Materials for organic electroluminescent devices

Abstract

The present invention relates to compounds of the formula (1) which are suitable for use in electronic devices, in particular organic electroluminescent devices, and to electronic devices which comprise these compounds.

Claims

1. A compound of formula (1), ##STR00394## where the following applies to the symbols and indices used: Ar is, identically or differently on each occurrence, an aromatic ring system selected from the group consisting of benzene, naphthalene, phenanthrene, fluorene, spirobifluorene, dibenzofuran and dibenzothiophene, each of which is optionally substituted by one or more radicals R.sup.1; Ar is optionally connected to Ar.sup.1 and/or to Ar.sup.2 by a group E; Ar.sup.1 and Ar.sup.2 are, identically or differently on each occurrence, an aromatic or heteroaromatic ring system having 6 to 60 C atoms selected from the group consisting of benzene, naphthalene, phenanthrene, dibenzofuran and dibenzothiophene, each of which is optionally substituted by one or more radicals R.sup.1, or unsubstituted spirobifluorene or a combination of two, three, four or five of these groups, which may in each case be identical or different; or Ar.sup.1 and Ar.sup.2 are, identically or differently on each occurrence, selected from formulae (9), (21), (26) or (27), where the dashed bond indicates the position of the bond to the nitrogen, and in each instance, Ar.sup.1 and Ar.sup.2 is optionally connected to one another, and/or Ar.sup.1 is optionally connected to Ar, and/or Ar.sup.2 is optionally connected to Ar, by a group E; ##STR00395## E is, identically or differently on each occurrence, selected from the group consisting of C(R.sup.1).sub.2, O, S and NR.sup.1; R is on each occurrence, identically or differently, H, D, F, Cl Br, I, CN, Si(R.sup.2).sub.3, a straight-chain alkyl group having 1 to 40 C atoms or a branched or cyclic alkyl group having 3 to 40 C atoms, each of which is optionally substituted by one or more radicals R.sup.2, where in each case one or more non-adjacent CH.sub.2 groups is optionally replaced by Si(R.sup.2).sub.2, CNR.sup.2, or CONR.sup.2, and where one or more H atoms is optionally replaced by D, F, Cl, Br or I, an aromatic or heteroaromatic ring system having 6 to 60 C atoms selected from the group consisting of benzene, naphthalene, phenanthrene, fluorene, spirobi-fluorene, dibenzofuran and dibenzothiophene, which may in each case be substituted by one or more radicals R.sup.2, or a combination of two, three, four or five of these groups, which may in each case be identical or different, an aryloxy group having 5 to 60 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.2, or an aralkyl group having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.2, where two or more adjacent substituents R or two or more adjacent substituents R.sup.1 may optionally form a mono- or polycyclic, aliphatic ring system, which is optionally substituted by one or more radicals R.sup.2; R.sup.1 is on each occurrence, identically or differently, H, D, F, CN, a straight-chain alkyl group having 1 to 40 C atoms or a branched or cyclic alkyl group having 3 to 40 C atoms, or an aromatic ring or heteroaromatic ring system having 6 to 60 C atoms selected from the group consisting of benzene, naphthalene, phenanthrene, dibenzofuran, and dibenzothiophene, or a combination of two, three, four or five of these groups, which may in each case be identical or different; R.sup.2 is on each occurrence, identically or differently, H, D, F, Cl, Br, I, Si(R.sup.3).sub.3, a straight-chain alkyl group having 1 to 40 C atoms or a branched or cyclic alkyl group having 3 to 40 C atoms, each of which is optionally substituted by one or more radicals R.sup.3, where one or more non-adjacent CH.sub.2 groups is optionally replaced by Si(R.sup.3).sub.2, CNR.sup.3 or CONR.sup.3 and where one or more H atoms is optionally replaced by D, F, Cl, Br or I, an aromatic ring system having 6 to 60 C atoms selected from the group consisting of benzene, naphthalene, phenanthrene, fluorene, spirobifluorene or a combination of two, three, four or five of these groups, which may in each case be identical or different, which may in each case be substituted by one or more radicals R.sup.3, an aryloxy group having 5 to 60 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.3, or an aralkyl group having 5 to 60 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.3, where two or more adjacent substituents R.sup.2 may optionally from a mono- or polycyclic, aliphatic ring system, which is optionally substituted by one or more radicals R.sup.3; R.sup.3 is selected from the group consisting of H, D, F, an aliphatic hydrocarbon radical having 1 to 20 C atoms, an aromatic ring system having 6 to 30 C atoms, in which one or more H atoms is optionally replaced by D or F, where two or more adjacent substituents R.sup.3 may form a mono- or polycyclic, aliphatic ring system with one another; m is 0, 1, 2 or 3; n is on each occurrence, identically or differently, 0, 1, 2, 3 or 4; p is 0, 1 or 2; wherein the compound of formula (1) is a mono-amine compound, and wherein the following compounds are excluded from the invention: ##STR00396##

2. The compound according to claim 1 of the formula (2), formula (3a), (3b), (4a) or formula (4b) ##STR00397## where symbols and indices used have the meanings given in claim 1.

3. The compound according to claim 1, wherein the groups Ar.sup.1 and Ar.sup.2 are selected, identically or differently on each occurrence, from the groups of the formulae (5) to (28), ##STR00398## ##STR00399## ##STR00400## ##STR00401## where symbols used have the meanings given in claim 1, and the dashed bond indicates the position of the bond from the group to the nitrogen.

4. The compound according to claim 1, wherein the groups Ar.sup.1 and Ar.sup.2 are selected, identically or differently on each occurrence, from the groups of the formulae (5a) to (28a), ##STR00402## ##STR00403## ##STR00404## where symbols used have the meanings given in claim 1, and the dashed bond indicates the position of the bond from the group to the nitrogen.

5. The compound according to claim 3, wherein Ar.sup.1 is a group of the formula (6), (7), (8), (9) or (21).

6. The compound according to claim 4, wherein Ar.sup.1 is a group of the formula (6a), (7a), (8a), (9a) or (21a).

7. The compound according to claim 1, wherein the groups Ar.sup.1 and Ar.sup.2 are different from one another.

8. The compound according to claim 1, wherein the group NAr.sup.1Ar.sup.2 has the structure of one of the formulae (29), (30), (31) or (32) or in that the group ArNAr.sup.1Ar.sup.2 has the structure of one of the formulae (33), (34), (35) or (36), ##STR00405## where symbols used have the meanings given in claim 1, and the dashed bond indicates the bond to the spirobifluorene or to Ar; ##STR00406## where symbols used have the meanings given in claim 1, and the dashed bond indicates the bond to the spirobifluorene.

9. The compound according to claim 1, wherein the group (Ar).sub.pstands for a group of one of the formulae (37) to (50), ##STR00407## ##STR00408## where symbols used have the meanings given in claim 1, and one dashed bond indicates the bond to the spirobifluorene and the other dashed bond indicates the bond to the nitrogen atom.

10. The compound according to claim 3, wherein Ar is, identically or differently on each occurrence, an aromatic ring system, where, for p=1 or 2, (Ar).sub.pis selected from the groups of the formulae (37) to (50); Ar here may also be connected to Ar.sup.1 and/or Ar.sup.2 by a group E; Ar.sup.1 and Ar.sup.2 are, identically or differently on each occurrence, an aromatic ring system selected from the groups of the formulae (5) to (28); or NAr.sup.1Ar.sup.2 stands for a group of one of the formulae (29) to (32); or ArNAr.sup.1Ar.sup.2 stands for a group of one of the formulae (33) to (36); ##STR00409## ##STR00410## E is on each occurrence, identically or differently, C(R.sup.1).sub.2, N(R.sup.1), O or S; R is selected on each occurrence, identically or differently, from the group consisting of H, D, F, Si(R.sup.2).sub.3, a straight-chain alkyl or alkoxy group having 1 to 10 C atoms or a branched or cyclic alkyl or alkoxy group having 3 to 10 C atoms, each of which is optionally substituted by one or more radicals R.sup.2, where one or more non-adjacent CH.sub.2 groups is optionally replaced by O and where one or more H atoms is optionally replaced by D or F, an aromatic ring system having 6 to 60 C atoms selected from the group consisting of benzene, naphthalene, phenanthrene, fluorene, spirobifluorene or a combination of two or three of these groups, which may in each case be identical or different, which may in each case be substituted by one or more radicals R.sup.2, where two or more adjacent substituents R may optionally form a mono- or polycyclic, aliphatic ring system, which is optionally substituted by one or more radicals R.sup.2; R.sup.1 is, if the radical R.sup.1 is bonded to Ar.sup.1 or Ar.sup.2, selected, identically or differently on each occurrence, from the group consisting of H, D, a straight-chain alkyl group having 1 to 10 C atoms or a branched or cyclic alkyl group having 3 to 10 C atoms; or R.sup.1 which is bonded to the carbon bridge in formula (29) or (33) is selected, identically or differently on each occurrence, from the group consisting of a straight-chain alkyl group having 1 to 10 C atoms, a branched or cyclic alkyl group having 3 to 10 C atoms or an aromatic ring system having 6 to 30 C atoms, which is optionally substituted by one or more radicals R.sup.2; the two radicals R.sup.1 here may also form an aliphatic or aromatic ring system with one another; or R.sup.1 which is bonded to the nitrogen bridge in formula (32) or (36) is selected from the group consisting of a straight-chain alkyl group having 1 to 10 C atoms, a branched or cyclic alkyl group having 3 to 10 C atoms or an aromatic ring system having 6 to 30 C atoms, which is optionally substituted by one or more radicals R.sup.2; R.sup.2 is selected on each occurrence, identically or differently, from the group consisting of H, D, a straight-chain alkyl group having 1 to 5 C atoms or a branched or cyclic alkyl group having 3 to 5 C atoms, or an aromatic ring system having 6 to 18 C atoms; R.sup.3 is selected from the group consisting of H, D, F, an aliphatic hydrocarbon radical having 1 to 10 C atoms, an aromatic ring system having 6 to 24 C atoms, in which one or more H atoms is optionally replaced by D or F, where two or more adjacent substituents R.sup.3 may form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system with one another; m is 0, 1 or 2; n is on each occurrence, identically or differently, 0, 1 or 2; p is 0, 1 or 2.

11. A process for the preparation of the compound according to claim 1 which comprises coupling a spirobifluorene derivative which is substituted in the 2-position by a reactive leaving group to a) a primary amine, followed by coupling to a further aromatic group which is substituted by a reactive leaving group, or b) to a secondary amine, or c) to a triarylamine derivative.

12. A formulation, comprising at least one compound according to claim 1 and at least one solvent.

13. A solution, dispersion or mini-emulsion comprising at least one compound according to claim 1 and at least one organic solvent.

14. A mixture comprising at least one compound according to claim 1 and at least one further compound.

15. An electronic device comprising the compound according to claim 1.

16. An electronic device comprising the formulation according to claim 12.

17. The electronic device according to claim 15, wherein the electronic device is an organic electroluminescent device (organic light-emitting diode, OLED), an organic integrated circuit (O-IC), an organic field-effect transistor (O-FET), an organic thin-film transistor (O-TFT), an organic light-emitting transistor (O-LET), an organic solar cell (O-SC), an organic dye-sensitised solar cell (ODSSC), an organic optical detector, an organic photoreceptor, na organic field-quench device (O-FQD), a light-emitting electrochemical cell (LEC), an organic laser diode (O-laser) or an organic plasmon emitting device.

18. The electronic device according to claim 16, wherein the electronic device is an organic electroluminescent device (organic light-emitting diode, OLED), an organic integrated circuit (O-IC), an organic field-effect transistor (O-FET), an organic thin-film transistor (O-TFT), an organic light-emitting transistor (O-LET), an organic solar cell (O-SC), an organic dye-sensitised solar cell (ODSSC), an organic optical detector, an organic photoreceptor, na organic field-quench device (O-FQD), a light-emitting electrochemical cell (LEC), an organic laser diode (O-laser) or an organic plasmon emitting device.

19. An organic electroluminescent device, wherein the compound according to claim 1 is employed as hole-transport material in a hole-transport or hole-injection or exciton-blocking layer or as matrix material for fluorescent or phosphorescent emitters.

20. An organic electroluminescent device, wherein the mixture according to claim 14 is employed as hole-transport material in a hole-transport or hole-injection or exciton-blocking layer or as matrix material for fluorescent or phosphorescent emitters.

21. The compound according to claim 1, wherein at least one of the groups Ar.sup.1 and Ar.sup.2 is an unsubstituted spirobifluorene.

22. The compound according to claim 1, wherein R is selected, identically or differently on each occurrence, from the group consisting of H, D, a straight-chain alkyl group having 1 to 10 C atoms or a branched or cyclic alkyl group having 3 to 10 C atoms, each of which may be substituted by one or more radicals R.sup.2, an aromatic ring system having 6 to 60 C atoms selected from the group consisting of benzene, naphthalene, phenanthrene, fluorene, spirobifluorene or a combination of two or three of these groups, which may in each case be identical or different, which may in each case be substituted by one or more radicals R.sup.2; R.sup.2 is selected, identically or differently on each occurrence, from the group consisting of H, D, a straight-chain alkyl group having 1 to 10 C atoms or a branched or cyclic alkyl group having 3 to 10 C atoms or an aromatic ring system having 6 to 30 C atoms, which is as defined above and which may in each case be substituted by one or more radicals R.sup.3; and R.sup.3 is selected from the group consisting of H, D, F, an aliphatic hydrocarbon radical having 1 to 20 C atoms, and an aromatic ring system having 6 to 30 C atoms, in which one or more H atoms may be replaced by D or F.

Description

EXAMPLES

(1) The following syntheses are carried out under a protective-gas atmosphere, unless indicated otherwise. The starting materials can be purchased from ALDRICH or ABCR. The numbers in square brackets in the case of the starting materials known from the literature are the corresponding CAS numbers.

A1) Biphenyl-2-yl-(9,9-spirobi-9H-fluoren-2-yl)amine

(2) ##STR00225##

(3) 1,1-Bis(diphenylphosphino)ferrocene (5.89 g, 10.6 mmol), palladium acetate (2.38 g, 10.6 mmol) and sodium tert-butoxide (88.6 g, 921 mmol) are added to a solution of biphenyl-2-ylamine (119.9 g, 709 mmol) and 2-bromo-9,9-spirobifluorene (280.3 g, 709 mmol) in degassed toluene (400 ml), and the mixture is heated under reflux for 20 h. The reaction mixture is cooled to room temperature, diluted with toluene and filtered through Celite. The filtrate is diluted with water and re-extracted with toluene, and the combined organic phases are dried and evaporated in vacuo. The residue is filtered through silica gel (heptane/dichloromethane) and crystallised from isopropanol. The product is obtained in the form of a pale-yellow solid. The yield is 298 g (87%).

(4) The following compounds are obtained analogously:

(5) TABLE-US-00004 Starting Starting Ex. material 1 material 2 Product Yield A2 90% A3 0 87% A4 68% A5 69% A6 0 83% A7 89% A8 65% A9 87% A10 0 74% A11 77%

B1) Biphenyl-4-ylbiphenyl-2-yl-(9,9-spirobi-9H-fluoren-2-yl)amine

(6) ##STR00256##

(7) Tri-tert-butylphosphine (4.4 ml of a 1.0 M solution in toluene, 4.4 mmol), palladium acetate (248 mg, 1.1 mmol) and sodium tert-butoxide (16.0 g, 166 mmol) are added to a solution of biphenyl-2-yl-(9,9-spirobi-9H-fluoren-2-yl)amine (53.0 g, 110 mmol) and 4-bromobiphenyl (32 g, 140 mmol) in degassed toluene (500 ml), and the mixture is heated under reflux for 2 h. The reaction mixture is cooled to room temperature, diluted with toluene and filtered through Celite. The filtrate is evaporated in vacuo, and the residue is crystallised from ethyl acetate/heptane. The crude product is extracted in a Soxhlet extractor (toluene) and purified by zone sublimation in vacuo twice (p=310.sup.4 mbar, T=298 C.). The product is isolated in the form of a pale-yellow solid (60 g, 87% of theory, purity >99.99% according to HPLC).

(8) The following compounds are obtained analogously:

(9) TABLE-US-00005 Starting Starting Ex. material 1 material 2 Product Yield B2 70% B3 0 72% B4 79% B5 77% B6 0 68% B7 68% B8 68% B9 0 63% B10 64% B11 65% B12 89% B13 0 65% B14 69% B15 65% B16 00 01 77% B17 comp. 02 03 04 77% B18 05 06 07 65% B19 08 09 0 65% B20 59% B21 61% B22 78% B23 0 77% B24 64% B25 69% B26 0 66% B27 75%

Example C

Synthesis of biphenyl-2-yl-(9,9-dimethyl-9H-fluoren-2-yl)-(9,9-spirobifluoren-2-yl)amine

(10) ##STR00335##

a) Biphenyl-2-yl-(9,9-dimethyl-9H-fluoren-2-yl)amine

(11) 1,1-Bis(diphenylphosphino)ferrocene (1.5 g, 2.7 mmol), palladium acetate (616 mg, 2.7 mmol) and sodium tert-butoxide (22.9 g, 238 mmol) are added to a solution of biphenyl-2-ylamine (31.0 g, 183 mmol) and 2-bromo-9,9-dimethyl-9H-fluorene (50.0 g, 183 mmol) in degassed toluene (400 ml), and the mixture is heated under reflux for 20 h. The reaction mixture is cooled to room temperature, diluted with toluene and filtered through Celite. The filtrate is diluted with water and re-extracted with toluene, and the combined organic phases are dried and evaporated in vacuo. The residue is filtered through silica gel (heptane/dichloromethane) and crystallised from isopropanol, giving biphenyl-2-yl-(9,9-dimethyl-9H-fluoren-2-yl)amine in the form of a pale-yellow solid (63.0 g, 95% of theory).

b) Biphenyl-2-yl-(9,9-dimethyl-9H-fluoren-2-yl)-(9,9-spirobifluoren-2-yl)amine

(12) Tri-tert-butylphosphine (4.4 ml of a 1.0 M solution in toluene, 4.4 mmol), palladium acetate (248 mg, 1.1 mmol) and sodium tert-butoxide (16.0 g, 166 mmol) are added to a solution of biphenyl-2-yl-(9,9-dimethyl-9H-fluoren-2-yl)amine (40.0 g, 111 mmol) and 2-bromo-9,9-spirobifluorene (56.9 g, 144 mmol) in degassed toluene (500 ml), and the mixture is heated under reflux for 2 h. The reaction mixture is cooled to room temperature, diluted with toluene and filtered through Celite. The filtrate is evaporated in vacuo, and the residue is crystallised from ethyl acetate/heptane. The crude product is extracted in a Soxhlet extractor (toluene) and purified by zone sublimation in vacuo twice (p=310.sup.4 mbar, T=298 C.). Biphenyl-2-yl-(9,9-dimethyl-9H-fluoren-2-yl)-(9,9-spirobifluoren-2-yl)amine is isolated in the form of a pale-yellow solid (20.4 g, 27% of theory, purity >99.99% according to HPLC).

(13) The following compounds can be obtained analogously:

(14) TABLE-US-00006 Starting Starting Ex. material 1 material 2 C1 C2 0 C3 C4 C5 0 C6 C7 Ex. Product Yield C1 73% C2 75% C3 79% C4 0 78% C5 65% C6 70% C7 80%

Example D

2-(9,9-Spirobi(9H-fluorene))-9,9-dimethyl-10-phenyl-9,10-dihydroacridine

(15) ##STR00364##

a) Synthesis of 2-chloro-9,9-dimethyl-9,10-dihydroacridine

(16) 30.3 g (116 mmol) of 2-[2-(4-chlorophenylamino)phenyl]propan-2-ol are dissolved in 700 ml of degassed toluene, a suspension of 93 g of polyphosphoric acid and 61.7 g of methanesulfonic acid is added, and the mixture is stirred at room temperature for 1 h and heated at 50 C. for 1 h. The batch is cooled, added to ice and extracted three times with ethyl acetate. The combined organic phases are washed with saturated sodium chloride solution, dried over magnesium sulfate and evaporated. Filtration of the crude product through silica gel with heptane/ethyl acetate (20:1) gives 25.1 g (89%) of 2-chloro-9,9-dimethyl-9,10-dihydroacridine as pale-yellow crystals.

b) Synthesis of 2-chloro-9,9-dimethyl-10-phenyl-9,10-dihydroacridine

(17) A degassed solution of 16.6 ml (147 mmol) of 4-iodobenzene and 30 g (123 mmol) of 2-chloro-9,9-dimethyl-9,10-dihydroacridine in 600 ml of toluene is saturated with N.sub.2 for 1 h. Then, firstly 2.09 ml (8.6 mmol) of P(tBu).sub.3, then 1.38 g (6.1 mmol) of palladium(II) acetate are added, and subsequently 17.7 g (185 mmol) of NaOtBu in the solid state are added to the solution. the reaction mixture is heated under reflux for 1 h. After the mixture has been cooled to room temperature, 500 ml of water are carefully added. The aqueous phase is washed with 350 ml of toluene and dried over MgSO.sub.4, and the solvent is removed in vacuo. Filtration of the crude product through silica gel with heptane/ethyl acetate (20:1) gives 32.2 g (81%) of 2-chloro-9,9-dimethyl-10-phenyl-9,10-dihydroacridine as pale-yellow crystals.

c) Synthesis of 2-(9,9-spirobi(9H-fluorene))-9,9-dimethyl-10-phenyl-9,10-dihydroacridine

(18) 39.6 g (110 mmol) of 9,9-spirobi[9H-fluoren]-2-ylboronic acid, 35.2 g (110 mmol) of 2-chloro-9,9-dimethyl-10-phenyl-9,10-dihydroacridine and 9.7 g (92 mmol) of sodium carbonate are suspended in 350 ml of toluene, 350 ml of dioxane and 500 ml of water. 913 mg (3.0 mmol) of tri-o-tolyl-phosphine and 112 mg (0.5 mmol) of palladium(II) acetate are added to this suspension, and the reaction mixture is heated under reflux for 16 h. After cooling, the organic phase is separated off, filtered through silica gel, washed three times with 200 ml of water and subsequently evaporated to dryness. The residue is recrystallised from toluene and from CH.sub.2Cl.sub.2/isopropanol and finally sublimed in a high vacuum.

(19) Yield: 52 g (100 mmol), 79% of theory, purity according to HPLC 99.9%.

Example E

Production of OLEDs

(20) OLEDs according to the invention and OLEDs in accordance with the prior art are produced by a general process in accordance with WO 2004/058911, which is adapted to the circumstances described here (layer-thickness variation, materials).

(21) The data for various OLEDs are presented in Examples C1-I68, Sol1-3 below (see Tables 1 and 2). Glass plates coated with structured ITO (indium tin oxide) in a thickness of 150 nm are coated with 20 nm of PEDOT (poly(3,4-ethylenedioxy-2,5-thiophene), applied by spin coating from water; purchased from H.C. Starck, Goslar, Germany) for improved processing. These coated glass plates form the substrates to which the OLEDs are applied. The OLEDs basically have the following layer structure: substrate/optional hole-injection layer (HIL)/hole-transport layer (HTL)/optional interlayer 1 (IL1)/optional interlayer 2 (IL2)/electron-blocking layer (EBL)/emission layer (EML)/optional hole-blocking layer (HBL)/electron-transport layer (ETL)/optional electron-injection layer (EIL) and finally a cathode. The cathode is formed by an aluminium layer with a thickness of 100 nm. The precise structure of the OLEDs is shown in Table 1. The materials required for the production of the OLEDs are shown in Table 3.

(22) All materials are applied by thermal vapour deposition in a vacuum chamber. The emission layer here always consists of at least one matrix material (host material) and an emitting dopant (emitter), with which the matrix material or matrix materials is (are) mixed by co-evaporation in a certain proportion by volume. An expression such as Ket1:FTPh:TEG1 (60%:30%:10%) here means that material Ket1 is present in the layer in a proportion by volume of 60%, FTPh is present in the layer in a proportion of 30% and TEG1 is present in the layer in a proportion of 10%. Analogously, the electron-transport layer may also consist of a mixture of two materials.

(23) The OLEDs are characterised by standard methods. 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 the luminous density, calculated from current/voltage/luminous density characteristic lines (IUL characteristic lines), and the lifetime are determined. The electroluminescence spectra are determined at a luminous density of 1000 cd/m.sup.2, and the CIE 1931 x and y colour coordinates are calculated therefrom. The expression U1000 in Table 2 denotes the voltage required for a luminous density of 1000 cd/m.sup.2. CE1000 and PE1000 denote the current and power efficiency respectively achieved at 1000 cd/m.sup.2. Finally, EQE1000 is the external quantum efficiency at an operating luminous density of 1000 cd/m.sup.2. The lifetime LT is defined as the time after which the luminous density has dropped from the initial luminous density L0 to a certain proportion L1 on operation at constant current. The expressions L0=4000 cd/m.sup.2 and L1=80% in Table 2 mean that the lifetime indicated in column LT corresponds to the time after which the initial luminous density of the corresponding OLED has dropped from 4000 cd/m.sup.2 to 3200 cd/m.sup.2. The values for the lifetime can be converted into a figure for other initial luminous densities with the aid of conversion formulae known to the person skilled in the art. The lifetime for an initial luminous density of 1000 cd/m.sup.2 is the usual specification here.

(24) The data for the various OLEDs are summarised in Table 2. Examples C1-C20 are comparative examples in accordance with the prior art, while Examples I1-I68 and Sol1-3 show data for OLEDs comprising materials according to the invention.

(25) Some of the examples are explained in greater detail below in order to illustrate the advantages of the compounds according to the invention. However, it should be pointed out that this only represents a selection of the data shown in Table 2. As can be seen from the table, significant improvements over the prior art are also achieved on use of the compounds according to the invention that are not mentioned in greater detail, in some cases in all parameters, but in some cases only an improvement in efficiency or voltage or lifetime can be observed. However, even the improvement of one of the said parameters represents a significant advance since different applications require optimisation with respect to different parameters.

(26) Use of Compounds According to the Invention as Hole-transport Materials

(27) OLEDs C1-C5 and C13-C20 are comparative examples which comprise hole-transport materials BPA1, NPB, CbzA1 and SpA-tb in accordance with the prior art. The materials according to the invention employed are compounds B1-B8, B10-B21, B23-B25, C, C1-C2, C4-C7 and D (Examples I1, I3, I6-I12, I15-I20, I22, I24-I31, I33-I68).

(28) The use of materials according to the invention gives, in particular, significant improvements in the current efficiency and lifetime. The operating voltage remains approximately the same compared with the prior art, which, owing to the improved current efficiency, results in an improvement in the power efficiency. Thus, for example, the use of compound B11 in an OLED comprising the blue-fluorescent dopant D1 gives an increase in the power efficiency of about 35% compared with NPB (Examples I17, C1).

(29) The lifetime can be increased by almost 70% compared with NPB if compound C is used (Examples I30, C2).

(30) In the case of the use of thicker layers, which can be employed, for example, for optimisation of the optical coupling-out efficiency and for improving the product yield, the materials according to the invention likewise exhibit advantages: whereas an increase in the layer thickness from 20 to 70 nm results in an increase in voltage of 0.6 V with compound SpA-tb, which contains a tert-butyl-substituted spirobifluorene, the voltage remains virtually unchanged in the case of the use of compound C (Examples C19, C20, I61, I62). Only a moderate increase in the voltage of 0.2 V is also obtained in the case of the use of compound C5, which contains only a substituted spirobifluorene. The same applies to compound B16, which contains two unsubstituted spirobifluorene units (Examples I63-I66).

(31) Use of Compounds According to the Invention as Matrix Materials in Phosphorescent OLEDs

(32) The materials according to the invention can also be employed as a component in mixed-matrix systems. In a mixed matrix, a first matrix component is mixed with a second matrix component and a dopant, which offers, in particular, an improvement in the lifetime compared with the single-matrix materials. In this case, however, an increase in the operating voltage and a reduction in the efficiency compared with single-matrix materials frequently arise in accordance with the prior art. The use of the compounds according to the invention enables improvements to be achieved here.

(33) Compared with CBP, an improvement in the voltage by 0.7 V, for example, is obtained through the use of B13 in combination with ST1, which is evident from a significant increase in the power efficiency by about 20% (Examples I23, C7). An improvement in the lifetime by about 50% arises through the replacement of CBP by compound B2 in a mixed matrix with Ket1 as the second component (Examples I5, C9). In combination with DAP1, the use of compound B9 likewise gives a significant improvement in the power efficiency (Examples I14, C12). This shows that the materials according to the invention can profitably be combined with very different classes of material in a mixed matrix.

(34) In combination with the red dopant TER1, good performance data (Example C6) are already obtained with material TSpA1. If materials B1 and B18 in accordance with the prior art are used, a further improvement can be achieved (Examples I2, I32). In particular, material B1, which contains only one spiro unit, exhibits an improvement of about 30% in the lifetime and 20% in the power efficiency compared with TSpA1 (Examples I2, C6).

(35) Use of Compounds According to the Invention as Solution-processed HTM

(36) Films with a thickness of 40 nm are produced on various substrates by spin coating from a formulation of 10 mg/ml of substance C in toluene. The sample is subsequently dried by heating at a temperature of 180 C. on a hotplate for 10 min. The sample is subsequently introduced into a vacuum evaporation unit, and an emission layer with a thickness of 30 nm consisting of M2:D4 (95%:5%) is applied by vapour deposition. An electron-transport layer having a thickness of 20 nm comprising ST2:LiQ (50%:50%) is subsequently applied by vapour deposition, and finally a cathode with a thickness of 100 nm comprising aluminium is applied by vapour deposition.

(37) Example Sol1: The layer sequence described is applied to the following substrate: ITO with a thickness of 50 nm on glass, to which a PEDOT layer with a thickness of 20 nm has been applied. The PEDOT layer is applied by spin coating from water as described above.

(38) Example Sol2: The layer sequence described is applied to the following substrate: ITO with a thickness of 50 nm on glass, to which an HAT-CN layer with a thickness of 20 nm has been applied. The HAT-CN layer is applied by evaporation in a vacuum unit.

(39) Example Sol3: The production is carried out as in the case of Sol2, with the exception that ST2:LiQ is replaced by material ETM2 as electron-transport layer and an LiF layer with a thickness of 1.5 nm as electron-injection layer.

(40) As revealed by Table 2, good to very good data are obtained with substance C processed from solution, in particular if the material is applied to an HAT-CN layer.

(41) TABLE-US-00007 TABLE 1 Structure of the OLEDs HIL HTL IL1 IL2 EBL EML HBL ETL EIL Ex. thickness thickness thickness thickness thickness thickness thickness thickness thickness C1 HATCN SpA1 NPB M1:D1 (95%:5%) Alq3 LiF 5 nm 140 nm 20 nm 30 nm 20 nm 1 nm C2 HATCN SpA1 NPB M1:D1 (95%:5%) ETM1:LiQ 5 nm 140 nm 20 nm 30 nm (50%:50%) 20 nm C3 HATCN SpA1 NPB M2:D2 (90%:10%) Alq.sub.3 LiF 5 nm 110 nm 20 nm 30 nm 20 nm 1 nm C4 HATCN SpNPB NPB M2:D3 (98.5%:1.5%) ST2:LiQ 5 nm 40 nm 20 nm 30 nm (50%:50%) 20 nm C5 SpA1 HATCN BPA1 Ket1:TEG1 (90%:10%) ST1:LiQ 70 nm 5 nm 90 nm 30 nm (50%:50%) 40 nm C6 SpA1 NPB Ket1:TSpA1:TER1 Ket1 Alq.sub.3 LiF 20 nm 20 nm (65%:25%:10%) 30 nm 10 nm 20 nm 1 nm C7 SpA1 HATCN BPA1 ST1:CBP:TEG1 ST1 ST1:LiQ 70 nm 5 nm 90 nm (30%:60%:10%) 30 nm 10 nm (50%:50%) 30 nm C8 SpA1 HATCN BPA1 ST1:TCTA:TEG1 ST1:LiQ 70 nm 5 nm 90 nm (30%:60%:10%) 30 nm (50%:50%) 30 nm C9 HATCN BPA1 Ket1:FTPh:TEG1 Ket1 ETM2 LiF 20 nm 20 nm (60%:30%:10%) 30 nm 10 nm 20 nm 1 nm C10 HATCN BPA1 Ket1:TCTA:TEG1 Ket1 ETM2 LiF 20 nm 20 nm (60%:30%:10%) 30 nm 10 nm 20 nm 1 nm C11 HATCN BPA1 Ket1:CBP:TEG1 Ket1 ETM2 LiF 20 nm 20 nm (60%:30%:10%) 30 nm 10 nm 20 nm 1 nm C12 SpA1 HATCN BPA1 DAP1:CBP:TEG1 ST1:LiQ 70 nm 5 nm 90 nm (30%:60%:10%) 30 nm (50%:50%) 30 nm C13 SpA1 HATCN BPA1 IC1:TEG1 (90%:10%) ST1 ST1:LiQ 70 nm 5 nm 90 nm 30 nm 10 nm (50%:50%) 30 nm C14 HATCN SpA1 HATCN BPA1 M2:D4 (95%:5%) ST1:LiQ LiQ 5 nm 140 nm 5 nm 20 nm 20 nm (50%:50%) 1 nm 30 nm C15 HATCN SpA1 HATCN NPB M2:D4 (95%:5%) ST1:LiQ LiQ 5 nm 140 nm 5 nm 20 nm 20 nm (50%:50%) 1 nm 30 nm C16 HATCN TIFA1 HATCN CbzA1 M2:D4 (95%:5%) ST2:LiQ LiQ 5 nm 140 nm 5 nm 20 nm 20 nm (50%:50%) 1 nm 30 nm C17 HATCN SpA1 HATCN CbzA1 IC1:TEG1 (90%:10%) ST2:LiQ LiQ 5 nm 140 nm 5 nm 20 nm 30 nm (50%:50%) 1 nm 40 nm C18 HATCN SpA1 HATCN CbzA1 CbzA1 M2:D4 (95%:5%) ST2:LiQ LiQ 5 nm 140 nm 5 nm 10 nm 20 nm 20 nm (50%:50%) 1 nm 30 nm C19 HATCN SpA1 HATCN SpA-tb IC1:TEG1 (90%:10%) ST2:LiQ LiQ 5 nm 130 nm 5 nm 20 nm 30 nm (50%:50%) 1 nm 40 nm C20 HATCN SpA1 HATCN SpA-tb IC1:TEG1 (90%:10%) ST2:LiQ LiQ 5 nm 80 nm 5 nm 70 nm 30 nm (50%:50%) 1 nm 40 nm I1 SpA1 HATCN B1 IC1:TEG1 (90%:10%) ST1 ST1:LiQ 70 nm 5 nm 90 nm 30 nm 10 nm (50%:50%) 30 nm I2 SpA1 NPB Ket1:B1:TER1 Ket1 Alq.sub.3 LiF 20 nm 20 nm (65%:25%:10%) 30 nm 10 nm 20 nm 1 nm I3 HATCN SpNPB B2 M2:D3 (98.5%:1.5%) ST2:LiQ 5 nm 40 nm 20 nm 30 nm (50%:50%) 20 nm I4 SpA1 HATCN BPA1 ST1:B2:TEG1 ST1 ST1:LiQ 70 nm 5 nm 90 nm (30%:60%:10%) 30 nm 10 nm (50%:50%) 30 nm I5 HATCN BPA1 Ket1:B2:TEG1 Ket1 ETM2 LiF 20 nm 20 nm (60%:30%:10%) 30 nm 10 nm 20 nm 1 nm I6 HATCN SpA1 B3 M1:D1 (95%:5%) ETM1:LiQ 5 nm 140 nm 20 nm 30 nm (50%:50%) 20 nm I7 HATCN SpA1 B4 M2:D2 (90%:10%) Alq.sub.3 LiF 5 nm 110 nm 20 nm 30 nm 20 nm 1 nm I8 HATCN SpA1 B5 M2:D2 (90%:10%) Alq.sub.3 LiF 5 nm 110 nm 20 nm 30 nm 20 nm 1 nm I9 HATCN SpA1 B6 M2:D2 (90%:10%) Alq.sub.3 LiF 5 nm 110 nm 20 nm 30 nm 20 nm 1 nm I10 HATCN SpA1 B7 M2:D2 (90%:10%) Alq.sub.3 LiF 5 nm 110 nm 20 nm 30 nm 20 nm 1 nm I11 HATCN SpA1 B8 M1:D1 (95%:5%) ETM1:LiQ 5 nm 140 nm 20 nm 30 nm (50%:50%) 20 nm I12 SpA1 HATCN B8 IC1:TEG1 (90%:10%) ST1 ST1:LiQ 70 nm 5 nm 90 nm 30 nm 10 nm (50%:50%) 30 nm I13 SpA1 HATCN BPA1 ST1:B9:TEG1 ST1 ST1:LiQ 70 nm 5 nm 90 nm (30%:60%:10%) 30 nm 10 nm (50%:50%) 30 nm I14 SpA1 HATCN BPA1 DAP1:B9:TEG1 ST1:LiQ 70 nm 5 nm 90 nm (30%:60%:10%) 30 nm (50%:50%) 30 nm I15 HATCN SpA1 B10 M1:D1 (95%:5%) ETM1:LiQ 5 nm 140 nm 20 nm 30 nm (50%:50%) 20 nm I16 SpA1 HATCN B10 Ket1:TEG1 (90%:10%) ST1:LiQ 70 nm 5 nm 90 nm 30 nm (50%:50%) 40 nm I17 HATCN SpA1 B11 M1:D1 (95%:5%) Alq3 LiF 5 nm 140 nm 20 nm 30 nm 20 nm 1 nm I18 HATCN SpA1 B11 M2:D2 (90%:10%) Alq.sub.3 LiF 5 nm 110 nm 20 nm 30 nm 20 nm 1 nm I19 SpA1 HATCN B11 IC1:TEG1 (90%:10%) ST1 ST1:LiQ 70 nm 5 nm 90 nm 30 nm 10 nm (50%:50%) 30 nm I20 HATCN SpNPB B12 M2:D3 (98.5%:1.5%) ST2:LiQ 5 nm 40 nm 20 nm 30 nm (50%:50%) 20 nm I21 SpA1 HATCN BPA1 ST1:B12:TEG1 ST1 ST1:LiQ 70 nm 5 nm 90 nm (30%:60%:10%) 30 nm 10 nm (50%:50%) 30 nm I22 HATCN SpNPB B13 M2:D3 (98.5%:1.5%) ST2:LiQ 5 nm 40 nm 20 nm 30 nm (50%:50%) 20 nm I23 SpA1 HATCN BPA1 ST1:B13:TEG1 ST1 ST1:LiQ 70 nm 5 nm 90 nm (30%:60%:10%) 30 nm 10 nm (50%:50%) 30 nm I24 HATCN SpA1 B14 M1:D1 (95%:5%) Alq3 LiF 5 nm 140 nm 20 nm 30 nm 20 nm 1 nm I25 HATCN SpA1 B14 M2:D2 (90%:10%) Alq.sub.3 LiF 5 nm 110 nm 20 nm 30 nm 20 nm 1 nm I26 HATCN SpA1 B15 M1:D1 (95%:5%) Alq3 LiF 5 nm 140 nm 20 nm 30 nm 20 nm 1 nm I27 HATCN SpA1 B15 M1:D1 (95%:5%) ETM1:LiQ 5 nm 140 nm 20 nm 30 nm (50%:50%) 20 nm I28 HATCN SpA1 B16 M1:D1 (95%:5%) ETM1:LiQ 5 nm 140 nm 20 nm 30 nm (50%:50%) 20 nm I29 HATCN SpA1 B17 M1:D1 (95%:5%) ETM1:LiQ 5 nm 140 nm 20 nm 30 nm (50%:50%) 20 nm I30 HATCN SpA1 B18 M1:D1 (95%:5%) ETM1:LiQ 5 nm 140 nm 20 nm 30 nm (50%:50%) 20 nm I31 HATCN SpNPB B18 M2:D3 (98.5%:1.5%) ST2:LiQ 5 nm 40 nm 20 nm 30 nm (50%:50%) 20 nm I32 SpA1 NPB Ket1:B18:TER1 Ket1 Alq3 LiF 20 nm 20 nm (65%:25%:10%) 30 nm 10 nm 20 nm 1 nm I33 SpA1 HATCN B19 IC1:TEG1 (90%:10%) ST1 ST1:LiQ 70 nm 5 nm 90 nm 30 nm 10 nm (50%:50%) 30 nm I34 SpA1 HATCN B20 IC1:TEG1 (90%:10%) ST1 ST1:LiQ 70 nm 5 nm 90 nm 30 nm 10 nm (50%:50%) 30 nm I35 SpA1 HATCN B21 IC1:TEG1 (90%:10%) ST1 ST1:LiQ 70 nm 5 nm 90 nm 30 nm 10 nm (50%:50%) 30 nm I36 HATCN SpA1 C M1:D1 (95%:5%) Alq3 LiF 5 nm 140 nm 20 nm 30 nm 20 nm 1 nm I37 HATCN SpA1 C M1:D1 (95%:5%) ETM1:LiQ 5 nm 140 nm 20 nm 30 nm (50%:50%) 20 nm I38 HATCN SpA1 C M2:D2 (90%:10%) Alq.sub.3 LiF 5 nm 110 nm 20 nm 30 nm 20 nm 1 nm I39 SpA1 HATCN C IC1:TEG1 (90%:10%) ST1 ST1:LiQ 70 nm 5 nm 90 nm 30 nm 10 nm (50%:50%) 30 nm I40 HATCN SpA1 HATCN C M2:D4 (95%:5%) ST2:LiQ LiQ 5 nm 140 nm 5 nm 20 nm 20 nm (50%:50%) 1 nm 30 nm I41 HATCN SpA1 HATCN C M2:D4 (95%:5%) ST1:LiQ LiQ 5 nm 140 nm 5 nm 20 nm 20 nm (50%:50%) 1 nm 30 nm I42 HATCN TIFA1 HATCN B1 M2:D4 (95%:5%) ST2:LiQ LiQ 5 nm 140 nm 5 nm 20 nm 20 nm (50%:50%) 1 nm 30 nm I43 HATCN TIFA1 HATCN C M2:D4 (95%:5%) ST2:LiQ LiQ 5 nm 140 nm 5 nm 20 nm 20 nm (50%:50%) 1 nm 30 nm I44 HATCN SpA1 HATCN C B18 M2:D4 (95%:5%) ST2:LiQ LiQ 5 nm 125 nm 5 nm 10 nm 20 nm 20 nm (50%:50%) 1 nm 30 nm I45 HATCN SpA1 HATCN C D M2:D4 (95%:5%) ST2:LiQ LiQ 5 nm 125 nm 5 nm 10 nm 20 nm 20 nm (50%:50%) 1 nm 30 nm I46 HATCN SpA1 HATCN C B19 M2:D4 (95%:5%) ST2:LiQ LiQ 5 nm 125 nm 5 nm 10 nm 20 nm 20 nm (50%:50%) 1 nm 30 nm I47 HATCN SpA1 HATCN C5 M2:D4 (95%:5%) ST2:LiQ LiQ 5 nm 140 nm 5 nm 20 nm 20 nm (50%:50%) 1 nm 30 nm I48 HATCN SpA1 HATCN CbzA1 C6 M2:D4 (95%:5%) ST2:LiQ LiQ 5 nm 140 nm 5 nm 10 nm 20 nm 20 nm (50%:50%) 1 nm 30 nm I49 HATCN SpA1 HATCN C6 IC1:TEG1 (90%:10%) ST2:LiQ LiQ 5 nm 140 nm 5 nm 20 nm 30 nm (50%:50%) 1 nm 40 nm I50 HATCN SpA1 HATCN C7 IC1:TEG1 (90%:10%) ST2:LiQ LiQ 5 nm 140 nm 5 nm 20 nm 30 nm (50%:50%) 1 nm 40 nm I51 HATCN SpA1 HATCN B22 IC1:TEG1 (90%:10%) ST2:LiQ LiQ 5 nm 140 nm 5 nm 20 nm 30 nm (50%:50%) 1 nm 40 nm I52 HATCN TIFA1 HATCN C1 M2:D4 (95%:5%) ST2:LiQ LiQ 5 nm 140 nm 5 nm 20 nm 20 nm (50%:50%) 1 nm 30 nm I53 HATCN SpA1 HATCN B23 IC1:TEG1 (90%:10%) ST2:LiQ LiQ 5 nm 140 nm 5 nm 20 nm 30 nm (50%:50%) 1 nm 40 nm I54 SpA1 HATCN B24 IC1:TEG1 (90%:10%) ST1 ST1:LiQ 70 nm 5 nm 90 nm 30 nm 10 nm (50%:50%) 30 nm I55 HATCN SpA1 HATCN B24 M2:D4 (95%:5%) ST2:LiQ LiQ 5 nm 140 nm 5 nm 20 nm 20 nm (50%:50%) 1 nm 30 nm I56 HATCN SpA1 HATCN B25 M2:D4 (95%:5%) ST2:LiQ LiQ 5 nm 140 nm 5 nm 20 nm 20 nm (50%:50%) 1 nm 30 nm I57 SpA1 HATCN C2 IC1:TEG1 (90%:10%) ST1 ST1:LiQ 70 nm 5 nm 90 nm 30 nm 10 nm (50%:50%) 30 nm I58 SpA1 HATCN C4 IC1:TEG1 (90%:10%) ST1 ST1:LiQ 70 nm 5 nm 90 nm 30 nm 10 nm (50%:50%) 30 nm I59 HATCN SpA1 HATCN CbzA1 B26 M2:D4 (95%:5%) ST2:LiQ LiQ 5 nm 140 nm 5 nm 10 nm 20 nm 20 nm (50%:50%) 1 nm 30 nm I60 HATCN SpA1 HATCN CbzA1 B27 M2:D4 (95%:5%) ST2:LiQ LiQ 5 nm 140 nm 5 nm 10 nm 20 nm 20 nm (50%:50%) 1 nm 30 nm I61 HATCN SpA1 HATCN C IC1:TEG1 (90%:10%) ST2:LiQ LiQ 5 nm 130 nm 5 nm 20 nm 30 nm (50%:50%) 1 nm 40 nm I62 HATCN SpA1 HATCN C IC1:TEG1 (90%:10%) ST2:LiQ LiQ 5 nm 80 nm 5 nm 70 nm 30 nm (50%:50%) 1 nm 40 nm I63 HATCN SpA1 HATCN C5 IC1:TEG1 (90%:10%) ST2:LiQ LiQ 5 nm 130 nm 5 nm 20 nm 30 nm (50%:50%) 1 nm 40 nm I64 HATCN SpA1 HATCN C5 IC1:TEG1 (90%:10%) ST2:LiQ LiQ 5 nm 80 nm 5 nm 70 nm 30 nm (50%:50%) 1 nm 40 nm I65 HATCN SpA1 HATCN B16 IC1:TEG1 (90%:10%) ST2:LiQ LiQ 5 nm 130 nm 5 nm 20 nm 30 nm (50%:50%) 1 nm 40 nm I66 HATCN SpA1 HATCN B16 IC1:TEG1 (90%:10%) ST2:LiQ LiQ 5 nm 80 nm 5 nm 70 nm 30 nm (50%:50%) 1 nm 40 nm I67 HATCN SpA1 HATCN B18 M2:D4 (95%:5%) ST2:LiQ LiQ 5 nm 140 nm 5 nm 20 nm 20 nm (50%:50%) 1 nm 30 nm I68 B6 HATCN BPA1 IC1:TEG1 (90%:10%) ST1 ST1:LiQ 70 nm 5 nm 90 nm 30 nm 10 nm (50%:50%) 30 nm

(42) TABLE-US-00008 TABLE 2 Data for the OLEDs U1000 CE1000 PE1000 EQE CIE x/y at L0 Lifetime Ex. (V) (cd/A) (lm/W) 1000 1000 cd/m.sup.2 (cd/m.sup.2) L1 % (h) C1 6.4 5.1 2.5 4.2% 0.14/0.15 6000 50 150 C2 4.7 8.1 5.4 6.3% 0.14/0.16 6000 50 145 C3 5.0 17 11 5.0% 0.28/0.61 25000 50 480 C4 4.3 9.8 7.1 7.6% 0.141/0.160 6000 50 210 C5 3.9 41 33 11.0% 0.36/0.61 4000 80 315 C6 4.3 7.7 5.6 10.8% 0.68/0.32 4000 80 360 C7 4.4 48 34 13.3% 0.37/0.60 4000 80 450 C8 4.2 43 32 12.0% 0.35/0.60 4000 80 195 C9 4.0 46 36 12.8% 0.36/0.61 4000 80 370 C10 3.9 42 34 11.6% 0.35/0.60 4000 80 175 C11 4.1 44 34 12.3% 0.36/0.61 4000 80 280 C12 4.6 47 32 13.2% 0.36/0.60 4000 80 490 C13 3.5 53 48 14.8% 0.36/0.60 4000 80 430 C14 4.2 7.0 9.5 7.4% 0.14/0.16 6000 50 250 C15 4.2 8.2 6.3 6.5% 0.14/0.16 6000 50 315 C16 4.4 7.6 5.4 5.4% 0.14/0.18 6000 65 240 C17 3.5 59 53 16.4% 0.37/0.60 10000 70 235 C18 4.3 8.4 6.1 6.5% 0.14/0.16 6000 50 320 C19 3.5 59 53 16.3% 0.37/0.60 10000 65 310 C20 4.1 57 43 15.9% 0.37/0.60 10000 65 210 I1 3.7 59 50 16.4% 0.36/0.60 4000 80 490 I2 4.2 9.0 6.7 12.8% 0.68/0.32 4000 80 460 I3 4.4 10.4 7.4 8.1% 0.14/0.16 6000 50 260 I4 4.0 51 40 14.2% 0.37/0.61 4000 80 620 I5 3.7 50 43 14.0% 0.37/0.61 4000 80 550 I6 4.6 9.1 6.3 7.1% 0.14/0.16 6000 50 130 I7 5.1 19 12 5.4% 0.28/0.61 25000 50 460 I8 5.1 18 11 5.2% 0.28/0.61 25000 50 520 I9 4.8 20 13 5.8% 0.28/0.61 25000 50 530 I10 5.0 18 11 5.3% 0.28/0.61 25000 50 430 I11 4.7 8.7 5.8 6.8% 0.14/0.15 6000 50 160 I12 3.4 58 54 16.1% 0.36/0.60 4000 80 420 I13 4.1 50 38 13.9% 0.37/0.61 4000 80 470 I14 3.9 52 41 14.4% 0.37/0.61 4000 80 460 I15 4.8 9.2 6.1 7.2% 0.14/0.15 6000 50 230 I16 4.0 46 36 12.8% 0.37/0.60 4000 80 470 I17 6.1 6.7 3.4 5.5% 0.14/0.15 6000 50 230 I18 5.2 20 12 5.7% 0.28/0.61 25000 50 620 I19 3.5 56 50 15.6% 0.36/0.60 4000 80 550 I20 4.5 11 7.6 8.4% 0.14/0.16 6000 50 290 I21 3.8 47 40 13.1% 0.36/0.62 4000 80 440 I22 4.5 11 7.3 8.2% 0.14/0.16 6000 50 270 I23 3.7 49 41 13.6% 0.36/0.62 4000 80 470 I24 6.2 6.2 3.1 5.1% 0.14/0.15 6000 50 175 I25 5.0 19 12 5.7% 0.28/0.61 25000 50 510 I26 6.3 6.4 3.2 5.3% 0.14/0.15 6000 50 190 I27 4.8 9.5 6.2 7.4% 0.14/0.15 6000 50 175 I28 4.5 8.7 6.1 6.8% 0.14/0.15 6000 50 180 I29 4.6 7.9 5.4 6.2% 0.14/0.16 6000 50 165 I30 4.8 9.5 6.3 7.4% 0.14/0.16 6000 50 245 I31 4.4 11 7.5 8.2% 0.14/0.160 6000 50 280 I32 4.4 8.2 5.9 11.6% 0.68/0.32 4000 80 420 I33 3.6 57 50 15.9% 0.36/0.60 4000 80 410 I34 3.8 58 49 16.1% 0.36/0.60 4000 80 380 I35 3.4 59 54 16.4% 0.37/0.60 4000 80 360 I36 6.2 6.6 3.3 5.4% 0.14/0.15 6000 50 215 I37 4.7 9.5 6.3 7.4% 0.14/0.16 6000 50 240 I38 5.2 19 12 5.7% 0.28/0.61 25000 50 610 I39 3.6 57 50 15.8% 0.36/0.60 4000 80 530 I40 4.2 10 7.4 7.7% 0.14/0.16 6000 50 390 I41 3.9 10.3 8.3 8.3% 0.14/0.16 6000 50 360 I42 4.5 8.3 5.7 5.9% 0.14/0.18 6000 65 280 I43 4.3 9.0 6.6 6.4% 0.14/0.18 6000 65 295 I44 4.3 9.0 6.3 7.3% 0.14/0.15 6000 65 185 I45 4.5 9.5 6.7 7.5% 0.14/0.16 6000 65 190 I46 4.7 10.5 6.9 8.5% 0.14/0.16 6000 65 165 I47 4.2 9.7 7.2 7.5% 0.14/0.16 6000 50 395 I48 4.3 10.1 7.7 8.4% 0.14/0.16 6000 50 300 I49 3.3 62 58 17.1% 0.37/0.60 10000 70 230 I50 3.4 61 57 17.3% 0.37/0.60 10000 70 240 I51 3.5 64 58 17.7% 0.37/0.60 10000 70 225 I52 4.2 9.9 7.4 7.8% 0.14/0.16 6000 50 340 I53 3.6 60 53 16.5% 0.37/0.60 10000 70 215 I54 3.5 56 49 15.4% 0.36/0.60 4000 80 495 I55 4.3 8.7 6.5 6.8% 0.14/0.16 6000 50 350 I56 4.2 9.5 7.0 7.3% 0.14/0.16 6000 50 355 I57 3.5 56 50 15.4% 0.36/0.60 4000 80 460 I58 3.6 59 52 16.3% 0.36/0.60 4000 80 490 I59 4.2 9.9 7.4 7.7% 0.14/0.60 6000 50 240 I60 4.2 9.5 7.1 7.4% 0.14/0.60 6000 50 290 I61 3.4 61 56 16.8% 0.37/0.60 10000 65 380 I62 3.5 60 54 16.5% 0.37/0.60 10000 65 370 I63 3.5 61 55 16.9% 0.37/0.60 10000 65 305 I64 3.7 59 50 16.3% 0.37/0.60 10000 65 270 I65 3.4 56 51 15.4% 0.37/0.60 10000 65 340 I66 3.6 55 47 15.3% 0.37/0.60 10000 65 345 I67 4.2 8.8 6.6 7.1% 0.14/0.16 6000 50 315 I68 3.4 55 50 15.1% 0.36/0.60 4000 80 465 Sol1 4.8 8.4 5.5 6.9% 0.14/0.15 6000 50 155 Sol2 4.7 6.8 4.6 5.5% 0.14/0.15 6000 50 260 Sol3 4.7 6.4 4.3 5.4% 0.14/0.14 6000 65 190

(43) TABLE-US-00009 TABLE 3 Structural formulae of the materials for the OLEDs 0 0 0