [0375] deposition via vacuum thermal evaporation; [0376] deposition via solution processing, preferably the processing may be selected from spin-coating, printing, casting; and/or [0377] slot-die coating.

[0378] According to various embodiments of the present invention, there is provided a method using: [0379] a first deposition source to release the compound of formula 1 according to the invention, and [0380] 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): [0381] 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.

[0382] 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 comprising 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.

[0383] According to various embodiments of the present invention, the method may further include the steps for forming an organic light-emitting diode (OLED), wherein [0384] on a substrate a first anode electrode is formed, [0385] on the first anode electrode an emission layer is formed, [0386] on the emission layer an electron transport layer stack is formed, preferably a first electron transport layer is formed on the emission layer and a second electron transport layer is formed on the first electron transport layer and the second electron transport layer comprises a compound of formula 1, [0387] and finally a cathode electrode is formed, [0388] 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, [0389] optional an electron injection layer is formed between the electron transport layer stack and the cathode electrode.

[0390] 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.

[0391] 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 compound of formula 1 according to the invention, optional a second electron transport layer, optional an electron injection layer, and a cathode.

[0392] 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.

[0393] 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

[0394] Compounds of formula 1 may be prepared as described below.

Preparation of 2-(dibenzo[b,d]furan-3-yl)-4-phenyl-6-(4-(10-phenylphenanthren-9-yl)phenyl)-1,3,5-triazine (J1)

[0395] ##STR00082##

[0396] A flask was flushed with nitrogen and charged with 2-chloro-4-(dibenzo[b,d] furan-3-yl)-6-phenyl-1,3,5-triazine (3.3 g, 9.2 mmol), 4,4,5,5-tetramethyl-2-(4-(10-phenylphenanthren-9-yl)phenyl)-1,3,2-dioxaborolane (4.6 g, 10.1 mmol), Pd(PPh3)4 (0.21 g, 0.18 mmol), and K2CO3 (2.5 g, 18.3 mmol). A mixture of deaerated tetrahydrofurane/water (4:1, 45 mL) was added and the reaction mixture was heated to 75° C. under a nitrogen atmosphere overnight. Then, additional Pd(PPh3)4 (0.03 g, 0.03 mmol) was added and the reaction mixture was heated to 75° C. under a nitrogen atmosphere overnight. After cooling down to 5° C., the resulting precipitate was isolated by suction filtration and washed with tetrahydrofurane (2×5 mL) and hexane (3×10 mL). The crude product was then dissolved in dichloromethane (4 L) and the organic phase was washed with water (3×500 mL). After drying over MgSO4, the organic phase was filtered through a silica gel pad. After rinsing with additional dichloromethane/methanol (100/1, 700 mL), the filtrate was concentrated under reduced pressure to 30 mL and hexane (30 mL) was added. The precipitate was collected by suction filtration and recrystallized (×2) in chlorobenzene (100 mL). The precipitate was collected by suction filtration to yield 4.3 g (72%). Final purification was achieved by sublimation. HPLC/ESI-MS: >99%, m/z=652 ([M+H]+).

Preparation of 2,4-diphenyl-6-(4′-(10-phenylphenanthren-9-yl)-[1,1′-biphenyl]-4-yl)-1,3,5-triazine (J2)

[0397] ##STR00083##

[0398] A flask was flushed with nitrogen and charged with 2,4-diphenyl-6-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-1,3,5-triazine (7.8 g, 18.0 mmol), 9-(4-bromophenyl)-10-phenylphenanthrene (7.4 g, 18.0 mmol), Pd(PPh3)4 (0.62 g, 0.54 mmol), and K.sub.2CO.sub.3 (5.0 g, 35.9 mmol). A mixture of deaerated dioxane/water (10:1, 198 mL) was added and the reaction mixture was heated to reflux under a nitrogen atmosphere overnight. After cooling down to room temperature, the resulting precipitate was isolated by suction filtration and washed with water and methanol. The crude product was then dissolved in chloroform (600 mL) and filtered through a silica gel pad. After rinsing with additional chloroform (200 mL), the filtrate was concentrated under reduced pressure to 200 mL and n-hexane (200 mL) was added. The precipitate was collected by suction filtration to yield 6.1 g (52%). Final purification was achieved by sublimation. HPLC/ESI-MS: >99%, m/z=638 ([M+H]+).

Preparation of 7-(4′-(10-phenylphenanthren-9-yl)-[1,1′-biphenyl]-3-yl)dibenzo[c,h]acridine (J3)

[0399] ##STR00084##

[0400] A flask was flushed with nitrogen and charged with 7-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)dibenzo[c,h]acridine (8.5 g, 17.6 mmol), 9-(4-bromophenyl)-10-phenylphenanthrene (8.0 g, 19.5 mmol), Pd(PPh3)4 (0.68 g, 0.59 mmol), and K2CO3 (5.4 g, 39.1 mmol). A mixture of deaerated dioxane/water (10:1, 215 mL) was added and the reaction mixture was heated to reflux under a nitrogen atmosphere overnight. After cooling down to room temperature, the resulting precipitate was isolated by suction filtration and washed with water (till neutral pH) and methanol. The crude product was then dissolved in hot chloroform (250 mL) and the organic phase was filtered through a silica gel pad. After rinsing with additional chloroform (200 mL), the filtrate was concentrated under reduced pressure. The precipitate was collected by suction filtration to yield 7.3 g (55%). Final purification was achieved by sublimation. HPLC/ESI-MS: 99.95%, m/z=684 ([M+H]+).

[0401] The chemical structure, molar mass, calculated HOMO, LUMO, dipole moment, melting point, glass transition temperature and rate onset temperature of compounds of formula 1 of example 1, example 2 and example 3 and comparative example 1 of C and C.sub.2 are shown in Table 1.

TABLE-US-00001 TABLE 1 Dipole Referred MW mp Tg T.sub.RO HOMO LUMO moment to as: Structure (g/mol) (°C.) (°C.) (°C.) (eV) (eV) (Debye) C1 Compar- ative example 1 [00085] 625.25 304 123 268 −5.81 −1.85  0.58 C2 Compar- ative example 2 [00086] 639.23 — 126 237 −5.81 −1.90  0.68 J1 Example 1 [00087] 651.23 318 161 258 −5.65 −1.93  0.83 J2 Example 2 [00088] 637.25 330 142 278 −5.65 −1.88  0.39 J3 Example 3 [00089] 683.26 334 170 270 −5.63 −1.73 513

General Procedure for Fabrication of OLEDs

[0402] For top emission devices, Example 1 and 2 of compounds J1 and J2 and comparative examples C.sub.1, a glass substrate was cut to a size of 50 mm×50 mm×0.7 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. 100 nm Ag were deposited on the glass substrate as anode at a pressure of 10.sup.−5 to 10.sup.−7 mbar to form the anode.

[0403] 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.-% 2,2′,2″-(cyclopropane-1,2,3-triylidene)tris(2-(p-cyanotetrafluorophenyl)acetonitrile) was vacuum deposited on the anode, to form a hole injection layer (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 was vacuum deposited on the HIL, to form a hole transport layer (HTL) having a thickness of 118 nm.

[0404] 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.

[0405] Then 97 vol.-% ABH 113 (Sun Fine Chemicals, Korea) as EML host and 3 vol.-% NUBD370 (Sun Fine Chemicals, Korea) as fluorescent blue dopant were deposited on the EBL, to form a blue-emitting EML with a thickness of 20 nm.

[0406] Then, a first electron transport layer (ETL1) is formed on the EML 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 with a thickness of 5 nm, see Table 2.

[0407] Then, the second electron transport layer (ETL2) is formed on the first electron transport layer (ETL1) with a thickness of 31 nm by depositing 50 vol.-% of a compound selected from J1 for example 1 and J2 for example 2 of formula 1 as matrix compound and 50 vol.-% of alkali organic complex LiQ, see Table 2; as well as for the comparative example C1 the second electron transport layer is formed on the first electron transport layer with a thickness of 31 nm by depositing 50 vol.-% of the compound of the comparative example C1 as matrix compound and 50 vol.-% of alkali organic complex LiQ, see Table 2.

TABLE-US-00002 TABLE 2 Performance of an organic electroluminescent device comprising a first electron transport layer (ETL1) and second electron transport layer (ETL2) comprising a compound of formula 1 of J1 and J2 as well as for the comparative example compound C1. Thickness Concentration of Alkali Concentration of electron Operating cd/A efficiency Matrix matrix compound organic alkali organic transport voltage at 10 at 10 mA/cm.sup.2 LT97 at 30 compound in ETL 2 (vol.-%) complex complex (vol.-%) layer (nm) mA/cm.sup.2 (V) (cd/A) mA/cm.sup.2 (h) Comparative C1 50 LiQ 50 31 3.7 8.0 33 example 1 Example 1 J1 50 LiQ 50 31 3.4 7.9 32 Example 2 J2 50 LiQ 50 31 3.5 7.9 42

[0408] Then, the electron injection layer is formed on the electron transporting layer by deposing Yb with a thickness of 2 nm.

[0409] Then, Ag is evaporated at a rate of 0.01 to 1 Å/s at 10.sup.−7 mbar to form a cathode with a thickness of 11 nm.

[0410] 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.

[0411] 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.

[0412] To assess the performance of the inventive examples compared to the prior art, the current efficiency is measured at 20° C. The current-voltage characteristic is determined using a Keithley 2635 source measure unit, by sourcing a voltage in V and measuring the current in mA flowing through the device under test. The voltage applied to the device is varied in steps of 0.1V in the range between 0V and 10V. Likewise, the luminance-voltage characteristics and CIE coordinates are determined by measuring the luminance in cd/m.sup.2 using an Instrument Systems CAS-140CT array spectrometer for each of the voltage values.

[0413] The cd/A efficiency at 10 mA/cm.sup.2 is determined by interpolating the luminance-voltage and current-voltage characteristics, respectively.

[0414] Lifetime LT of the device is measured at ambient conditions (20° C.) and 30 mA/cm.sup.2, using a Keithley 2400 source meter, and recorded in hours.

[0415] The brightness of the device is measured using a calibrated photo diode. The lifetime LT is defined as the time till the brightness of the device is reduced to 97% of its initial value.

Technical Effect of the Invention

[0416] Compound C.sub.1 is a state of the art compound. As can be seen in Table 1, the compounds of formula 1 of the example 1, 2 and 3 have a higher melting point and higher glass transition temperature as compared to the comparative example 1. The rate onset temperature is in a range suitable for mass production.

[0417] As can be seen in Table 2, the operating voltage at 10 mA/cm.sup.2 of organic electronic devices comprising the compound of formula 1 is improved; see examples 1 and 2, over organic electronic devices comprising the compound C1 of the comparative example.

[0418] 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.