ORGANIC ELECTRONIC DEVICE COMPRISING A COMPOUND OF FORMULA (I), DISPLAY DEVICE COMPRISING THE ORGANIC ELECTRONIC DEVICE AS WELL AS COMPOUNDS OF FORMULA (I)

Abstract

The present invention is directed to benzo diphenyl fluorene compound, represented by formula (I).

Claims

1.-17. (canceled)

18. A benzo diphenyl fluorene compound, represented by formula (I): ##STR00154## wherein Ar.sup.4 is represented by formula (Ia) or (Ib), ##STR00155## wherein the asterix * denotes the binding position of (Ia) and (Ib), and wherein Ar=Ar.sup.1 and Ar.sup.1 is selected from substituted or unsubstituted C.sub.6 to C.sub.24 aryl, or substituted or unsubstituted C.sub.3 to C.sub.25 heteroaryl, at least one substituent on Ar.sup.1 is selected from C.sub.1 to C.sub.6 alkyl, C.sub.6 to C.sub.12 aryl, C.sub.3 to C.sub.12 heteroaryl; R.sup.a, R.sup.b, R.sup.c and R.sup.d are independently selected from H, C.sub.1 to C.sub.6 alkyl, C.sub.6 to C.sub.18 aryl, and C.sub.2 to C.sub.18 heteroaryl, and one of the R.sup.a, R.sup.b, R.sup.c or R.sup.d represents a single bond that bonds to N of formula (I), optional two of adjacent substituents selected from the group of R.sup.a, R.sup.b, R.sup.c and R.sup.d form a substituted or unsubstituted condensed ring system, wherein at least one substituent on the condensed ring system is independently selected from C.sub.1 to C.sub.6 alkyl, C.sub.6 to C.sub.12 aryl, and C.sub.2 to C.sub.12 heteroaryl; R.sup.e, R.sup.f, R.sup.g, and R.sup.h are independently selected from H, C.sub.1 to C.sub.6 alkyl, C.sub.6 to C.sub.18 aryl, and C.sub.2 to C.sub.18 heteroaryl; X.sup.1 is selected from O, S, NAr.sup.1a; Ar.sup.1a is selected from C.sub.6 to C.sub.12 aryl; or Ar=Ar.sup.2 and Ar.sup.2 is selected from C.sub.6 to C.sub.12 aryl or C.sub.2 to C.sub.25 heteroaryl; R.sup.a2, R.sup.b2, R.sup.c2 and R.sup.d2 are independently selected from H, C.sub.1 to C.sub.6 alkyl, C.sub.6 to C.sub.18 aryl, and C.sub.2 to C.sub.18 heteroaryl, and one of the R.sup.a2, R.sup.b2, R.sup.c2 or R.sup.d2 represents a single bond that bonds to N of formula (I), optional two of adjacent substituents selected from the group of R.sup.a2, R.sup.b2, R.sup.c2 and R.sup.d2 form a substituted or unsubstituted condensed ring system, wherein at least one substituent on the condensed ring system is independently selected from C.sub.1 to C.sub.6 alkyl, C.sub.6 to C.sub.12 aryl or C.sub.2 to C.sub.12 heteroaryl; R.sup.e2, R.sup.f2, R.sup.g2, and R.sup.h2 are independently selected from H, C.sub.1 to C.sub.6 alkyl, C.sub.6 to C.sub.18 aryl, and C.sub.2 to C.sub.18 heteroaryl; X.sup.2 is selected from O, S, NAr.sup.2b, CR.sup.1bR.sup.2b, SiR.sup.1bR.sup.2b; Ar.sup.2b is selected from C.sub.6 to C.sub.12 aryl; and R.sup.1b and R.sup.2b are independently selected from C.sub.1 to C.sub.6 alkyl, C.sub.6 to C.sub.12 aryl or C.sub.2 to C.sub.12 heteroaryl.

19. The benzo diphenyl fluorene compound according to claim 18, wherein the compound of formula (I) is represented by a compound selected from the group comprising formula (Ic), (Id) or (Ie), wherein formula (Ic) is: ##STR00156## wherein Ar.sup.1 is selected from substituted or unsubstituted C.sub.6 to C.sub.24 aryl, or substituted or unsubstituted C.sub.8 to C.sub.25 heteroaryl, at least one substituent on Ar.sup.1 is selected from C.sub.1 to C.sub.6 alkyl, C.sub.6 to C.sub.12 aryl, C.sub.8 to C.sub.12 heteroaryl; R.sup.a, R.sup.b, R.sup.c and R.sup.d are independently selected from H, C.sub.1 to C.sub.6 alkyl, C.sub.6 to C.sub.18 aryl, and C.sub.2 to C.sub.18 heteroaryl, and one of the R.sup.a, R.sup.b, R.sup.c or R.sup.d represents a single bond that bonds to N of formula (I), optional two of adjacent substituents selected from the group of R.sup.a, R.sup.b, R.sup.c and R.sup.d form a substituted or unsubstituted condensed ring system, wherein at least one substituent on the condensed ring system is independently selected from C.sub.1 to C.sub.6 alkyl, C.sub.6 to C.sub.12 aryl or C.sub.2 to C.sub.12 heteroaryl; R.sup.e, R.sup.f, R.sup.g, and R.sup.h are independently selected from H, C.sub.1 to C.sub.6 alkyl, C.sub.6 to C.sub.18 aryl, and C.sub.2 to C.sub.18 heteroaryl; X.sup.1 is selected from O, S, Nar.sup.1a; Ar.sup.1a is selected from C.sub.6 to C.sub.12 aryl; formula (Id) is: ##STR00157## wherein Ar.sup.2 is selected from C.sub.6 to C.sub.12 aryl or C.sub.5 to C.sub.25 heteroaryl; R.sup.a2, R.sup.b2, R.sup.c2 and R.sup.d2 are independently selected from H, C.sub.1 to C.sub.6 alkyl, C.sub.6 to C.sub.18 aryl, and C.sub.2 to C.sub.18 heteroaryl, and one of the R.sup.a2, R.sup.b2, R.sup.c2 or R.sup.d2 represents a single bond that bonds to N of formula (Ib), optional two of adjacent substituents selected from the group of R.sup.a2, R.sup.b2, R.sup.c2 and R.sup.d2 form a substituted or unsubstituted condensed ring system, wherein at least one substituent on the condensed ring system is independently selected from C.sub.1 to C.sub.6 alkyl, C.sub.6 to C.sub.12 aryl or C.sub.2 to C.sub.12 heteroaryl; R.sup.e2, R.sup.f2, R.sup.g2, and R.sup.h2 are independently selected from H, C.sub.1 to C.sub.6 alkyl, C.sub.6 to C.sub.18 aryl, and C.sub.2 to C.sub.18 heteroaryl; X.sup.2 is selected from O, S, NAr.sup.2b, CR.sup.1bR.sup.2b, SiR.sup.1bR.sup.2b; Ar.sup.2b is selected from C.sub.6 to C.sub.12 aryl; and R.sup.1b and R.sup.2b are independently selected from C.sub.1 to C.sub.6 alkyl, C.sub.6 to C.sub.12 aryl or C.sub.2 to C.sub.12 heteroaryl; formula (Ie) is: ##STR00158## wherein Ar.sup.3 is selected from biphenyl, X.sup.3 is selected from O, S, NAr.sup.2b, CR.sup.1bR.sup.2b; Ar.sup.2b is selected from C.sub.6 to C.sub.12 aryl; and R.sup.1b and R.sup.2b are independently selected from C.sub.1 to C.sub.6 alkyl, C.sub.6 to C.sub.12 aryl or C.sub.2 to C.sub.12 heteroaryl.

20. The benzo diphenyl fluorene compound according to claim 18, wherein for formula (Ic) X.sup.1 is selected from O or NAR.sup.2.

21. The benzo diphenyl fluorene compound according to claim 18, wherein for formula (Id) X.sup.2 is selected from O, NAR.sup.2b, CR.sup.1bR.sup.2b and SiR.sup.1bR.sup.2b.

22. The benzo diphenyl fluorene compound according to claim 18, wherein for formula (Ie) X.sup.3 is selected from O, S and SiR.sup.1bR.sup.2b.

23. The benzo diphenyl fluorene compound according to claim 18, wherein for formula (Ic) Ar.sup.1 is selected from substituted or unsubstituted C.sub.6 to C.sub.13 aryl, and substituted or unsubstituted C.sub.12 heteroaryl.

24. The benzo diphenyl fluorene compound according to claim 18, wherein for formula (Id) Ar.sup.2 is selected from C.sub.6 to C.sub.10 aryl.

25. The benzo diphenyl fluorene compound according to claim 18, wherein Ar, Ar.sup.1 and Ar.sup.2 are selected from the group comprising of B1 to B13: ##STR00159## ##STR00160## wherein the asterix * denotes the binding position of Ar, Ar and/or Ar.sup.2.

26. The benzo diphenyl fluorene compound according to claim 18, wherein Ar.sup.1 is selected from the group of B1 to B12.

27. The benzo diphenyl fluorene compound according to claim 18, wherein Ar.sup.2 is selected from the group of B1 to B12.

28. The benzo diphenyl fluorene compound to claim 18, wherein Ar.sup.4 is selected from the group comprising of D1 to D7: ##STR00161## wherein the asterix * denotes the binding position of Ar.sup.4.

29. The benzo diphenyl fluorene compound according to claim 18, wherein the compound of formula I is selected from the group comprising of A1 to A37: ##STR00162## ##STR00163## ##STR00164## ##STR00165## ##STR00166## ##STR00167## ##STR00168## ##STR00169## ##STR00170## ##STR00171##

30. An organic semiconductor layer comprising a benzo diphenyl fluorene compound of formula I according to claim 18.

31. The organic semiconductor layer according of claim 30, wherein the semiconductor layer is selected from the group comprising a hole injection layer or hole transport layer.

32. The organic semiconductor layer according of claim 30, wherein the organic semiconductor layer comprises in addition an organic p-dopant.

33. The organic semiconductor layer according of claim 32, wherein the organic p-dopant is a radialene compound.

34. The organic semiconductor layer according of claim 32, wherein the organic p-dopant is a radialene compound of formula (II) ##STR00172## wherein in formula (1) A.sup.1 are independently selected from a group (1) ##STR00173## Ar.sup.1 is independently selected from substituted or unsubstituted C.sub.6 to C.sub.36 aryl and substituted or unsubstituted C.sub.2 to C.sub.36 heteroaryl; if Ar.sup.1 is substituted, the one or more substituents are independently selected from an electron-withdrawing group, F, CN, partially perfluorinated or perfluorinated alkyl, NO.sub.2; A.sup.2 and A.sup.3 are independently selected from a group (2) ##STR00174## Ar.sup.2 and Ar.sup.3 are independently selected from substituted or unsubstituted C.sub.6 to C.sub.36 aryl and substituted or unsubstituted C.sub.2 to C.sub.36 heteroaryl; and if Ar.sup.2 and Ar.sup.3 are substituted, the one or more substituents are independently selected from an electron-withdrawing group, F, CN, partially perfluorinated or perfluorinated alkyl, NO.sub.2; each R is independently selected from an electron-withdrawing group.

35. An organic electronic device comprising at least one semiconductor layer according to claim 30.

36. The organic electronic device according of claim 35, comprising an anode layer, a cathode layer and at least one organic semiconductor layer, wherein at least one organic semiconductor layer is arranged between the anode layer and the cathode layer.

37. The organic electronic device according of claim 35, wherein the organic electronic device is an organic light emitting diode (OLED), a light emitting device, thin film transistor, a battery, a display device, an organic photovoltaic cell (OPV), a solar cell, a perovskite solar cell, a photoconductor, photodiode or a photodetector.

Description

DESCRIPTION OF THE DRAWINGS

[0532] The aforementioned components, as well as the claimed components and the components to be used in accordance with the invention in the described embodiments, are not subject to any special exceptions with respect to their size, shape, material selection and technical concept such that the selection criteria known in the pertinent field can be applied without limitations.

[0533] Additional details, characteristics and advantages of the object of the invention are disclosed in the dependent claims and the following description of the respective figures which in an exemplary fashion show preferred embodiments according to the invention. Any embodiment does not necessarily represent the full scope of the invention, however, and reference is made therefore to the claims and herein for interpreting the scope of the invention. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are intended to provide further explanation of the present invention as claimed.

[0534] FIG. 1 shows a simplified schematic illustration of an organic electronic device without substrate according to the present invention;

[0535] FIG. 2 shows a simplified schematic illustration of an organic electronic device with substrate according to the present invention;

[0536] FIG. 3 shows a simplified schematic illustration of an organic electronic device with substrate according to the present invention;

[0537] FIG. 4 shows a simplified schematic illustration of an organic electronic device with substrate according to the present invention.

[0538] FIG. 5 shows the power conversion efficiency of a perovskite solar cell comprising the inventive compound A3 (N-(9,9-dimethyl-9H-fluoren-2-yl)-N-(11,11-diphenyl-11H-benzo[a]fluoren-9-yl)dibenzo[b,d]furan-1-amine) or N-([1,1-biphenyl]-4-yl)-9,9-dimethyl-N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-9H-fluoren-2-amine as a comparative compound at 23?2? C. after 0 h and after ageing at 85? C. at 450 h.

[0539] Hereinafter, the figures are illustrated in more detail with reference to examples. However, the present disclosure is not limited to the following figures.

[0540] Herein, when a first element is referred to as being formed or disposed on or onto a second element, the first element can be disposed directly on the second element, or one or more other elements may be disposed there between. When a first element is referred to as being formed or disposed directly on or directly onto a second element, no other elements are disposed there between.

[0541] FIG. 1 shows a simplified schematic illustration of an organic electronic device without substrate according to the present invention. The organic electronic device 1 is a solar cell and comprises a first electrode 2. On the first electrode 2 an organic semiconductor layer is applied. On the top of the organic semiconductor layer 4 second electrode 7 is deposited

[0542] FIG. 2 shows a simplified schematic illustration of an organic electronic device with substrate according to the present invention. The organic electronic device 1 is a solar cell and comprises a first electrode 2, which is arranged on a substrate 3. On the first electrode 2 an organic semiconductor layer is applied. On the top of the organic semiconductor layer 4 second electrode 7 is deposited

[0543] FIG. 3 shows a simplified schematic illustration of an organic electronic device with substrate according to the present invention. The organic electronic device 1 is a solar cell and comprises a first electrode 2. On the first electrode 2 a hole transport layer (HTL) 4 is deposited. The hole transport layer (HTL) 4. On the hole transport layer (HTL) 4 an photoactive layer 5 is deposited. On the photoactive layer an electron transport layer 6 is deposited. The electron transport layer (ETL) 6. On the top of the electron transport layer 6 a second electrode 7 is deposited.

[0544] FIG. 4 shows a simplified schematic illustration of an organic electronic device with substrate according to the present invention. The organic electronic device 1 is a solar cell and comprises a first electrode 2, which is arranged on a substrate 3. On the first electrode 2 a hole transport layer (HTL) 4 is deposited. The hole transport layer (HTL) 4. On the hole transport layer (HTL) 4 an photoactive layer 5 is deposited. On the photoactive layer an electron transport layer 6 is deposited. The electron transport layer (ETL) 6. On the top of the electron transport layer 6 a second electrode 7 is deposited.

[0545] FIG. 5 shows the power conversion efficiency in percent over the lifetime (ageing time) of a perovskite solar cell comprising the inventive A3 (N-(9,9-dimethyl-9H-fluoren-2-yl)-N-(11,11-diphenyl-11H-benzo[a]fluoren-9-yl)dibenzo[b,d]furan-1-amine) according to invention or a comparative compound according to Table 8 (N-([1,1-biphenyl]-4-yl)-9,9-dimethyl-N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-9H-fluoren-2-amine) at 23?2? C. after 0 h and after ageing at 85? C. at 450 h.

[0546] Hereinafter, one or more exemplary embodiments of the present invention will be described in detail with, reference to the following examples. However, these examples are not intended to limit the purpose and scope of the one or more exemplary embodiments of the present invention.

Experimental Data/Synthesis of Compounds/Synthesis of Intermediates Synthesis of methyl 5-chloro-2-(naphthalen-2-yl)benzoate

[0547] ##STR00059##

[0548] A flask was flushed with nitrogen and charge with methyl 2-bromo-5-chlorobenzoate (50 g, 0.20 mol), naphthalen-2-ylboronic acid (34.4 g, 0.20 mol), Pd(PPh.sub.3).sub.4 (11.6 g, 0.01 mol), K.sub.2CO.sub.3 (82.9 g, 0.60 mol), 1000 mL of dioxane and 300 mL of distilled water and stirred for 12 hours at 120? C. After the reaction was terminated, it was cooled down to room temperature. The organic layer was decanted and dried over MgSO.sub.4. The drying agent was filtered off, and the solvent in the organic phase were evaporated under vacuum, and purified by column chromatography. (methyl 5-chloro-2-(naphthalen-2-yl)benzoate was obtained. (47.5 g, yield 80%)

Synthesis of (5-chloro-2-(naphthalen-2-yl)phenyl)diphenylmethanol

[0549] ##STR00060##

[0550] A flask was flushed with nitrogen and charge with 5-chloro-2-(naphthalen-2-yl)benzoate (50 g, 0.17 mol) and 1000 mL of THF. After cooling temperature at ?78? C., phenyl magnesium bromide 1M in THF solution 430 mL (0.43 mol) was adding slowly and stirred for 1 hour at same temperature. After that, stirred for 24 hours at room temperature. After the reaction was terminated, the reaction was quenched by 500 mL of distilled water. The organic layer was decanted and dried over MgSO.sub.4. The drying agent was filtered off, and the solvent in the organic phase were evaporated under vacuum, and purified by column chromatography. ((5-chloro-2-(naphthalen-2-yl)phenyl)diphenylmethanol was obtained. (57.2 g, yield 80%)

Synthesis of 9-chloro-11,11-diphenyl-11H-benzo[a]fluorene

[0551] ##STR00061##

[0552] A flask was flushed with nitrogen and charge with (5-chloro-2-(naphthalen-2-yl)phenyl)diphenylmethanol (50 g, 0.12 mol), 5.2 mL of conc. HCl and 780 mL of AcOH and stirred for 6 hour at 110? C. After the reaction was terminated, it was cooled down to room temperature. After the reaction was terminated, the reaction was quenched by 500 mL of distilled water. The organic layer was decanted and dried over MgSO.sub.4. The drying agent was filtered off, and the solvent in the organic phase were evaporated under vacuum, and purified by column chromatography. 9-chloro-11,11-diphenyl-11H-benzo[a]fluorene was obtained. (19.3 g, yield 40%)

Synthesis of N-([1,1-biphenyl]-2-yl)-9,9-dimethyl-9H-fluoren-2-amine

[0553] ##STR00062##

[0554] A flask was flushed with nitrogen and charge with 2-bromo-1,1-biphenyl (11.7 g, 1 eq, 50 mmmol), 9,9-dimethyl-9H-fluoren-2-amine (12.6 g, 1.2 eq, 60 mmol), Pd.sub.2(dba).sub.3 (1.3 g, 0.03 eq, 1.5 mmol), P(t-Bu).sub.3 (1.01 g, 0.1 eq, 5 mmol), NaO(t-Bu) (14.42 g, 3 eq, 150 mmol) and toluene (400 mL) and stirred for 12 hours at 80? C. After the reaction was terminated, it was cooled down to room temperature. The organic layer was decanted and dried over MgSO.sub.4. The drying agent was filtered off, and the solvent in the organic phase were evaporated under vacuum, and purified by column chromatography. N-([1,1-biphenyl]-2-yl)-9,9-dimethyl-9H-fluoren-2-amine; CAS 1198395-24-2, was obtained. (14.5 g, yield 80%) Synthesis of N-([1,1-biphenyl]-2-yl)-9,9-dimethyl-9H-fluoren-3-amine

##STR00063##

[0555] A flask was flushed with nitrogen and charge with 3-bromo-9,9-dimethyl-9H-fluorene (13.7 g, 1 eq, 50 mmmol), [1,1-biphenyl]-2-amine (10.2 g, 1.2 eq, 60 mmol), Pd.sub.2(dba).sub.3 (1.3 g, 0.03 eq, 1.5 mmol), P(t-Bu).sub.3 (1.01 g, 0.1 eq, 5 mmol), NaO(t-Bu) (14.42 g, 3 eq, 150 mmol) and toluene (400 mL) and stirred for 12 hours at 80? C. After the reaction was terminated, it was cooled down to room temperature. The organic layer was decanted and dried over MgSO.sub.4. The drying agent was filtered off, and the solvent in the organic phase were evaporated under vacuum, and purified by column chromatography. N-([1,1-biphenyl]-2-yl)-9,9-dimethyl-9H-fluoren-3-amine; CAS 1421789-39-0, was obtained. (13.6 g, yield 75%)

Synthesis of N-(9,9-dimethyl-9H-fluoren-2-yl)dibenzo[b,d]furan-1-amine

[0556] ##STR00064##

[0557] A flask was flushed with nitrogen and charge with 1-bromodibenzo[b,d]furan (12.4 g, 1 eq, 50 mmmol), 9,9-dimethyl-9H-fluoren-2-amine (12.6 g, 1.2 eq, 60 mmol), Pd.sub.2(dba).sub.3 (1.3 g, 0.03 eq, 1.5 mmol), P(t-Bu).sub.3 (1.01 g, 0.1 eq, 5 mmol), NaO(t-Bu) (14.42 g, 3 eq, 150 mmol) and toluene (400 mL) and stirred for 12 hours at 80? C. After the reaction was terminated, it was cooled down to room temperature. The organic layer was decanted and dried over MgSO.sub.4. The drying agent was filtered off, and the solvent in the organic phase were evaporated under vacuum, and purified by column chromatography. N-(9,9-dimethyl-9H-fluoren-2-yl)dibenzo[b,d]furan-1-amine; CAS 2225845-23-6, was obtained. (15.4 g, yield 82%)

Synthesis of N-(9,9-dimethyl-9H-fluoren-2-yl)dibenzo[b,d]furan-3-amine

[0558] ##STR00065##

[0559] A flask was flushed with nitrogen and charge with 3-bromodibenzo[b,d]furan (12.4 g, 1 eq, 50 mmmol), 9,9-dimethyl-9H-fluoren-2-amine (12.6 g, 1.2 eq, 60 mmol), Pd.sub.2(dba).sub.3 (1.3 g, 0.03 eq, 1.5 mmol), P(t-Bu).sub.3 (1.01 g, 0.1 eq, 5 mmol), NaO(t-Bu) (14.42 g, 3 eq, 150 mmol) and toluene (400 mL) and stirred for 12 hours at 80? C. After the reaction was terminated, it was cooled down to room temperature. The organic layer was decanted and dried over MgSO.sub.4. The drying agent was filtered off, and the solvent in the organic phase were evaporated under vacuum, and purified by column chromatography. N-(9,9-dimethyl-9H-fluoren-2-yl)dibenzo[b,d]furan-3-amine; CAS 1427556-50-0, was obtained. (16.0 g, yield 85%)

Synthesis of N,9-diphenyl-9H-carbazol-2-amine

[0560] ##STR00066##

[0561] A flask was flushed with nitrogen and charge with 2-bromo-9-phenyl-9H-carbazole (16.1 g, 1 eq, 50 mmmol), aniline (5.6 g, 1.2 eq, 60 mmol), Pd.sub.2(dba).sub.3 (1.3 g, 0.03 eq, 1.5 mmol), P(t-Bu).sub.3 (1.01 g, 0.1 eq, 5 mmol), NaO(t-Bu) (14.42 g, 3 eq, 150 mmol) and toluene (400 mL) and stirred for 3 hours at 60? C. After the reaction was terminated, it was cooled down to room temperature. The organic layer was decanted and dried over MgSO.sub.4. The drying agent was filtered off, and the solvent in the organic phase were evaporated under vacuum, and purified by column chromatography. N,9-diphenyl-9H-carbazol-2-amine; CAS 1427316-55-9, was obtained. (11.7 g, yield 70%)

Synthesis of 7,7-dimethyl-N-phenyl-7H-fluoreno[4,3-b]benzofuran-5-amine

[0562] ##STR00067##

[0563] A flask was flushed with nitrogen and charge with 5-bromo-7,7-dimethyl-7H-fluoreno[4,3-b]benzofuran (18.2 g, 1 eq, 50 mmmol), aniline (5.6 g, 1.2 eq, 60 mmol), Pd.sub.2(dba).sub.3 (1.3 g, 0.03 eq, 1.5 mmol), P(t-Bu).sub.3 (1.01 g, 0.1 eq, 5 mmol), NaO(t-Bu) (14.42 g, 3 eq, 150 mmol) and toluene (400 mL) and stirred for 3 hours at 60? C. After the reaction was terminated, it was cooled down to room temperature. The organic layer was decanted and dried over MgSO.sub.4. The drying agent was filtered off, and the solvent in the organic phase were evaporated under vacuum, and purified by column chromatography. 7,7-dimethyl-N-phenyl-7H-fluoreno[4,3-b]benzofuran-5-amine was obtained. (13.5 g, yield 72%)

Synthesis N-([1,1-biphenyl]-2-yl)-N-(9,9-dimethyl-9H-fluoren-2-yl)-11,11-diphenyl-11H-benzo[a]fluoren-9-amine (A2)

[0564] ##STR00068##

[0565] A flask was flushed with nitrogen and charge with 9-chloro-11,11-diphenyl-11H-benzo[a]fluorine (20.15 g, 1.0 eq, 50 mmol), N-([1,1-biphenyl]-2-yl)-9,9-dimethyl-9H-fluoren-2-amine (18.07 g, 1.0 eq, 50 mmol; CAS 1198395-24-2), Pd.sub.2(dba).sub.3 (1.3 g, 0.03 eq, 1.5 mmol), P(t-Bu).sub.3 (1.01 g, 0.1 eq, 5 mmol), NaO(t-Bu) (14.42 g, 3 eq, 150 mmol) and toluene (500 mL) and stirred for 12 hours at 110? C. After the reaction was terminated, it was cooled down to room temperature. The organic layer was decanted and dried over MgSO.sub.4. The drying agent was filtered off, and the solvent in the organic phase were evaporated under vacuum. The crude product was dissolved in toluene, and then the resulting solution was filtered over silica using toluene as eluent. The organic solution was evaporated under vacuum, and acetone was added. And then the suspension was stirred at room temperature till precipitation. The solid was filtered, rinsed with acetone and dried overnight at 60? C. under vacuum, 18.78 g of crude product was obtained. Further purification was achieved by means of gradient sublimation. (Sublimation yield 91%, HPLC purity 100% after sublimation)

Synthesis N-([1,1-biphenyl]-2-yl)-N-(9,9-dimethyl-9H-fluoren-3-yl)-11,11-diphenyl-11H-benzo[a]fluoren-9-amine (A3)

[0566] ##STR00069##

[0567] A flask was flushed with nitrogen and charge with 9-chloro-11,11-diphenyl-11H-benzo[a]fluorine (20.65 g, 1.025 eq, 51.25 mmol), N-([1,1-biphenyl]-2-yl)-9,9-dimethyl-9H-fluoren-3-amine (18.07 g, 1.0 eq, 50 mmol; CAS 1421789-39-0), Pd.sub.2(dba).sub.3 (1.3 g, 0.03 eq, 1.5 mmol), P(t-Bu).sub.3 (1.01 g, 0.1 eq, 5 mmol), NaO(t-Bu) (14.42 g, 3 eq, 150 mmol) and toluene (400 mL) and stirred for 12 hours at 110? C. After the reaction was terminated, it was cooled down to room temperature. The organic layer was decanted and dried over MgSO.sub.4. The drying agent was filtered off, and the solvent in the organic phase were evaporated under vacuum. The crude product was dissolved in toluene, and then the resulting solution was filtered over silica using toluene as eluent. The organic solution was evaporated under vacuum, and acetone was added. And then the suspension was stirred at room temperature till precipitation. The solid was filtered, rinsed with acetone and dried overnight at 60? C. under vacuum, 22.70 g of crude product was obtained. Further purification was achieved by means of gradient sublimation. (Sublimation yield 90%, HPLC purity 99.97% after sublimation)

Synthesis N-(9,9-dimethyl-9H-fluoren-2-yl)-N-(11,11-diphenyl-11H-benzo[a]fluoren-9-yl)dibenzo[b,d]furan-1-amine (A5)

[0568] ##STR00070##

[0569] A flask was flushed with nitrogen and charge with 9-chloro-11,11-diphenyl-11H-benzo[a]fluorine (20.15 g, 1.0 eq, 50 mmol), N-(9,9-Dimethyl-9H-fluoren-2-yl)-1-dibenzofuranamine (18.77 g, 1.0 eq, 50 mmol; CAS 2225845-23-6), Pd.sub.2(dba).sub.3 (1.3 g, 0.03 eq, 1.5 mmol), P(t-Bu).sub.3 (1.01 g, 0.1 eq, 5 mmol), NaO(t-Bu) (14.42 g, 3 eq, 150 mmol) and toluene (400 mL) and stirred for 12 hours at 110? C. After the reaction was terminated, it was cooled down to room temperature. The organic layer was decanted and dried over MgSO.sub.4. The drying agent was filtered off, and the solvent in the organic phase were evaporated under vacuum. The crude product was dissolved in toluene, and then the resulting solution was filtered over silica using toluene as eluent. The organic solution was evaporated under vacuum, and acetone was added. And then the suspension was stirred at room temperature till precipitation. The solid was filtered, rinsed with acetone and dried overnight at 60? C. under vacuum, 17.30 g of crude product was obtained. Further purification was achieved by means of gradient sublimation. (Sublimation yield 94%, HPLC purity 100% after sublimation)

Synthesis N-(9,9-dimethyl-9H-fluoren-2-yl)-N-(11,11-diphenyl-11H-benzo[a]fluoren-9-yl)dibenzo[b,d]furan-3-amine (A6)

[0570] ##STR00071##

[0571] A flask was flushed with nitrogen and charge with 9-chloro-11,11-diphenyl-11H-benzo[a]fluorine (20.65 g, 1.025 eq, 51.25 mmol), N-(9,9-dimethyl-9H-fluoren-2-yl)dibenzo[b,d]furan-3-amine (18.77 g, 1.0 eq, 50 mmol; CAS 1427556-50-0), Pd.sub.2(dba).sub.3 (1.3 g, 0.03 eq, 1.5 mmol), P(t-Bu).sub.3 (1.01 g, 0.1 eq, 5 mmol), NaO(t-Bu) (14.42 g, 3 eq, 150 mmol) and toluene (400 mL) and stirred for 12 hours at 110? C. After the reaction was terminated, it was cooled down to room temperature. The organic layer was decanted and dried over MgSO.sub.4. The drying agent was filtered off, and the solvent in the organic phase were evaporated under vacuum. The crude product was dissolved in toluene, and then the resulting solution was filtered over silica using toluene as eluent. The organic solution was evaporated under vacuum, and acetone was added. And then the suspension was stirred at room temperature till precipitation. The solid was filtered, rinsed with acetone and dried overnight at 60? C. under vacuum, 26.87 g of crude product was obtained. Further purification was achieved by means of gradient sublimation. (Sublimation yield 96%, HPLC purity 99.88% after sublimation)

Synthesis N-(11,11-diphenyl-11H-benzo[a]fluoren-9-yl)-N,9-diphenyl-9H-carbazol-2-amine (A12)

[0572] ##STR00072##

[0573] A flask was flushed with nitrogen and charge with 9-chloro-11,11-diphenyl-11H-benzo[a]fluorine (20.65 g, 1.025 eq, 51.25 mmol), N,9-diphenyl-9H-carbazol-2-amine (16.72 g, 1.0 eq, 50 mmol; CAS 1427316-55-9), Pd.sub.2(dba).sub.3 (1.3 g, 0.03 eq, 1.5 mmol), P(t-Bu).sub.3 (1.01 g, 0.1 eq, 5 mmol), NaO(t-Bu) (14.42 g, 3 eq, 150 mmol) and toluene (400 mL) and stirred for 12 hours at 110? C. After the reaction was terminated, it was cooled down to room temperature. The organic layer was decanted and dried over MgSO.sub.4. The drying agent was filtered off, and the solvent in the organic phase were evaporated under vacuum. The crude product was dissolved in toluene, and then the resulting solution was filtered over silica using toluene as eluent. The organic solution was evaporated under vacuum, and acetone was added. And then the suspension was stirred at room temperature till precipitation. The solid was filtered, rinsed with acetone and dried overnight at 60? C. under vacuum, 28.61 g of crude product was obtained. Further purification was achieved by means of gradient sublimation. (Sublimation yield 94%, HPLC purity 99.96% after sublimation)

Synthesis N-(11,11-diphenyl-11H-benzo[a]fluoren-9-yl)-7,7-dimethyl-N-phenyl-7H-fluoreno[4,3-b]benzofuran-5-amine (A16)

[0574] ##STR00073##

[0575] A flask was flushed with nitrogen and charge with 9-chloro-11,11-diphenyl-11H-benzo[a]fluorine (20.65 g, 1.025 eq, 51.25 mmol), 7,7-dimethyl-N-phenyl-7H-fluoreno[4,3-b]benzofuran-5-amine (18.77 g, 1.0 eq, 50 mmol), Pd.sub.2(dba).sub.3 (1.3 g, 0.03 eq, 1.5 mmol), P(t-Bu).sub.3 (1.01 g, 0.1 eq, 5 mmol), NaO(t-Bu) (14.42 g, 3 eq, 150 mmol) and toluene (400 mL) and stirred for 12 hours at 110? C. After the reaction was terminated, it was cooled down to room temperature. The organic layer was decanted and dried over MgSO.sub.4. The drying agent was filtered off, and the solvent in the organic phase were evaporated under vacuum. The crude product was dissolved in toluene, and then the resulting solution was filtered over silica using toluene as eluent. The organic solution was evaporated under vacuum, and acetone was added. And then the suspension was stirred at room temperature till precipitation. The solid was filtered, rinsed with acetone and dried overnight at 60? C. under vacuum, 24.50 g of crude product was obtained. Further purification was achieved by means of gradient sublimation. (Sublimation yield 94%, HPLC purity 99.73% after sublimation)

DETAILED DESCRIPTION

[0576] The invention is furthermore illustrated by the following examples which are illustrative only and non-binding.

HOMO and LUMO

[0577] The HOMO and LUMO are calculated with the program package TURBOMOLE V6.5 (TURBOMOLE GmbH, Litzenhardtstrasse 19, 76135 Karlsruhe, Germany). The optimized geometries and the HOMO and LUMO energy levels of the molecular structures are determined by applying the hybrid functional B3LYP with a 6-31G* basis set in the gas phase. If more than one conformation is viable, the conformation with the lowest total energy is selected.

Thermogravimetric Analysis

[0578] The term TGA5% denotes the temperature at which 5% weight loss occurs during thermogravimetric analysis and is measured in ? C.

[0579] The TGA5% value may be determined by heating a 9-11 mg sample in a thermogravimetric analyzer at a heating rate of 10 K/min in an open 100 ?L aluminum pan, under a stream of nitrogen at a flow rate of 20 mL/min in the balance area and of 30 mL/min in the oven area.

[0580] The TGA5% value may provide an indirect measure of the volatility and/or decomposition temperature of a compound. In first approximation, the higher the TGA5% value the lower is the volatility of a compound and/or the higher the decomposition temperature.

[0581] According to one embodiment, the TGA5% value of compound of formula (I) is selected in the range of ?270? C. and 450? C.; preferably of ?280? C. and ?440? C., also preferred of ?295? C. and ?430? C.

Glass Transition Temperature

[0582] The glass transition temperature, also named Tg, is measured in ? C. and determined by Differential Scanning Calorimetry (DSC).

[0583] The glass transition temperature 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.

General Procedure for Fabrication of OLEDs

[0584] A 15 ?/cm.sup.2 glass substrate with 90 nm ITO (available from Corning Co.) was cut to a size of 50 mm?50 mm?0.7 mm, ultrasonically washed with isopropyl alcohol for 5 minutes and then with pure water for 5 minutes, and washed again with UV ozone for 30 minutes, to prepare the anode.

[0585] Then, compound of N-([1,1-biphenyl]-4-yl)-9,9-dimethyl-N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-9H-fluoren-2-amine (F3) or compound of formula (Ia) according to Table 3 and 4,4,4-((1E,1E,1E)-cyclopropane-1,2,3-triylidenetris(cyanomethanylylidene))tris(2,3,5,6-tetrafluorobenzonitrile) were co-deposited in vacuum on the anode, to form a HIL having a thickness of 10 nm. The composition of the HIL can be seen in Table 3.

[0586] Then, compound of N-([1,1-biphenyl]-4-yl)-9,9-dimethyl-N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-9H-fluoren-2-amine or a compound of formula (I) according to Table 3 was vacuum deposited on the HIL, to form a first HTL having a thickness of 128 nm.

[0587] Then N-(4-(dibenzo[b,d]furan-4-yl)phenyl)-N-(4-(9-phenyl-9H-fluoren-9-yl)-phenyl)-[1,1-biphenyl]-4-amine (CAS 1824678-59-2) was vacuum deposited on the HTL, to form an electron blocking layer (EBL) having a thickness of 5 nm.

[0588] Then 97 vol.-% H09 (H09 tradename and available by Sun Fine Chemicals, Korea) as EML host and 3 vol.-% BD200 (BD200 tradename and available by Sun Fine Chemicals, Korea) as fluorescent blue dopant were co-deposited on the EBL, to form a first blue-emitting EML with a thickness of 20 nm.

[0589] Then the hole blocking layer (HBL) is formed with a thickness of 5 nm by depositing 2-(3-(9,9-dimethyl-9H-fluoren-2-yl)-[1,1-biphenyl]-3-yl)-4,6-diphenyl-1,3,5-triazine on the emission layer.

[0590] Then, the electron transporting layer (ETL) having a thickness of 31 nm is formed on the hole blocking layer by co-depositing 50 wt.-% 4-(4-(4-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)naphthalen-1-yl)-[1,1-biphenyl]-4-carbonitrile and 50 wt.-% LiQ.

[0591] Then, the cathode having a thickness of 100 nm is formed on the ETL by depositing A1 at a rate of 0.01 to 1 ?/s at 10.sup.7 mbar.

[0592] 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.

[0593] 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 U in V and measuring the current in mA flowing through the device under test. The voltage applied to the device is varied in steps of 0.1V in the range between 0V and 10V. Likewise, the luminance-voltage characteristics and CIE coordinates are determined by measuring the luminance in cd/m.sup.2 using an Instrument Systems CAS-140CT array spectrometer (calibrated by Deutsche Akkreditierungsstelle (DAkkS)) for each of the voltage values. The cd/A efficiency at 10 mA/cm2 is determined by interpolating the luminance-voltage and current-voltage characteristics, respectively.

[0594] In bottom emission devices, the emission is predominately Lambertian and quantified in percent external quantum efficiency (EQE). To determine the efficiency EQE in % the light output of the device is measured using a calibrated photodiode at 10 mA/cm2.

[0595] 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 will be higher compared to bottom emission devices. To determine the efficiency EQE in % the light output of the device is measured using a calibrated photodiode at 10 mA/cm.sup.2.

[0596] 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.

[0597] 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.

[0598] The increase in operating voltage AU is used as a measure of the operational voltage stability of the device. This increase is determined during the LT measurement and by subtracting the operating voltage after 1 hour after the start of operation of the device from the operating voltage after 100 hours.

[00001]$?U=[U100h)-U\left(1h\right)]$

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

General Procedure for Fabrication of Vacuum-Processed Perovskite Solar Cells

[0599] ITO coated glass substrates are patterned by photolithography to limit the active area of the solar cell and allow for easy contacting of the top electrode.

[0600] Materials used are: p-type dopant 4,4,4-((1E,1E,1E)-cyclopropane-1,2,3-triylidenetris(cyanomethanylylidene))tris(2,3,5,6-tetrafluorobenzonitrile), the hole transport material as shown in Table 8 and n-type dopant N1,N4-bis(tri-p-tolylphosphoranylidene)benzene-1,4-diamine (PhIm). The electron transport material is fullerene (C60). The precursor materials for the perovskite light absorbing layer are PbI2 and CH3NH3I (MAI).

[0601] With regard to characterization of the embodiments prepared, grazing incident X-ray diffraction (GIXRD) pattern are collected at room temperature on an Empyrean PANanalytical powder diffractometer using the Cu K?1 radiation. Typically, three consecutive measurements are collected and averaged into single spectra. The surface morphology of the thin films is analyzed using atomic force microscopy (AFM, Multimode SPM, Veeco, USA). Scanning Electron Microscopy (SEM) images is performed on a Hitachi S-4800 microscope operating at an accelerating voltage of 2 kV over Platinum-metallized samples. Absorption spectra are collected using a fiber optics based Avantes Avaspec2048 Spectrometer.

[0602] Characterization of the solar cells is performed as follows: The external quantum efficiency (EQE) is estimated using the cell response at different wavelength (measured with a white light halogen lamp in combination with band-pass filters), where the solar spectrum mismatch is corrected using a calibrated Silicon reference cell (MiniSun simulator by ECN, the Netherlands).

[0603] The current density-voltage (J-V) characteristics are obtained using a Keithley 2400 source measure unit and under white light illumination, and the short circuit current density is corrected taking into account the device EQE. The electrical characterization was validated using a solar simulator by Abet Technologies (Model 10500 with an AM1.5G xenon lamp as the light source). Before each measurement, the exact light intensity is determined using a calibrated Si reference diode equipped with an infrared cut-off filter (KG-3, Schott). The J-V curves are recorded between ?0.2 and 1.2 V with 0.01V steps, integrating the signal for 20 ms after a 10 ms delay. This corresponds to a speed of about 0.3 V s-1.

[0604] For ageing the solar cell at 85? C. samples are measured at 0 h and then put on a hot plate (Stuart SV160) of 85? C. for 450 h. Samples are characterized after sample has reached room temperature.

[0605] The device layout used for the solar cells configurations consists in four equal pixels (area of 0.06 cm2, defined as the overlap between the patterned ITO and the top metal contact) measured through a shadow masks with 0.01 cm2 aperture. For hysteresis study, different scan rates (0.1, 0.5 and 1 Vs?1) are used, biasing the device from ?0.2 to 1.2 V with 0.01 V steps and vice versa. Light intensity dependence measurements are done by placing 0.1, 1, 10, 20, 50% neutral density filters (LOT-QuantumDesign GmbH) between the light source and the device.

[0606] Further, with regard to device preparation, ITO-coated glass substrates are subsequently cleaned with soap, water and isopropanol in an ultrasonic bath, followed by UV-ozone treatment. They are transferred to a vacuum chamber integrated into a nitrogen-filled glovebox (MBraun, H2O and O2<0.1 ppm) and evacuated to a pressure of 1.Math.10-6 mbar. The vacuum chamber is equipped with six temperature controlled evaporation sources (Creaphys) fitted with ceramic crucibles. The sources are directed upwards with an angle of approximately 900 with respect to the bottom of the evaporator. The substrate holder to evaporation sources distance is approximately 20 cm. Three quartz crystal microbalance (QCM) sensors are used, two monitoring the deposition rate of each evaporation source and a third one close to the substrate holder monitoring the total deposition rate.

[0607] For thickness calibration, firstly the materials hole transport materials according to Table 8 and 4,4,4-((1E,1E,1E)-cyclopropane-1,2,3-triylidenetris(cyanomethanylylidene))tris(2,3,5,6-tetrafluorobenzonitrile), C60 and PhIm are individually sublimed. A calibration factor is obtained by comparing the thickness inferred from the QCM sensors with that measured with a mechanical profilometer (Ambios XP1). Then these materials are co-sublimed at temperatures ranging from 150? C.-190? C. for 4,4,4-((1E,1E,1E)-cyclopropane-1,2,3-triylidenetris(cyanomethanylylidene))tris(2,3,5,6-tetrafluorobenzonitrile) to 250? C.-315? C. for the hole transport material according to Table 8 and C60, and the evaporation rate is controlled by separate QCM sensors and adjusted to obtain the desired doping concentration. In general, the deposition rate for hole transport material according to Table 8 and C60 is kept constant at 0.8 ? s-1 or 0.5 ? s-1. 4,4,4-((1E,1E,1E)-cyclopropane-1,2,3-triylidenetris(cyanomethanylylidene))tris(2,3,5,6-tetrafluorobenzonitrile) was deposited at a rate of 0.08 ? s-1. Phim was deposited at a rate of 0.15 ? s-1.

Undoped hole transport materials according to Table 8 were deposited at a rate of 0.8 ? s-1 and undoped C60 layers are deposited at a rate of 0.5 ? s-1.

[0608] An ITO-coated glass substrates are subsequently cleaned with soap, water and isopropanol in an ultrasonic bath, followed by UV-ozone treatment to prepare the anode.

[0609] Then 10 weight % of 4,4,4-((1E,1E,1E)-cyclopropane-1,2,3-triylidenetris(cyanomethanylylidene))tris(2,3,5,6-tetrafluorobenzonitrile) and 90 weight % of a hole transport material according Table 8 is co-deposited in vacuum on the anode to form a doped hole transport layer having a thickness of 40 nm, wherein the hole transport material is deposited at 250-315? C. at 8?10?6 mbar.

[0610] Then the same hole transport material as for the doped hole transport layer (Table 8) is deposited in vacuum on the doped hole transport layer to form an undoped hole transport layer having a thickness of 10 nm, wherein the hole transport material is deposited at 250-315? C. at 8?10?6 mbar.

[0611] Once the deposition on the ITO is completed, the chamber is vented with dry N2 to replace the crucibles with those containing the precursor materials for the perovskite light absorbing layer deposition, PbI2 and CH3NH3I. The vacuum chamber is evacuated again to a pressure of 10-6 mbar, and the perovskite films (light absorbing layer) are then obtained by co-deposition of the two precursors.

[0612] The calibration of the deposition rate for the CH3NH3I is difficult due to non-uniform layers and the soft nature of the material which impedes accurate thickness measurements. Hence, the source temperature of the CH3NH3I is kept constant at 70? C. and the CH3NH3I:PbI2 ratio is controlled off line using grazing incident x-ray diffraction by adjusting the PbI2 deposition temperature. The optimum deposition temperatures are 250? C. for the PbI2 and 70? C. for the CH3NH3I. After deposition of a 500 nm thick perovskite film, the chamber is vented and the crucibles replaced with those containing C60 and PhIm, and evacuated again to a pressure of 10-6 mbar. This process of exchanging crucibles is done to minimize possible cross-contamination between the organic materials and the perovskite precursors. A light-absorption layer (perovskite layer) is formed.

[0613] Then pure C60 is deposited at 8?10?6 mbar and 420? C. on the light-absorption layer (perovskite layer) to form an undoped electron transport layer having a thickness of 10 nm.

[0614] Then 30 weight % of Phim and 70 weight % of C60 is co-deposited on the undoped electron transport layer having a thickness of 40 nm to from a doped electron transport layer, wherein C60 is deposited at 8?10?6 mbar and 420? C. and Phim at 150-190? C. at 8?10-6.

[0615] In a single evaporation run five substrates (3 by 3 cm) are prepared, each substrate containing four cells. Generally, one substrate is reserved for a reference configuration. Finally the substrates are transferred to a second vacuum chamber where the silver electrode (100 nm thick) is deposited at a rate of 0.7 ? s-1 for 20 min and 1.8 to 2.4 ? s-1 after 20 min at 6?10-6 mbar.

[0616] Layer stack details are given in Table 6.

Technical Effect

[0617] Table 1: Calculated HOMO, LUMO and dipole moment of compounds of formula (Ia) and (Ib)

[0618] The HOMO and LUMO are calculated with the program package TURBOMOLE V6.5 (TURBOMOLE GmbH, Litzenhardtstrasse 19, 76135 Karlsruhe, Germany). The optimized geometries and the HOMO and LUMO energy levels of the molecular structures are determined by applying the hybrid functional B3LYP with a 6-31G* basis set in the gas phase. If more than one conformation is viable, the conformation with the lowest total energy is selected.

TABLE-US-00001 TABLE 1 Calculated HOMO, LUMO and dipole moment of compounds of formula (Ia) and (Ib) Dipole Molecular HOMO LUMO moment weight Compound Structure [eV] [eV] [debye] [g/mol] Comp. [00074] 8.83 4.61 0.00 384.27 Comparative example 1 [00075] ?4.68 ?0.90 eV 2.13 678.86 A1 [00076] 4.6825 1.1523 0.5353 727.93 A2 [00077] 4.7362 1.1115 0.7560 727.93 A3 [00078] 4.7964 1.2478 0.8304 741.92 A4 [00079] 4.7141 1.2336 0.6440 741.92 A5 [00080] 4.6905 1.2053 0.7655 741.92 A6 [00081] 4.8062 1.2071 0.9481 741.92 A7 [00082] 4.6975 1.2484 1.1138 A8 [00083] 4.6506 1.1977 0.8072 A9 [00084] 4.6686 1.1928 1.5584 A10 [00085] 4.6736 1.1645 1.8471 700.87 A11 [00086] 4.7022 1.2100 2.0510 A12 [00087] 4.6764 1.1783 1.5764 A13 [00088] 4.9660 1.2572 0.9906 715.85 A14 [00089] 4.806 1.2325 0.8894 741.92 A34 [00090] 4.7067 1.2406 0.6969 744.03 A35 [00091] 4.7234 1.2442 0.9493 758.01 A36 [00092] 4.7679 1.2430 0.8740 687.87

TABLE-US-00002 TABLE 2 Glass transition temperature of the inventive compounds and comparative compounds Tg Glass Transition Onset (from DSC 10K7min) Compound Structure Novamat Comparative example 1 [00093] 126 A1 [00094] 141 A2 [00095] 141 A3 [00096] 156 A4 [00097] 155 A10 [00098] 142 A14 [00099] 160 A36 [00100] 137
d.n.=data needed in particular if compound is available yet

[0619] It is apparent from Table 2 that the glass transition temperature are much higher for the inventive compounds in comparison to the comparative compound.

[0620] A high glass transition temperature may be beneficial for the stability of an organic electronic device, and for the manufacturing process of an organic electronic device.

TABLE-US-00003 TABLE 3 Performance data of OLED containing the inventive compounds or comparative compounds Voltage EQE at rise at V at 10 30mA/cm.sup.2 Structure Conc. 10mA/cm.sup.2 mA/cm.sup.2 LT at (1-100h) No (p-HIL) [Vol %] HTL [V] [%] 30mA/cm.sup.2 [V] Ex.1 A1 [00101] 2 [00102] 3.82 9.81 94.5 0.036 F3 Ex.2 A1 [00103] 2 [00104] 3.66 9.32 111.3 0.055 A1 Ex 3 A36 [00105] 3 [00106] 3.76 9.61 107.89 0.016 F3 Ex. 4 A36 [00107] 3 [00108] 3.68 8.22 181.26 0.040 A36 Ex 5 A3 [00109] 3 [00110] 3.83 9.79 78.22 0.025 F3 Ex 6 A3 [00111] 3 [00112] 3.69 9.04 87.91 0.060 A3 Ex 7 A2 [00113] 2 [00114] 3.86 9.70 105.82 0.068 F3 Ex 8 A2 [00115] 2 [00116] 3.82 10.02 106.95 0.111 A2 Ex. 9 A4 [00117] 2 [00118] 3.86 9.90 118.58 0.045 F3 Ex. 10 A4 [00119] 2 [00120] 3.72 9.53 138.85 0.028 A4 Ex 11 A10 [00121] 4 [00122] 3.88 10.32 123.69 0.052 F3 Ex 12 A10 [00123] 4 [00124] 3.74 10.88 95.64 0.046 A10 Ex 13 A14 [00125] 6 [00126] 3.84 10.39 103.38 0.039 F3 Ex 14 A14 [00127] 6 [00128] 3.82 10.50 117.63 0.103 A14

[0621] As can be seen in Table 3, the devices containing a compound according to formula (Ia) as a HTL exhibits all a lower operating voltage, a higher life time, a higher external quantum efficiency and/or a reduced increase of the operating voltage over time.

[0622] The compounds according to the present invention exhibits a lower dipole moment, see Table 4.

TABLE-US-00004 TABLE 4 Di- HO- LU- pole- MO- HO- LU- MO + E_ mo- Structure 1 MO MO 1 gap ment S1 T1 [00129] 5.4353 4.5999 1.1158 0.8245 3.4841 2.5131 3.0786 2.3300 A37 [00130] 5.1963 4.6113 1.1253 1.0599 3.4860 3.1808 3.0515 2.3306 P1-prior art [00131] 5.1939 4.6247 1.1490 1.0813 3.4757 2.8086 3.0319 2.3329 P2-prior art

[0623] The compounds of the present invention also exhibits a lower HOMO-1 level than the prior art compounds, see Table 5.

TABLE-US-00005 TABLE 5 HOMO- Dipole Molecular 1 HOMO LUMO LUMO + 1 moment weight Compound Structure [eV] [eV] [eV] [e S1 T1 [debye] [g/mol] A37 [00132] 5.4353 4.5999 1.1158 0.8245 3.0786 2.3300 2.5131 700.89 P1-Prior art [00133] 5.1963 4.6113 1.1253 1.0599 3.0515 2.3306 3.1808 801.01 P2-Prior art [00134] 5.1939 4.6247 1.1490 1.0813 3.0319 2.3329 2.8086 738.93 Comp. [00135] ?8.83 ?4.61 3.48 2.52 0.00 384.27 Comparative example 1 [00136] ?5.36 ?4.68 ?0.90 0.79 3.33 2.64 2.13 678.86 A1 [00137] 5.5136 4.6825 1.1523 0.8701 3.1120 2.3395 0.5353 727.93 A2 [00138] 5.5453 4.7362 1.1115 0.8214 3.1896 2.3535 0.7560 727.93 A3 [00139] 5.581 4.7964 1.2478 1.0082 3.1163 2.3494 0.8304 741.92 A4 [00140] 5.5836 4.7141 1.2336 1.0052 3.0505 2.3322 0.6440 741.92 A5 [00141] 5.5632 4.6905 1.2053 1.0288 3.0631 2.3299 0.7655 741.92 A6 [00142] 5.5619 4.8062 1.2071 1.0462 3.1429 2.3586 0.9481 741.92 A7 [00143] 5.5730 4.6975 1.2484 1.0946 3.0263 2.3304 1.1138 818.03 A8 [00144] 5.5361 4.6506 1.1977 1.1536 2.9819 2.3234 0.8072 818.03 A9 [00145] 5.3856 4.6686 1.1928 0.9502 3.0629 2.3336 1.5584 750.95 A10 [00146] 5.3700 4.6736 1.1645 0.7933 3.0950 2.3448 1.8471 700.87 A11 [00147] 5.3794 4.7022 1.2100 0.9348 3.0653 2.3404 2.0510 790.97 A12 [00148] 5.3741 4.6764 1.1783 0.9711 3.0707 2.3389 1.5764 790.97 A13 [00149] 5.6885 4.9660 1.2572 1.0157 3.2818 2.3895 0.9906 715.85 A14 [00150] 5.5792 4.806 1.2325 1.0515 3.0712 2.3576 0.8894 741.92 A34 [00151] 5.59 4.7067 1.2406 1.01 3.04 2.33 0.6969 744.03 A35 [00152] 5.58 4.7234 1.2442 1.06 3.05 2.34 0.9493 758.01 A36 [00153] 5.6208 4.7679 1.2430 0.8771 3.1012 2.3468 0.8740 687.87

[0624] A low operating voltage may be beneficial for reduced power consumption and improved battery life, in particular in mobile devices.

[0625] An improved external quantum efficiency may be beneficial for reduced power consumption and improved battery life, in particular in mobile devices.

[0626] An improved lifetime is beneficial for improved long-term stability of organic electronic devices.

[0627] A reduced increase in operating voltage over time is an indication for improved stability of the electronic device. An increase in lifetime is important for improved stability of the electronic device.

[0628] The aforementioned components, as well as the claimed components and the components to be used in accordance with the invention in the described embodiments, are not subject to any special exceptions with respect to their size, shape, material selection and technical concept such that the selection criteria known in the pertinent field can be applied without limitations.

[0629] Additional details, characteristics and advantages of the object of the invention are disclosed in the dependent claims and the following description of the respective figures which in an exemplary fashion show preferred embodiments according to the invention. Any embodiment does not necessarily represent the full scope of the invention, however, and reference is made therefore to the claims and herein for interpreting the scope of the invention. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are intended to provide further explanation of the present invention as claimed.

Table 6: List of Compounds Used for Solar Cells

[0630]

TABLE-US-00006 TABLE 6 Compound Name IUPAC name Reference Comparative N-([1,1-biphenyl]-4-yl)-9,9-dimethyl- compound N-(4-(9-phenyl-9H-carbazol-3- (CC) yl)phenyl)-9H-fluoren-2-amine A3 N-(9,9-dimethyl-9H-fluoren-2-yl)- US2005121667A1 N-(11,11-diphenyl-11H- US2005139810A1 benzo[a]fluoren- 9-yl)dibenzo[b,d]furan-1-amine p-dopant 4,4,4-((1E,1E,1E)-cyclopropane- 1,2,3-triylidenetris(cyano- methanylylidene))tris(2,3,5,6- tetrafluorobenzonitrile) MAPI MAPbI3 prepared in-situ from precursor materials PbI.sub.2 and CH.sub.3NH.sub.3I (MAI) PhIm N1,N4-bis(tri-p- WO2012175219A1 tolylphosphoranylidene)benzene- 1,4-diamine (PhIm) CAS 51870-56-5 C60 Fullerene-C60 Reed, Bolskar, CAS 99685-96-8 Chem. Rev. 100, 1075 (2000)

Table 7: Over of Layer Stack of Inventive Solar Cell and Comparative Example

[0631]

TABLE-US-00007 TABLE 7 Cell name Layer Stack Inventive ITO/p-dopant(10 wt %): A3[40 nm]/A3[10 nm]/MAPI[500 nm]/ pervoskite C60[10 nm]/C60(30 wt %: Phim[40 nm]/Ag solar cell Comparative ITO/p- pervoskite dopant(10 wt %): CC[40 nm]/CC[10 nm]/MAPI[500 nm]/ solar Cell C60[10 nm]/C60: Phim(30 wt %)[40 nm]/Ag

Table 8: Performance of Inventive Solar CellAged at 85? C.

[0632]

TABLE-US-00008 TABLE 8 PCE (%) after 450 h Hole transport material Hole transport material J.sub.SC at 85? C./PCE of doped hole of the undoped hole (mA V.sub.OC FF PCE (%) after oh transport layer transport layer cm.sup.?2) (mV) (%) (%) at 23 ? 2? C. Comparative N-([1,1-biphenyl]-4- N-([1,1-biphenyl]-4-yl)- 19.7 1.03 64% 13.0% example at yl)-9,9-dimethyl-N-(4- 9,9-dimethyl-N-(4-(9- 23 ? 2? C. (9-phenyl-9H- phenyl-9H-carbazol-3- After 0 h carbazol-3-yl)phenyl)- yl)phenyl)-9H-fluoren- 9H-fluoren-2-amine 2-amine Comparative N-([1,1-biphenyl]-4- N-([1,1-biphenyl]-4-yl)- 19.5 0.99 44% 8.5% 0.65 example aged yl)-9,9-dimethyl-N-(4- 9,9-dimethyl-N-(4-(9- at 85? C. after (9-phenyl-9H- phenyl-9H-carbazol-3- 450 h carbazol-3-yl)phenyl)- yl)phenyl)-9H-fluoren- 9H-fluoren-2-amine 2-amine Inventive N-(9,9-dimethyl-9H- N-(9,9-dimethyl-9H- 19.8 1.01 66% 13.2% example at fluoren-2-yl)-N-(11,11- fluoren-2-yl)-N-(11,11- 23 ? 2? C. diphenyl-11H- diphenyl-11H - After 0 h benzo[a]fluoren-9- benzo[a]fluoren-9- yl)dibenzo[b,d]furan-1- yl)dibenzo[b,d]furan-1- amine (A3) amine (A3) Inventive N-(9,9-dimethyl-9H- N-(9,9-dimethyl-9H- 19.6 1.08 67% 14.2% 1.08 example at fluoren-2-yl)-N-(11,11- fluoren-2-yl)-N-(11,11- aged at diphenyl-11H - diphenyl-11H- 85? C. after benzo[a]fluoren-9- benzo[a]fluoren-9- 450 h yl)dibenzo[b,d]furan-1- yl)dibenzo[b,d]furan-1- amine (A3) amine (A3)

[0633] After the inventive perovskite solar cell containing compound A3 is aged at 85? C. for 450 h, the power conversion efficiency is constant or even improved as can be seen from Table 8 and FIG. 5. In contrast, the comparative perovskite solar cell exhibits a strong reduction of the power conversion efficiency when it is aged at 85? C. for 450 h as can be seen from Table 8 and FIG. 5.

[0634] Thus, the inventive perovskite solar cell containing an inventive compound may exhibit an unexpected high power conversion efficiency even after ageing at 85? C. for 450 h.

[0635] The fill factor FF of the inventive perovskite solar cell is constant even after ageing at 85? C. for 450 h. In contrast, the fill factor FF of the comparative perovskite solar cell decrease remarkably after ageing at 85? C. for 450 h as can be seen from Table 8.

[0636] Thus, the inventive solar cell may be very robust or stable at very harsh conditions.