Materials for electronic devices

Abstract

The invention relates to compounds with benzindenofluorene base bodies having a structure of formula (I): ##STR00001##
and to the use thereof in electronic devices, in particular in organic electroluminescent devices.

Claims

1. A compound of formula (I): ##STR00286## wherein the groups Ar.sup.1 are naphthyl groups, which are optionally substituted by one or more radicals R.sup.1, and the groups Ar.sup.2 are phenyl groups, which are optionally substituted by one or more radicals R.sup.2; or one of the two groups Ar.sup.1 is a phenyl group, which is optionally substituted by one or more radicals R.sup.1, and the other of the two groups Ar.sup.1 is a naphthyl group, which is optionally substituted by one or more radicals R.sup.1, and the groups Ar.sup.1 are phenyl groups, which are optionally substituted by one or more radicals R.sup.2 X.sup.1 is on each occurrence, identically or differently, BR.sup.3, C(R.sup.3).sub.2, C(R.sup.3).sub.2C(R.sup.3).sub.2, C(R.sup.3).sub.2O, C(R.sup.3).sub.2S, R.sup.3CCR.sup.3, R.sup.3CN, Si(R.sup.3).sub.2, Si(R.sup.3).sub.2Si(R.sup.3).sub.2, CO, O, S, SO, SO.sub.2, NR.sup.3, PR.sup.3, or P(O)R.sup.3; R.sup.1, R.sup.2, and R.sup.3 are on each occurrence, identically or differently, 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, a straight-chain alkyl or alkoxy group having 1 to 20 C atoms, a branched or cyclic alkyl or alkoxy group having 3 to 20 C atoms, or an alkenyl or alkynyl group having 2 to 20 C atoms, wherein the above-mentioned groups are optionally substituted by one or more radicals R.sup.4 and wherein one or more CH.sub.2 groups in the above-mentioned groups are optionally 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, or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.4, and wherein two or more radicals R.sup.3 are optionally linked to one another so as to define a ring; R.sup.4 is on each occurrence, identically or differently, 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, a straight-chain alkyl or alkoxy group having 1 to 20 C atoms, a branched or cyclic alkyl or alkoxy group having 3 to 20 C atoms, or an alkenyl or alkynyl group having 2 to 20 C atoms, wherein the above-mentioned groups are optionally substituted by one or more radicals R.sup.5 and wherein one or more CH.sub.2 groups in the above-mentioned groups are optionally 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, or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.5, and wherein two or more radicals R.sup.4 are optionally linked to one another so as to define a ring; R.sup.5 is on each occurrence, identically or differently, H, D, F, or an aliphatic, aromatic, or heteroaromatic organic radical having 1 to 20 C atoms, wherein one or more H atoms are optionally replaced by D or F, and wherein two or more substituents R.sup.5 are optionally linked to one another so as to define a ring.

2. The compound of claim 1, wherein the bonds from the groups Ar.sup.2 to the adjacent group Ar.sup.1 or Ar.sup.2 are each present in the para-position to one another.

3. The compound of claim 1, wherein X.sup.1 is selected on each occurrence, identically or differently, from the group consisting of C(R.sup.3).sub.2, C(R.sup.3).sub.2C(R.sup.3).sub.2, C(R.sup.3).sub.2O, Si(R.sup.3).sub.2, O, S, and NR.sup.3.

4. The compound of claim 1, wherein X.sup.1 is C(R.sup.3).sub.2.

5. The compound of claim 1, wherein R.sup.2 is H or D.

6. An oligomer, polymer, or dendrimer comprising one or more compounds of claim 1, wherein the bond(s) to the polymer, oligomer, or dendrimer are optionally localised at any position in formula (I) substituted by R.sup.1, R.sup.2, or R.sup.3.

7. A formulation comprising at least one compound of claim 1 and at least one solvent.

8. A formulation comprising at least one oligomer, polymer, or dendrimer of claim 6 and at least one solvent.

9. An electronic device comprising at least one oligomer, polymer, or dendrimer of claim 6, wherein the electronic device is 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.

10. The electronic device of claim 9, wherein the electronic device is selected from the group consisting of organic electroluminescent devices comprising a cathode, an anode, and at least one organic layer, wherein the at least one organic layer comprises the at least one oligomer, polymer, or dendrimer.

11. The electronic device of claim 10, wherein the at least one oligomer, polymer, or dendrimer is present as a hole-transport material in a hole-transport layer, as an emitting compound in an emitting layer, or as a matrix compound in an emitting layer.

12. An electronic device comprising at least one compound of claim 1, wherein the electronic device is 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.

13. The electronic device of claim 12, wherein the electronic device is selected from the group consisting of organic electroluminescent devices comprising a cathode, an anode, and at least one organic layer, wherein the at least one organic layer comprises the at least one compound.

14. The electronic device of claim 13, wherein the at least one compound is present as a hole-transport material in a hole-transport layer, as an emitting compound in an emitting layer, or as a matrix compound in an emitting layer.

15. A process for preparing a compound of claim 1, comprising the steps of performing at least one metal-catalysed coupling reaction and performing at least one ring-closure reaction.

Description

WORKING EXAMPLES

A) Synthesis Examples

A-1) Variant I

(1) The procedure is in accordance with the following general scheme:

(2) ##STR00174##

(3) TABLE-US-00004 Compound Synthesis/yield Int-a1 Commercially available Int-a2 Commercially available Int-a3 Bioorg. & Med. Chem. Lett., 2012, 22, 5108-5113 Int-a4 0 Tetrahedron 2001, 57, 10047-10053 Int-a5 Synthesis 2003, 16, 2470-2472 Int-a6 J. Mat. Chem. 2009, 19, 4148-4156 Int-a7 Org. Lett. 2008, 10, 773-776 Int-a8 WO 2012/ 60283 A1

(4) Compound Int-b

(5) 2,7-Dibromo-9,9-dimethyl-9H-fluorene (130 g, 369 mmol), bis(pinacolato)-diborane (225 g, 886 mmol) and potassium acetate (217 g, 2.22 mol) are suspended in 1.4 l of dioxane. The solution is degassed and saturated with argon. PdCl.sub.2(dppf)-CH.sub.2Cl.sub.2 (15 g, 18 mmol) is then added. The reaction mixture is heated at the boil under a protective-gas atmosphere for 4 h. The mixture is filtered and washed with dioxane. After filtration of the crude product, the residue remaining is extracted with THF in a Soxhlet extractor, then filtered. The yield is 137 g (83% of theory) as a grey solid. Purity>95% (NMR in CDCl.sub.3).

(6) The following compounds are prepared analogously:

(7) TABLE-US-00005 Compound Yield Int-b1 83% Int-b2 80% Int-b3 50% Int-b4 0 75% Int-b5 85% Int-b6 90% Int-b7 80% Int-b8 70%

(8) Compound I

(9) 2,7-Bispinacolato-9,9-dimethyl-9H-fluorene (137 g, 307 mmol), 1-bromonaphthalene-2-carboxylic acid (173 g, 620 mmol) and tripotassium phosphate monohydrate (283 g, 1.23 mol) are suspended in a water/toluene/dioxane mixture (1:1:1, 1.5 l). The solution is degassed and saturated with argon. Tri(o-tolyl)phosphine (22.4 g, 73 mmol) and palladium(II) acetate (2.76 g, 12.3 mmol) are then added. The reaction mixture is heated at the boil under a protective-gas atmosphere for 5.5 h. The phases are separated, and the aqueous phase is washed with toluene. The organic phase is dried over Na.sub.2SO.sub.4 and evaporated in a rotary evaporator. The mixture is filtered through silica gel and AlOx with toluene and evaporated in a rotary evaporator. The yellow oil is dried in a vacuum drying cabinet and is not purified.

(10) The yellow oil in 500 ml of THF is added dropwise to a mixture of cerium(III) trichloride (166 g, 670 mmol) and 500 ml of THF. The reaction mixture is stirred at room temperature for 1 h, then cooled to 0 C. Methyl-magnesium chloride (813 ml, 3M in THF) is added dropwise at this temperature. The reaction mixture is stirred overnight. 500 ml of water are added to the batch, which is then filtered with THF. The phases of the mother liquor are separated. The organic phase is dried over Na.sub.2SO.sub.4 and evaporated in a rotary evaporator. The yellow oil is dried in a vacuum drying cabinet and is not purified further.

(11) The yellow oil and polyphosphoric acid (446 g, 4.56 mol) are suspended in 1 l of dichloromethane. Methanesulfonic acid (296 ml, 4.56 mol) is slowly added dropwise. The reaction mixture is stirred for 1 h. 700 ml of ethanol are added. The batch is filtered, and the residue remaining is recrystallised from toluene. The yield is 109 g (68% of theory) as a yellow solid. Purity 99.7% (HPLC).

(12) The following compounds are prepared analogously:

(13) TABLE-US-00006 Compound Yield Ia 68% Ib 70% Ic 80% Id 00 59% Ie 01 52% If 02 64% Ig 03 45% Ih 04 48%

(14) Compound Int-c

(15) Ia (80 g, 152 mmol) is dissolved in 500 ml of DCM. Br.sub.2 (16 ml, 311 mmol) in 300 ml of DCM is added dropwise at 0 C. The reaction mixture is stirred at room temperature overnight. 20 ml of sodium thiosulfate solution are added, and the mixture is stirred for 15 min. The batch is filtered with ethanol. The residue remaining is recrystallised three times from toluene. The yield is 60 g (57% of theory) as a grey solid. Purity 96.3% (HPLC).

(16) The following compounds are prepared analogously:

(17) TABLE-US-00007 05 Compound 06 Yield Int-c1 07 57% Int-c2 08 65% Int-c3 09 58% Int-c4 0 50% Int-c5 65% Int-c6 69% Int-c7 48% Int-c8 52%

(18) ##STR00215##

(19) Compound II

(20) Int-c (17 g, 24 mmol), K.sub.4[Fe(CN).sub.6]*3H.sub.2O (10.5 g, 24 mmol) and sodium carbonate (7.9 g, 75 mmol) are suspended in 400 ml of DMF. The solution is degassed and saturated with argon. S-Phos (816 mg, 2 mmol) and palladium(II) acetate (223 mg, 1 mmol) are then added. The reaction mixture is heated at the boil under a protective-gas atmosphere overnight. The reaction mixture is cooled, then evaporated in a rotary evaporator. The resultant solid is extracted with toluene over aluminium oxide in a Soxhlet extractor, then recrystallised 7 from chloroform. The yield is 2.5 g (17.5% of theory) as a grey solid. Purity 99.9% (HPLC).

(21) The following compounds are prepared analogously:

(22) TABLE-US-00008 Compound Yield IIa 17.5% IIb 26% IIc 10% IId 0 11% IIe 8% IIf 21% IIg 8% IIh 10%

(23) ##STR00225##

(24) Compound III

(25) Int-c (800 mg, 1.5 mmol), benzeneboronic acid (342 mg, 3 mmol) and tripotassium phosphate monohydrate (1.08 g, 4.7 mmol) are suspended in a water/toluene/dioxane mixture (1:1:1, 6 ml). The solution is degassed and saturated with argon. Tri(o-tolyl)phosphine (43 mg, 0.14 mmol) and palladium(II) acetate (10 mg, 0.05 mmol) are then added. The reaction mixture is heated at the boil under a protective-gas atmosphere overnight. The phases are separated, and the aqueous phase is washed with toluene. The organic phase is dried over Na.sub.2SO.sub.4 and evaporated in a rotary evaporator. The mixture is filtered through silica gel and AlOx with toluene and evaporated in a rotary evaporator. The solid is recrystallised from toluene. The yield is 505 mg (64% of theory) as a yellow solid. Purity 99% (HPLC).

(26) The following compounds are prepared analogously:

(27) TABLE-US-00009 Compound Yield IIIa 64% IIIb 42% IIIc 59% IIId 0 5% IIIe 12% IIIf 26% IIIg 46% IIIh 8% IIIi 12% IIIj 83% IIIk 21% IIIl 28% IIIm 25% IIIn 0 15% IIIo 78% IIIq 18% IIIr 51%

(28) ##STR00244##

(29) ##STR00245##

(30) Compound Int-d

(31) 2,4-Dimethylphenylamine (1.12 ml, 8.9 mmol), 4-bromodibenzofuran (2 g, 8.1 mmol) and sodium tert-butoxide (1.9 g, 20 mmol) are suspended in 150 ml of toluene. The solution is degassed and saturated with argon. PdCl.sub.2(dppf)-CH.sub.2Cl.sub.2 (132 mg, 162 mmol) is then added. The reaction mixture is heated at the boil under a protective-gas atmosphere overnight. The mixture is filtered through silica gel and AlOx with toluene and evaporated in a rotary evaporator. The oil is purified over a silica-gel column with heptane. The yield is 1.9 g (82% of theory) as a pale-brown oil. Purity 94% (HPLC).

(32) The following compounds are prepared analogously:

(33) TABLE-US-00010 Compound Yield Int-d1 82% Int-d2 30% Int-d3 80% Int-d4 0 85% Int-d5 90% Int-d6 88%

(34) Compounds IVa and IVb

(35) Int-c (1 g, 1.46 mmol), the dibenzofuran compound (903 mg, 3.14 mmol) and sodium tert-butoxide (421 mg, 4.38 mmol) are suspended in 40 ml of toluene. The solution is degassed and saturated with argon. Tri-tert-butyl-phosphine (117 l, 1M in toluene) and palladium(II) acetate (48 mg, 0.06 mmol) are then added. The reaction mixture is heated at the boil under a protective-gas atmosphere for 4 h. The mixture is filtered through silica gel and AlOx with toluene and evaporated in a rotary evaporator. The product is recrystallised three times from toluene. The yield is 200 mg (13% of theory) as a pale-brown oil. Purity 96.7% (HPLC).

(36) TABLE-US-00011 Compound Yield IVa 13% IVb 16% IVc 8% IVd 12% IVe 80% IVf 8% IVg 0 10%

A-2) Variant II

(37) The procedure is in accordance with the following general scheme:

(38) ##STR00261##

(39) Compound V

(40) Int-e (10 g, 20 mmol), K.sub.4[Fe(CN).sub.6]*3H.sub.2O (4.3 g, 10 mmol) and sodium carbonate (3.3 g, 31 mmol) are suspended in 150 ml of DMF. The solution is degassed and saturated with argon. S-Phos (336 mg, 0.82 mmol) and palladium(II) acetate (92 mg, 0.41 mmol) are then added. The reaction mixture is heated at the boil under a protective-gas atmosphere overnight. The reaction mixture is cooled, then evaporated in a rotary evaporator. The resultant solid is extracted with toluene over aluminium oxide in a Soxhlet extractor, then recrystallised 7 from chloroform. The yield is 5.3 g (67% of theory) as a yellow solid. Purity 99.6% (HPLC).

(41) Compound Int-f

(42) Compound V (3 g, 7.7 mmol) is dissolved in 25 ml of DCM. Br.sub.2 (394 l, 7.7 mmol) in 25 ml of DCM is added dropwise at 0 C. The reaction mixture is stirred at room temperature overnight. 10 ml of sodium thiosulfate solution are added, and the mixture is stirred for 15 min. The batch is filtered with ethanol. The residue remaining is recrystallised three times from heptane/toluene 1:1. The yield is 1.7 g (44% of theory) as a yellow solid. Purity 94% (HPLC).

(43) Compound VI

(44) Compound Int-f (1 g, 2.2 mmol), 1-bromonaphthalene-2-carboxylic acid (649 mg, 2.5 mmol) and tripotassium phosphate monohydrate (1.5 g, 6.5 mmol) are suspended in a water/toluene/dioxane mixture (1:1:1, 30 ml). The solution is degassed and saturated with argon. Trio-tolyl)-phosphine (79 mg, 0.3 mmol) and palladium(II) acetate (9.7 mg, 0.04 mmol) are then added. The reaction mixture is heated at the boil under a protective-gas atmosphere for 7 h. The phases are separated, and the aqueous phase is washed with toluene. The organic phase is dried over Na.sub.2SO.sub.4 and evaporated in a rotary evaporator. The mixture is filtered through silica gel and AlOx with toluene and evaporated in a rotary evaporator. The yellow solid is dried in a vacuum drying cabinet and is not purified further.

(45) The yellow solid in 20 ml of THF is added dropwise to a mixture of cerium(III) trichloride (600 mg, 2.37 mmol) and 20 ml of THF. The reaction mixture is stirred at room temperature for 1 h, then cooled to 0 C. Methyl-magnesium chloride (1.25 ml, 3M in THF) is added dropwise at this temperature. The reaction mixture is stirred overnight. 20 ml of water are added to the batch, which is then filtered with THF. The phases of the mother liquor are separated. The organic phase is dried over Na.sub.2SO.sub.4 and evaporated in a rotary evaporator. The yellow solid is dried in a vacuum drying cabinet and is not purified.

(46) The yellow solid and polyphosphoric acid (2.1 g, 21.5 mol) are suspended in 30 ml of dichloromethane. Methanesulfonic acid (1.4 ml, 21.5 mol) is slowly added dropwise. The reaction mixture is stirred for 1 h. 30 ml of ethanol are added. The batch is filtered, and the residue remaining is recrystallised from toluene. The yield is 809 mg (75% of theory) as a yellow solid. Purity 97% (HPLC).

(47) Compound Int-g

(48) Compound VI (809 mg, 1.6 mmol) is dissolved in 25 ml of DCM. Br.sub.2 (83 l, 1.6 mmol) in 25 ml of DCM is added dropwise at 0 C. The reaction mixture is stirred at room temperature overnight. 10 ml of sodium thiosulfate solution are added, and the mixture is stirred for 15 min. The batch is filtered with ethanol. The residue remaining is recrystallised three times from heptane/toluene 1:1. The yield is 790 mg (85% of theory) as a yellow solid. Purity 96% (HPLC).

(49) Compound VII

(50) Int-g (790 mg, 1.3 mmol), benzeneboronic acid (342 mg, 3 mmol) and tripotassium phosphate monohydrate (1.08 g, 4.7 mmol) are suspended in a water toluene/dioxane mixture (1:1:1, 6 ml). The solution is degassed and saturated with argon, Tri(o-tolyl)phosphine (43 mg, 0.14 mmol) and palladium(II) acetate (10 mg, 0.05 mmol) are then added. The reaction mixture is heated at the boil under a protective-gas atmosphere overnight. The phases are separated, and the aqueous phase is washed with toluene. The organic phase is dried over Na.sub.2SO.sub.4 and evaporated in a rotary evaporator. The mixture is filtered through silica gel and AlOx with toluene and evaporated in a rotary evaporator. The solid is recrystallised from toluene. The yield is 675 mg (73% of theory) as a yellow solid. Purity 97% (HPLC).

(51) The following compounds are prepared analogously:

(52) TABLE-US-00012 Compound Yield VIIa 55% VIIb 69%

B) Device Examples: Production of the OLEDs

(53) OLEDs according to the invention and OLEDs in accordance with the prior art are produced by a general process in accordance with WO 04/058911, which is adapted to the circumstances described here (layer-thickness variation, materials).

(54) The data for various OLEDs are presented in the following examples (see Tables 1 to 3). The substrates used are glass substrates which have been coated with structured ITO (indium tin oxide) in a thickness of 50 nm. The OLEDs have in principle the following layer structure: substrate/hole-injection layer1 (95% of HTL1+5% of HIL, 20 nm)/hole-transport layer (HTL, thickness indicated in Table 1)/emission layer (EML, 20 nm) electron-transport layer (ETL, 20 nm)/electron-injection layer (EIL, 3 nm) and finally a cathode. The cathode is formed by an aluminium layer with a thickness of 100 nm. A layer of Clevios P VP AI 4083 (purchased from Heraeus Clevios GmbH, Leverkusen) with a thickness of 20 nm is applied as buffer by spin coating. All remaining materials are applied by thermal vapour deposition in a vacuum chamber. The structure of the OLEDs is shown in Table 1. The materials used are shown in Table 3.

(55) The emission layer (EML) always consists of at least one matrix material (host=H) and an emitting compound (dopant=D), which is admixed with the matrix material in a certain proportion by volume by co-evaporation. An expression such as H1:D1 (97%:3%) here means that material H1 is present in the layer in a proportion by volume of 97% and D1 is present in the layer in a proportion of 3%.

(56) The OLEDs are characterised by standard methods. For this purpose, the electroluminescence spectra are recorded, the current efficiency (measured in cd/A) and the external quantum efficiency (EQE, measured in percent as a function of the luminous density assuming Lambert emission characteristics are calculated from current/voltage/luminous density characteristic lines (IUL characteristic lines), and finally the lifetime of the components is determined. The electroluminescence spectra are recorded at a luminous density of 1000 cd/m.sup.2, and the CIE 1931 x and y colour coordinates are calculated therefrom. The expression EQE @ 1000 cd/m.sup.2 denotes the external quantum efficiency at an operating luminous density of 1000 cd/m.sup.2. The lifetime LT95 @ 1000 cd/m.sup.2 is the time which passes until the initial luminance has dropped by 5% from 1000 cd/m.sup.2. The data obtained for the various OLEDs are summarised in Table 2.

(57) Use of the Compounds According to the Invention as Emitters in Fluorescent OLEDs

(58) Compounds D3, D4, D5, D6, D7, D8, D9, D10, D11 and D12 according to the invention are employed individually as emitters in the emitting layer of OLEDs (structure see Table 3). The matrix material used in the emitting layer here is compound V-H2. The OLEDs obtained are E4 to E6 and E9 to E15. They exhibit a very good lifetime in the case of deep-blue emission (Table 2). Compared with emitter materials known from the prior art (V-D1 and V-D2, cf. V1 to V3), the lifetime is considerably improved, with constant quantum efficiency.

(59) In particular the comparison with material V-D1 shows the improvement achieved by the bisindenofluorene basic structure according to the invention compared with the indenofluorene basic structure known from the prior art.

(60) Use of the Compounds According to the Invention as Matrix Materials in Fluorescent OLEDs

(61) Example E7, in which compound H3 according to the invention is employed as matrix material, likewise exhibits a good lifetime and quantum efficiency in the case of deep-blue emission (Table 2). This confirms the good suitability of the compounds according to the invention as matrix materials in the emitting layer.

(62) Use of the Compounds According to the Invention as Hole-Transport Materials in OLEDs

(63) Example E8, in which compound H3 according to the invention is employed as hole-transport material in the hole-transport layer, likewise exhibits a good lifetime and quantum efficiency in the case of deep-blue emission (Table 2). This confirms the good suitability of the compounds according to the invention as hole-transporting compounds.

(64) TABLE-US-00013 TABLE 1 Structure of the OLEDs HTL Material EML Ex. Thickness/nm Material V1 HTL3 V-H1(97%):V-D1(3%) 195 nm V2 HTL3 V-H2(97%):V-D1(3%) 195 nm V3 HTL3 V-H2(97%):V-D2(3%) 195 nm E4 HTL3 V-H2(97%):D3(3%) 195 nm E5 HTL3 V-H2(97%):D4(3%) 195 nm E6 HTL3 V-H2(97%):D5(3%) 195 nm E7 HTL2 H3(95%):D3(1%) 20 nm E8 D3 V-H2(95%)V-D2(5%) 20 nm E9 HTL3 V-H2(97%):D6(3%) 195 nm E10 HTL3 V-H2(97%):D7(3%) 195 nm E11 HTL3 V-H2(97%):D8(3%) 195 nm E12 HTL3 V-H2(97%):D9(3%) 195 nm E13 HTL3 V-H2(97%):D10(3%) 195 nm E14 HTL3 V-H2(97%):D11(3%) 195 nm E15 HTL3 V-H2(97%):D12(3%) 195 nm

(65) TABLE-US-00014 TABLE 2 Data of the OLEDs EQE @ LT95 @ 1000 cd/m.sup.2 1000 cd/m.sup.2 CIE Ex. % [h] x y V1 7.5 90 0.13 0.13 V2 7.8 110 0.13 0.14 V3 7.9 90 0.13 0.10 E4 7.4 350 0.14 0.11 E5 7.6 320 0.14 0.14 E6 6.9 150 0.14 0.13 E7 6.9 120 0.13 0.13 E8 7.3 140 0.13 0.14 E9 7.0 140 0.14 0.11 E10 7.2 370 0.14 0.14 E11 7.8 140 0.13 0.10 E12 7.6 280 0.14 0.25 E13 7.5 270 0.13 0.09 E14 7.3 280 0.14 0.11 E15 7.8 350 0.14 0.26

(66) TABLE-US-00015 TABLE 3 Structures of the materials used HIL ETL HTL1 EIL HTL2 0 HTL3 V-H1 V-H2 V-D1 V-D2 D3 D4 D5 H3 D6 0 D7 D8 D9 D10 D11 D12