MATERIALS FOR ELECTRONIC DEVICES

Abstract

The present application relates to compounds of the formula (I) or (II), to processes for preparing such compounds, and to electronic devices comprising one or more such compounds, and to the use of such compounds in electronic devices.

Claims

1.-20. (canceled)

21. A compound of a formula (I) or (II) ##STR00634## where the groups and indices that occur are as follows: Ar.sup.1 is the same or different at each instance and is selected from aromatic ring systems which have 6 to 40 aromatic ring atoms and are substituted by R.sup.2 radicals, and heteroaromatic ring systems which have 5 to 40 aromatic ring atoms and are substituted by R.sup.2 radicals; Ar.sup.L is the same or different at each instance and is selected from aromatic ring systems which have 6 to 40 aromatic ring atoms and are substituted by R.sup.3 radicals, and heteroaromatic ring systems which have 5 to 40 aromatic ring atoms and are substituted by R.sup.3 radicals; E is selected from single bond, C(R.sup.0).sub.2, C(R.sup.0).sub.2C(R.sup.0).sub.2, CR.sup.0CR.sup.0, NR.sup.0, O, S, SO, SO.sub.2 and a group ##STR00635## where the bonds marked with * are the bonds to the Ar.sup.1 groups; R.sup.0 is the same or different at each instance and is selected from F, CN, Si(R.sup.4).sub.3, N(R.sup.4).sub.2, OR.sup.4, straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more R.sup.1 radicals may be joined to one another and may form a ring; where the alkyl, alkoxy, alkenyl and alkynyl groups mentioned and the aromatic ring systems and heteroaromatic ring systems mentioned are each substituted by R.sup.4 radicals; and where one or more CH.sub.2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups mentioned may be replaced by R.sup.4CCR.sup.4, CC, Si(R.sup.4).sub.2, CO, CNR.sup.4, C(O)O, C(O)NR.sup.4, NR.sup.4, P(O)(R.sup.4), O, S, SO or SO.sub.2; R.sup.1 is the same or different at each instance and is selected from D, F, CN, Si(R.sup.4).sub.3, N(Ar.sup.2).sub.2, N(R.sup.4).sub.2, OR.sup.4, straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more R.sup.1 radicals may be joined to one another and may form a ring; where the alkyl, alkoxy, alkenyl and alkynyl groups mentioned and the aromatic ring systems and heteroaromatic ring systems mentioned are each substituted by R.sup.4 radicals; and where one or more CH.sub.2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups mentioned may be replaced by R.sup.4CCR.sup.4, CC, Si(R.sup.4).sub.2, CO, CNR.sup.4, C(O)O, C(O)NR.sup.4, NR.sup.4, P(O)(R.sup.4), O, S, SO or SO.sub.2; Ar.sup.2 is the same or different at each instance and is selected from aromatic ring systems having 6 to 40 aromatic ring atoms and heteroaromatic ring systems having 5 to 40 aromatic ring atoms, where the aromatic ring systems and heteroaromatic ring systems are each substituted by R.sup.2 radicals; R.sup.2 is the same or different at each instance and is selected from H, D, F, Cl, Br, I, C(O)R.sup.4, CN, Si(R.sup.4).sub.3, N(R.sup.4).sub.2, P(O)(R.sup.4).sub.2, OR.sup.4, S(O)R.sup.4, S(O).sub.2R.sup.4, straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more R.sup.2 radicals may be joined to one another and may form a ring; where the alkyl, alkoxy, alkenyl and alkynyl groups mentioned and the aromatic ring systems and heteroaromatic ring systems mentioned are each substituted by R.sup.4 radicals; and where one or more CH.sub.2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups mentioned may be replaced by R.sup.4CCR.sup.4, CC, Si(R.sup.4).sub.2, CO, CNR.sup.4, C(O)O, C(O)NR.sup.4, NR.sup.4, P(O)(R.sup.4), O, S, SO or SO.sub.2; R.sup.3 is the same or different at each instance and is selected from H, D, F, Cl, Br, I, C(O)R.sup.4, CN, Si(R.sup.4).sub.3, N(R.sup.4).sub.2, P(O)(R.sup.4).sub.2, OR.sup.4, S(O)R.sup.4, S(O).sub.2R.sup.4, straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more R.sup.3 radicals may be joined to one another and may form a ring; where the alkyl, alkoxy, alkenyl and alkynyl groups mentioned and the aromatic ring systems and heteroaromatic ring systems mentioned are each substituted by R.sup.4 radicals; and where one or more CH.sub.2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups mentioned may be replaced by R.sup.4CCR.sup.4, CC, Si(R.sup.4).sub.2, CO, CNR.sup.4, C(O)O, C(O)NR.sup.4, NR.sup.4, P(O)(R.sup.4), O, S, SO or SO.sub.2; R.sup.4 is the same or different at each instance and is selected from H, D, F, Cl, Br, I, C(O)R.sup.5, CN, Si(R.sup.5).sub.3, N(R.sup.5).sub.2, P(O)(R.sup.5).sub.2, OR.sup.5, S(O)R.sup.5, S(O).sub.2R.sup.5, straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more R.sup.4 radicals may be joined to one another and may form a ring; where the alkyl, alkoxy, alkenyl and alkynyl groups mentioned and the aromatic ring systems and heteroaromatic ring systems mentioned are each substituted by R.sup.5 radicals; and where one or more CH.sub.2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups mentioned may be replaced by R.sup.5CCR.sup.5, CC, Si(R.sup.5).sub.2, CO, CNR.sup.5, C(O)O, C(O)NR.sup.5, NR.sup.5, P(O)(R.sup.5), O, S, SO or SO.sub.2; R.sup.5 is the same or different at each instance and is selected from H, D, F, Cl, Br, I, CN, alkyl or alkoxy groups having 1 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more R.sup.5 radicals may be joined to one another and may form a ring; and where the alkyl, alkoxy, alkenyl and alkynyl groups, aromatic ring systems and heteroaromatic ring systems mentioned may be substituted by one or more radicals selected from F and CN; a is 1, 2 or 3; b is 0, 1, 2, 3 or 4; c is 0, 1, 2, 3 or 4; d is 0, 1, 2, 3 or 4; e is 0, 1, 2 or 3; f is 0, 1, 2, 3 or 4; where e and f are not both simultaneously 0; g is 0, 1, 2, 3 or 4; h is 0, 1, 2, 3 or 4; n is 0, 1, 2 or 3, where, in the case that n=0, the nitrogen atom and the carbon atom of the spirobifluorene are bonded directly to one another, and where, in the case that n=2, two Ar.sup.L radicals are bonded to one another in a chain, and where, in the case that n=3, three Ar.sup.L radicals are bonded to one another in a chain; m is 0 or 1, where, in the case that m=0, the E group is absent and the Ar.sup.1 groups are not bonded to one another; where the compound bears an H or D in all positions in the six-membered ring of the spirobifluorene where no R.sup.1 radical is bonded.

22. The compound according to claim 21, wherein Ar.sup.1 is the same or different at each instance and is selected from the group consisting of benzene, biphenyl, terphenyl, quaterphenyl, naphthyl, fluorenyl, especially 9,9-dimethylfluorenyl and 9,9-diphenylfluorenyl, benzofluorenyl, spirobifluorenyl, indenofluorenyl, indenocarbazolyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, benzofuranyl, benzothiophenyl, benzofused dibenzofuranyl, benzofused dibenzothiophenyl, and phenyl substituted by a group selected from naphthyl, fluorenyl, spirobifluorenyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, pyridyl, pyrimidyl and triazinyl, where the groups are each substituted by R.sup.2 radicals.

23. The compound according to claim 21, wherein the index m is 0.

24. The compound according to claim 21, wherein Ar.sup.L is the same or different at each instance and is selected from the group consisting of phenyl, biphenyl, naphthyl, phenanthrenyl, fluorenyl, carbazolyl, dibenzofuranyl and dibenzothiophenyl, each substituted by R.sup.3 radicals.

25. The compound according to claim 21, wherein R.sup.1 is the same at each instance.

26. The compound according to claim 21, wherein R.sup.1 is the same or different at each instance and is selected from the group consisting of straight-chain alkyl groups having 1 to 20 carbon atoms, branched or cyclic alkyl groups having 3 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms, where the alkyl groups mentioned and the aromatic ring systems and heteroaromatic ring systems mentioned are each substituted by R.sup.4 radicals.

27. The compound according to claim 21, wherein the compounds bear an H in all positions in the six-membered ring of the spirobifluorene where no R.sup.1 is bonded.

28. The compound according to claim 21, wherein R.sup.2 is the same or different at each instance and is selected from H, D, F, CN, Si(R.sup.4).sub.3, N(R.sup.4).sub.2, straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where the alkyl and alkoxy groups mentioned, the aromatic ring systems mentioned and the heteroaromatic ring systems mentioned are each substituted by R.sup.4 radicals; and where one or more CH.sub.2 groups in the alkyl or alkoxy groups mentioned may be replaced by CC, R.sup.4CCR.sup.4, Si(R.sup.4).sub.2, CO, CNR.sup.4, NR.sup.4, O, S, C(O)O or C(O)NR.sup.4; and R.sup.3 is the same or different at each instance and is selected from H, D, F, CN, Si(R.sup.4).sub.3, N(R.sup.4).sub.2, straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where the alkyl and alkoxy groups mentioned, the aromatic ring systems mentioned and the heteroaromatic ring systems mentioned are each substituted by R.sup.4 radicals; and where one or more CH.sub.2 groups in the alkyl or alkoxy groups mentioned may be replaced by CC, R.sup.4CCR.sup.4, Si(R.sup.4).sub.2, CO, CNR.sup.4, NR.sup.4, O, S, C(O)O or C(O)NR.sup.4; and R.sup.4 is the same or different at each instance and is selected from H, D, F, CN, Si(R.sup.5).sub.3, N(R.sup.5).sub.2, straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where the alkyl and alkoxy groups mentioned, the aromatic ring systems mentioned and the heteroaromatic ring systems mentioned are each substituted by R.sup.5 radicals; and where one or more CH.sub.2 groups in the alkyl or alkoxy groups mentioned may be replaced by CC, R.sup.5CCR.sup.5, Si(R.sup.5).sub.2, CO, CNR.sup.5, NR.sup.5, O, S, C(O)O or C(O)NR.sup.5.

29. The compound according to claim 21, wherein index a is 1 or 2, and the index b is 1 or 2.

30. The compound according to claim 21, wherein index c is 0, and that index d is 0.

31. The compound according to claim 21, wherein it conforms to formula (I).

32. The compound according to claim 21, wherein formula (I) conforms to one of the following formulae: ##STR00636## where the groups and indices that occur are as defined in claim 21, and where a is 0, 1 or 2, and b is 0, 1, 2 or 3, and where an H is bonded to all positions in the six-membered ring of the spirobifluorene where no R.sup.1 radical is bonded; and ##STR00637## where the groups and indices that occur are as defined in claim 21, and where a is 0 or 1, and b is 0, 1 or 2, and where an H is bonded to all positions in the six-membered ring of the spirobifluorene where no R.sup.1 radical is bonded.

33. The compound according to claim 21, wherein formula (II) conforms to one of the following formulae: ##STR00638## where the groups and indices that occur are as defined in claim 21, and where an H is bonded to all positions in the six-membered ring of the spirobifluorene where no R.sup.1 radical is bonded.

34. The compound according to claim 21, wherein it conforms to one of the following formulae: ##STR00639## where the groups that occur are as defined in claim 21, and where b is 0, 1, 2 or 3, and f=0, 1, 2 or 3, and where an H is bonded to all positions in the six-membered ring of the spirobifluorene where no R.sup.1 radical is bonded; and ##STR00640## where the groups that occur are as defined in claim 21, and where an H is bonded to all positions in the six-membered ring of the spirobifluorene where no R.sup.1 radical is bonded, and where m is 0.

35. A process for preparing a compound of formula (I) or (II) according to claim 21, characterized in that a biphenyl derivative substituted by two halogen atoms and substituted by at least one organic radical is reacted with a fluorenone derivative.

36. An oligomer, polymer or dendrimer containing one or more compounds according to claim 21, wherein the bond(s) to the polymer, oligomer or dendrimer may be localized at any desired positions substituted by R.sup.0, R.sup.1, R.sup.2 or R.sup.3 in formula (I) or (II).

37. A formulation comprising at least one compound according to claim 21 and at least one solvent.

38. A formulation comprising at least one polymer, oligomer or dendrimer according to claim 36 and at least one solvent.

39. An electronic device comprising at least one compound according to claim 21.

40. An electronic device comprising least one polymer, oligomer or dendrimer according to claim 36.

41. The electronic device according to claim 39, wherein the device is an organic electroluminescent device and comprises an anode, cathode and at least one emitting layer, and in that the compound is present in a hole-transporting layer or in an emitting layer of the device.

Description

EXAMPLES

A) Synthesis Examples

Synthesis of 4-bromo-2,7-di-tert-butyl-9,9-spirobi(fluorene) 1a

[0204] ##STR00468##

[0205] 44.6 g (105.2 mmol) of 2,2-dibromo-4,4-di-tert-butyl-1,1-biphenyl is dissolved in 300 ml of dried THE in a baked-out flask. The reaction mixture is cooled to 78 C. At this temperature, 39.3 ml of a 2.5 M solution of n-BuLi in hexane (98.2 mmol) is slowly added dropwise. The mixture is stirred at 70 C. for a further 1 hour. Subsequently, 12.6 g of 9H-fluoren-9-one (70.1 mmol) is dissolved in 300 ml of THE and added dropwise at 70 C. After the addition has ended, the reaction mixture is left to warm up gradually to room temperature, the reaction is stopped with NH.sub.4Cl, and then the mixture is concentrated on a rotary evaporator. The solid matter is dissolved in 500 ml of toluene, and then 720 mg (3.8 mmol) of p-toluenesulfonic acid is added. The mixture is heated under reflux for 6 hours, then allowed to cool down to room temperature and admixed with water. The precipitated solids are filtered off with suction and washed with heptane (40.10 g, 68% yield).

[0206] The remaining residue is recrystallized from heptane/toluene. The substance is finally sublimed under high vacuum; purity is 99.9% determined by HPLC.

[0207] The yield is 19.2 g (54% of theory).

[0208] The following compounds are prepared in an analogous manner:

TABLE-US-00004 Ex. Fluorenone Br-Biphenyl Spirofluorene 1b [00469] [00470] [00471] 1c [00472] [00473] [00474] 1d [00475] [00476] [00477] 1e [00478] [00479] [00480] 1f [00481] [00482] [00483] 1g [00484] [00485] [00486] 1h [00487] [00488] [00489] 1i [00490] [00491] [00492] 1j [00493] [00494] [00495] 1k [00496] [00497] [00498] 1l [00499] [00500] [00501] 1m [00502] [00503] [00504] 1n [00505] [00506] [00507]

Synthesis of 2,7-di-tert-butyl-N,N-bis(9,9-dimethyl-9H-fluoren-2-yl)-9,9-spirobi[fluorene]-4-amine 2a

[0209] ##STR00508##

[0210] 14.6 g of N-(9,9-dimethyl-9H-fluoren-2-yl)-9,9-dimethyl-9H-fluorene-2-amine (36.4 mmol) and 4-bromo-2,7-di-tert-butyl-9,9-spirobi(fluorene) (17.6 g, 34.7 mol) are dissolved in 250 ml of toluene. The solution is degassed and saturated with N2. It is subsequently admixed with 1 g (5.1 mmol) of S-Phos and 1.6 g (1.7 mmol) of Pd.sub.2(dba).sub.3 and then 5 g of sodium tert-butoxide (52.05 mmol) is added. The reaction mixture is heated to boiling under a protective atmosphere overnight. The mixture is subsequently partitioned between toluene and water, and the organic phase is washed three times with water and dried over Na.sub.2SO.sub.4 and concentrated by rotary evaporation. After the crude product has been filtered through silica gel with toluene, the remaining residue is recrystallized from heptane/toluene. The substance is finally sublimed under high vacuum, purity is 99.9% determined by HPLC.

[0211] The yield is 7.1 g (25% of theory).

[0212] The following compounds are prepared in an analogous manner:

TABLE-US-00005 Ex. Spirofluorene Amine Product 2b [00509] [00510] [00511] 2c [00512] [00513] [00514] 2d [00515] [00516] [00517] 2e [00518] [00519] [00520] 2f [00521] [00522] [00523] 2g [00524] [00525] [00526] 2h [00527] [00528] [00529] 2i [00530] [00531] [00532] 2j [00533] [00534] [00535] 2l [00536] [00537] [00538] 2m [00539] [00540] [00541] 2n [00542] [00543] [00544] 2o [00545] [00546] [00547] 2p [00548] [00549] [00550] 2q [00551] [00552] [00553] 2r [00554] [00555] [00556] 2s [00557] [00558] [00559] 2t [00560] [00561] [00562] 2u [00563] [00564] [00565] 2v [00566] [00567] [00568]

Synthesis of N-(4-{2,7-di-tert-butyl-9,9-spirobi[fluoren]-4-yl}phenyl)-N-(9,9-dimethyl-9H-fluoren-2-yl)-9,9-dimethyl-9H-fluorene-2-amine 3a

[0213] ##STR00569##

[0214] 23.5 g (39 mmol) of N-(9,9-dimethyl-9H-fluoren-2-yl)-9,9-dimethyl-N-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]-9H-fluorene-2-amine and 21.3 g (42 mmol) of 4-bromo-2,7-di-tert-butyl-9,9-spirobi(fluorene) are suspended in 400 ml of dioxane and 13.7 g of caesium fluoride (90 mmol). 4.0 g (5.4 mmol) of bis(tricyclohexylphosphine)palladium dichloride is added to this suspension, and the reaction mixture is heated under reflux for 18 h. After cooling, the organic phase is removed, filtered through silica gel, washed three times with 80 ml of water and then concentrated to dryness. After the crude product has been filtered through silica gel with toluene, the remaining residue is recrystallized from heptane/toluene and finally sublimed under high vacuum, purity is 99.9% determined by HPLC.

[0215] The yield is 11 g (31% of theory).

[0216] The following compounds are prepared in an analogous manner:

TABLE-US-00006 Ex. Spirofluorene Amine Product 3b [00570] [00571] [00572] 3c [00573] [00574] [00575] 3d [00576] [00577] [00578] 3e [00579] [00580] [00581] 3f [00582] [00583] [00584]

Synthesis of 2,7-di-tert-butyl-5-(4-chlorophenyl)-9,9-spirobi[fluorene] 4a

[0217] ##STR00585##

[0218] 10.7 g (69 mmol) of 4-chlorophenylboronic acid, 35 g (69 mmol) of 4-bromo-2,7-di-tert-butyl-9,9-spirobi(fluorene) and 5.4 g (5 mmol) of Pd(Ph.sub.3P).sub.4 are dissolved in 600 ml of THF. The solution is degassed and saturated with N2, and 155 ml of 2 M of potassium carbonate solution is added gradually to this suspension. The reaction mixture is heated to boiling under a protective atmosphere overnight. The mixture is subsequently partitioned between toluene and water, and the organic phase is washed three times with water and dried over Na.sub.2SO.sub.4 and concentrated by rotary evaporation. The residue is purified by crystallization with MeOH. Yield: 25 g (67% of theory). Purity by HPLC>98%.

[0219] The following compounds are prepared in an analogous manner:

TABLE-US-00007 Ex. Spirofluorene Boronic acid Product 4b [00586] [00587] [00588] 4c [00589] [00590] [00591] 4d [00592] [00593] [00594] 4e [00595] [00596] [00597] 4f [00598] [00599] [00600]

Synthesis of N-(4-{2,7-di-tert-butyl-9,9-spirobi[fluorene]-4-yl}phenyl)-N-(9,9-dimethyl-9H-fluoren-2-yl)-9,9-dimethyl-9H-fluorene-2-amine 5a

[0220] ##STR00601##

[0221] 11.2 g (28 mmol) of N-(9,9-dimethyl-9H-fluoren-2-yl)-9,9-dimethyl-9H-fluorene-2-amine and 14.6 g (27 mmol) of the 2,7-di-tert-butyl-5-(4-chlorophenyl)-9,9-spirobi[fluorene] are dissolved in 225 ml of toluene. The solution is degassed and saturated with N2. It is subsequently admixed with 2.1 ml (2.1 mmol) of tri-tert-butylphosphine solution (1 M in toluene) and 0.98 g (1 mmol) of Pd.sub.2(dba).sub.3 and then 5.1 g of sodium tert-butoxide (53 mmol) is added. The reaction mixture is heated to boiling under a protective atmosphere overnight. The mixture is subsequently partitioned between toluene and water, and the organic phase is washed three times with water and dried over Na.sub.2SO.sub.4 and concentrated by rotary evaporation. After the crude product has been filtered through silica gel with toluene, the remaining residue is recrystallized from heptane/toluene. The substance is finally sublimed under high vacuum; purity is 99.9% determined by HPLC. The yield is 6 g (26% of theory).

[0222] The following compounds are prepared in an analogous manner:

TABLE-US-00008 Ex. Product Amine Product 5b [00602] [00603] [00604] 5c [00605] [00606] [00607] 5d [00608] [00609] [00610] 5e [00611] [00612] [00613] 5f [00614] [00615] [00616] 5g [00617] [00618] [00619]

B) Device Examples

1) General Production Process for the OLEDs and Characterization of the OLEDs

[0223] Glass plates which have been coated with structured ITO (indium tin oxide) in a thickness of 50 nm form the substrates to which the OLEDs are applied.

[0224] The OLEDs basically have the following layer structure: substrate/hole injection layer (HIL)/hole transport layer (HTL1)/optional second hole transport layer (HTL2)/electron blocker layer (EBL)/emission layer (EML)/electron transport layer (ETL1)/optional second electron transport layer (ETL2)/electron injection layer (EIL) and finally a cathode. The cathode is formed by an aluminium layer of thickness 100 nm. The exact structure of the OLEDs can be found in the tables which follow. The materials required for production of the OLEDs are shown in a table below.

[0225] All materials are applied by thermal vapour deposition in a vacuum chamber. In this case, the emission layer consists of at least one matrix material (host material) and an emitting dopant (emitter) which is added to the matrix material(s) in a particular proportion by volume by co-evaporation. Details given in such a form as H:SEB (95%:5%) mean here that the material H is present in the layer in a proportion by volume of 95% and SEB in a proportion of 5%.

[0226] In an analogous manner, the electron transport layer and the hole injection layer also consist of a mixture of two materials. The structures of the materials that are used in the OLEDs are shown in Table 3.

[0227] The OLEDs are characterized in a standard manner. For this purpose, the electroluminescence spectra, the external quantum efficiency (EQE, measured in %) as a function of the luminance, calculated from current-voltage-luminance characteristics assuming Lambertian radiation characteristics, and the lifetime are determined. The parameter EQE @ 10 mA/cm.sup.2 refers to the external quantum efficiency which is attained at 10 mA/cm.sup.2. The lifetime LT is defined as the time after which the luminance drops from the starting luminance to a certain proportion in the course of operation with constant current density. An LT90 figure means here that the lifetime reported corresponds to the time after which the luminance has dropped to 90% of its starting value. The figure @60 mA/cm.sup.2 means here that the lifetime in question is measured at 60 mA/cm.sup.2.

2) Use of the Inventive Compounds in the EBL of Blue-Fluorescing OLEDs

[0228] OLEDs are produced with the following structure:

TABLE-US-00009 TABLE 1a OLED structure HIL HTL1 HTL2 EBL EML ETL EIL Thickness/ Thickness/ Thickness/ Thickness/ Thickness/ Thickness/ Thickness/ Ex. nm nm nm nm nm nm nm E1 HTM: p- HTM HTM-1: p- HTM-1 H:SEB ETM:LiQ LiQ dopant (5%) 180 nm dopant 10 nm (95%:5%) (50:50%) 1 nm 20 nm (5%) 20 nm 30 nm 20 nm E2 HTM: p- HTM HTM-2: p- HTM-2 H:SEB ETM:LiQ LiQ dopant (5%) 180 nm dopant 10 nm (95%:5%) (50:50%) 1 nm 20 nm (5%) 20 nm 30 nm 20 nm E3 HTM: p- HTM HTM-3: p- HTM-3 H:SEB ETM:LiQ LiQ dopant (5%) 180 nm dopant 10 nm (95%:5%) (50:50%) 1 nm 20 nm (5%) 20 nm 30 nm 20 nm

[0229] OLEDs E1, E2 and E3 show the use of compounds HTM-1, HTM-2 and HTM-3 according to the application in the EBL of blue-fluorescing OLEDs.

[0230] The OLEDs show the following values for external quantum efficiency:

TABLE-US-00010 TABLE 2a OLED data EQE @ 10 mA/cm.sup.2 (%) E1 8.8 E2 8.5 E3 9.1

3) Use of the Inventive Compounds in the EBL of Green-Phosphorescing OLEDs

[0231] OLEDs are produced with the following structure:

TABLE-US-00011 TABLE 1b OLED structure HIL HTL EBL EML ETL1 ETL2 EIL Thickness/ Thickness/ Thickness/ Thickness/ Thickness/ Thickness/ Thickness/ Ex. nm nm nm nm nm nm nm E4 HTM: p- HTM HTM-1 TMM-1 (59%) ETM ETM:LiQ LiQ dopant (5%) 220 nm 10 nm TMM- 10 nm (50:50%) 1 nm 20 nm 2(29%):TEG(12%) 30 nm 30 nm E5 HTM: p- HTM HTM-2 TMM-1 (59%) ETM ETM:LiQ LiQ dopant (5%) 220 nm 10 nm TMM- 10 nm (50:50%) 1 nm 20 nm 2(29%):TEG(12%) 30 nm 30 nm E6 HTM: p- HTM HTM-3 TMM-1 (59%) ETM ETM:LiQ LiQ dopant (5%) 220 nm 10 nm TMM-2 10 nm (50:50%) 1 nm 20 nm (29%):TEG(12%) 30 nm 30 nm

[0232] OLEDs E4, E5 and E6 show the use of compounds HTM-1, HTM-2 and HTM-3 according to the application in the EBL of green-phophorescing OLEDs.

[0233] The OLEDs show the following values for external quantum efficiency:

TABLE-US-00012 TABLE 2b OLED data EQE @ 10 mA/cm.sup.2 (%) E4 17.3 E5 18.6 E6 18.8
3) Comparison Between Compound of the Invention and Comparative Compound when Used as HTM in Blue-Fluorescing OLEDs

[0234] OLEDs are produced with the following structure:

TABLE-US-00013 TABLE 1c OLED structure HIL HTL1 EBL EML ETL EIL Thickness/ Thickness/ Thickness/ Thickness/ Thickness/ Thickness/ Ex. nm nm nm nm nm nm E7 HTM-1: p- HTM-1 EBM H:SEB ETM:LiQ LiQ dopant (5%) 180 nm 10 nm (95%:5%) (50:50%) 1 nm 20 nm 20 nm 30 nm E8- HTM-comp: p- HTM- EBM H:SEB ETM:LiQ LiQ comp dopant (5%) comp 10 nm (95%:5%) (50:50%) 1 nm 20 nm 180 nm 20 nm 30 nm

[0235] E7 shows the use of the inventive compound HTM-1 in the HIL and HTL of a blue-fluorescing OLED. E8-comp shows the use of the comparative compound HTM-comp in an otherwise identical construction.

[0236] The following results are obtained:

TABLE-US-00014 TABLE 2c OLED data Change in EQE @ Change in lifetime 10 mA/cm.sup.2 LT90@60 mA versus comparative versus comparative compound HTM compound HTM E7 +4% +3% E8-comp +1% 6%

[0237] The results show that compound HTM-1 results in distinctly better performance data of the OLED than compound HTM-comp.

TABLE-US-00015 TABLE 3 Materials used [00620] [00621] [00622] [00623] [00624] [00625] [00626] [00627] [00628] [00629] [00630] [00631] [00632] [00633]