MATERIALS FOR ELECTRONIC DEVICES

Abstract

The invention relates to phenanthrene compounds comprising one or more arylamino groups. Said compounds can be used in electronic devices, in particular OLED's.

Claims

1.-20. (canceled)

21. A compound of one of formulae (I-3) to (I-8) ##STR00228## ##STR00229## where the symbols that occur are as follows: R R is the same or different at each instance and is selected from H, D, F, C(O)R.sup.6, CN, Si(R.sup.6).sub.3, N(R.sup.6).sub.2, P(O)(R.sup.6).sub.2, OR.sup.6, S(O)R.sup.6, S(O).sub.2R.sub.6, 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 which have 6 to 40 aromatic ring atoms and may be substituted by one or more R.sup.6 radicals, and heteroaromatic ring systems which have 5 to 40 aromatic ring atoms and may be substituted by one or more R.sup.6 radicals, where the alkyl, alkoxy, alkenyl and alkynyl groups mentioned may each be substituted by one or more R.sup.6 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.6CCR.sup.6, CC, Si(R.sup.6).sub.2, CO, CNR.sup.6, C(O)O, C(O)NR.sup.6, NR.sup.6, P(O)(R.sup.6), O, S, SO or SO.sub.2; R.sup.2, R.sup.3 are the same or different at each instance and are selected from H, D, F, C(O)R.sup.6, CN, Si(R.sup.6).sub.3, P(O)(R.sup.6).sub.2, OR.sup.6, S(O)R.sup.6, S(O).sub.2R.sub.6, 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 which have 6 to 40 aromatic ring atoms and may be substituted by one or more R.sup.6 radicals, and heteroaromatic ring systems which have 5 to 40 aromatic ring atoms and may be substituted by one or more R.sup.6 radicals, where the alkyl, alkoxy, alkenyl and alkynyl groups mentioned may each be substituted by one or more R.sup.6 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.6CCR.sup.6, CC, Si(R.sup.6).sub.2, CO, CNR.sup.6, C(O)O, C(O)NR.sup.6, NR.sup.6, P(O)(R.sup.6), O, S, SO or SO.sub.2; R.sup.6 is the same or different at each instance and is selected from H, D, F, C(O)R.sup.7, CN, Si(R.sup.7).sub.3, N(R.sup.7).sub.2, P(O)(R.sup.7).sub.2, OR.sup.7, S(O)R.sup.7, S(O).sub.2R.sub.7, 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 which have 6 to 40 aromatic ring atoms and may be substituted by one or more R.sup.7 radicals, and heteroaromatic ring systems which have 5 to 40 aromatic ring atoms and may be substituted by one or more R.sup.7 radicals, where the alkyl, alkoxy, alkenyl and alkynyl groups mentioned may each be substituted by one or more R.sup.7 radicals, where one or more CH.sub.2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups mentioned may be replaced by R.sup.7CCR.sup.7, CC, Si(R.sup.7).sub.2, CO, CNR.sup.7, C(O)O, C(O)NR.sup.7, NR.sup.7, P(O)(R.sup.7), O, S, SO or SO.sub.2, and where two or more R.sup.6 substituents may be joined to one another and may form a ring; R.sup.7 is the same or different at each instance and is selected from H, D, F, CN and aliphatic, aromatic or heteroaromatic organic radicals having 1 to 20 carbon atoms, in which one or more hydrogen atoms may also be replaced by D, F or CN; 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 may be substituted by one or more R.sup.4 radicals, and heteroaromatic ring systems which have 5 to 40 aromatic ring atoms and may be substituted by one or more R.sup.4 radicals; Ar.sup.2 is the same or different at each instance and is selected from aromatic ring systems which have 6 to 40 aromatic ring atoms and may be substituted by one or more R.sup.4 radicals, and heteroaromatic ring systems which have 5 to 40 aromatic ring atoms and may be substituted by one or more R.sup.4 radicals; R.sup.4 is the same or different at each instance and is selected from H, D, F, C(O)R.sup.6, CN, Si(R.sup.6).sub.3, N(R.sup.6).sub.2, P(O)(R.sup.6).sub.2, OR.sup.6, S(O)R.sup.6, S(O).sub.2R.sub.6, 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 which have 6 to 40 aromatic ring atoms and may be substituted by one or more R.sup.6 radicals, and heteroaromatic ring systems which have 5 to 40 aromatic ring atoms and may be substituted by one or more R.sup.6 radicals, where the alkyl, alkoxy, alkenyl and alkynyl groups mentioned may each be substituted by one or more R.sup.6 radicals, where one or more CH.sub.2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups mentioned may be replaced by R.sup.6CCR.sup.6, CC, Si(R.sup.6).sub.2, CO, CNR.sup.6, C(O)O, C(O)NR.sup.6, NR.sup.6, P(O)(R.sup.6), O, S, SO or SO.sub.2, and where two or more R.sup.4 substituents may be joined to one another and may form a ring;

22. The compound as claimed in claim 21, wherein Ar.sup.1 is the same or different at each instance and is selected from aromatic ring systems which have 12 to 24 aromatic ring atoms and optionally substituted by one or more R.sup.4 radicals.

23. The compound as claimed in claim 21, wherein two Ar.sup.1 groups bonded to the same nitrogen atom are not the same.

24. The compound as claimed in claim 21, wherein the Ar.sup.1 groups each contain at least one group selected from benzene, naphthalene, phenanthrene, fluoranthene, biphenyl, terphenyl, quaterphenyl, fluorene, spirobifluorene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, indole, isoindole, carbazole, indolocarbazole, indenocarbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzimidazole, pyrimidine, pyrazine or triazine, each optionally substituted by one or more R.sup.4 radicals.

25. The compound as claimed in claim 21, wherein Ar.sup.2 is the same or different at each instance and is selected from aromatic ring systems which have 6 to 13 aromatic ring atoms and optionally substituted by one or more R.sup.4 radicals.

26. The compound as claimed in claim 21, wherein R.sup.4 are the same or different at each instance and are selected from H, D, F, CN, Si(R.sup.6).sub.3, 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 which have 6 to 24 aromatic ring atoms and optionally substituted by one or more R.sup.6 radicals, and heteroaromatic ring systems which have 5 to 24 aromatic ring atoms and optionally substituted by one or more R.sup.6 radicals, where the alkyl and alkoxy groups mentioned may each be substituted by one or more R.sup.6 radicals and where one or more CH.sub.2 groups in the alkyl and alkoxy groups mentioned may be replaced by CC, R.sup.6CCR.sup.6, Si(R.sup.6).sub.2, CO, CNR.sup.6, NR.sup.6, O, S, C(O)O or C(O)NR.sup.6.

27. The compound as claimed in claim 21, wherein R.sup.6 is the same or different at each instance and is selected from H, D, F, CN, Si(R.sup.7).sub.3, 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 which have 6 to 24 aromatic ring atoms and optionally substituted by one or more R.sup.7 radicals, and heteroaromatic ring systems which have 5 to 24 aromatic ring atoms and optionally substituted by one or more R.sup.7 radicals, where the alkyl and alkoxy groups mentioned may each be substituted by one or more R.sup.7 radicals and where one or more CH.sub.2 groups in the alkyl and alkoxy groups mentioned may be replaced by CC, R.sup.7CCR.sup.7, Si(R.sup.7).sub.2, CO, CNR.sup.7, NR.sup.7, O, S, C(O)O or C(O)NR.sup.7.

28. A process for preparing the compound as claimed in claim 21, wherein a phenanthrene compound substituted by a leaving group in the 1 and/or 4 position is reacted in a coupling reaction with a diarylamino compound or with a triarylamino compound substituted by a leaving group.

29. An oligomer, polymer or dendrimer containing one or more compounds as claimed in claim 21, wherein the bond(s) to the polymer, oligomer or dendrimer may be localized at any desired positions substituted by R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.6 or R.sup.7 in formulae (I-3) to (I-8).

30. A formulation comprising at least one compound as claimed in claim 21, and at least one solvent.

31. An electronic device selected from the group consisting of organic integrated circuits, organic field-effect transistors, organic thin-film transistors, organic light-emitting transistors, organic solar cells, organic optical detectors, organic photoreceptors, organic field-quench devices, organic light-emitting electrochemical cells, organic laser diodes and organic electroluminescent devices, comprising at least one compound as claimed in claim 21.

32. The electronic device as claimed in claim 31, wherein the device is an organic electroluminescent devices comprising cathode, anode and at least one organic layer comprising at least one compound as claimed in claim 21.

33. The electronic device as claimed in claim 32, wherein the compound is present as hole transport material in a hole transport layer, an electron blocker layer or a hole injection layer, or as an emitting compound in an emitting layer, or as matrix compound together with one or more emitting compounds in an emitting layer.

Description

WORKING EXAMPLES

A) Synthesis Examples

A-1) Compounds of the (1) Type

Synthesis of Biphenyl-4-yl(9,9-Dimethyl-9H-Fluoren-2-yl)Phenanthren-4-ylamine (I-1)

[0140] ##STR00074##

Intermediate: phenanthren-4-yl trifluoromethanesulfonate

[0141] 20 g (103 mmol) of 4-hydroxyphenanthrene (CAS no.: 7651-86-7, synthesis described in Tetrahedron 2010, 66(12), 2111) and 42.8 mL of pyridine (309 mmol) are dissolved in 130 mL of CH.sub.2Cl.sub.2. At 5 C., 21.2 mL (128 mmol) of trifluoromethanesulfonic anhydride are added. The mixture is stirred for a further 5 hours. The mixture is subsequently partitioned between CH.sub.2Cl.sub.2 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 yield is 29.4 g (87% of theory).

Biphenyl-4-yl(9,9-dimethyl-9H-fluoren-2-yl)phenanthren-4-ylamine (1-1)

[0142] 29.4 g of the triflate (90 mmol) and 32.6 g of biphenyl-4-yl(9,9-dimethyl-9H-fluoren-2-yl)amine (90 mmol) are dissolved in 340 mL of toluene. The solution is degassed and saturated with N.sub.2. Thereafter, 2.2 g (5.4 mmol) of SPhos and 4.13 g of palladium-dba (4.5 mmol) are added. Subsequently, 17.3 g of sodium tert-butoxide (180 mmol) are added. The reaction mixture is heated to 85 C. under a protective atmosphere for 4 h. The mixture is subsequently partitioned between toluene and water, and the organic phase is washed three times with water, 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 and then sublimed under high vacuum. The purity is 99.9%. The yield is 38 g (80% of theory).

[0143] Analogously to the above-described synthesis of compound (1-1), the following compounds (1-2) to (1-8) are prepared:

TABLE-US-00001 Reactant 1 Reactant 2 Product Yield 1-2 [00075] [00076] [00077] 75% 1-3 [00078] [00079] [00080] 82% 1-4 [00081] [00082] [00083] 86% 1-5 [00084] [00085] [00086] 77% 1-6 [00087] [00088] [00089] 73% 1-7 [00090] [00091] [00092] 81% 1-8 [00093] [00094] [00095] 75%

A-2) Compounds of the (2) Type

Synthesis of biphenyl-4-yl(9,9-dimethyl-9H-fluoren-2-yl)(4-phenanthren-4-ylphenyl)amine (compound (2-1))

[0144] ##STR00096##

[0145] Precursor: biphenyl-4-yl(4-chlorophenyl)(9,9-dimethyl-9H-fluoren-2-yl)amine

##STR00097##

[0146] 40 g of biphenyl-4-yl(9,9-dimethyl-9H-fluoren-2-yl)amine (111 mmol) and 26.4 g of 4-chloroiodobenzene (111 mmol) are dissolved in 700 mL of toluene. The solution is degassed and saturated with N.sub.2. Thereafter, 4.4 mL (4.4 mmol) of a 1 M tri-tert-butylphosphine solution and 0.5 g (2.21 mmol) of palladium(II) acetate are added thereto, and then 15.9 g of sodium tert-butoxide (166 mmol) are added. The reaction mixture is heated to boiling under a protective atmosphere for 5 h. 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 yield is 47 g (90% of theory).

Intermediate: biphenyl-4-yl(9,9-dimethyl-9H-fluoren-2-yl)[4-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)phenyl]amine

[0147] 20 g (42 mmol) of biphenyl-4-yl(4-chlorophenyl)(9,9-dimethyl-9H-fluoren-2-yl)amine, 12.5 g (50.8 mmol) of bis(pinacolato)diborane and 12.5 g (127 mmol) of potassium acetate are suspended in 400 mL of dioxane. To this suspension are added 1.04 g (1.27 mmol) of 1,1-bis(diphenylphosphino)ferrocenedichloropalladium(II) complex with DCM. The reaction mixture is heated under reflux for 16 h. After cooling, the organic phase is removed, washed three times with 200 mL of water and then concentrated to dryness. The residue is recrystallized from toluene (21.7 g, 91% yield).

[0148] In an analogous manner thereto, the following compounds are prepared:

TABLE-US-00002 Reactant 1 Product Yield [00098] [00099] 87% [00100] [00101] 94% [00102] [00103] 82% [00104] [00105] 89% [00106] [00107] 77% [00108] [00109] 89% [00110] [00111] 95%

Biphenyl-4-yl(9,9-dimethyl-9H-fluoren-2-yl)(4-phenanthren-4-ylphenyl)amine (compound (2-1))

[0149] 23 g (40.8 mmol) of biphenyl-4-yl(9,9-dimethyl-9H-fluoren-2-yl)[4-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)phenyl]amine, 12.1 g (37.1 mmol) of phenanthren-4-yl trifluoromethanesulfonate, 7.78 g of sodium metaborate (55.6 mmol) and 54 L of hydrazinium hydroxide are suspended in 600 mL of THF. 0.52 g (0.742 mmol) of bis(triphenylphosphine)palladium dichloride is added to this suspension, and the reaction mixture is heated under reflux for 24 h. After cooling, the organic phase is removed, filtered through silica gel, washed three times with 100 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%. The yield is 17 g (75% of theory).

[0150] Analogously, the following compounds (2-2) to (2-8) are prepared:

TABLE-US-00003 Reactant 1 Reactant 2 Product Yield 2-2 [00112] [00113] [00114] 78% 2-3 [00115] [00116] [00117] 71% 2-4 [00118] [00119] [00120] 82% (CAS no.: 51958-51-1) 2-5 [00121] [00122] [00123] 89% 2-6 [00124] [00125] [00126] 69% 2-7 [00127] [00128] [00129] 88% (CAS no.: 51958-51-1) 2-8 [00130] [00131] [00132] 84% (CAS no.: 51958-51-1) 2-9 [00133] [00134] [00135] 87% (CAS no.: 51958-51-51)

A-3) Compounds of the (3) Type

Synthesis of biphenyl-4-yl(9,9-dimethyl-9H-fluoren-2-yl)phenanthren-1-ylamine (compound (3-1))

[0151] ##STR00136##

[0152] 20 g of 1-bromophenanthrene (CAS no.: 51958-51-1) (78 mmol) and 26.7 g of biphenyl-4-yl(9,9-dimethyl-9H-fluoren-2-yl)amine (74 mmol) are dissolved in 500 mL of toluene. The solution is degassed and saturated with N.sub.2. Thereafter, 3.1 mL (3.1 mmol) of a tri-tert-butyiphosphine solution and 0.35 g (1.56 mmol) of palladium(II) acetate are added thereto. Subsequently, 11.6 g of sodium tert-butoxide (117 mmol) are added. The reaction mixture is heated to boiling under a protective atmosphere for 3 h. 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 and finally sublimed under high vacuum; purity is 99.9% (HPLC). The yield is 33 g (80% of theory).

[0153] Analogously, the following compounds (3-2) to (3-6) are prepared:

TABLE-US-00004 Reactant 1 Reactant 2 Product Yield 3-2 [00137] [00138] [00139] 65% 3-3 [00140] [00141] [00142] 75% 3-4 [00143] [00144] [00145] 78% 3-5 [00146] [00147] [00148] 81% 3-6 [00149] [00150] [00151] 69%

A-4) Compounds of the (4) Type

Synthesis of N*4*-biphenyl-4-yl-N*4*-(9,9-dimethyl-9H-fluoren-2-yl)-N*1*,N*1*-di-p-tolylphenanthrene-1,4-diamine (4-1)

[0154] ##STR00152##

[0155] Precursor: 1-bromophenanthren-4-ol

##STR00153##

[0156] 40.0 g (206 mmol) of 4-phenanthrol are initially charged in 500 mL of acetonitrile. Subsequently, a solution of 38.5 g (216 mmol) of NBS in 100 mL of CH.sub.3CN is added dropwise in the dark at 15 C., the mixture is allowed to come to RT and stirring is continued at this temperature for 4 h. Subsequently, 250 mL of water are added to the mixture and extraction is effected with CH.sub.2Cl.sub.2. The organic phase is dried over MgSO.sub.4 and the solvents are removed under reduced pressure. The product is subjected to extractive stirring with hot hexane and filtered off with suction.

[0157] Yield: 42.5 g (154 mmol), 75% of theory

Intermediate: 1-(di-p-tolylamino)phenanthren-4-ol

[0158] Analogously to the synthesis described above under A-3), the following compounds are also prepared:

TABLE-US-00005 Reactant 1 Reactant 2 Product Yield [00154] [00155] [00156] 76% [00157] [00158] [00159] 69% [00160] [00161] [00162] 78%

[0159] Analogously to the synthesis of the phenanthren-4-yl trifluoromethanesulfonate intermediate described, the following compounds are also prepared:

TABLE-US-00006 Reactant 1 Product Yield [00163] [00164] 86% [00165] [00166] 89% [00167] [00168] 93%

[0160] Analogously to the manner described above for compounds of the formula (1-1), the following compounds (4-2) to (4-4) are prepared:

TABLE-US-00007 Reactant 1 Reactant 2 Product Yield 4-2 [00169] [00170] [00171] 68% 4-3 [00172] [00173] [00174] 61% 4-4 [00175] [00176] [00177] 69%

A-5) Compounds of the (5) Type

Bis(9,9-dimethyl-9H-fluoren-2-yl)(4-phenylphenanthren-1-yl)amine (5-1)

[0161] ##STR00178##

[0162] Analogously to the manner described above under (2-1), the following compounds (5-2) to (5-4) are also prepared:

TABLE-US-00008 Reactant 1 Reactant 2 Product Yield 5-2 [00179] [00180] [00181] 68% 5-3 [00182] [00183] [00184] 61% 5-4 [00185] [00186] [00187] 69%

A-6) Compounds of the (6) Type

Biphenyl-4-yl{1-[4-(bis(biphenyl-4-yl)amino)phenyl]phenanthren-4-yl}(9,9-dimethyl-9H-fluoren-2-yl)amine (6-1)

[0163] ##STR00188## ##STR00189##

[0164] Analogously to the synthesis described above under A-2), the following compounds are also prepared:

TABLE-US-00009 Reactant 1 Reactant 2 Product Yield [00190] [00191] [00192] 82% [00193] [00194] [00195] 85% [00196] [00197] [00198] 69%

[0165] Analogously to the synthesis of the phenanthren-4-yl trifluoromethanesulfonate intermediate described, the following compounds are also prepared:

TABLE-US-00010 Reactant 1 Product Yield [00199] [00200] 81% [00201] [00202] 93% [00203] [00204] 89%

[0166] Analogously to the synthesis described above for (I-1), the following compounds (6-2) to (6-4) are prepared:

TABLE-US-00011 Reactant 1 Reactant 2 Product Yield 6-2 [00205] [00206] [00207] 58% 6-3 [00208] [00209] [00210] 52% 6-4 [00211] [00212] [00213] 63%

B) Device Examples

[0167] OLEDs of the invention and OLEDs according to the prior art are produced by a general method according to WO 04/058911, which is adapted to the circumstances described here (e.g. materials).

[0168] In the inventive examples 11-19 which follow and in reference examples C1-C4, the data of various OLEDs are presented. Substrates used are glass plates coated with structured ITO (indium tin oxide) of thickness 50 nm. The OLEDs have the following layer structure: substrate/p-doped hole transport layer (HIL1)/hole transport layer (HTL)/p-doped hole transport layer (HIL2)/hole transport layer (EBL)/emission layer (EML)/electron transport layer (ETL)/electron injection layer (EIL) and finally a cathode. In each of examples C3, C4 and 14-19, the layers HIL2 and EBL are omitted. The cathode is formed by an aluminum layer of thickness 100 nm. The materials required for production of the OLEDs are shown in table 1, and the various component structures in table 2.

[0169] All materials are applied by thermal vapor deposition in a vacuum chamber. In this case, the emission layer always consists of at least one matrix material (host material) and an emitting dopant (emitting compound) which is added to the matrix material(s) in a particular proportion by volume by co-evaporation. Details given in such a form as H1:SEB(5%) mean here that the material H1 is present in the layer in a proportion by volume of 95% and SEB in a proportion by volume of 5%. In an analogous manner, the electron transport layers or the hole injection layers may also consist of a mixture of two or more materials.

[0170] The OLEDs are characterized in a standard manner. For this purpose, the electroluminescence spectra, the current efficiency (measured in cd/A), the power efficiency (measured in lm/W) and the external quantum efficiency (EQE, measured in percent) as a function of luminance, calculated from current-voltage-luminance characteristics (IUL characteristics) assuming Lambertian radiation characteristics, and also the lifetime are determined. The electroluminescence spectra are determined at a luminance of 1000 cd/m.sup.2, and the CIE 1931 x and y color coordinates are calculated therefrom. The parameter EQE @ 10 mA/cm.sup.2 refers to the external quantum efficiency at a current density of 10 mA/cm.sup.2. LD80 @ 60 mA/cm.sup.2 is the lifetime before the OLED, given a starting brightness at constant current of 60 mA/cm.sup.2, has fallen to 80% of the starting intensity.

TABLE-US-00012 TABLE 1 Structures of the materials used [00214] F4TCNQ [00215] HIM [00216] H1 [00217] SEB [00218] ETM [00219] LiQ [00220] HTM1 [00221] HTM2 [00222] HTM3 [00223] HTM4 [00224] HTMC1 [00225] HTMC2 [00226] HTM5 [00227] HTM6

TABLE-US-00013 TABLE 2 Structure of the OLEDs HTL EBL EML EIL HIL1 Thickness/ HIL2 Thickness/ Thickness/ ETL Thickness/ Exp. Thickness/nm nm Thickness/nm nm nm Thickness/nm nm C1 HIM: F4TCNQ(5%) HIM HTMC1: F4TCNQ(5%) HTMC1 H1: SEB(5%) ETM: LiQ(50%) LiQ 20 nm 155 nm 20 nm 20 nm 20 nm 30 nm 1 nm C2 HIM: F4TCNQ(5%) HIM HTMC2: F4TCNQ(5%) HTMC2 H1: SEB(5%) ETM: LiQ(50%) LiQ 20 nm 155 nm 20 nm 20 nm 20 nm 30 nm 1 nm I1 HIM: F4TCNQ(5%) HIM HTM1: F4TCNQ(5%) HTM1 H1: SEB1(5%) ETM: LiQ(50%) LiQ 20 nm 155 nm 20 nm 20 nm 20 nm 30 nm 1 nm I2 HIM: F4TCNQ(5%) HIM HTM2: F4TCNQ(5%) HTM2 H1: SEB1(5%) ETM: LiQ(50%) LiQ 20 nm 155 nm 20 nm 20 nm 20 nm 30 nm 1 nm I3 HIM: F4TCNQ(5%) HIM HTM3: F4TCNQ(5%) HTM3 H1: SEB1(5%) ETM: LiQ(50%) LiQ 20 nm 155 nm 20 nm 20 nm 20 nm 30 nm 1 nm C3 HTMC1: F4TCNQ(5%) HTMC1 H1: SEB1(5%) ETM: LiQ(50%) LiQ 20 nm 180 nm 20 nm 30 nm 1 nm C4 HTMC2: F4TCNQ(5%) HTMC2 H1: SEB1(5%) ETM: LiQ(50%) LiQ 20 nm 180 nm 20 nm 30 nm 1 nm I4 HTM4: F4TCNQ(5%) HTM4 H1: SEB1(5%) ETM: LiQ(50%) LiQ 20 nm 180 nm 20 nm 30 nm 1 nm I5 HTM3: F4TCNQ(5%) HTM3 H1: SEB1(5%) ETM: LiQ(50%) LiQ 20 nm 180 nm 20 nm 30 nm 1 nm I6 HTM2: F4TCNQ(5%) HTM2 H1: SEB1(5%) ETM: LiQ(50%) LiQ 20 nm 180 nm 20 nm 30 nm 1 nm I7 HTM1: F4TCNQ(5%) HTM1 H1: SEB1(5%) ETM: LiQ(50%) LiQ 20 nm 180 nm 20 nm 30 nm 1 nm I8 HTM5: F4TCNQ(5%) HTM5 H1: SEB1(5%) ETM: LiQ(50%) LiQ 20 nm 180 nm 20 nm 30 nm 1 nm I9 HTM6: F4TCNQ(5%) HTM6 H1: SEB1(5%) ETM: LiQ(50%) LiQ 20 nm 180 nm 20 nm 30 nm 1 nm

Example 1

[0171] In example 1, three inventive substances (HTM1, HTM2 and HTM3) and two reference substances (HTMC1, HTMC2) are compared in an OLED having a blue-fluorescing emitting layer. The compounds are each used in hole-transporting layers of the OLED.

[0172] The reference sample C1, containing a 3-phenanthrene compound, is compared with two components of the invention containing a 4-phenanthrene (I1) or a 1-phenanthrene compound (I2). The lifetime LD80 at 60 mA/cm.sup.2 is much better in the case of the inventive samples I1 (357 h) and I2 (381 h) than the reference sample C1 (128 h).

[0173] The external quantum efficiency at 10 mA/cm.sup.2 of the inventive compound formed from sample 13 (of a 4-phenanthrene compound) is much better at 7.7% than that of the reference sample C2 at only 6.6%. The reference sample C2 contains a 3-phenanthrene compound.

Example 2

[0174] In the case of OLEDs having a blue-fluorescing emitting layer (in a reduced design; direct injection of the holes from the HTL into the EML), the reference samples C3 (6.8%) and C4 (4.2%) have lower quantum efficiency at 10 mA/cm.sup.2 than the inventive samples 14 (7.9%) and I5 (7.7%). The lifetime (80%) at 60 mA/cm.sup.2 of the inventive samples I6 (356 h) and I7 (218 h) is also greater than in the case of the references C3 (106 h) and C4 (43 h). In this example too, the reference samples contain 3-phenanthrene compounds. The inventive samples I4, I5, I6 and I7 contain 1-phenanthrene compounds or 4-phenanthrene compounds.

Example 3

[0175] In addition, two components 18 and 19 comprising the inventive compounds HTM5 and HTM6 are produced. These two compounds are characterized in that they have a phenyl group between the phenanthrene group and the diarylamino group. The components are produced with a reduced design like those of example 2. For components 18 and 19, external quantum efficiencies of 7.3% and 8.1% respectively are measured.